TW201224121A - Compositions and methods for texturing of silicon wafers - Google Patents

Abstract

Pre-texturing composition for texturing silicon wafers having one or more surfactants. Methods of texturing silicon wafers having the step of wetting said wafer with a pre-texturing composition having one or more surfactants followed by a texturing step.

Description

201224121 VI. INSTRUCTIONS: Cross-references to related applications. The present invention claims US Provisional Application No. 61/416,998, filed on November 24, 2010 (Attorney Docket No. 〇7482Z) and 2〇ι年年月二二申U.S. Provisional Application No. 61/530,760 (Attorney Docket No. 07482Z2), the entire disclosure of which is incorporated herein by reference. TECHNICAL FIELD OF THE INVENTION The present invention relates to a pre-textured composition of a textured tantalum wafer and a method thereof, the pre-textured composition having one or more surfactants. [Prior Art] The present invention relates to the texturing of a photovoltaic wafer surface. In order to improve the conversion efficiency of light energy, it is desirable to have a very low reflective surface. For example, single crystal germanium, in a method called texturing, can be achieved by anisotropic etching of a twinned circle to form a pyramidal structure on the surface. It is desirable to have a uniform and dense distribution of the cone on the surface of the wafer to achieve a low reflectance. 0 The desired width of the 3 hypothalamus is less than 10 μm and the size is uniform. A small, uniform pyramid structure ensures good coverage of the passivation layer, which is then deposited on top of the textured surface to prevent loss of efficiency. The smaller and uniform pyramid structure also ensures that the metal contact lines printed on the surface of the crucible are narrower, allowing more light energy to pass through to the surface of the stone for photoelectric conversion.

The prior art reference materials include: WO 2009120631 A2, CN 101634026 A, CN 101634027 A, DE 102007058829 A1, 201224121 WO 2009119995 A2, US 4137123 A, CN 101217173 A, CN 1983644 A, CN 1983645 A, JP 200912381 1 A, EP 944114 A2, EP 1 890338 A1, Basu, PK et al. ' Solar Energy Materials & Solar Cells (2010), 94(6), 1049-1054, Basu PK et al., Renewable Energy (2009), 34(12), 2571 -2576, WO 2009071333, Gangopadhyay U. et al., Solar Energy Materials & Solar Cells (2006), 90 (18-19), 3094-3101 and WO 2008022671. SUMMARY OF THE INVENTION The present invention provides a pre-textured composition for use in a method of texturing a germanium wafer comprising a surfactant; and comprising one or more cationic, nonionic, amphoteric and anionic surfactants and A pre-textured composition of the mixture thereof. The present invention further provides a pre-textured composition for a texturing process for tantalum wafers comprising or additionally comprising one or more polyoxosiloxane surfactants. The invention further provides various pre-textured compositions comprising or consisting essentially of one or more surfactants and water or one or more surfactants, water and acid. The invention further provides a pre-textured composition for texturing methods comprising one or more cationic, nonionic, amphoteric and anionic surfactants and water, and/or one or more polyoxynitrides Surfactant and water or one or more cationic, nonionic, amphoteric and anionic surfactants, water and acid, and/or one or more polyoxyalkylene surfactants, water and acid, by or Basically composed of them. Any of the above compositions may additionally comprise one or more acids and/or one or more bases and/or 201224121 - or more antifoaming agents and / or - or other additives, substantially by or by And so on. The present invention further provides a method of texturing a wafer wafer comprising the step of wetting the wafer with the present invention comprising one or more surfactants or more pre-textured compositions; and another texture fossil a method of wafer comprising the step of wetting the wafer with a pre-textured composition comprising a cationic, nonionic, amphoteric, anionic surfactant and/or a polyoxyalkylene surfactant; & A method of texture dicing, comprising a τ column step: wetting the wafer with a pre-textured composition comprising a surfactant and wetting the wafer with an etch composition. Any of the above pre-textured compositions can be used in the method of the present invention. The composition of the present invention can be used in the texturing method of the present invention to process tantalum wafers or substrates or tantalum films deposited on different types of substrates (the wording substrates or wafers are mutually compatible herein and in the scope of the patent application) Exchange used to represent all of this). Silicon wafers processed in accordance with these inventions can be used to fabricate photovoltaic cells. Wafers that are subjected to the compositions and/or methods of the present invention exhibit improved texturization uniformity and reduced reflectivity over wafers that are not subjected to such processing. Other benefits that may be achieved by the methods and/or compositions of the present invention may include one or more of the following: (1) creating a pyramidal structure on the surface of the wafer that has a high density and has less than one 〇μηη, or an average height of less than 8 μηη or less than 5 μηη or less than 4 μηι; (the average cone height often exceeds 丨〇μιη without the treatment according to the invention.) (2) lowering the textured surface Reflectance; (3) shorten the time required to form a cone and/or form a textured surface with low reflectivity; (4) reduce the sensitivity of the texture 201224121 quality to the isopropanol concentration in the texturing method, and In some embodiments, texturing can be performed without any isopropyl alcohol or any additives needed to promote texturing in the one or more texturing compositions, (5) when the texturing When the pre-textured composition and step are used in the method, the need for additives in the textured (etched) composition or solution to improve the quality and throughput of texturing can be reduced or eliminated; (6) a reduction in the total amount of ruthenium etched in the physicochemical step; (7) a growth bath life of the texturing composition, the texturing composition also means a texturing or etching solution; (8) an improved coverage of the passivation layer; The metal contact line printed on the front side of the crystal face is narrow; (10) improving the wettability of the surface of the crucible prior to texturing; and (11) improving the electrical test parameters of the solar cell. Electrical test parameters may include, for example, short circuit current, open circuit voltage, and photoelectric conversion efficiency. Pre-texturing using compositions or formulations used in the texturing methods of the present invention (these words can be used interchangeably in the text), compared to conventional prior art texturing methods, will be textured for some embodiments. The time is shortened to 30 minutes or less, 2 minutes or less, 1 minute or less, or 5 minutes or less. This results in reduced processing times for some embodiments and thus increased throughput of the wafer processing. In some embodiments, when the pre-textured compositions or formulations are used in the texturing method of the present invention, the cone size and density and wafer reflectivity also change weakly or significantly over time. Sensitivity to the concentration of one or more texturing compositions in the one or more texturing baths during the method is weak, resulting in improved robustness of the method's. Therefore, if there is a program instability condition, longer or shorter can be used. The texturing time' is not detrimental to the performance of the photovoltaic device. 201224121 [Embodiment] Photovoltaic single crystal wafer processing typically involves the following initial steps: cleaning to remove any contamination and removal of the cut wafer (cut from the scales) typical of the saw blade stain in concentrated alkali solution The damage is then textured in a dilute alkaline solution to create a (four) texture on the surface that will reduce the reflectivity of the surface and allow more light energy to be converted into electricity to increase the efficiency of the wafer. Processing with respect to polycrystalline germanium wafers may involve the following initial steps: cleaning to remove any contamination directly' followed by texturing. What we want is as low as possible. Our invention provides compositions and methods for improving the texturing of the wafer surface. Our invention relates to treating the wafer surface with a pre-textured composition comprising one or more surfactants or solutions. One or more surfactants and one or more solvents (possibly water). In the case of a textured single wafer wafer, the composition modified the wafer surface and resulted in a high nucleation density cone, resulting in an expected small cone uniform distribution. With respect to polycrystalline germanium wafers, this surface modification improves the uniformity of the textured surface and results in lower surface reflectivity. The composition of the present invention can be used in at least one pre-texturing step in a multi-step process for texturing a wafer, which can be a single crystal substrate (e.g., Si<100>4 Si<lll>), microcrystalline germanium Substrate, polycrystalline germanium substrate, strained germanium substrate, amorphous germanium substrate, doped or undoped polycrystalline germanium substrate, glass, sapphire or any type of germanium containing substrate. The substrate can also be a ruthenium film deposited on a different type of substrate such as a metal, glass or polymer. The pre-texturing step of performing the texturing step is a pre-treatment 201224121 step involving the use of the composition of the present invention comprising a surfactant or a mixture of more than one surfactant in solution. It is believed that the composition comprising one or more surfactants will improve the reflectivity of the circle after or during the pre-texturing step and the texturing step. The 8H pre-texturing step can use the composition of the present invention comprising the surfactant, and the texturing step can be any standard texturing using any known etching composition or etching solution (also known as wet etchant). Or the last name step. For example, the texturing step can use any standard texturing solution in a standard texturing bath. Pre-texturing of the shawl in the pre-texturing step will provide an additional benefit of the composition cleaning the surface of the stone. After the texturing method is completed, the texturing quality is improved with the formation of high density, the small cones for the single crystal case and the more uniform textured surface for the polysilicon case, resulting in lower reflectivity. The pre-textured composition of the invention as described above comprises one or more surfactants. Any type of surfactant, fresh ionic, cationic, nonionic, amphoteric surfactant or a combination thereof can be used. In some embodiments, the surfactants used in the compositions of the present invention are those which reduce the use of the guillotine and the pre-textured composition of the present invention (more than 5 in the chain) 0^^ = a molecule having a large or long carbon atom bond β t , an atom) and having a polar group and a non-polar group in the molecule. The pre-textured composition may be a surfactant or at least one selected from the group consisting of nonionic all-type surfactants, including, but not limited to, alkylphenol ethoxylates, alcohols, and ethyl alcohol. Propylene glycols, polyoxyethylated thiol materials, known as long-chain s-esters (the use of "long 201224121 chain ~ private °Hail chain has more than 5 carbon, for example, in many specific examples" ^Long bond can contain 5 to 20, delete carbon), natural fatty acid of Ganzi class #装glyceride, propylene glycol ester, sorbitol ester, polyoxyethylene 4 gal, ga Glycol g-type, polyoxyethylated fatty acids, melamines, block diols, polyoxyethylated polyoxins, n-alkyl bromones, alkyl polyglycosides a polyoxyalkylene surfactant and a fluorinated surfactant or a mixture of these and any of the surfactants disclosed herein. The polyoxygenated surfactant may be referred to as a polymerized oxygenator or polyoxygen. And is a mixed inorganic organic polymer with chemical milk called 'where R is an organic group such as A Base, ethyl or phenyl, and n greater than 1. The polyoxyalkylene surfactants can be added to the pre-textured compositions at a concentration of from 1 to 1% by weight. An amount of up to 1% by weight. An example of a commercially available polyoxyalkylene surfactant is DOW Antifoam 1430. The pre-textured composition may comprise one or more surfactants, at least it may comprise Nonionic surfactants for processing compositions. Nonionic surfactants include, but are not limited to, alkylphenol ethoxylates such as TRITON®®-100, Χ_705, χ_114, χ_1〇2, χ_45, X 1 5 Tergitol® ΝΡ-9, ΝΡ-30 (available from Dow Chemicals); alcohol ethoxylates such as: TergitolTM 15-S-7, 15-S-30, TMN-6, TMN-10 (available from Dow Chemicals); polyethylene glycols (molecular weight between 100 and 1000000); and acetylene glycols or mixtures thereof or mixtures with any of the surfactants disclosed herein. Examples of acetylene glycol surfactants Including 201224121 manufactured by Air Products and Chemicals Co., Ltd.

