WO2017188177A1 - 半導体基板用エッチング液 - Google Patents

半導体基板用エッチング液 Download PDF

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WO2017188177A1
WO2017188177A1 PCT/JP2017/016177 JP2017016177W WO2017188177A1 WO 2017188177 A1 WO2017188177 A1 WO 2017188177A1 JP 2017016177 W JP2017016177 W JP 2017016177W WO 2017188177 A1 WO2017188177 A1 WO 2017188177A1
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etching
group
semiconductor substrate
hydroxystyrene
etching solution
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PCT/JP2017/016177
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English (en)
French (fr)
Japanese (ja)
Inventor
成明 赤木
義輝 鎌田
伸 大八木
斎田　利典
山本　裕三
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攝津製油株式会社
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Priority to CN201780039143.5A priority Critical patent/CN109314052A/zh
Priority to JP2018514579A priority patent/JPWO2017188177A1/ja
Publication of WO2017188177A1 publication Critical patent/WO2017188177A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an etching solution for a semiconductor substrate, particularly an etching solution for a semiconductor substrate for a solar cell. Furthermore, this invention relates to the etching power recovery agent, the manufacturing method of the semiconductor substrate for solar cells, and the semiconductor substrate for solar cells.
  • Patent Document 1 discloses that an alkaline etching solution contains a specific aliphatic carboxylic acid and silicon to stabilize the etching rate when etching the substrate surface, and to achieve a desired size. A method of uniformly forming the pyramid-shaped irregularities on the substrate surface is described. Further, there are conventional techniques such as Patent Document 2 and Patent Document 3.
  • the inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that by using a hydroxystyrene polymer that satisfies certain conditions, the surface quality and texture structure homogeneity can be greatly improved, the productivity is excellent, and the continuous use (long-run) property can be greatly improved.
  • the present invention has been completed.
  • the present inventors have found that production stability and texture quality can be further improved by using at least one selected from a specific chelating agent and a specific organic compound in the above composition. More specifically, the present invention provides the following.
  • the gist of the present invention is as follows.
  • An alkaline etching solution for treating the surface of a semiconductor substrate for solar cells comprising at least one hydroxystyrene-based polymer represented by the general formula (1), and an alkaline agent,
  • the total of monomers and oligomers represented by n of 1 to 8 contained in the hydroxystyrene polymer of the general formula (1) is 3.5% or less of the hydroxystyrene polymer.
  • Etchant [2] An etching power recovering agent which is added to the etching liquid after treating the semiconductor substrate for solar cells with the etching liquid according to the above [1], and recovers the etching power of the etching liquid.
  • Etching power recovery agent for etchant [3] Manufacture of a semiconductor substrate for a solar cell, comprising an etching step of etching the substrate surface of the semiconductor substrate for solar cell with the etching solution according to [1] to form pyramidal irregularities on the substrate surface. Method; [4] A semiconductor substrate for solar cells, the surface of which is etched with the etching solution according to [1]; and [5] a solar cell comprising the semiconductor substrate for solar cells according to [4]. ; It is about.
  • the present invention it is possible to form a texture on a solar cell semiconductor substrate in a shorter time on a relatively low temperature side, and it is excellent in continuous productivity and product storage stability, and a surface with low light reflectance can be stably obtained.
  • the effect is demonstrated.
  • the pyramid-shaped irregularities with an average of 3 ⁇ m or less are stably formed, and the surface shape showing a light reflectance of 10% or less, which was not obtained by the prior art, is not influenced by lot fluctuation of the etching solution raw material. It can be stably applied to the semiconductor substrate.
  • by increasing the number of batches for continuous production it is possible to improve production throughput, drastically reduce production cost per sheet, drastically reduce wastewater treatment load and cost, and reduce surface defects, resulting in superior texture quality.
  • FIG. 1 is a schematic diagram showing an outline of micromask theory.
  • FIG. 2 is a scanning electron micrograph showing the surface structure of the semiconductor substrate after the etching process in Example 6 of the present specification. This figure shows the substrate after the treatment with the etching solution in the first batch.
  • FIG. 3 is a scanning electron micrograph showing the surface structure of the semiconductor substrate after the etching process in Comparative Example 2 of the present specification. In this figure, since “clearance” is confirmed at a position surrounded by a white dotted line, this substrate is not preferable as a semiconductor substrate.
  • FIG. 4 is a scanning electron micrograph showing the surface structure of the semiconductor substrate after the etching process in Comparative Example 5 of the present specification.
  • FIG. 5 is a photograph showing the surface structure of the semiconductor substrate after the etching process in Comparative Example 2 of the present specification. In this figure, since a comet-like defect was confirmed on the substrate surface, this substrate is not preferable as a semiconductor substrate.
  • FIG. 6 is a diagram showing a photograph of the state in which the etching solution is foamed and criteria for determining foamability.
  • FIG. 7 is a scanning electron micrograph showing the surface structure of the semiconductor substrate after the etching process. The masking agent appears black at the apex of the pyramid, surrounded by a circle.
  • FIG. 8 is a diagram showing the result of EDX analysis of the portion of the substrate of FIG. 7 that appears black at the apex portion of the pyramid and the slope of the pyramid.
  • the etching solution of the present invention is an alkaline aqueous solution for treating the surface of a semiconductor substrate for solar cells, contains at least one alkali component, and satisfies the certain condition and the total amount of oligomers of octamer or less. Is characterized by containing a hydroxystyrene-based polymer whose content is 3.5% or less. It is preferable that at least one selected from the group consisting of a specific lignin sulfonic acid and a salt of lignin sulfonic acid is contained in the etching solution of the present invention.
  • At least one alkali component, polyhydroxystyrene in which the total amount of monomers and oligomers of octamer or less is 3.5% or less, lignin sulfonic acid and / or lignin Examples include a composition containing a sulfonate.
  • m, k and p are 0, u is 1, and R 1 to R 3 are H, which is polyhydroxystyrene.
  • a composition comprising at least one alkali component and a hydroxystyrene polymer other than polyhydroxystyrene (hereinafter sometimes referred to as “polyhydroxystyrene derivative”).
