CN104576831B - A kind of monocrystalline silicon piece is without alcohol process for etching and flocking additive thereof - Google Patents

A kind of monocrystalline silicon piece is without alcohol process for etching and flocking additive thereof Download PDF

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CN104576831B
CN104576831B CN201410850205.9A CN201410850205A CN104576831B CN 104576831 B CN104576831 B CN 104576831B CN 201410850205 A CN201410850205 A CN 201410850205A CN 104576831 B CN104576831 B CN 104576831B
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wool
making herbs
etching
making
additive
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CN104576831A (en
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瞿辉
徐春
曹玉甲
吕晓华
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Jiangsu Shunfeng Photovoltaic Technology Co Ltd
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Jiangsu Shunfeng Photovoltaic Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0236Special surface textures
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
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Abstract

The present invention relates to a kind of monocrystalline silicon piece without alcohol process for etching and flocking additive, first silicon chip is joined in pretreatment fluid, silicon chip is carried out pretreatment, pretreatment time 60s 300s, is then added in Woolen-making liquid carry out making herbs into wool;Monocrystal silicon process for etching is: deionized water is heated to 70 DEG C 90 DEG C, adds sodium hydroxide or potassium hydroxide, obtains monocrystal silicon making herbs into wool corrosive liquid.When using this flocking additive making herbs into wool, it is not necessary to isopropanol or ethanol etc., it is possible to obtain tiny, uniform, intensive pyramid matte, reduce making herbs into wool cost, it is to avoid environmental pollution;Adding pretreating process before making herbs into wool, after can making making herbs into wool, silicon chip is cleaner, reduces white macula fingerprint etc. and does over again, has certain practical value.