Surfynol® 485, 465 and 2502 and Dynol® 604. The pre-textured composition may comprise one or more surfactants, at least one of which may comprise an anionic surfactant such as a linear alkyl benzene sulfonate (LAS), a linear fatty acid and/or a salt thereof, a coconut Oil fatty acid derivatives, tall oil acid derivatives, sarcosides, acetamidine polypeptides, secondary alkyl benzoate, lignosulfonates, N-mercapto-positive -alkyl taurate, fatty alcohol sulfate (FAS), petrochemical sulfonate, secondary alkane sulfonate (SAS), paraffin sulfonate, fatty alcohol ether sulfate (Faes) , a-olefin olefinic acid esters, thiosuccinic acid esters, alkylnaphthalene sulfonates, isethionates, sulfates, sulfated linear primary alcohols, sulfated polycondensation An oxyethylenated linear alcohol, a sulfated triglyceride oil, a phosphatide and a polyphosphate, and a perfluorinated anionic surfactant or a mixture of these and any of the surfactants disclosed herein. The textured compositions may comprise a-olefin sulfonates having the structure: R-ch = ch S03Na + wherein R is an alkyl group, for example, a linear alkyl group having from 1 to 18 carbons. The pre-textured composition may comprise one or more surfactants, at least " may comprise a cationic surfactant comprising long chain amines and salts thereof, diamines and polyamines And their salts, seasonal salts, polyoxyethylene chain (4), quarter-polyoxyethylene (p(III) long-bond amines and amine oxides and these (4) surfactants An example of a cationic surfactant is by a Muds _

10 201224121

Tomadyne 102 manufactured by Chemicals, Inc. The pre-textured composition may comprise one or more surfactants, at least one of which may comprise an amphoteric surfactant, the amphiphilic surfactant comprising, a simple amino acid, a pyridyl derivative (eg, glycine, beet) Mixtures of bases and alanines, imidazolines, thiobetaines and amine oxides, and mixtures of these and any of the surfactants disclosed herein. Commercially available surfactants useful in the texturized compositions of the present invention include: Hostapur® SAS, a secondary alkanesulfate-sodium salt manufactured by Clariant, Inc.; Calfax® DBA70, manufactured by Pilot Chemical Company. C12 (branched) diphenyl ether dicarboxylic acid; Calfoam ® ES-302 (sodium lauryl ether sulfate) manufactured by Pilot Chemical Company; Calfoam ® ALS-30 (sodium lauryl sulfate) manufactured by Pilot Chemical Company ); AEROSOL® NPES-3030 P Mystery sulfate vinegar manufactured by CYTEC CANADA Co., Ltd.; and Dequest® 'sulfonated acrylic base polymer from ThermPhos. Still other exemplary surfactants, the compositions of the present invention may include acetylene glycol type surfactants, alcohol (primary and secondary) ethoxylates, phenyl ethoxylates, amine ethoxylates. Compounds, glucosides, glucosamines, polyethylene glycols, poly(ethylene glycol-co-propylene glycol) or other surfactants provided in the following references: by Rock Valley, New Jersey Published by Manufacturers Confectioners Publishing Co.

McCutcheon’s Emulsifiers and Detergents, 2000 North American edition. Any surfactant or a mixture of such surfactants may be used in the pre-textured composition of the present invention in any amount or at a concentration of from 〇〇J% by weight to 30% by weight 'or 2 to 30% by weight, Or 6 wt% to 30 wt 11 201224121 wt%, or (Μ wt% to 20 wt%, or 〇 5 wt% to 2 wt%, or ^ to 20 wt% ' or 2 to 2 wt%, or i Up to 15% by weight, or higher than 5 to 30% by weight 'or h5 to 2% by weight or 〇5 to ι〇% by weight. Or containing more than 〇.〇1% by weight, or Μ% by weight, or higher than A surfactant solution of 1 to 5 wt%, or more than 5% by weight or more than 6% by weight, or greater than w% by weight, may also be used in the pre-textured compositions. In embodiments, the pre-textures: the composition is an aqueous solution. Note that weight percent (% by weight), like all weight % herein, is the total weight of the pre-textured, textured or other solution, composition or formulation. For reference, any volume % defined in the text is also pre-textured as described or The total volume of the solution, composition or formulation is based on. The useful surfactant can be purified by appropriate techniques to remove metallic impurities. Purification of the surfactant can be a preliminary step in the preparation of the pre-textured composition of the present invention. - There is a material purification technique for performing ion exchange of the surfactant. In most embodiments, the pre-textured formulations are made by immersing all components in a suitable container (which can be a bath) The composition is stirred and mixed. If necessary, the composition can be heated during mixing to aid in the formation of the solution. Further, the surfactant used in the pre-textured composition of the present invention can be an anion. One or more of a type of surfactant or a surfactant having a sulfate or sulfo functional group or a secondary alkanesulfonate surfactant or an alkyl sulfate surfactant or a mixture thereof. It can be used in the form of the free acid and the salt. The surfactant having a sulfonate group can have the following structure:

12 201224121 R1 - CH - R2

I so3x wherein R and R are independently a linear or cyclic alkyl group or a phenyl group or a combination thereof, which typically contains from 1 to 20 carbons and is hydrogen or any cation including Na, K, tetramethylammonium, and day B. Alkyl ammonium, triethanolamine or ammonium. In some embodiments, the sulfo surfactants comprise a linear alkyl group. An example of such a surfactant is the Hostapur® SAS surfactant commercially available from Curant, which comprises a molecule having the following structure: - ICHgIg - CH - {CHila - m + n = 10 to 14; sulfonate groups The group is distributed on the carbon chain such that the carbon chain is mainly a substituted secondary carbon atom. Further, the surfactant used in the pre-textured composition of the present invention may be a fatty alcohol sulfate vinegar, which is derived from Sulfonation of a fatty alcohol having a carbon chain length of from 8 to 2 atoms. An example of a surfactant that can be used in the pre-textured composition of the present invention is a compound having the formula ci2H250.(C2H40)2.S03.Na. Sodium lauryl sulfate. For such surfactants that are commercially produced, the carbon chain length can vary from 1 carbon atom to 18 carbon atoms. The surfactant may also contain a plurality of different carbon chain lengths. The distribution of surfactants. Another example of a surfactant that can be used in the pre-textured composition of the present invention comprises sodium laureth sulfate having the following structure: 13 201224121

Wherein "η" is the number of ethoxylate groups in the surfactant chain and can vary from 1 to 5. The length of the carbon chain can vary from 10 carbon atoms to 18 carbon atoms for such commercially produced surfactants. The surfactant may also contain a distribution of a plurality of different carbon chain length surfactants. The pre-textured composition of the present invention may comprise a n-alkyl betaine surfactant. These surfactants are amphoteric in nature and exhibit anionic character at acidic 卩11 and cationic characteristics at basic Η. Another example of a surfactant that can be used in the pre-textured composition is NN-dimethyl-N-dodecylglycine betaine having the linear formula CH3(CH2)8-14CH2N+(CH3)2CH2COO Na , sold under the registered name of Empigen® BB by Sigma Aldrich Chemicais. Another example is N-N-dimethyldodecylglycine betaine having this linear molecular formula CH3(CH2)8.14CH2N+(CH3)2CH2CO〇-Na. The carbon chain length can vary from 10 carbon atoms to 18 carbon atoms for such commercially produced surfactants. The surfactant may also contain a plurality of different carbon chain length surfactant distributions. Other examples of alkyl betain base surfactants include myristyl betaine, coco beet test, cocoamido beet test and oleyl beet test. The pre-textured composition may comprise one or more surfactants selected from the surfactants disclosed above. In one embodiment, a polyoxyalkylene-containing surfactant is added to the pre-textured composition comprising the first surfactant or interfacial surfactant mixture to improve the texturing properties. The 201224121 surfactant can be A/Ma any other type of anionic, amphoteric, cationic or nonionic interface/tongue agent. In some embodiments, the first surfactant 遝6 is selected from the group of surfactants, which comprise an alkyl sulphate, a succinic acid-salt, a secondary succinic acid ester. , fatty alcohol sulfates, alcohol ether sulfates _,. A-olefin sulfonates and alkyl betaines. The interface/tongue of the poly-stone-containing oxygen element is described as A" also 143 〇. The concentration of the polyoxyalkylene-containing surfactant may range from 0.001% by weight to 2% by weight when used as the first surfactant, and the concentration of the surfactant- or surfactant mixture may be between 11% by weight to 10% by weight. In another embodiment, a less soluble hydrophobic surfactant molecule can be dissolved using a surfactant. Any solvolysis surfactant surfactant can be used to increase the solubility of a sparingly soluble surfactant such as an acetylene glycol surfactant. The choice of the one or more surfactants may depend on their ability to improve the surface of the wafer to nucleate the cone and clean the surface. The surfactant-containing pre-textured composition may also include one or more additives to promote cleaning and/or texturing (etching) of the wafer surface. Cleaning the additive will help remove debris remaining on the surface, for example, if there are fragments, even after the blade stain removal step. The pre-textured composition of the present invention may optionally comprise one or more components, including inorganic or organic acids, bases, chelating agents, fractions, sizing agents, antifoaming agents or mixtures thereof. For example, 'acids and bases and other additives can be added to the pre-textured composition to improve its cleaning performance. Organic acids can be used to improve the effectiveness of trace metals, organic, beneficial % a t, human β kicks and inorganic residues. Organic acids can be selected from a wide range of acids, including but limited to 15 201224121 in: oxalic acid 'citric acid, butadiene, malic acid, malonic acid, glucuronic acid, glutaric acid, ascorbic acid, formic acid, acetic acid, B Diaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycine acid, aniline, cystamine, sulfonic acid, various derivatives of sulfonic acid, and the like, or mixtures thereof, and salts of these acids can also be used. Mixtures of these acids/salts can also be used. The pre-textured composition may additionally comprise inorganic acids and/or salts thereof. These inorganic acids and salts thereof can be used in combination with other organic acids and/or salts thereof. Examples of the inorganic acid include hydrogen acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, sulfamic acid, and the like. Mixtures of these acids/salts can also be used. The pre-textured composition of the present invention may contain any amount of an acid and/or a salt thereof (acid/salt) or hydrazine to 30% by weight or 0.001 to 30% by weight of an acid/salt. The acid may be present in any amount or in the range of from 0.1 to 1% by weight or to 5% by weight. Combinations of acids and salts can also be used to buffer the solution at the desired pH level. When the acid/salt is added to the pre-textured composition, it is often between 0.25 and 1% by weight or between 〇5 to 5 based on the total weight of the pre-textured composition. The amount between the % by weight "acids/salts" can also be added to the etch/texture composition. When the acid/salt is added to the etching composition, it is often between 〇 to 1% by weight or between 〇 to 5% by weight based on the total weight of the etching composition. use. In some embodiments, the pre-textured and/or textured compositions are free or substantially free (regardless of where they are applied "substantially free" means less than 0.001% by weight unless otherwise stated herein Indicates] Acids and / or acid mixtures and their salts.