  • polyhydroxystyrene derivative a hydroxystyrene polymer other than polyhydroxystyrene
  • a composition further containing lignin sulfonic acid and / or lignin sulfonate is more preferable.
  • the etching solution of the present invention further contains a specific chelating agent, silicic acid and / or silicate.
  • features of the present invention are product stability, low foaming at the time of etching even after repeated continuous processing on the pilot line, no overflow of the bathtub, excellent etching solution storage stability, mass production use
  • the long run characteristic fluctuation at the time is small.
  • consumption of components and generation of by-products due to etching reaction can be suppressed, which is very advantageous for improving long run performance.
  • Such a feature is very convenient for mass production use.
  • This feature is focused on the amount of monomer / oligomer impurities in the polymer used as the main masking agent among a wide variety of possible factors, and the control of this amount contributed to further improvement of the effect. Is based on what has been found by the inventors. When such a feature is small, the texture quality at the time of long run is not stable, the yield is deteriorated, and eventually the processing cost per wafer is increased, which becomes a big obstacle for industrial use.
  • “Mask agent” refers to an agent that acts to adsorb and protect the substrate surface during etching of silicon.
  • Si metal is protected by organic substances adsorbed on the silicon surface, and is protected from etching [dissolution].
  • the surrounding fast-dissolving surface melts, the slow-dissolving surface remains undissolved, and the pyramid There is an idea that the shape remains undissolved (Fig. 1). Although this masking agent has been discussed without evidence, the inventors have succeeded in making this observation for the first time.
  • the etching solution of the present invention is alkaline. Specifically, the pH at 25 ° C. is preferably in the range of 12 to 14, and preferably in the range of 13 to 14.
  • the pH of the etching solution can be set within a desired range by appropriately changing the amount and concentration of an alkali agent described later.
  • m and n are m ⁇ 0 and n ⁇ 3, respectively, and are arbitrary numbers satisfying the range in which the weight average molecular weight of the polymer represented by the general formula (1) is 1000 to 50,000.
  • K, p and u are 0 ⁇ k ⁇ 2, 0 ⁇ p ⁇ 2 and 0 ⁇ u ⁇ 2, respectively, provided that k, p and u are average values in the polymer;
  • R 1 to R 3 Is H or an alkyl group having 1 to 5 carbon atoms;
  • X is a structural unit of a polymerizable vinyl monomer;
  • Y and Z are the same or different, and
  • a substituent selected from the group consisting of an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms (wherein M is H, an alkali metal, an alkaline earth metal, or an organic cation (for example, an amine)
  • Y 1 and Y 4 are halogens
  • Y 2 ⁇ and Y 3 ⁇ are counter ions (eg, halogen ions, organic acid anions, inorganic acid anions (eg, nitrate ions), etc.)
  • R 4 to R 8 are the same or different and are a linear or branched alkyl group, an alkyl derivative group, an aromatic group or H, and R 6 and R 7 are N groups.
  • R 9 to R 15 may be the same or different, and are a linear or branched alkyl group, an alkyl derivative group, an aromatic group, or H; q, s , T are each 0 or 1; r is 0 1 or 2.).
  • the hydroxystyrene type polymer represented by this is mentioned. Such polymers and derivatives thereof may be used alone or in combination of two or more.
  • m, n, k, p, and u are arbitrary numbers (real numbers) within a certain range.
  • k and p are naturally integers, if considered for each block of the structural unit, m is an integer, and if considered for each molecule, n is an integer. is there.
  • the polymer in its essence is a mixture, and it is more appropriate to consider the nature of the polymer as a property of the mixture than to question its individual building blocks. Accordingly, in the present invention, m, n, k, p, and u are displayed as average values in the polymer.
  • the hydroxystyrene-based polymer includes polyhydroxystyrene and polyhydroxystyrene derivatives.
  • the polyhydroxystyrene is one in which m, k and p are 0, u is 1 and R 1 to R 3 are H in the general formula (1).
  • the weight average molecular weight of polyhydroxystyrene is 1000 to 50,000, and n is an arbitrary number of 3 or more.
  • the preferred weight average molecular weight of polyhydroxystyrene is 1000 to 20,000, more preferably 1000 to 10,000. From the viewpoint of easy availability of polyhydroxystyrene, those having a weight average molecular weight of 1000 or more are preferable, and those having a weight average molecular weight of 50,000 or less are preferable from the viewpoint of uniformity of pyramid size.
  • the hydroxystyrene-based polymer represented by the general formula (1) has hydroxystyrene, hydroxy- ⁇ -, which may or may not have a substituent represented by Y or Z in the general formula (1).
  • Homopolymers or copolymers of only hydroxystyrene monomers such as methylstyrene or hydroxy- ⁇ -ethylstyrene, or these hydroxystyrene monomers and other polymerizable vinyl monomers ( For example, it may be a copolymer with a monomer that provides the structural unit X).
  • the hydroxystyrene monomer of the polymerization unit may be an ortho form, a meta form, a para form or a mixture thereof, but a para form or a meta form is preferred.
  • hydroxystyrene polymer represented by the general formula (1) is a copolymer
  • other vinyl monomers that is, monomers providing the structural unit X include anionic and cationic Examples thereof include known compounds such as ionic monomers such as nonionic monomers, methacrylates, vinyl esters, vinyl ethers, malates, fumarate, and ⁇ -olefins.
  • these compounds include acrylic acid, methacrylic acid, maleic acid, or their anhydrides and unsaturated carboxylic acid monomers such as monoalkyl esters and carboxyethyl vinyl ether, styrene sulfonic acid, allyl sulfonic acid, etc.