Description

A kind of monocrystalline silicon piece is without alcohol process for etching and flocking additive thereof
Technical field
The present invention relates to area of solar cell, especially a kind of monocrystalline silicon piece is without alcohol process for etching and making herbs into wool thereof Additive.
Background technology
In solaode preparation process, in order to improve solar battery efficiency, need at monocrystalline silicon piece table Face makes matte, effective suede structure so that incident sunlight silicon chip surface formed secondary reflection or Multiple reflections, increases the utilization rate of light so that more photon is absorbed product in the region near pn-junction Raw photo-generated carrier, these photo-generated carriers are easier to be collected, and therefore add the collection of photo-generated carrier Efficiency.
Conventional process for etching typically uses sodium hydroxide or potassium hydroxide, adds suitable isopropanol and sodium silicate Mixed solution carry out making herbs into wool.Its shortcoming is: making herbs into wool pyramid is uneven, original silicon chip apparent condition The volatile quantities such as asking high, chemical cost is bigger, and it is relatively big that process for etching controls difficulty, isopropanol are big, need Constantly adjusting liquid, operation easier is high, thus brings making herbs into wool outward appearance rework rate the highest, and cell piece conversion ratio is relatively low Problem.
One is disclosed at application number (201310394735.2) " fine-hair maring using monocrystalline silicon slice additive and using method thereof " Kind of additive component is: Polyethylene Glycol, sodium benzoate, citric acid, hydrolytic polymaleic anhydride, sodium acetate and The water of surplus.Additionally provide the etching method of a kind of monocrystalline silicon piece simultaneously, utilize above-mentioned Woolen-making liquid to monocrystal silicon Sheet carries out making herbs into wool.This additive need not use substantial amounts of isopropanol or ethanol, substantially reduces Woolen-making liquid COD, reduces making herbs into wool cost, reduces environmental pollution." a kind of at application number (201210474010.X) Low cost fine-hair maring using monocrystalline silicon slice additive " disclose a kind of monocrystalline flocking additive, its component is: chelating agent, Mel, perfluorinated surfactant and deionized water composition.This additive need not add add during making herbs into wool Add agent and have wider technological operation scope and higher solution shelf life.Although both the above additive is the most not Need to add isopropanol, reduce the COD of making herbs into wool waste liquid, reduce making herbs into wool cost, but after all there is making herbs into wool Matte white macula white point, finger-marks equal proportion are higher, the more sordid problem of matte outward appearance.
Summary of the invention
The technical problem to be solved in the present invention is: proposes a kind of monocrystalline silicon piece and adds without alcohol process for etching and making herbs into wool thereof Adding agent, it is possible to chemical reaction is uniformly carried out, matte outward appearance is cleaner, and rework rate is lower.
The technical solution adopted in the present invention is: a kind of monocrystalline silicon piece, without alcohol process for etching, comprises the following steps:
1) preparation pretreatment fluid: by the oxidant that mass ratio is 0.1wt%~10wt%, mass ratio is 0.1wt%~5 The alkali of wt%, joins in the water of surplus, and mix homogeneously is heated to 60 DEG C-80 DEG C;
2) preparation flocking additive: by the tetramethylolmethane of 0.05wt%~5wt%, three second of 0.1wt%~5wt% Hydramine, the sodium lignin sulfonate of 0.01wt%~5wt%, join in the water of surplus, be uniformly mixed preparation Become additive;
3) preparation Woolen-making liquid: by step 2) additive prepared joins in aqueous slkali, and mix homogeneously is prepared Becoming Woolen-making liquid, flocking additive is 0.1~5:100 with the mass ratio of aqueous slkali;
4) silicon chip is immersed in step 1) in preparation making herbs into wool pretreatment fluid in, pretreatment fluid temperature is 60 DEG C-80 DEG C, pretreatment time 60s~300s;Silicon chip is immersed in deionized water after completing by pretreatment, water temperature For room temperature, washing time is 60s-300s;Step 3 is joined after having washed) in the Woolen-making liquid prepared, system Floss temperature is 70 DEG C-90 DEG C, making herbs into wool time 600s~1500s.
Further, step 1 of the present invention) in, oxidant is sodium hypochlorite, hypochlorous acid and peroxide Change one or more in hydrogen;Described alkali is dilute sodium hydroxide, dilute potassium hydroxide, sodium carbonate, bicarbonate Sodium, ammonia and organic base etc. therein one or more.
Further say, step 3 of the present invention) in, described aqueous slkali is that mass fraction is The sodium hydroxide of 0.1%-5% or potassium hydroxide solution.
The component of flocking additive of the present invention includes: sodium lignin sulfonate, tetramethylolmethane, triethanolamine and Deionized water;Each constituent mass degree is: tetramethylolmethane 0.05wt%-5wt%, triethanolamine 0.1wt%-5wt%, sodium lignin sulfonate 0.01wt%-5wt%, surplus is deionized water.This additive is used to enter Row fine-hair maring using monocrystalline silicon slice, it is not necessary to add isopropanol and ethanol, decrease the COD of Woolen-making liquid, reduce making herbs into wool Cost.
The invention has the beneficial effects as follows: silicon chip is carried out pretreatment, the organic washing agent that silicon chip surface is remained Remove clean, the white macula white point ratio of silicon chip outward appearance after making herbs into wool can be reduced, reduce matte rework rate, favorably In the process stabilizing of crystal silicon solar energy battery, there is good practical value;And the floss at monocrystalline silicon piece When face makes, it is not necessary to use substantial amounts of isopropanol or ethanol, substantially reduce Woolen-making liquid COD, and can obtain Uniformly, tiny, intensive matte pyramid.