16 201224121 The pre-textured composition used in the method of the present invention may additionally comprise one or more bases. The base may be selected from a range of chemicals including, but not limited to, argon oxidation, oxidization, oxidized quarters, amines, guanidiene carbonate, and organic bases. These bases can be used alone or in combination with other bases. Examples of suitable organic bases include, but are not limited to, hydroxylamines, ethylene glycol, glycerin, organic amines (eg, primary, secondary or secondary aliphatic amines, alicyclic amines, aromatic amines, and Heterocyclic amines, ammonia, and quaternary ammonium hydroxides. Specific examples of such hydroxylamines include: transamines (NH2〇H), N-methylhydroxylamine, N,N-dimethylhydroxylamine, and N,N-Diethylhydroxylamine. Specific examples of the primary aliphatic amine include: monoethanolamine, ethylenediamine, and 2-(2-aminoethylamino)ethanol. Designated examples of the secondary aliphatic amines Including: diethanolamine, N-nonylaminoethanol, dipropylamine, and 2-ethylaminoethanol. Specific examples of the tertiary aliphatic amines include: dimethylaminoethanol and ethyldiethanolamine. Specific examples of the alicyclic amines include: % hexylamine and dicyclohexylamine. Specific examples of the aromatic amines include: benzoguanamine, benzhydrylamine, and N-methylbenzylamine. Specific examples of the amine include: pyrrole, pyrrolidine, pyrrolidone, pyridine, morpholine, pyrazine, hexahydropyridine, N-hydroxyethyl hexahydropyridine, oxazole And thiazoles. Specific examples of quaternary ammonium salts include: tetradecyl hydroxide (TMAH), tetraethyl hydride, tetrapropyl oxyhydroxide, trimethylethyl hydroxide, and hydration (2_ Ethyl)trimethylammonium, (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide and (1-hydroxypropyl)trimethylammonium hydroxide The formulations may contain any amount: from 0 to 20% by weight or from 5% to 5% by weight. When such bases are added to the pre-textured composition, they often follow the pre-pattern 17 201224121 The total weight of the physicochemical composition is used in an amount of between 1 and 1% by weight or between 5% and 5% by weight. The pre-textured composition may contain 5% by weight or A base of between 0.5 and 10% by weight or between ～5% by weight. In some embodiments, the pre-textured composition of the genus or the like is free or substantially free of alkalis. The pH can be controlled by adjusting the concentration of acids and bases. The pH can be used to control the adsorption of the surfactant on the surface of the substrate and thereby subsequent texturing. The factor of the texture quality obtained in the step. The pre-textured composition of the present invention may additionally comprise one or more chelating agents. The chelating agents may be selected from, but not limited to, ethylenediaminetetraacetic acid (EDTA), N. - Hydroxyethyl ethylenediamine triacetic acid (NHEDTA), nitrilotriacetic acid (NTA), diethylenetriamine pentaacetic acid (dptA), ethanol diglycolate, citric acid, glucuronic acid, oxalic acid, Filling with acid, tartaric acid, methyl diphosphonic acid, amino sulfonium methylene phosphonic acid, ethylene diphosphonic acid, hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropyl-1, 1_Diphosphonic acid, ethylamino bismethylene phosphonic acid, dodecylamino bis-indenylphosphonic acid, nitrogen sulfonium phosphinic acid, ethylenediamine bis-indenylphosphonic acid, ethylenediamine肆 曱 曱 phosphinoic acid, hexane diamine 肆 methylene phosphonic acid, diethylene triamine pentadecylphosphonic acid and 1,2-propane diamine tetramethylene phosphonic acid or ammonium salts, organic amine salts Classes, malonic acid, succinic acid, dimercaptosuccinic acid, glutaric acid, maleic acid, phthalic acid, fumaric acid, poly-revalic acids such as tricarbaryl acid ), C-burn-1, 1,2,3-tetracarboxylic acid, Dingxuan-1,2,3,4-tetrazoic acid, pyromellitic acid, ruthenium acid such as glycolic acid, β-hydroxypropionic acid, citric acid, malic acid , tartaric acid, 18 201224121 propionic acid, diglycolic acid, water, salicylic acid, gallic acid, multi-ages such as catechol, pyrogallic acid, phosphoric acids such as pyrophosphoric acid, polyphosphoric acid, heterocyclic Group compounds such as 8-hydroxyquinoline and diketones such as a-dipyridylethenylacetone. The pre-textured composition of the present invention may contain a chelating agent in any amount or concentration of from 9% to 10% by weight or from 0.01 to 10% by weight. In some embodiments, the pre-textured composition is free or substantially free of chelating agents. The pre-textured composition of the present invention may additionally comprise one or more antifoaming agents. The antifoaming agents may be selected from, but not limited to, polylithic dry burning, organic dish 1 scorpion, polyethylene glycol/polypropylene glycol copolymer containing ethylene oxide/propylene oxide (EO/p 〇) is a bottom defoaming agent, an alcohol 'white oil or vegetable oil, and the paraffin is a long-chain fatty alcohol, a fatty acid soap or an ester. These formulations may contain any amount or amount of antifoaming agent in an amount of from 0.0001% by weight to 5% by weight or from 〇1% by weight to 5% by weight. Some compositions, such as some polyoxyalkylene surfactants, can simultaneously exert the utility of defoamers and surfactants. An example of a defoamer is DOW Antifoam 1430. In some embodiments, the pre-textured composition is free or substantially free of antifoaming agents. The pre-textured composition of the present invention may additionally comprise one or more dispersing agents. The dispersant may be selected from, but not limited to, an anionic dispersant, a nonionic dispersant, a cationic dispersant, and an amphoteric dispersant; and a polymerizable dispersant containing an acrylate as a copolymerization component. Examples of the water-soluble anionic dispersant include triethanolamine lauryl sulfate, lauryl sulfate, polyoxyethylene alkyl ether triethanolamine sulfate, and acrylamido-methyl-propanesulfonic acid (for example, Acrylic acid 2 - acrylamidyl 2 - methyl propyl sulphonic acid 19 201224121 polymer) and mixture and polycarboxylic acid type κ. Dispersing agent. Examples of the water-soluble type of powder include polyoxyethylene ionic olefinic lauryl ether, polyoxyethylene decantylene oxyethylene stearin, polyoxyethylene sulphide, sputum, porphyrin oleyl ether, polyether, Polyoxyethylene octyl phenyl ether, polygas reflux alcohol _ biological, polyoxyethylene dehydrated mountain (four) early laurate, polyoxyethylene said = mountain _ brown (four) rare to water mountain (four) alcohol single hard = two? Oxyethylene ethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene π milk c埽 sorbitan trioleate, polyoxyethylene water sorbent Sugar alcohol tetraoleic acid brewing, polyethylene glycol monolaurate vinegar, polyethylene glycol monostearic acid vinegar, polyethylene glycol distearate vinegar, polyethylene glycol monooleic acid brewing, polyoxyethylene ethoxylate The base amine, the polyoxyethylene hardening sesame oil and the decyl aryl alcohol amine. Examples of such water-soluble cationic dispersing agents include polyvinyl sulfonamide, cocoamine acetate, and stearylamine acetate. Examples of such water-soluble amphoteric dispersing agents include lauryl beet test, stearic beet test, oxidized lauryl-methylamine and 2-hospital-N-竣methyl-Ν-Μethyl miso-stained beet test. The compositions of the present invention may contain dispersing agents in any amount or in an amount of from 5% by weight to 5% by weight or from 0% by weight to 3% by weight. In some embodiments, the pre-textured composition is free or substantially free of dispersing agents. The pre-textured composition may contain other additives such as sugars or sugar alcohols such as xylitol, mannitol, glucose, and the like. The pre-textured compositions may contain any amount or amounts of such additives ranging from 0% to 50% by weight or from 1% to 1% by weight. In some embodiments the pre-textured composition is free or substantially free of additives. "Hai pre-textured composition may contain concentrations ranging from 〇 to 5〇% by weight or 〇