  • Unsaturated sulfonic acid monomers vinylphosphonic acid, unsaturated phosphate monomers such as vinyl phosphate, ⁇ , ⁇ -unsaturated carboxylic acid amides such as acrylamide and methacrylamide, methyl acrylate, methyl methacrylate, acrylic Ethyl acid, maleic acid, fumaric acid diester, ⁇ , ⁇ -unsaturated carboxylic acid ester, methylolacrylamide and other unsaturated carboxylic acid substituted amides, acrylonitrile, methacrylonitrile, ⁇ , ⁇ -unsaturated Carboxylic acid nitrile, vinyl acetate, vinyl chloride, chloro vinegar
  • divinyl compounds such as divinylbenzene, vinylidene compounds, aromatic vinyl compounds typified by styrene, heterocyclic vinyl compounds typified by vinylpyridine and vinylpyrrolidone, vinyl ketone compounds, monoolefin compounds such as propylene, butadiene
  • any of these monomers is not particularly limited, and any of these monomers can be used. However, when a polymer is formed, for example, those showing the following structural units are preferably used.
  • the hydroxystyrene polymer in the present invention may be a homopolymer or a copolymer of only hydroxystyrene monomers, but other polymerizable vinyl monomers, that is, the structural unit X is
  • the ratio of the vinyl monomer / hydroxystyrene monomer is preferably, for example, from 10/1 to 20/1 in molar ratio. is there.
  • the proportion of the vinyl monomer providing the structural unit X exceeds 20 times the amount (molar ratio) of the hydroxystyrene monomer, the effect of the hydroxystyrene monomer will not be exhibited, which is not preferable. If the proportion of the monomer is less than 10 times, the effect of copolymerization is not exhibited, so there is no need to intentionally copolymerize with the vinyl monomer. Therefore, in the present invention, the number of structural units X of the vinyl monomer is m ⁇ 0.
  • examples of the substituent of the hydroxystyrene monomer include the following (i) to (vi).
  • M is H, an alkali metal, an alkaline earth metal or an organic cation (for example, amines), for example, Li, Na, K, Mg, Ca, Sr, Ba, etc. are preferable.
  • Introduction of a sulfone group can be achieved by a conventional sulfonation method using fuming sulfuric acid or sulfuric anhydride as a sulfonating agent.
  • R 4 to R 8 are the same or different and are a linear or branched alkyl group, an alkyl derivative group, an aromatic group, or H, and R 6 and R 7 are bonded via a N group. It does not matter if it is formed.
  • Y 2 ⁇ represents a counter ion such as a halogen ion, an organic acid anion, or an inorganic acid anion.
  • examples of the linear or branched alkyl group include those having 1 to 36 carbon atoms (for example, a methyl group), and examples of the alkyl derivative group include a hydroxyalkyl group, an aminoalkyl group, a phosphoalkyl group, and a mercaptoalkyl group.
  • Examples of the aromatic group include a benzyl group substituted with a linear or branched alkyl group having 1 to 16 carbon atoms.
  • Preferred examples include an aromatic group substituted with a linear or branched alkyl group, a hydroxyalkyl group, or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • the introduction of the tertiary amino group can easily give —CH 2 —N (R 6 ) (R 7 ) by a Mannich reaction using, for example, a dialkylamine and formaldehyde.
  • the introduction of the quaternary ammonium base can be easily carried out by, for example, the Mentokin reaction with an alkyl halide for the tertiary amination product.
  • R 4 and R 5 are the same as described above, and R 9 to R 12 are the same or different and each represents a linear or branched alkyl group, an alkyl derivative group, an aromatic group, or H.
  • W is S or O
  • q is 0 or 1
  • r is 0, 1 or 2.
  • the linear or branched alkyl group has 1 to 36 carbon atoms
  • the alkyl derivative group includes a hydroxyalkyl group, an aminoalkyl group, a mercaptoalkyl group, a phosphoalkyl group and the like
  • the aromatic group includes And a phenyl group substituted with a linear or branched alkyl group having 1 to 16 carbon atoms.
  • Preferred examples include an aromatic group substituted with a linear or branched alkyl group having 18 carbon atoms, a hydroxyalkyl group, or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • a hydroxystyrene polymer represented by the formula (iii-2) is first halogenated or halomethylated and then trivalent. It is obtained by reacting a phosphorus compound (Arbuzov reaction) and then rearranging it.
  • R 4 and R 5 are the same as defined above, and R 13 , R 14 and R 15 are the same or different and represent a linear or branched alkyl group, an alkyl derivative group, an aromatic group, or H. .
  • S represents 0 or 1.
  • Y 3 ⁇ represents a counter ion such as a halogen ion, an organic acid anion, or an inorganic acid anion.
  • This hydroxystyrene-based polymer containing a phosphonium group is produced, for example, by halogenomethylation (for example, —CH 2 Cl) by reacting hydrogen halide and formaldehyde as disclosed in JP-B-61-34444.
  • halogenomethylation for example, —CH 2 Cl
  • Y 1 and Y 4 represent halogen, and R 4 , R 5 and R 6 are the same as described above.
  • t represents 0 or 1;
  • the number of Y and Z that are substituents of the hydroxystyrene monomer is an average value in the polymer, and 0 ⁇ k ⁇ 2, 0 ⁇ p ⁇ 2, Further, the number u of OH is 0 ⁇ u ⁇ 2.
  • the hydroxystyrene polymer that can be used as a constituent of the etching solution in the present invention has a weight average molecular weight in the range of 1,000 to 50,000, preferably in the range of 1,000 to 20,000, It is preferably in the range of 1000 to 10,000. From the viewpoint of availability of the polymer, those having a weight average molecular weight of 1000 or more are preferable. From the viewpoint of efficient pyramid formation at low temperature and short time and uniformity of pyramid size, the weight average molecular weight is 5 10,000 or less are preferable.
  • JP-A-51-105389, JP-B-62-136, JP-B-57-4791 and the like can be effectively used as a method for synthesizing the hydroxystyrene polymer.
  • p-ethylphenol is synthesized by dehydrogenation using p-ethylphenol as a starting material, and this is obtained by radical polymerization.
  • the synthesis is usually completed in a state in which a monomer of a reaction raw material and an oligomer of a polymerization intermediate obtained by polymerizing molecules of dimer to decamer are mixed. After that, the product is processed through a purification process.
  • the price is industrially usable, and it is in accordance with the purpose of the present invention to reduce monomer and oligomer impurities to the extent that texture formation is possible and acceptable. There is no need to reduce these to unnecessary purity at cost.