20 201224121 to 5% by weight of oxidant, such as tribasic acid 'peroxide and hypo-acid salt. In some embodiments, the pre-textured composition is free or substantially free of such pre-textured compositions and may also include a corrosion inhibitor to prevent exposure to the pre-textured treatment composition resulting in corrosion of the processing equipment material. Button: A typical corrosion inhibitor may comprise the following compounds, for example. , anal triazole, amine-sit, benzodiazole, methylbenzotriazole, mercaptobenzothiazole. The pre-textured compositions may also include corrosion inhibitors such as ascorbic acid which are chemically reducing in nature. In some embodiments, the pre-textured composition is free or substantially free of corrosion inhibitors. The pre-textured composition is typically an aqueous composition and comprises water as a solvent, such as water, deionized water or pure water; however, conventional solvents may also be used in place of or in addition to water, which are known to those skilled in the art. Alcohols, glycols and acetone. The pre-textured compositions typically comprise greater than or more than 3% by weight, or between 50% or more than 7% by weight or between 1 and 99.9 weights, based on the total weight of the composition. Water between % or between 50 and 95% by weight or between 80 and 99% by weight. The pre-textured compositions typically comprise one or more surfactants and water (deionized water) or one or more surfactants and/or one or more acids and/or one or more classes and/or Or one or more defoamers and/or other additives' consist of or consist essentially of, and the remainder is water (deionized water). One embodiment of the pre-textured composition of the present invention comprises one or more surfactants (for example, '5 to 5% by weight, which has previously been listed as useful weight percent of such surfactants and other components ), one or more organic acids 21 201224121 (for example, 〇〇1 t0 5 Fan Wu 0/, 丄 reset / 〇), one or more of any base (for example H 〇 to 5 f amount - or More optional antifoam (for example, 〇 weight /.) and one or more of any corrosion inhibitor (for example, 〇 to weight 2: /〇) 'and the remainder is water (up to 99% by weight) In some embodiments, the pre-textured composition of the present invention and/or any etching composition used in the method of the present invention is free or substantially free of isopropanol (IPA). The pre-textured and/or textured compositions used in the present invention are free or substantially free of di- or poly-based alcohols. In some embodiments, the pre-texture used in the present invention and/or Or the i σ substance is free or substantially free of alcohol. In some embodiments, such pre-texturing And/or the texturized composition is free or substantially free of fluorine-containing interfacial activity. J. The wafer is conditioned by the pre-textured composition of the present invention and by the textured group σ. The wafer may be wetted by flooding, spraying, dipping or other palatable means. In some cases the pre-textured composition and/or the texturing composition must be agitated to ensure that the composition is in the texture. The method of the present invention is in close contact with the surface of the substrate. The texturing method of the present invention may be a multi-step texturing method 'which includes to; a pre-texturing step followed by a texturing step. The multi-step texturing method may also Including - or more rinsing steps, - or more cleaning steps, one or more arbitrary blade stain removal steps, and/or other steps. The wafer may be prior to or during texturing of the saw blade stain removal step The pre-textured composition of the present invention is wetted prior to the (etching) step or prior to both the saw blade stain removal and the texturing step. In a particular case, the wafer may be as described in the present application 22 201224121 After the texturing step Physical and chemical processing does not require any ore flake removal step in this processing sequence. From the viewpoint of improving the quality and speed of the wafer texturing step, the pre-texturing process is currently treated as The step before the step (the step before the texturing step) with the rinsing step in between seems to be the most efficient. The pre-texturing process using the composition of this month can also be reduced to the time required to achieve full texturing on the surface. The wafers may be rinsed in separate rinse steps before and after the pre-texturing and/or texturing step. The wetting may be performed at room temperature or elevated temperature, for example, in the texturing method. In any step, c 〇 C or 1 〇 to 9 〇. (: The wafer may be wetted by the pre-textured composition of the present invention for a period of time, which may be a pre-textured composition according to the present invention. The method applied to the wafer changes. Typically, processing a single wafer on the conveyor belt through the texturing method has a relatively long processing time compared to a batch scale impregnation texturing method. The pre-texturing step and/or the texturing step can each be in the range of 1 second to 1 hour. A preferred pre-texturing step or texturing step time can be between 2 and 3 minutes. The timing of such pre-texturing and/or texturing steps can be shortened by increasing the temperature of the texturing bath used for each of those steps. Examples of such standard texturing combinations and (etching compositions) for roughening or etching the substrate have been disclosed in the prior art and are known to those skilled in the art. Some examples of conventional texturing compositions will be described below. The standard texturing compositions used in the texturing step of the present invention may be solid and free of surfactants. Substantially free of surfactants means less 乂 23 201224121 0.0001 重晋〇 / recognition and two, < The texturizing composition can be used to formulate a texturized composition; however, when a wafer with residual surfactant from a pre-step of the present invention is combined with the texturing, ' Some surfactants may be introduced into the texturing bath when the door is wet. The etching composition can be any composition that provides the desired reflectivity of one or more surfaces of the wafer. The etching compositions can be alkaline or acidic etched'. Alkaline etching compositions are typically used for single crystal wafers and acid J, . σ species are typically used for polycrystalline wafers. The acid engraved composition comprises one or more acids in a solvent and may comprise one or more of the following: HF' ΗΝΟ3 and Η4Ρ〇3, carboxylic acids (eg, acetic acid) and other acids or acid mixtures, for example The above are useful in the pre-textured composition. A conventional texturizing solution for polycrystalline germanium is an isotropic etching composition comprising an acid mixture comprising one or more acids selected from the group consisting of HF and hydrazine 3. The textured composition may also or in addition may comprise any of the inorganic or organic acids and/or oxidizing agents described above for use in the pre-textured compositions of the present invention. In a specific embodiment of the method of the invention, the alkaline or acidic rinse is followed by a texturing step using the texturing composition. The acid etching solution typically has a mixture of acids or acids in a solvent (e.g., ionic water (DI) or water) at a concentration between about 5 weight percent and about 70 weight percent. The residual composition or texturing (button engraving) composition can be an alkaline etching composition. Examples of the alkaline etching composition include those containing one or more hydroxides in the solvent. The one or more hydroxides may be selected from the group consisting of potassium hydroxide (KOH), sodium hydroxide (NaOH), aqueous ammonia (NH4〇H), tetramethylammonium hydroxide (TMAH; or (CH3)4NOH) or the like. Alkaline component in solution

24 201224121 Medium 'typically in the water, group. Alternatively or additionally, the alkaline etching composition may comprise the bases described above for use in the pre-textured composition. The test solution may have a concentration of KOH or other hydroxide in deionized water at a concentration between about 5% by weight and about 15% by weight. The oligomeric or acidic etching solution may also contain one or more additives, such as chelating agents, antifoaming agents, dispersing agents, to improve the texturing of the surface of the crucible. A list of additives known to improve the texturing effect includes alcohols (for example, isopropyl alcohol (IPA)) and polyethers (including polypropylene glycol (ppg)), polyethylene glycol (PEG) copolymers, and Glycol, poly(4-vinylphenol) (PVP), desertified poly(4-ethylene), polystyrene (psSA), Joncryle polymer (experimental C3H402), phenol (C6Hs〇H) ), o-cresol, m-cresol and p-cresol, polyphenols, hydrocolloids (such as starch, cellulose, pectin, animal glue and xanthan gum. The concentration of the additive can vary depending on the texture) The enthalpy of the solution is up to 25 wt%. The present invention does not limit the etch composition and any known etch composition can be used in the texturing step after the pre-texturing step of the present invention. Over-rinsing may allow the pre-textured composition of the present invention to increase cone density (in terms of single crystal wafers) and improve texturing quality in subsequent texturing (etching) steps of the texturing process (in the case of polycrystalline wafers) In terms of efficiency, the aspect is not good. Leaving thick chemical residues on and/or leaving chemical cross-contamination in the texturing bath may interfere with the chemical reaction of the surface of the crucible during the textured surface resulting in poor texturing. Regarding the specific composition, processing equipment And processing strips 25 201224121 pieces can be optimized for rinsing conditions to achieve good results. A variety of different rinsing techniques can be used to wet the wafer. Examples include spraying the rinsing composition onto the surface of the wafer, Immersed in an overflow rinse tank and a quick dump flush (QDR) cycle in the rinse tank. This rinse tank may be described in Figure 1 on a wet bench tool. A flow chart of one embodiment of a surface texturing process sequence 100. Although the process method 1 exemplifies a solar cell process, the process sequence 1 may be beneficially used to form other structures and applications. Textured surface. In one embodiment, the processing sequence discussed below is performed on an automated production line that has The processed substrate is transferred to a series of processing bath mechanical devices that are suitable for performing all of the processing steps discussed below. Although not shown in @!, alternative embodiments of the processing sequence 100 may include other Steps, for example, drying steps and/or other rinsing steps between the respective labor steps of the following statements. These other rinsing steps prevent excessive exposure to the processing chemicals during each step and reduce the adjacent processing bath Intermittent and contaminated opportunities, for example, result from chemical remnants. In the specific embodiment of the figure, the texturing method includes the physical and chemical steps 1G4A and the texturing step dirty' and any other steps. The steps of the invention may include means for imparting the composition used in each step. The processing sequence 100 begins at step 102 by providing a top surface and a bottom surface write (four) substrate as depicted in Figure 2A. The substrate can have a thickness of about 2 〇 2 between about 100 μηι and about 400 Å. In a specific embodiment, the substrate 200 can be a single crystal substrate (e.g., Si<i> or Si<Π1>), a microcrystalline substrate, a polycrystalline substrate, a strained crucible. Substrate, non-doped substrate doped or undoped polycrystalline dream substrate, glass, sapphire or any type of germanium containing substrate. In a specific embodiment in which the substrate 200 is desirably a n-type crystalline ruthenium substrate, donor-type atoms are incorporated into the crystalline ruthenium substrate during the substrate formation process t. Suitable examples of donor atoms include, but are not, phosphorus (P) arsenic (As), antimony (Sb). Alternatively, in a specific embodiment in which a p-type crystalline soil material is desired, an acceptor-type atom may be incorporated into the crystalline ruthenium substrate during the formation of the substrate. When 1 〇 3 Α and 1 〇 3B, the substrate (10) is optionally pre-cleaned by the texturing method (for example, steps 104A to F) and/or the substrate fan is optionally treated for (4) soil removal. The step of deleting may be performed prior to the ship and vice versa, or it may be cleaned and removed by a single step (not shown). In an alternative embodiment (not shown), the pre-cleaning procedure is A multi-step process that removes unwanted contamination, surface fouling, and/or other materials that may affect subsequent curing steps. Yes - in the example: in the step ship, the pre-cleaning process can wet the substrate by an acid solution and / or: agent to remove surface particles, all of the oxides (4) Other contaminants are carried out. The pre-cleaning solution can be a = (10) aqueous solution 'which has a between. 1:10. To about 4:1. 0 avatar 11 and: a mixture of ionic water. In the text - 1 has eight? The H liquid is an aqueous solution of hydrogen fluoride (HF), and the concentration between the amount and the concentration of about 4% by weight is between about 1% by weight and about 2% by weight of the 27 201224121 HF 'and the remainder is deionized water. (For example, up to 99.9 weight / 〇). The smectic cleaning solution may comprise ozonated deionized water in which about 1 to 3 ppm of ozone is disposed in deionized water. The pre-cleaning procedure can be carried out on the substrate for between about 5 seconds and about 6 seconds, for example from about 3 seconds to about 240 seconds, for example about 12 seconds. The pre-cleaning solution can also be Standard Clean Solution 1 (SCI), Standard Cleaning Solution 2 (SC2) or other suitable and cost effective cleaning solution that can be used to clean the ruthenium containing substrate. (SC1 consists of nH4〇h (28% by weight), Η2〇2 (3〇% by weight) and deionized water. The typical formula is 1: 1: 5, often used at 7 (^C; however, it can contain A higher proportion of water. SC2 consists of HC1 (73% by weight), h202 (30% by weight), deionized water, initially produced at a ratio of 1: 1: 5, often used at 7 °c, however, It may comprise a higher proportion of water.) In one embodiment, the pre-cleaning procedure comprises immersing the substrate in an aqueous solution comprising 2% by volume hydrofluoric acid (HF) at a temperature of between about 丨In a further embodiment, the pre-cleaning procedure comprises immersing the substrate in a volume comprising 3 vol% nitric acid (HN〇3) and 5% vol% hydrofluoric acid (HF), the remainder of the deionization The HN type of water, the trough liquid passes between about 2 and about 丨〇 minutes. In the embodiment, the 1 minute cleaning and saw blade fouling removal procedure using the HN solution is used to carry out the texture. All wafer sawing contamination is removed prior to the method (steps 1〇4A to F). The HN/month cleaning procedure should be compared to sawn and water rinsed substrates. The Cr, Cu, Fe and Ni contamination will be reduced (see w〇2〇〇9/120631 A2). The substrate can be rinsed with a mixture of 0.5% isopropanol (IPA) and deionized water after the HN cleaning procedure. (This flushing step is not shown.) 28 201224121 In a specific embodiment, the saw blade fouling removal procedure (steps 1〇3B) is performed to remove any physical fouling produced by the previous sawing procedure. In one embodiment, The saw blade fouling removal processing step 103B is performed after the acid etching step 103 A (such as the HN cleaning procedure discussed above) and before the steps 104 to F. In a specific embodiment, the saw blade soil removal removal program can include Etching the substrate in a saw blade fouling removal bath comprising between about 5% and 45% by volume potassium hydroxide (K 〇Η) and the remainder of the deionized water. In one embodiment, the saw The sheet fouling removal procedure can include etching the substrate for about 22 minutes in a saw blade fouling removal bath maintained at 70% (20% by volume of Η0 去 in deionized water. In another embodiment, Saw blade deface removal procedure included in the hold The substrate is etched in a saw blade fouling removal bath consisting of 2% by volume of κ〇η in deionized water at 80 ° C for about 10,000 minutes. The substrate is typically after the saw blade fouling removal procedure. Rinse with warm deionized water, for example, 3 minutes (this step is not shown in Figure!). In another embodiment, the saw blade fouling removal procedure can include 45 volumes remaining at Μ °C % of the saw blade in deionized water is decontaminated to remove the substrate from the bath for about 45 seconds. In step 104A, the first step of the texturing method, the substrate 2 is pre-textured The step is wetted by a pre-textured composition of the invention comprising a surfactant. The substrate 2 can be wetted by flooding, spraying, dipping or other suitable means. This wetting can be carried out in a bath. Examples of Shangchun pre-textured compositions have been described above and include the following = Example Reveals: The wetting can be accomplished at room temperature or elevated temperature, for example 〇% to 150 gamma or 10 to 120. 0: or 30 to 11〇〇c. The wetting time varies with a number of different methods, and in the case of a pre-textured bath, it can be varied for a single wafer relative to the batch-to-human scale method. This processing time can range from 1 second to 1 hour. The preferred processing time for the pre-texturing step can be between 20 seconds and 30 minutes, or between 1 minute and 1 minute. The wafer surface is typically not altered by the pre-textured composition after the pre-texturing step. If the wafer has a substantially smooth surface prior to wetting with the pre-textured composition, it should have a substantially smooth surface after the pre-texturing step without substantial changes in the texture. For example, the shai pre-texturing step typically does not cause a substantial change in reflectivity until the wafer is wetted with the texturing (etching) composition. Substantially smooth surface means that the surface of the substrate having less than 10%, less than 5%, or less than 2 Å/0 is roughened or covered by a cone. Following the pre-texturing step 1 〇 4A is any rinsing step 104B. The rinsing step typically comprises wetting the substrate with water or deionized water; however, the rinsing composition may also comprise a small amount of additives as previously described (eg, acids, bases, chelating agents, antifoaming agents, corrosion inhibition) Agents, etc.). This rinsing step is utilized to prevent the chemicals of the pre-textured bath from remaining to the subsequent steps of the process. The rinsing step typically involves immersing the substrate in a bath of water or deionized water for 10 minutes or less or 5 minutes or less. The need and timing of the rinsing step depends on a number of factors associated with the pre-texturing step and the steps that may or may not follow the rinsing step 104A. Regarding the pre-texturing step, the higher the surfactant weight percentage in the pre-textured composition and the longer the contact time between the substrate and the pre-textured composition or the temperature during the pre-texturing step High, the more rinsing steps are needed. Further, the time required for the rinsing step may be longer or shorter depending on a number of 30 201224121 factors, such as agitation of the flushing bath and/or addition of a cleaning agent or the like in the rinsing composition. If the texturing step 1A4A is followed by any one or more of the optional pre-cleaning and/or saw blade stain removal steps 104c and/or 1〇4D, in some embodiments the rinsing step 1〇 4B can be removed from the program. The one or more optional pre-cleaning and/or saw blade fouling removal steps 104C and/or 104D will result in the removal of any retained chemicals. In some embodiments without a separate pre-cleaning step 103 and/or a saw blade stain removal step 103B, the pre-texturing step ι〇4 can perform one or more of those additional functions, and pre-texture with the pre-texturing The composition and thereafter wet the surface of the substrate with the texturized composition to achieve the purpose of roughening (texturing) the surface in a subsequent texturing step. The texturing composition formulation used in step 1A4A can be used as is or adjusted to provide pre-texturing that can be improved, cleaned and/or removed by the flakes and/or pre-textured. Formula. In some embodiments, the texturing method can include any pre-cleaning and/or arbitrary saw blade fouling removal steps prior to performing the texturing method (e.g., steps 1A 4A through F). One or more of steps 1〇4C and 1〇4D may be added to or substituted for one or more of steps 1 〇 3 A and 103B before the pre-texturing step. As with steps 1〇3 8 and ι〇3Β above, step i〇4d can be performed before 104 C and vice versa, or a single step (not shown) can be used to clean and remove the saw blade fouling. Each of the above statements regarding steps i 〇 3 A and 1 〇 3B applies to steps 104C and ΐ〇 4 ϋ as if they were repeated separately. In any particular embodiment, another pre-texturing step (not shown) may be followed by step 20124121 and/or 31201224121. (If both steps 104C and 104D are present in the texture Method,

^^ - c is followed by step 104D or). In a specific embodiment, the texturing method can include the step of wetting the substrate with the pre-textured composition to remove the combination The step of wetting the substrate and the step of wetting the substrate with a textured (etched) composition. This embodiment may be additionally iced. Example j additionally includes - or more steps of rinsing the substrate with the rinse composition. The step of washing may be performed before and/or after one or more or all of the steps. This particular embodiment also includes another step of wetting the substrate with a pre-cleaning composition prior to the pre-texturing step. At step 104E, the substrate 200 is wetted by texturing (etching) the composition. The etching composition is any etching composition and can be standard or other known etching compositions. The etching composition or texturing (etching) composition is used to roughen, etch or texture at least one surface of the substrate. The substrate 200 can be wetted by flooding, spraying, dipping or other suitable means. In some cases, the texturizing composition must be agitated to ensure that the composition remains in intimate contact with the surface of the substrate during the texturing process. In the case of a single crystal wafer, the texturing composition will be anisotropically engraved with the substrate 200 to provide a textured surface 212 of the substrate 200, as depicted in Figure 2B. As a result, the substrate 200 is etched to form a cone 2 14 on the textured surface 2 12 . It is noted that the texturing (etching) composition may simultaneously etch the upper surface 204 and the bottom surface 206 of the substrate 200. The textured surface may be formed on one or both sides of the substrate 200. The roughness of the textured surface 212 can be formed by the texturing table

32 201224121 The shape, height, size and depth of the cone 214 on the face 212 are estimated. Generally, s ' is defined as the average difference between the peaks 210 to 213 measured on a region of the substrate surface. In general, the average height is defined as the peak 210 to valley measured on one of the surface of the substrate by using a mechanical profilometer, an optical profilometer, or other optical detection technique (eg, confocal microscopy, 3D SEM image). The average difference between 213, or the average height. These embodiments measure the equivalent value of the nominal height (n〇minal height). This nominal height is measured using a 2-D cross-sectional SEM image. Visual inspection The height of the nominal cone is measured by the height of the cone represented by most of the cones in the section. In some embodiments, the average height of the cones is between about 0. 5 μηι to about 10 μηη, for example, between about i μηι to about 8 μηι, or from about 1 to about 5. Μ〇1. In other embodiments, the average height 208 of the cones is from 锥体5 or about 3 μηι from the apex of the cone or peak 21 to the valley 213 thereof. Regarding polycrystalline germanium, the surface roughness will increase and the reflectance will decrease. The composition or texturing composition may be any composition effective to texturize the surface of the substrate, including any known texturing solution, in most embodiments an aqueous solution. In one embodiment, the texturizing composition is an alkaline solution in which one or more other additives may be present and is maintained at a temperature between about 5 〇〇c and about 95 〇c. In another embodiment, the alkaline solution for etching the tantalum substrate may comprise 3 3 Jc hydroxide (KOH) 'sodium hydroxide (Na〇H), ammonia (NH4〇H), and niobium oxide Methyl money (TMAH; or (CH3) 4NOH), or other mixtures, or other similar aqueous solutions. The alkaline solution may have between KOH or other hydroxide or hydroxide mixture between about 1 weight percent and about 15 weight percent of deionized water 33 201224121 (DI), or about about 10% by weight of deionized water. 3 weight percent KOH or other hydroxide or hydroxide mixture. Most alkaline texturing solutions contain more than 50% water, or between 50 and 99% water or between 70 and 98% water. The texturing (etching) composition may comprise an acid such as HF and an oxidizing agent. These kinds of solutions are known to be very effective in texturing polycrystalline ruthenium surfaces. The most commonly used oxidant is nitric acid. The texturing solution may also contain other additives such as carboxylic acids, mineral acids, water, and other additives. The most common additions include acetic acid, acid filling, and acid breakdown. Most acidic texturing solutions contain between 1 and 70% by weight water or between 5 and 50% by weight water. Examples of the texturizing formulation may comprise from 5 wt% to 70 wt% water, from 5 wt% to 60 wt% hydrofluoric acid, and from 2 wt% to 6 wt% nitric acid (or another suitable oxidant) And 〇 to 5% by weight of one or more additives. The crystallization can be carried out by exposing the polycrystalline ruthenium sheet to the etch solution for 10 seconds to 10 minutes at a temperature of 0 to 40 °C. It is known that better results can be obtained by lowering the temperature. In other embodiments, the texturing (etching) composition can include an additive added thereto. Other additives include wetting agents, which may be selected from the group of materials such as alcohols (IpA) and polyethers (including polypropanol (PPG)), polyethylene glycol (pEG). Copolymer, tetraethylene glycol and its group & and its derivatives. The components of the texturized composition can be selected to have a point of ignition and high solubility to prevent the wetting agent from burning, evaporating or precipitating during the process.