  • the total of the monomer of the reaction raw material and the oligomer of the reaction intermediate, particularly the oligomer of octamer or less contained in the hydroxystyrene polymer of the general formula (1) is 3.5% or less of the hydroxystyrene polymer. This is very important.
  • oligomer amount is sensitively involved in etching characteristics and pyramid formation.
  • the total amount of these is preferably 3.5% or less, more preferably 2.5% or less, and most preferably 2% or less. If it exceeds 3.5%, the stability of the etching solution deteriorates. First, the etching amount significantly increases, and the texture surface unevenness, defects, uniformity, etc. deteriorate.
  • the texture is stable under low temperature and short time conditions. Quality cannot be obtained.
  • it is difficult to use because the basic etching characteristics change over time, such as the amount of change exceeds 50% after 1 month storage at 40 ° C. compared to immediately after compounding.
  • the thickness of the wafer usually used is about 100 to 170 ⁇ m, and the mechanical strength is insufficient such as easy cracking, resulting in a decrease in product yield.
  • a portion where a pyramid is not formed at the base of the pyramid a gap occurs, which causes a reduction in reflectance and a poor appearance, which deteriorates texture quality and has a great influence. This phenomenon appears remarkably under low temperature and short time conditions.
  • the concentration of the solvent component in the hydroxystyrene polymer is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less.
  • Solvent components include toluene, THF, ethylene glycol, phenol, paracresol and the like.
  • the concentration of the solvent component of the hydroxystyrene polymer can be measured by a known measurement method, or can be known from the product catalog of the supplier of the hydroxystyrene polymer.
  • the weight average molecular weight of the hydroxystyrene-based polymer is a value obtained by the same method as the molecular weight / molecular weight distribution measurement method using GPC of lignin sulfonic acid and its salt described later.
  • polar groups such as amino groups, phosphoric acid groups, and sulfone groups (not including hydroxyl groups and aromatic rings) in hydroxystyrene polymers is indicative of the solubility of the polymer in alkaline aqueous solution and the disappearance during etching. It is preferable in terms of foamability.
  • the preferred polar group density range is between 0.01 and 5 on average per 500 units of molecular weight of the polymer. When the polar group density is less than 0.01, the solubility in an aqueous solution and the defoaming property tend to be reduced, and when it exceeds 5, the uniformity of the pyramid shape in the semiconductor substrate for solar cells tends to be impaired.
  • Factors such as the molecular weight, structural unit, polar group type and density, main chain type, and the like of the polymer and derivatives thereof are important factors that play an essential role for the etching solution of the present invention.
  • the concentration of the polyhydroxystyrene component, ie, “at least one hydroxystyrene polymer represented by the general formula (1)” in the etching solution of the present invention is preferably in the range of 1 to 50,000 ppm, for example. A range of ⁇ 30,000 ppm is more preferred, and a range of 50 ⁇ 10,000 ppm is even more preferred.
  • the concentration is preferably 1 ppm or more from the viewpoint of effectively removing bubbles generated during the etching process and efficiently forming irregularities, particularly a pyramid shape, on the substrate surface. From the viewpoint of the appearance quality, 50,000 ppm or less is preferable.
  • Lignin sulfonic acid or lignin sulfonate are compounds obtained by treating pulp waste liquor by-produced during pulp production by various methods, and the main component is lignin sulfonate or lignin sulfonic acid.
  • the chemical structure of lignin is a compound having a phenylpropane group as a basic skeleton and a three-dimensional network structure.
  • Lignin sulfonic acid and lignin sulfonate are given various names depending on the isolation method. For example, when lignin is obtained as a residue, lignin sulfate, lignin hydrochloride, copper ammonium lignin, periodate lignin and the like can be mentioned.
  • Inorganic reagent lignin sulfonic acid, alkali lignin, thiolignin, chlorlignin
  • Acidic organic reagent alcohol lignin, dioxane lignin, phenol lignin, thioglycolic acid Lignin, acetic acid lignin, hydrotropic lignin
  • hydrochloric acid organic reagent Brauns natural lignin, acetone lignin, Nord lignin, Bjorkman lignin and the like.
  • lignin sulfonic acid or a salt thereof obtained by sulfonation using the above-mentioned isolated lignin or a derivative thereof may be used.
  • lignin sulfonic acid and lignin sulfonate that have undergone chemical modification such as oxidation treatment to increase carboxyl groups can also be used in the present invention.
  • the lignin sulfonic acid and lignin sulfonate that can be used in the present invention may contain impurities during pulp production, but the smaller the amount, the better. When there are many impurities, shape collapse will occur in a part of the pyramid, and the uniformity of the pyramid shape tends to be impaired.
  • Lignin sulfonic acid and lignin sulfonate are manufactured and sold by a large number of pulp manufacturers.
  • the molecular weight ranges from 1.8 to 1,000,000 and is rich in variety such as various sulfonation degrees, various salts, chemically modified products, and those prepared with heavy metal ions.
  • the present inventors have found that not all of these various lignin sulfonic acids and salts thereof are suitable for the purpose of the present invention, and that the effect varies depending on the thing, or a specific lignin sulfonic acid or a salt thereof.
  • the present inventors have found that anisotropic etching of a silicon semiconductor substrate proceeds well, a concavo-convex structure (pyramid shape) is formed well, and the achievement of the object of the present invention is greatly improved.
  • the lignin sulfonic acid or a salt thereof that can be suitably used in the present invention satisfies all the following conditions 1) to 3).
  • a low molecular component having a molecular weight of less than 1000 and a high molecular component having a molecular weight of 100,000 or more are very little or completely removed. Specifically, the molecular weight distribution has a peak between 1000 and 100,000, preferably between 2000 and 60,000, and at least 50% by mass or more of the component is present in this molecular weight region.
  • Sulfone group density ie, degree of sulfonation
  • Those having 0 to 3 carboxyl groups per 500 molecular weight units Those having 0 to 3 carboxyl groups per 500 molecular weight units.