34 201224121 In one embodiment of the texturing (etching) composition, is added to . The or more surface modifying additives of the woven texturing composition comprise a wetting agent and an etch additive. In general, the additive is selected such that it improves the texturing process on the surface of the substrate, such as accelerating or suppressing the etch rate across the surface of the substrate to minimize localized variations in etch rate and improve formation. The uniformity of the texture. The wetting agent also prevents dissolved components etched from the surface of the substrate from adhering to the surface of the substrate. In one embodiment, the yoke button additive is a lanthanide material. In one embodiment, the surname additive is a material such as poly(4-vinylphenol) (pvp), brominated poly(4-vinylphenol), polystyrenesulfonic acid (PSSA), J〇 Ncryl polymer (experimental formula C3H4〇2), phenol (QHsOH), o-cresol, m-cresol and p-cresol, polydecylphenol, combinations thereof and derivatives thereof and the like. Other additives that may be included in the texturing (etching) composition include hydrocolloids such as starch, cellulose, pectin, animal glue, and xanthan gum to improve the texturizing properties of the composition. The texturizing composition may also be Optionally comprising acids and/or bases and salts thereof, corrosion inhibitors, oxidizing agents, antifoaming agents, integrators, and other additives described above in relation to the pre-textured compositions of the present invention', in some embodiments The additives are based on the above amounts relating to the pre-textured compositions. Examples of the texturing (etching) compositions comprise a potassium oxyhydroxide (KOH) aqueous solution containing a peg compound. An amount of 2 〇 ppm and about 5 〇 000 ppm is added to the alkaline solution. The texturing or etching composition for single crystal ruthenium etching is typically heated to between about 50 〇 C and about 95 ° during the last name. The temperature between C, or between 35 201224121 and about 75 ° C to about 85 ° C, for example about 8 ° C 3 C. The texturing (etching) composition for polycrystalline germanium typically operates at 〇 to 4 ° c. The texture method uses its package 3 to use the literary and physicochemical The pre-texturing step and texturing step of the composition, as well as any rinsing and/or cleaning and/or saw blade fouling and/or other steps, can be performed for a period of about 90 minutes, for example between about 15 minutes and about Between 60 minutes, for example between about 30 minutes and about 4 minutes. The pre-texturing step can be between 1 second and 1 hour or between 20 seconds and 30 minutes. 5 minutes to 3 minutes or 10 minutes to 3 minutes. Other steps that are part of the texturing method, for example, one or more rinsing steps before and/or after the pre-texturing step and the texturing step Each can take between 15 seconds and 10 minutes or between 1 minute and 5 minutes. Other cleaning or saw blade stain removal steps that may be part of the texturing process can each take from 1 minute to 15 minutes or 5 minutes to 10 minutes. Min. In one embodiment, the pre-texturing step of the pre-textured composition of the present invention (which comprises a surfactant) is used, followed by a texturing step using an etched composition. The etch composition is not or substantially Does not contain the pre-pattern The hydrazine surfactant is used in the hydration step or it does not contain or substantially exclude the surfactant used in any of the compositions of the invention listed herein or it does not contain or substantially does not contain any surfactant. In the example, the composition of the invention is free or substantially free of wetting agents and/or additives. In one embodiment, it comprises 4% by weight of potassium hydroxide (ΚΟΗ), 2% by weight of isopropyl alcohol (纹理) and the remaining portion of the textural composition of the water in the Ο Λ η -η-.. ^ touch the substrate for 5 to 30 minutes. Other texturizing compositions comprise about 2 to 5% by volume of hydroxide Potassium (K〇H) and the rest of the water, the texture

36 201224121 The composition is maintained at a temperature of about 79 to 80 ° C for about 30 minutes, which may or may not contain additives. Since the results of surface texturization uniformity and surface roughness have a large impact on the performance of solar cells, the control and optimization of the processing results and uniformity across the surface of the substrate are important factors in the formation of solar cell devices. Specific embodiments of the invention described herein may utilize texturing methods that are free or substantially free of volatile additives such as isopropanol; to reduce processing costs, improve processing results, 'reduce process variability, and reduce alcohol Use associated fire and safety issues. Alternatively, the texturing process can be substantially free of alcohol' which means that the composition used in the texturing step comprises less than 1% by weight or less than 0.5% by weight of an alcohol, such as IPA. It is believed that the application of the pre-texturing step (step 104A) may reduce the need for alcohol in the texturing step (step 104E) and/or may reduce the processing time required for the texturing step 'in some cases than in the absence of the invention The conventional method of pre-texturing steps is shortened by about 50% or more. In addition, the 'pre-textured composition of the present invention comprising the pre-texturing step described herein and/or the texturing method is found when applied to a single crystal tantalum substrate as compared to conventional textured substrates. A relatively large number of smaller irregular cones per unit area can be provided on a single crystal solar substrate that are evenly spread over the surface of the substrate while providing improved reflectivity results. The increased number of smaller cones is an advantage because the cone size variations and density variations of the cones are lower than conventionally formed textures. It is believed that the pre-textured composition and step provides a plurality of texturized compositions that generally promote uniform initiation of the texturing process to provide a more uniform texture across the surface of the substrate. . After the texturing step 104E is completed, any rinsing step can be performed, for example, a water rinsing step as described above and/or a drying step (not shown) can be performed to remove some, most or substantially all texturing of the circle. (etching) the composition and any other residual chemicals on the surface of the substrate. The drying procedure can include drying the substrate with a stream of nitrogen or a stream of clean dry air. After the texturing method (step 1〇4) is performed on the surface of the substrate, the substrate reflectance is lowered by about 40 to 60% or more. The following examples illustrate the pre-textured compositions and methods of the present invention. EXAMPLES The treatment of the following Examples 1 to 4 was carried out on a single crystal wafer. Rectangular sheets of each side in the range of 3 to 5 cm in size were agitated by 6 〇〇 RpM with a stir bar in a 6 〇〇 ml glass beaker. Each method uses 4 pieces and the reported data is an average of 4 pieces. The film is vertically cooled in the beaker using a fastener which is also used to cover the beaker lid. Unless otherwise indicated, it is flushed by overflow flushing with a deionization flow rate of approximately 100 ml/min. If the temperature of the step is not specified, the temperature is room temperature. If only a portion of the composition is specified in the text, the remainder is deionized water. Example 1 A raw cut monocrystalline solar grade wafer was obtained from two different sources. These ones

38 201224121 The round system is processed in different processing sequences to achieve the texturing of the surface.

>~ In some embodiments, the solution is treated with a solution where the solution refers to 4% by weight of oxalic acid and 1.5% by weight of H〇Stapure SAS (purified by ion exchange) and the remainder of the water. Formula! . The wafers are processed using 3 different texturing methods. The 3 different sets (A B and c) are carried out as follows in the order in which they occur (丨, η, iii, etc.): Method A: (i) at 80. (: Remove the saw decontamination in 2 〇 wt% K 〇 H solution (the remaining part of deionized water) for 1 ; minutes; (Π) 3 minutes deionized water rinse; (iii) at 80. (: Textured in a solution of 4% by weight KOH and 2% 〇/0 isopropyl alcohol (IPA) (remaining part of deionized water) for 2 ; minutes; and (^) 3 minutes with deionized water rinsing. Method B. (i) 50. Immersed in Formulation 1 for 5 minutes; (1)) 3 minutes of deionized water rinse (iii) 10% by weight of KOH solution at 80 ° C to remove saw decontamination for 10 minutes; (iv) 3 minutes of deionization Water rinse; (v) texturize in a solution containing 4% by weight KOH and 2% isopropanol (IPA) (remaining part of deionized water) at 8 °C for 20 minutes; and (vi) 3 Minute deionized water rinse. Method C: (1) Remove the stain for 10 minutes at 20 °C in KOH solution at 80 °C, (ii) rinse with deionized water for 3 minutes; (iii) immerse in the formula at 5 〇.c 1 minute 5 minutes; (W) 3 minutes deionized water rinse; (v) texture at 80 ° C in a solution containing 4 wt% KOH and 2 wt% isopropanol (IPA) (remaining part of deionized water) 20 minutes ; and (vi) 3 minutes to rinse with water. 39 201224121 After these texturing methods, use an integrating sphere (Perkin-Elmer

Lambda 900) measures reflectivity on its own wafer. The weighted average reflectance is found in the wavelength range from 3〇〇 to 830 nm. Spectral irradiance data for weighted average reflectance calculations were obtained by R Huistrom, R. Bird and C. Riordan 'Spectral solar irradiance data sets for selected terrestrial conditions," Solar Cells, Vol. 15, pp. 365-391. Reflectance data for two-source wafers after processing by Method A, B, or C. The nominal cone height is measured using the most representative cone heights in the mask based on the SEM of the cross-section of each wafer. 1 source 1 crystal source 2 crystal Β processing order average reflectance % reflectance standard deviation nominal cone dimension (μπι) average reflectance % standard deviation of the nominal cone dimension (μπι) A 14.25 0.03 9.9 20.37 2.48 13.4 B 13.54 0.11 4.2 12.39 0.28 4.4 C 13.57 0.34 1.6 12.99 0,62 1.9 at 65. Slant angle scanning electron micrograph (SEM) of textured wafers prepared by methods a, b and c. Figure 3 A. The first source wafers processed by methods A, B, and C are shown in B and c, respectively, and the second source wafers processed by methods a, B, and C are shown in Figures 4a, B, and C, respectively. Hai table and the SEM See formula sheet 1 using the treated wafers result in lower reflectivity and a lower cone height of the table and in the micrograph shows the test performed, when the recipe just prior to the step of texturing 1