  • the measurement of molecular weight and molecular weight distribution in said 1) is implemented by the GPC (gel permeation chromatography) method shown below.
  • A Sample preparation Add the same mass of water to the sample to prepare a sample for GPC.
  • B Column A guard column TSX (manufactured by Tosoh Corporation), one HXL (6.5 mm ⁇ ⁇ 4 cm), one TSK3000HXL (7.8 mm ⁇ ⁇ 30 cm), and one TSK2500HXL (7.8 mm ⁇ ⁇ 30 cm) are used. Connect guard column-3000HXL-2500HXL in order from the inlet side.
  • C Standard material Polystyrene (manufactured by Tosoh Corporation) is used.
  • the type of lignin sulfonate that can be used in the present invention is not particularly limited, and the above lignin sulfonic acid Na salt, K salt, Ca salt, ammonium salt, Cr salt, Fe salt, Al salt, Mn salt, Mg Any salt or the like can be used in the present invention.
  • lignin sulfonic acid or a salt thereof obtained by chelating heavy metal ions such as Fe, Cr, Mn, Mg, Zn, and Al can be used in the present invention.
  • lignin sulfonic acid or a salt thereof further added with another organic compound or organic polymer such as naphthalene or phenol can also be used in the present invention.
  • the concentration of “at least one selected from the group consisting of lignin sulfonic acid and its salt” in the etching solution of the present invention is preferably in the range of 0.001 to 10,000 ppm, for example. From the viewpoint of effectively removing bubbles generated during the etching process, and further efficiently forming irregularities on the substrate surface, particularly pyramid shape, the concentration is preferably 0.001 ppm or more, more preferably 0.1 ppm or more, 2 ppm or more is more preferable, and 20 ppm or more is more preferable.
  • a lignin sulfonic acid and its salt may be used individually by 1 type, and may use 2 or more types together.
  • At least one component selected from the group consisting of the following chelating agents, silicic acid and silicate is further contained in the alkaline etching solution, so that the initial rise and texture quality can be further improved.
  • the chelating agent that can be suitably used in the present invention is an organic chelate compound.
  • the organic chelate compound include a chelate compound containing a carboxyl group and / or a carboxylate group in the molecule and / or a salt thereof, a chelate compound containing a phosphonic acid (salt) group or a phosphoric acid (salt) group in the molecule, and And / or a salt thereof and other chelate compounds.
  • the specific example of the chelating agent which can be used conveniently in this invention is described.
  • Examples of the chelate compound and / or salt thereof containing a carboxyl group and / or a carboxylate group in the molecule include a hydroxycarboxylic acid having a hydroxyl group and / or a salt thereof and a carboxylic acid having no hydroxyl group and / or a salt thereof.
  • Examples of the hydroxycarboxylic acid and / or its salt include citric acid (salt), lactic acid (salt), gallic acid (salt) and the like.
  • carboxylic acids having no hydroxyl group and / or salts thereof include ethylenediaminetetraacetic acid (salt), diethylenetriaminepentaacetic acid (salt), hydroxyethyl-iminodiacetic acid (salt), 1,2-diaminocyclohexanetetraacetic acid (salt), Ethylenetetramine hexaacetic acid (salt), nitrilotriacetic acid (salt), ⁇ -alanine diacetate (salt), aspartate diacetate (salt), methylglycine diacetate (salt), iminodisuccinic acid (salt), serine diacetate (salt) , Aspartic acid (salt) and glutamic acid (salt), pyromellitic acid (salt), benzopolycarboxylic acid (salt), cyclopentanetetracarboxylic acid (salt), etc., carboxymethyloxysuccinate, oxydisuccinate,
  • Chelating agents containing a phosphonic acid (salt) group or phosphoric acid (salt) group in the molecule and / or salts thereof include methyldiphosphonic acid (salt), aminotri (methylenephosphonic acid) (salt), 1-hydroxy Ethylidene-1,1-diphosphonic acid (salt), nitrilotrismethylenephosphonic acid (salt), ethylenediaminetetra (methylenephosphonic acid) (salt), hexamethylenediaminetetra (methylenephosphonic acid) (salt), propylenediaminetetra (methylene) Phosphonic acid) (salt), diethylenetriaminepenta (methylenephosphonic acid) (salt), triethylenetetramine hexa (methylenephosphonic acid) (salt), triaminotriethylamine hexa (methylenephosphonic acid) (salt), trans-1,2- Cyclohexanediaminetetra (methylenephosphonic acid) (salt) Glycol ether
  • chelating agents include N, N'-bis (salicylidene) -1,2-ethanediamine, N, N'-bis (salicylidene) -1,2-propanediamine, N, N'-bis (salicylidene) -1,3-propanediamine and N, N′-bis (salicylidene) -1,4-butanediamine.
  • examples of the salt include those described above.
  • one type of chelate compound may be used alone, or two or more types may be used in combination.
  • nitrilotriacetic acid ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylene chloride
  • a preferable chelating agent that can be used in the alkaline etching solution for treating the surface of the semiconductor substrate for solar cells of the present invention.
  • the concentration of the chelating agent in the etching solution of the present invention is not particularly limited, but is preferably 0.1 to 50,000 ppm. If the said density
  • a more preferable range of the concentration is from 1 to 10,000 ppm, and more preferably from 2 to 5,000 ppm. This range is also effective in terms of storage stability of the product.
  • metal ions in the etching solution can be sequestered, and as a result, a semiconductor having a high-performance concavo-convex shape in which a decrease in light absorption efficiency and a decrease in power generation efficiency are prevented.
  • a substrate can be created.
  • the type of silicic acid and / or silicate that can be contained in the etching solution of the present invention is not particularly limited, but is preferably at least one selected from the group consisting of metal silicon, silica, silicic acid, and silicate. .
  • the silicate is preferably an alkali metal silicate, for example, sodium silicate such as sodium orthosilicate (Na 4 SiO 4 .nH 2 O) and sodium metasilicate (Na 2 SiO 3 .nH 2 O), Examples thereof include potassium silicates such as K 4 SiO 4 .nH 2 O and K 2 SiO 3 .nH 2 O, and lithium silicates such as Li 4 SiO 4 .nH 2 O and Li 2 SiO 3 .nH 2 O. These silicates can be used by adding the compound itself to the etching solution, or by directly dissolving silicon materials such as silicon wafers, silicon ingots, silicon cutting powders or silicon dioxide in an alkaline agent.