40 201224121 Get the best results. Example 2 The original cut single crystal wafer obtained from the third source was treated by the method C described in Example 1, except that the formulation 1 of Example 1 was replaced with a plurality of different pre-textured formulations of Table 2. (Formulation of Example 1 is also included in Table 2) Table 2 Formulation # Oxalic acid concentration (% by weight) Hostapur SAS (purified acid state) (% by weight) Water (% by weight) 1 4 1.5 95.5 2 4 0 96 3 0 1.5 98.5 4 0.8 0.3 98.9 5 0.4 0.15 99.45 Table 3 summarizes the average percent reflectance of Example 2 and the nominal cone height of the wafer and also includes the data for Formulation 1 of Example 1. Table 3 Formulation # Average reflectance (%) Nominal cone height (μηι) 1 12.99 1.9 2 15.67 13.45 3 12.11 4 4 12.63 5.75 5 13.13 11.77 41 201224121 This example shows that the surfactant is present in the pre-textured combination The reflectance and cone height will be reduced and it may be better for some embodiments to have more than 5 〇 15 % by weight of the surfactant in the pre-textured composition. Example 3 A wafer of a second source was processed using methods A B and C in order to investigate the effect of texturing time on the pyramidal structure; however, the texturing time of the wafer was varied. The texturing times used were 5 minutes, 10 minutes, 15 minutes, and 20 minutes, respectively. At 65. The tilt angle is taken in each method using a SEM representative of the wafers treated with the respective texturing time. The SEM of the wafer processed by Method A in conjunction with the 5 minute texturing step is shown in Figure 5-8. The SEM of the wafer processed by Method A in conjunction with the 1 minute minute texturing step is shown in Figure 5B. The SEM of the wafer processed by Method A in conjunction with the 15 minute texturing step is shown in Figure 5C. The SEM of the wafer processed using method a in conjunction with the 20 minute texturing step is shown in Figure 5D. The SEM of the wafer processed by Method B in conjunction with the 5 minute texturing step is shown in Figure 6a. The SEM of the wafer processed by Method B in conjunction with the 1 minute minute texturing step is shown in Figure 6B. The SEM of the wafer processed by the method 1 and the 8 dreaming texturing step is shown in Fig. 6C. The Sem of the wafer processed by the user, b, and the 20-minute texturing step is shown in FIG. 6D. The SEM of the wafer processed by Method C in conjunction with the 5 minute texturing step is shown in Figure 7A. The SEM of the wafer treated by Method C in conjunction with the 10 minute texturing step is shown in Figure 7B. Figure 7C shows the use of the square, 戍L with 15 minutes. 42 201224121 The texturing step is a SEM of the wafers processed by the township. The SEM of the wafer processed using method c in conjunction with the 2 minute minute texturing step is shown in Figure 7D. Fig. 8 is a graph showing the percentage of reflectance versus the texturing time for the circle processed by the methods A, B and c of the present embodiment. Micrographs and graphs show that the texturing time to achieve a low reflective surface is increased without exposure to the pre-textured composition of the present invention (e.g., formulation (10). Exposure to Formulation i in Method 3 or Method c, It is faster to produce a lower percentage of reflectivity. These short photos show that in the case of Method A, (Fig. 5A i D) it takes a long time to nucleate the cone over the entire surface. The wafer exposed to Formulation i 'On the other hand, the 'display cones shown in Figures 6-8 to D and 7A to D cover the entire surface in a shorter texturing time. Now it is believed that the surfactant in the pre-textured composition can Improving the surface of the wafer 'can promote cone nucleation during the texturing process. Example 4 A variety of surfactants are used in the pre-textured compositions of the present invention. For this embodiment, Method D is used. : (i) etching the original cut wafer in 2〇% K〇H solution at 8〇〇c for 1 minute; rinsing for 3 minutes; (iii) immersing the sheets in various kinds at room temperature 5 minutes in different pre-textured compositions (as marked by the formula in Table 4), The pre-textured compositions each contained 1.5% by weight of the surfactant shown in Table 4; (d) rinsed the sheets with deionized water for 3 minutes using an overflow rinse; and (v) followed by 4 at 80 C. The KOH solution was used to treat the films. The average reflectance was measured. 43 201224121 The lower the reflectance, the better the texturing effect. Table 4 Formulation # Surfactant Average Reflectance (%) Standard Deviation 6 Tergitol 15-S-7 31.12 4.75 7 Triton X-100 31.99 3.89 8 Tergitol NP-9 32.79 4.26 9 Tergitol TMN-6 31.58 2.08 10 Calfax DBA70 35.63 1.99 11 Purified Hostapur SAS (1.5%) + Dynol 604 (0.5%) 26.58 3.75 12 Purified Hostapur SAS (1.5%) + Surfynol 2502 (0.5%) 27.32 2.46 13 Polyethylene glycol (molecular weight 300) 36.72 0.63 14 Empigen BB 37.02 0.82 15 Surfynol 485 27.94 1.88 16 Surfynol 465 36.73 0.58 17 Tomadyne 102 38.07 0.61 18 1- Xin continued Acid 37.63 0.36 19 Polyethylene glycol (molecular weight 1500) 27.83 3.81 20 Polyethylene glycol (molecular weight 10000) 37.45 0.48 21 Tergitol 15-S-30 36.51 1.47 22 Triton X-705 33.45 0.99 23 Tergitol NP30 33.83 0.32 24 Purifie d Hostapur SAS 14.76 1.32 25 Glycolic acid ethoxylate lauryl ether (molecular weight 739) 32.39 1.27 26 Dequest P9030 34.12 1.79 27 No impregnation treatment 38.55 0.12 44 201224121 5 The lower average reflectance (%) of the sea indicates that the dipping After the pre-texturing process, the surface of the wafer is covered by the cone. With respect to this embodiment, IPA is not used in the texturing (touching) step, and the texturing time is limited, and many of the pre-textured compositions of the present invention can still nucleate the cone and achieve a reflection of less than 35%. rate. Example 5 The effect of an alkaline pre-textured composition on the texturing of the tantalum wafer was evaluated without isopropanol. Formulation 28 consisted of i wt% κ〇Η and 3 wt/〇 Hostapur SAS surfactant (purified acid state) with the remainder being deionized water. The original cut single crystal wafer was treated with a 20% KOH solution for 5 minutes at 65 ° C to remove the saw blade contamination from the surface, followed by deionized water rinse for 3 minutes. After this step, the wafer was exposed to Formulation 28 for 15 minutes and then subjected to 1 cycle of Rapid Tipping Flush (QDR) in deionized water in a wet cleaning station. The next steps are at 80. (: texturing in a bath consisting of 4% KOH, the remaining part of deionized water for 40 minutes. No IPA was added. The reflectance of the films was measured. The weighted average reflectance in the wavelength range of 300 to 830 nm was found. 17.8%. Figure 9 is a top down SEM image of the wafer produced by the method described in Example 5, showing that the cone coverage on the surface is uniform. Example 6 Pre-texturing with and without Formulation 1 The effect of IPA concentration on reflectivity is evaluated. The wafer is processed under the following conditions: 45 201224121 Method E - (1) Remove the saw blade contamination by 20 wt% KOH at 65 ° C for 1 min, (u) Rinse with deionized water for 3 minutes at room temperature, (丨 (1) used in deionized water 4 wt 〇 / 0 k 〇 h with 0.25 wt%, 〇 5 wt%, 1 wt% or 2 wt% isopropyl The alcohol and the remaining part of the deionized water were textured '(lv) and rinsed with deionized water for 3 minutes at room temperature. Method F - (1) Remove the saw blade fouling at 25% by weight K〇H at 65 °C (ii) rinsing with deionized water for 3 minutes at room temperature (1) immersed in 8 〇〇C 1 minute in i, (iv) followed by 1 cycle of rapid dumping rinse (qDR) with deionized water in a wet cleaning station, (v) 4 wt% K0H in deionized water with 0 25 wt% 〇5 wt/〇, 1 wt/〇 or 2 wt% isopropanol and the remaining part of deionized water is textured '(v) rinsed with deionized water for 3 minutes at room temperature. Figure 1 0 shows in texture The method F using Formulation i before was much less sensitive to the concentration of isopropanol than Method E. Example 7 Separation of single crystal silicon wafers (1) cm χ 5 cm) according to the following respective treatment methods: Method G: i) At 80. (: Remove the saw blade in a 20% KOH solution for 5 minutes, followed by 6 minutes of deionized water rinse, (丨丨) at 8 ° C. Contains 4% KOH + 2% isopropanol (IPA) The solution was textured for a number of different times, followed by a 6 minute deionized water rinse (cycle rate of approximately 6666 container volume/min). Method H: i) immersed in Formula 1 for 5 minutes at 80oC, followed by 6

46 201224121 min Deionized water rinse (circulation rate is about 8oC in 6% KOH solution for 6 minutes deionized water rinse, (Hi) in isopropanol (IPA) solution in textured polyion water rinse. 〇·66 Container volume / min), (1) Remove the saw blade stain for 5 minutes, then at 4 ° κ〇Η + 2% different times at 80 ° C, followed by 6 minutes to the deionized water overflow rinse used in the above examples The flow rate is approximately 6 liters per minute, which is equivalent to 〇'66 container volume per minute. The texturing step measures the nightmare by measuring the weight change of the wafer just before and after the texturing step and calculating the total thickness of the layer by the cut density of 2 33 . Wafer reflectivity measurements were performed on a φ ρ η Εΐ Lambda 900 UV/VIS/NIR spectrometer. The instrument is equipped with an integrating sphere to obtain a reflected light dose. Table 5 provides the etch rate data and the weighted average 0/0 of the reflectance from 3 〇〇 to 83 〇 nms. table 5

Exposing the lithographic wafers to Formulation 1 results in a decrease in the texturing step > while reducing the reflectance after the texturing step. 47 201224121 It is known that the accumulation of ruthenium in the lyophilized solution by the texturing solution will shorten the bath life of the texturing solution. The gentleman's m straw is applied by the pre-texturing process of the formulation in this disclosure, which will reduce the rate of enthalpy loss during graining and secondary physicochemicals, and shorten the time required for texturing, resulting in the texture. The accumulation after the treatment-batch #circle in the chemical bath will be reduced compared to the case where the treatment is not used before the texturing step. As a result of the lower cumulative rate of 石g田%石夕, in the case of using the ten pre-textured composition of the present invention prior to the texturing step, more batches of wafers can be textured with the same texturing solution bath. . Example 8 Table 6 provides a composition of Formulations 29 to 33 comprising an antifoaming agent D〇w