  • the silicate compound obtained as above may be used as a silicate.
  • JIS No. 1 silicate is preferable from the viewpoint of availability.
  • the content of silicic acid and / or silicate in the etching solution of the present invention (the content of silicic acid when containing only silicic acid, the content of silicate when containing only silicate, silicic acid and When silicate is included, the total amount thereof is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.2 to 3% by mass.
  • the silicon material or silicon dioxide is dissolved and supplied, the above concentration range is preferable in terms of Si atoms.
  • the content of the above silicic acid and / or silicate affects the stabilization of the etching rate.
  • the content of silicic acid and / or silicate that stabilizes the etching rate varies depending on conditions such as the concentration of an alkaline agent described later and the temperature of the etching solution during etching. For this reason, what is necessary is just to determine the content of the optimal silicic acid and / or silicate according to the density
  • the alkali agent is a component necessary for forming pyramidal irregularities on the substrate surface when the substrate surface is etched with an etching solution.
  • the type of alkali agent contained in the etching solution of the present invention is not particularly limited, and both organic alkali and inorganic alkyl can be used.
  • organic alkali for example, a quaternary ammonium salt such as tetramethylammonium hydroxide, an alkanolamine and the like are preferable.
  • inorganic alkali hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide are preferable, and sodium hydroxide or potassium hydroxide is particularly preferable. These alkali agents may be used alone or in combination of two or more.
  • the concentration of alkali in the etching solution is not particularly limited, but is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, and further preferably 2 to 20% by mass.
  • the alkali concentration is 0.5% by mass or more, the durability of the etching solution is remarkably increased, and even when the etching solution is repeatedly used, unevenness of a desired size can be uniformly formed on the substrate surface. it can. If it exceeds 50% by mass, the viscosity of the solution in which the hydroxystyrene-based polymer is dissolved becomes high, and handling becomes difficult, which is not preferable.
  • the etching solution of the present invention may contain other components as long as the effects of the present invention are not impaired.
  • an amino acid, a high molecular polymer, glycol ethers or the like as an auxiliary agent, it is possible to enhance the effect (acquiring incident light into the substrate efficiently) by including a hydroxystyrene-based polymer.
  • the solvent of the etching solution of the present invention is preferably water.
  • the etching solution may contain components such as an antioxidant (for example, sodium ascorbate) and sodium sulfite.
  • the method for preparing the etching solution of the present invention is not particularly limited, and a conventionally known method can be employed.
  • the composition of the etching solution of the present invention is preferably in the above-mentioned composition range when used, but the composition at the time of shipment can also be made into a conch in order to reduce transportation costs. 10 times or more concocted shipment is preferable.
  • the etching solution of the present invention by adding an alkaline aqueous solution in which a hydroxystyrene-based polymer is dissolved to an etching solution gradually deteriorated by etching a semiconductor substrate for solar cells, pyramidal unevenness forming ability The effect of recovering is high.
  • a high-quality uneven structure can be stably obtained by adding about 5 to 50% by volume of the initial blending amount at regular intervals of etching. Therefore, the alkaline aqueous solution of the hydroxystyrene polymer in the present invention can be used as an etching power recovery agent.
  • the composition of the etching power recovery agent of the present invention includes a hydroxystyrene-based polymer represented by the above general formula (1) and the alkaline agent, and further includes lignin sulfonic acid, the lignin sulfonic acid. It is more preferable to include at least one selected from the group consisting of a salt of the above, a chelating agent, the silicic acid, and a salt of the silicic acid.
  • Etching power can be recovered by adding an alkaline agent to an etching solution that has deteriorated due to repeated processing of a semiconductor substrate for solar cells. Furthermore, in order to improve the uniformity of the pyramid shape and the uniformity of the entire surface, the deteriorated etching solution can be obtained by adding the hydroxystyrene-based polymer represented by the general formula (1) together with an alkali agent. The number of etching batches can be increased without replacement. Since the initial bath etching solution can be used continuously, there is an effect of increasing industrial value.
  • the method for manufacturing a solar cell semiconductor substrate of the present invention includes an etching step of etching the substrate surface of the solar cell semiconductor substrate with the etching solution of the present invention to form irregularities on the substrate surface.
  • the semiconductor substrate for solar cells is preferably a single crystal silicon substrate (whether p-type or n-type), but a single crystal semiconductor substrate using a semiconductor compound such as copper / indium or gallium arsenide can also be used.
  • the method of bringing the etching solution of the present invention into contact with the substrate surface is not particularly limited, but a method of immersing the semiconductor substrate for solar cells in the etching solution is preferable.
  • the production method of the present invention will be described by taking the dipping method as an example.
  • the etching step in the dipping method is, for example, a step of putting the etching solution of the present invention in a predetermined container and immersing the solar cell semiconductor substrate therein.
  • the temperature of the etching solution in the container is not particularly limited and can be appropriately set. However, in consideration of production and quality, it is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and still more preferably. 70 ° C. or higher, more preferably 75 ° C. or higher, further preferably 80 ° C. or higher. From the same viewpoint, it is preferably 98 ° C. or lower, more preferably 95 ° C. or lower, and further preferably 90 ° C. or lower.
  • the immersion time of the solar cell semiconductor substrate in the etching solution in the etching step is not particularly limited and can be appropriately set. However, in consideration of production and quality, it is preferably 1 minute or more, more preferably 2 Min. Or more, more preferably 3 min. Or more, further preferably 5 min. Or more, further preferably 10 min. Or more. From the same viewpoint, it is preferably 40 minutes or less, more preferably 30 minutes or less, and still more preferably 20 minutes or less. It is.
  • the etching solution of the present invention since the etching solution of the present invention is used, pyramidal irregularities of a desired size are uniformly formed on the substrate surface of a larger number of semiconductor substrates for solar cells than before. Can be formed. Furthermore, what has a composition of the etching agent of this invention can be added in an etching tank as an etching power recovery agent which recovers etching power. By using an etching power recovery agent in this way, the number of continuous use of the etching process can be increased, which is preferable.
  • the average size of the pyramid shape formed on the surface of the semiconductor substrate for solar cells after etching can be set to 0.1 to 3 ⁇ m.
  • the light reflectance of the solar cell semiconductor substrate after etching can be greatly reduced.
  • the light reflectance at a wavelength of 600 nm of the semiconductor substrate for solar cell after etching can be set to 10% or less.
  • the method for measuring the light reflectance is as described later.
  • the semiconductor substrate for solar cells manufactured by the manufacturing method of the present invention is a semiconductor substrate for solar cells manufactured using the etching solution of the present invention, and the substrate surface preferably has a maximum side length of the bottom of 1 to
  • the upper limit is 3 ⁇ m, more preferably the upper limit is 2.5 ⁇ m, still more preferably the upper limit is 2 ⁇ m, and uniform pyramid-like irregularities are formed.
  • a semiconductor substrate for solar cells with high productivity and low reflectance can be obtained.
  • the pyramidal irregularities are convex portions formed by arranging pyramidal (quadrangular pyramidal) convex portions on the surface of the semiconductor substrate for solar cells.
  • the average size of the pyramid shape formed on the substrate surface is preferably 0.1 to 3 ⁇ m, more preferably 0.5 to 2.5 ⁇ m, and 1.0 to 2.5 ⁇ m. More preferably.
  • the average size is preferably 0.1 ⁇ m or more from the viewpoint of light reflectivity reduction and impurity diffusion distribution characteristics such as P and B in the battery fabrication process, and from the viewpoint of productivity, the average size is 3 ⁇ m or less. It is preferable that Such a pyramid shape having an average size can be achieved by the manufacturing method of the present invention using the etching solution of the present invention.
  • the light reflectance is very small, for example, preferably 10% or less, more preferably 9.5% or less, and even more preferably 9.0% or less.
  • pyramidal irregularities of a desired size are formed without gaps on the surface of the semiconductor substrate for a solar cell formed by etching using the etching solution of the present invention. Therefore, the semiconductor substrate surface for solar cells formed by etching using a conventionally known etching solution and the semiconductor substrate surface for solar cells formed by etching using the etching solution of the present invention have pyramidal unevenness. A distinction can be made based on the size variation, the size of the interval between the pyramidal projections, and the like.
  • a solar cell can be produced by a known method using the semiconductor substrate for solar cell of the present invention.
  • Solar cells comprising such a semiconductor substrate for solar cells are also encompassed by the present invention.
  • Examples 1 to 23 and Comparative Examples 1 to 10 An n-type single crystal silicon substrate (a square with a side of 125 mm and a thickness of 160 ⁇ m) having a crystal orientation (100) plane on the etching solution prepared according to the composition shown in Table 1A, the conditions shown in Table 1A, And immersed at 50 to 90 ° C. for 1 to 40 minutes.
  • Table 1B shows the results obtained by observing the substrate surface after the etching treatment with the naked eye, a laser microscope, and a scanning electron microscope.
  • the chelating agent used was DTPA (diethylenetriaminepentaacetic acid).
  • a specific etching process is as described in [Etching process] below. The pH at 25 ° C.
  • the etching solution contained sodium sulfite (Example 2, Example 20 and Comparative Example 5) or sodium ascorbate (Example 10) as additive 3 at a predetermined concentration.
  • Table 1B describes an example in which the substrate was evaluated after the first batch etching process.
  • the long run properties of Examples 3 and 6 and Comparative Examples 2 and 6 in which the long run properties were compared were evaluated on the final batch of wafers, respectively.
  • “-” in each table indicates that the concentration of the corresponding component is 0 ppm or that the corresponding evaluation item was not measured or evaluated.
  • etching container As an etching container, an approximately 3L cylindrical tank made of SUS304 was used, and 3L of an etching solution was put into the tank, and the temperature was raised from below using a SUS casting heater to maintain the temperature range at a set temperature ⁇ 1 ° C. The number of substrates loaded was one. After removing from the etching solution, the substrate was immediately rinsed with running water and dried with warm air. The substrate after drying was evaluated according to the following criteria.
  • the long run property is confirmed by using an approximately 24L box-shaped tank made of SUS304, putting 16L of etching solution into the tank, raising the temperature with an IH heater from the bottom, and setting the temperature range to 90 ° C ⁇ 1 ° C of the set temperature. And was processed without liquid circulation stirring. The number of substrates loaded was 48. This was processed multiple times as one batch. A jig was designed so as not to obstruct liquid convection, and substrates were inserted at intervals of 4 mm. After the processing time reached 15 minutes, the substrate was taken out of the etching solution together with the cassette, and then rinsed with running water was immediately performed and dried with warm air. The substrate after drying was evaluated according to the following criteria.
  • the evaluation of the long run property is shown as an average value of all the substrates.
  • the long run properties of the etching solutions of some examples and comparative examples were evaluated. The plate was set, and the alkali was exhausted at that time, so the exhausted KOH was determined by an automatic titrator and the equivalent amount of KOH or NaOH was replenished every batch. In addition, for the replenishment of the etching solution, a 30-fold concentrated product was prepared and replenished at 130 mL / batch. The evaluation results are shown in Table 1B. A specific etching process is as described in [Etching process] below.
  • the long run property was evaluated by the number of batches until a substrate having a reflectance of 600 nm exceeding 10% appeared.
  • Foaming property The foaming property was evaluated as the amount of foaming after 100 mL of the prepared etching solution was dispensed into a plastic container and vibrated up and down manually for 10 seconds. Evaluation was performed visually. A: Foaming small B: Foaming during C: Foaming large FIG. 6 shows specific photographs and criteria.