Antifoam 1430. Dow Antifoam 1430 is a proprietary polyoxyalkylene emulsion (polyoxane surfactant) manufactured by Dow Chemicals. The defoaming compound is added to reduce the volume of foam produced in the process using a foaming surfactant. High foam volumes may be undesirable because the bubble bed may overflow the process tank and may also cause problems when handling the processing solution. Although the polyoxyalkylene defoamer (polyoxygenated surfactant) is used primarily for foam control, it unexpectedly provides the benefit of reducing the size of the cone. 48 201224121 Table 6 Formulation # Oxalic acid (% by weight) Hostapur SAS (purified acid state) (% by weight) KOH (% by weight) Dow 1430 Concentration Antifoam (% by weight) Water (% by weight) 29 1 2 1.54 0 95.46 30 1 2 1.54 0.0025 95.46 31 1 2 1.54 0.005 95.46 32 1 2 1.54 0.01 95.45 33 1 2 1.54 0.05 95.41 (In order to calculate the added amount without the verification of the analytical data, the dummy is added. • Dow Antifoam 1430 is a pure compound.) The processing sequence is to process the single crystal wafer: (i) pre-texturing immersion in one of Formulations 1 and 29 i 33 at 8 °c for 5 minutes, followed by 6 hours of deionized water overflow rinsing; And (丨丨) texturing in +4% IPA solution for 15 minutes. Comparative texturing studies without any pre-textured impregnation were also performed. The wafers were etched in a 3% KOH + 4% IPA solution for 15 minutes at 80oC. The measurement consisted of: (1) measuring the contact angle with deionized water droplets on the surface of the stone before and after texturing, and (2) measuring the loss of germanium caused by texturing according to the method described in Example 7, (3) The reflectance measurement as in the above Example 1 and (4) the average cone size measurement as in the above Example 1. Contact angle measurements were made using a Rame Hart goniometer. Waiting for water droplets 49 201224121 After the rounded surface is placed, the contact angle is measured. About 1 〇 seconds. Table 7 Pre-textured solution 29 Contact angle after texturing 48.22 Contact angle before texturing 10.2 矽 Loss (μηι) - ----- 10.03 Average reflectance (%) ~~--- 13.60 Cone height (micron) 3.07 30 50.89 8.7 8.99 13.19 2.99 31 67.05 7.5 9.16 14.41 2.67 32 62.68 9.8 6.80 14.77 1.89 33 68.12 11.6 10.27 14.44 1.88 1 68.53 7.4 9.75 15.46 6.13 No pre-texturing treatment 56.31 16.6 18.36 14.31 11.30 The composition of the invention comprising Dow Antifoam 1430 exhibits a reduced cone size. The reduced cone size (height) is to reduce the roughness of the textured surface, which may be beneficial to improve the consistency of the passivation layer subsequently deposited on the surface and to reduce the line width of the screen printing on the surface. The results also show that the pre-textured impregnation will reduce the contact angle of the day-to-night surface, which may contribute to cone nucleation. Table 8 provides the foaming data produced using the Ross Miles foam testing equipment. The foam height was measured at 0 and 5 minutes after the foam was produced.

50 201224121 Table / Bead Height (cm) Formula

About or at least the addition of % will be sufficient to inhibit foaming of the formulation. Example 9 is used to treat a single crystal wafer using the following processing sequence (bn - : 〇 (4) in a 2〇% K〇H solution to remove ore Loss of 5 minutes 'receiver 6 minutes deionized water rinse, (9) force 80 〇 C under immersion in formula 6 5 knives ' followed by 6 minutes deionized water rinse (circulation rate approx. .6 two container volume / min)' ( Iii) Textured in a solution containing *wt% k〇h+2 wt❶/〇 isopropanol (ΙΡΑ) at 8 °c for 5 minutes followed by 6 minutes of deionized water rinse. Formulation 34 was 2% by weight. Dodecyl sulfate sodium salt (from sigma Aihi Co., Ltd.) + 98% by weight of water. Formulation 35 is 2% by weight of sodium laureth sulfate (2 ethoxylate group) (according to the trade name) Rh〇dapex@ ES_2, product of Rh〇dia Co., Ltd.) Square 36 is 2 weight ❶/. n,N-dimercapto-N-dodecylammonic acid beet test, 51 201224121 N-(alkane Base C10-C16)-N,N-dimethylglycine betaine (obtained from sigma Aldrich GmbH according to Empigen® BB cleaner). Formulation 37 is 2 weights Oleic acid sulfonate (obtained from pil〇tChemicals under the trade name Calfoam® 〇S-45S). Measure the reflectivity on the wafer after texturing as described previously. Formula Weighted Average Reflectance (4 〇〇 to 830 nm) 34 15.83 35 ---- 14.50 36 14.84 37 18.25 The pre-texturing process of the present invention enables low reflectance to be achieved in a short texturing time. [Schematic Description] FIG. 1 depicts one specific in accordance with the present invention. Embodiments Flowchart of a method of surface texturing on a tantalum substrate; FIGS. 2A to 2B depict partial cross-sectional views of different stages of the corresponding method; a FIGS. 3A to 3C are as described in the embodiment Scanning electron micrographs of the processed single crystal germanium wafers according to methods a, b and . ', , and Figs. 4A to 4C are according to the methods A, U and 52, respectively, as described in the examples. 201224121 C. Scanning electron micrograph of single crystal singular round of the first source treated. FIG. 5A to 5D are a plurality of different etching times according to method a as described in Example 3 (5 minutes respectively) , 1 minute, 15 minutes and 20 minutes) Scanning electron micrographs of a single source germanium wafer of the second source. Figures 6A through 6D illustrate the use of multiple different characterization times according to method B as described in Example 3 (5 minutes, 1 minute, 15 minutes, respectively). 20 minutes) Scanned electron micrograph of the treated single-crystal germanium wafer of the second source. Figures 7A to 7D are a plurality of different cooking times according to method c as described in Example 3 (5 minutes respectively, Scanning electron micrographs of single-crystal dream wafers of the first source at 1 minute, 15 minutes, and 2 minutes. Figure 8 is a graph of percent reflectance versus graining (etching) time for wafers treated using the three different texturing methods described in Example 3. Figure 9 is a top-down scanning electron micrograph of a wafer processed in accordance with the inventive method of Example 5. "1 〇 is a graph of the percentage of reflectance that is useful and not treated with the pre-textured composition for the IPA concentration in the textured (etched) composition. For ease of understanding, the same reference number is used where appropriate to indicate ^ The same elements are common to the following figures. It is to be understood that the following drawings are merely by way of example, and exemplary embodiments of the invention are not intended to Component Symbol Description 200 Substrate 204 Upper Surface 206 Bottom Surface. 208 Cone Average Degree 210 Peak 212 Textured Surface 213 Valley 214 Cone

Claims (1)

201224121 VII. Scope of Patent Application·· Wherein the composition package 1. A pre-textured composition of textured enamel wafer containing one or more surfactants. It comprises a surfactant or a pre-textured composition as in the scope of the patent application, more a mixture of anionic, cationic, nonionic and amphoteric. 3. The pre-textured composition of claim </ RTI> wherein the one or more surfactants comprise at least one surfactant selected from the group consisting of: phenyl ethoxylates , polyoxyethylated polyoxypropylene glycols, polyoxyethylated mercaptans, long-chain (four) from the purpose, natural fatty acid glycerin and polyglycerol vinegar, propylene glycol vinegar, sorbitol diacetate Sorbitan vinegar, polyoxyethylene glycol g, polyoxyethylene fatty acids, alkanolamines, acetylene glycols, polyoxyethylated polyoxyalkylenes: n-alkyl decane, Classes, alkylpolysaccharides, polyoxetane surfactants, fluorochemical surfactants, octyl and nonylphenol ethoxylates, acetylene glycol type surfactants, alcohol ethoxylates, Phenyl ethoxylates, amines = oxylates, glucosamines, glucosamines, glucosamines, polyethylene glycols, and poly(ethylene glycol-co-propylene glycol) or mixtures thereof. 4. The pre-textured composition of claim 1, wherein the one or more surfactants comprise at least - a surfactant selected from the group consisting of: a linear fatty acid and/or Salt, raspberry oil fatty acid 55 201224121 derivative, tall oil acid derivative, sarcosides, acetylated peptides, lignosulfonates, N-mercapto-n-alkane Tertyl sulfonates, petrosulfonates, paraffin sulfonates, thiosuccinates, alkyl naphthenates, isethionates, sulfates, Sulfated linear primary alcohols, sulfated polyoxyethylated linear alcohols, sulfated triglyceride oils, phosphates and polyphosphates, and perfluorinated anionic surfactants or mixtures thereof. 5. The pre-textured composition of claim 3, wherein the one or more surfactants comprise at least one surfactant selected from the group consisting of long chain amines and salts thereof Classes, diamines and polyamines and salts thereof, quaternary ammonium salts, polyoxyethylated long chain amines, quaternized polyoxyethylated (P0E) long chain amines, amine oxides, simple amine groups An N-alkyl derivative of an acid, a glycine acid, a betaine and an aminopropionic acid, an imidazoline and a thio beet, or a mixture thereof. 6. The pre-textured composition of claim 1, wherein the one or more surfactants comprise one or more surfactants selected from the group consisting of linear alkyl benzene sulfonates Acid esters (LAS), secondary alkyl benzene sulfonates, fatty alcohol sulfates (FAS), secondary alkane sulfonates (sas), fatty alcohol ether sulfates (FAES), a-olefin sulfonates Acid esters, alkyl betain base surfactants and polyoxyalkylene surfactants. 7. The pre-textured composition of claim 3, wherein the one or 56 201224121 More surfactants comprise at least one surfactant selected from the group consisting of secondary alkane sulfate, lauryl sulfate, lauryl ether sulfate and N-(alkyl C10-C16 )-N,N-dimercaptoglycine betaine or a mixture thereof. 8. The pre-textured composition of claim 7, further comprising one or more organic acids, one or more of any base, one or more of any defoaming agent, and one or more of any corrosion Inhibitor. 9. The pre-textured composition of claim 1, wherein the one or more surfactants comprise a surfactant having the structure: R1 - CH - R2 I so3x wherein R and r2 independently comprise 1 An alkyl group or a phenyl group of up to 20 carbon atoms and X is a gas or a cation selected from the group consisting of Na, K, tetramethyl sulphide, tetraethyl sulphate, triethanolamine, and money. 10. The pre-textured composition of claim 9, further comprising a polysulfide surfactant. 11. The pre-textured composition of claim 1, wherein the interface 57 201224121 contains one or more secondary fuming ester surfactants. 12. The pre-textured composition of claim i, wherein the one or more surfactants are present in the composition in an amount of from 1% by weight to 5% by weight based on the total weight of the composition and The composition additionally comprises water. 13. A method of texturing a germanium wafer comprising the steps of: wetting the wafer with a pre-textured composition comprising one or more surfactants. 14. A method of texturing a germanium wafer comprising the steps of: wetting a wafer with a pre-textured composition comprising one or more anionic, cationic, nonionic, and amphoteric surfactants, or mixtures thereof . 15. The method of claim 13, wherein the one or more surfactants comprise at least one interface selected from the group consisting of: a tongue agent: a linear alkyl benzoate ( LAS), secondary alkyl phthalate, fatty alcohol sulfate (FAS), secondary alkane sulfonate (Sas), fatty alcohol ether sulfate (FAES), a-olefin sulfonate, An alkyl betain base surfactant and a polyoxyalkylene surfactant or a mixture thereof. The method of claim 14, further comprising the step of: wetting the wafer with the etch composition after the step of wetting the wafer with the pre-textured composition described above. 58 201224121 17. The method of claim 16, further comprising the step of rinsing the wafer with a rinsing solution between the wet steps described above. 18. The method of claim 16, further comprising the step of wetting the wafer with a saw blade damage removal composition or a pre-cleaning composition prior to any of the wetting steps. 19. The method of claim 18, wherein the etching composition is substantially free of surfactant. 59