  • Clearance is a phenomenon in which minute gaps (flat portions) in which no pyramids are formed between the pyramids remain, resulting in deterioration of reflectance and poor visual appearance. Evaluation is carried out with a scanning atomic microscope (SEM). Three fields of view of the target substrate are observed at a magnification of 5000, and the number is evaluated. A: No clearance B: 5 clearances / surface or less C: 5 clearances / surface or more
  • Pyramid shape collapse is the degree of pyramid chipping or slope failure, and is determined by observing it with a scanning electron microscope at a magnification of 5000 times.
  • Comet-like defect A comet-like defect is a vertically elongated, drop-like scratch observed on the surface of a substrate after etching. A: The comet-like defect defined above does not exist on the substrate surface. B: Comet-like defects defined above are present in a range of less than 3 area% of the substrate surface. C: Comet-like defects defined above are present in the range of 3 area% or more and less than 5 area% on the substrate row surface. D: The comet-like defects defined above are present in the range of 5% by area or more on the substrate surface.
  • etching solutions prepared in the examples With respect to the etching solutions prepared in the examples, the storage stability of the following etching solutions was evaluated. After preparing the etchants, they were stored at 40 ° C. for 1 month. Then, etching processing was performed by the method shown in each corresponding example using each etching solution after storage, and the amount of etching and the substrate surface after processing were evaluated 5000 times using a scanning electron microscope. And the evaluation of the substrate surface using the etching solution before storage and the evaluation of the substrate surface using the etching solution after storage were compared, and the storage stability was evaluated according to the following criteria.
  • A The change rate of the etching amount is less than 50% as compared with immediately after the preparation, and even when the etching solution after storage is used, the collapse of the pyramid shape on the substrate surface is not recognized.
  • B The change rate of the etching amount is 50 to 100%, and the texture shape collapse is not recognized.
  • C The change rate of the etching amount is 50 to 100%, and the texture shape collapse is recognized.
  • D The rate of change in the etching amount is 100% or more, and the deformation of the texture is observed.
  • Pyramid size The substrate surface was observed with a laser microscope, and the pyramid size was measured for ten pyramid shapes from the largest. This was performed for 3 fields of view and averaged to obtain an average pyramid size. Some of the substrates were also observed with a scanning electron microscope.
  • the above laser microscope uses Keyence Corporation's Laser Microscope VK-X100, was photographed at 100x objective lens (20x eyepiece), 2000x magnification, printed on paper, and the bottom size of the pyramid Measurement was made and the base size was defined as a pyramid size.
  • the scanning electron microscope was observed with CARLE ZEISS ULTRA55 or HITACHI SU3500 at an acceleration voltage of 1 to 10 kV.
  • FIG. 3 shows the scanning electron micrograph which shows the surface structure of the board
  • FIG. 4 shows scanning electron micrographs showing the surface structure of the substrate after being etched in the comparative example.
  • Reflectance of the substrate after etching The reflectance is measured by using a spectrophotometer (with an integrating sphere) manufactured by HITACHI UH4150, measuring the light reflectance (2 fields of view) at a wavelength of 300 to 1200 nm, and reflecting the light at a wavelength of 600 nm. Comparison was made using the average value of the rates.
  • Etching amount was determined by measuring the substrate mass difference before and after the etching reaction using a CP224S precision balance manufactured by SARTORIUS.
  • general-purpose means a grade of monomer + oligomer of 0.1% or more, which is mainly used for general industrial use (surface treatment agent, polymer flocculant, etc.).
  • the term “monomer + oligomer” used in semiconductor photoresists and the like is less than 0.1%, and “monomer + oligomer” is a polymer having n of 1 to 8 in the general formula (1). Refers to the total amount.
  • the method for measuring the total amount of monomers and oligomers in which n is 1 to 8 in the hydroxystyrene polymer represented by the general formula (1) is the GPC (gel permeation chromatography) shown below. ).
  • A Sample preparation Water was added so that the sample concentration was 1.0 wt% to prepare a sample for GPC.
  • B Column One guard column (6.0 mm ⁇ ⁇ 4 cm, manufactured by Tosoh Corporation) and three TSKgel G4000Hxl (7.8 mm ⁇ ⁇ 30 cm) were used. The guard column and G-4000Hxl were connected in this order from the inlet side.
  • C Standard material Polystyrene (manufactured by Tosoh Corporation) was used.
  • D The eluent tetrahydrofuran (THF) was used.
  • E Column temperature was 25 ° C.
  • F Detector A RI (differential refractive index) detector was used.
  • the total of monomers and oligomers represented by n of 1 to 8 contained in the hydroxystyrene polymer of the general formula (1) is 3.5% or less of the hydroxystyrene polymer (Examples 1 to 23)
  • Examples 1 to 23 Was used, it was possible to produce a substrate having a low reflectance and a pyramid size within a predetermined range even at a low temperature of 60 ° C. or less or for a short time of 3 minutes or less.
  • the manufactured substrate was an excellent substrate with few surface defects.
  • the etching solutions of Examples 1 to 23 had low foaming properties, long long run properties, and excellent storage stability.
  • the silicon substrate after etching was observed with a high resolution SEM (10,000 times). The results are shown in FIG.
  • the mask agent is black at the top of the pyramid.
  • the black part was carbon, and the carbon was not detected at the EDX level on the pyramid slope (Fig. 8). It can be seen from FIG. 7 (1000 times) that a plurality of masks that appear black are detected.
  • the etching solution of the present invention can be used as an etching solution when etching the surface of a semiconductor substrate for solar cells.

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JPH06188236A (ja) * 1992-09-17 1994-07-08 Internatl Business Mach Corp <Ibm> シリコンの選択的エッチングのための方法および組成物
JP2011515872A (ja) * 2008-03-25 2011-05-19 アプライド マテリアルズ インコーポレイテッド 結晶太陽電池の表面クリーニング及び凹凸形成プロセス
JP2012114449A (ja) * 2010-11-24 2012-06-14 Air Products & Chemicals Inc シリコンウェハーのテクスチャ形成用の組成物及び方法
WO2014010471A1 (ja) * 2012-07-09 2014-01-16 攝津製油株式会社 エッチング液、エッチング力回復剤、太陽電池用半導体基板の製造方法、及び太陽電池用半導体基板
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