Detailed description of the invention
Presently in connection with embodiment, the present invention is further detailed explanation.
Embodiment one
Use tetramethylolmethane, sodium lignin sulfonate, triethanolamine and deionized water to be configured to monocrystalline making herbs into wool to add Agent, wherein the concentration of tetramethylolmethane is 0.2wt%, and the concentration of sodium lignin sulfonate is 0.1%, triethanolamine Concentration is 0.5wt%, and the sodium hydroxide that then flocking additive of preparation joins mass fraction 1wt% is water-soluble In liquid, the mass ratio without alcohol monocrystalline flocking additive Yu deionized water is 1:100, is then added by this Woolen-making liquid Heat is to 75 DEG C.Using hydrogen peroxide, ammonia and deionized water preparation pretreatment fluid, wherein hydrogen peroxide is dense Degree is 1wt%, and the concentration of ammonia is 0.5wt%, and this pretreatment fluid is heated to 60 DEG C.By area it is first The monocrystalline silicon piece of 156mm × 156mm, thickness about 200um is put in preprocessing solution, carries out pretreatment, Pretreatment time is 150s, then by silicon chip extracting, washes 30s, then is put into by silicon chip in Woolen-making liquid, carry out Making herbs into wool, making herbs into wool time 1080s, after making herbs into wool completes, cleans, dries, weigh loss of weight, and be observed reflection Rate and matte pattern.Gained silicon chip loss of weight 0.55g-0.75g, reflectance about 11%,.Obtained matte gold Word tower microscope size is uniform, tiny, intensive, and pyramid size is at 2um-5um.
Embodiment two
Use tetramethylolmethane, sodium lignin sulfonate, triethanolamine and deionized water to be configured to monocrystalline making herbs into wool to add Agent, wherein the concentration of tetramethylolmethane is 0.4wt%, and the concentration of sodium lignin sulfonate is 0.3%, triethanolamine Concentration is 0.5wt%, and then the flocking additive of preparation joins the sodium hydroxide water of mass fraction 1.5wt% In solution, the mass ratio without alcohol monocrystalline flocking additive Yu deionized water is 1.5:100, then by this Woolen-making liquid It is heated to 80 DEG C.Use sodium hypochlorite, sodium hydroxide and deionized water preparation pretreatment fluid, wherein hypochlorous acid The concentration of sodium is 1wt%, and the concentration of sodium hydroxide is 0.5wt%, and this pretreatment fluid is heated to 70 DEG C.First The monocrystalline silicon piece that area is 156mm × 156mm, thickness about 200um is put in preprocessing solution, enters Row pretreatment, pretreatment time is 120s, then by silicon chip extracting, washes 60s, then silicon chip is put into making herbs into wool In liquid, carry out making herbs into wool, making herbs into wool time 1080s, after making herbs into wool completes, clean, dry, weigh loss of weight, go forward side by side Row observation reflectance and matte pattern.Gained silicon chip loss of weight 0.55g-0.75g, reflectance about 11%, gold word Tower matte size is at 2um-5um.
Embodiment three
Use tetramethylolmethane, sodium lignin sulfonate, triethanolamine and deionized water to be configured to monocrystalline making herbs into wool to add Agent, wherein the concentration of tetramethylolmethane is 0.6wt%, and the concentration of sodium lignin sulfonate is 0.5%, triethanolamine Concentration is 1wt%, and the sodium hydroxide that then flocking additive of preparation joins mass fraction 2wt% is water-soluble In liquid, the mass ratio without alcohol monocrystalline flocking additive Yu deionized water is 2:100, is then heated by this Woolen-making liquid To 75 DEG C.Using hypochlorous acid, sodium carbonate and deionized water preparation pretreatment fluid, the most hypochlorous concentration is 1wt%, the concentration of sodium carbonate is 0.5wt%, and this pretreatment fluid is heated to 70 DEG C.It is first 156mm by area The monocrystalline silicon piece of × 156mm, thickness about 200um is put in preprocessing solution, carries out pretreatment, locates in advance The reason time is 150s, then by silicon chip extracting, washes 60s, then is put into by silicon chip in Woolen-making liquid, carry out making herbs into wool, Making herbs into wool time 1200s, after making herbs into wool completes, cleans, dries, weigh loss of weight, and be observed reflectance and floss Face pattern.Gained silicon chip loss of weight 0.55g-0.75g, reflectance about 10.8%, pyramid matte size exists 1.5um-5um。
The detailed description of the invention of the simply present invention described in description above, various illustrations are not to this Bright flesh and blood is construed as limiting, and person of an ordinary skill in the technical field is permissible after having read description The most described detailed description of the invention is made an amendment or deformed, without departing from the spirit and scope of the invention.

Claims (4)

1. a monocrystalline silicon piece is without alcohol process for etching, it is characterised in that comprise the following steps:
1) preparation pretreatment fluid: by the oxidant that mass ratio is 0.1wt%~10wt%, mass ratio is 0.1wt%~5 The alkali of wt%, joins in the water of surplus, and mix homogeneously is heated to 60 DEG C-80 DEG C;
2) preparation flocking additive: by the tetramethylolmethane of 0.05wt%~5wt%, three second of 0.1wt%~5wt% Hydramine, the sodium lignin sulfonate of 0.01wt%~5wt%, join in the water of surplus, be uniformly mixed preparation Become additive;
3) preparation Woolen-making liquid: by step 2) additive prepared joins in aqueous slkali, and mix homogeneously is prepared Becoming Woolen-making liquid, flocking additive is 0.1~5:100 with the mass ratio of aqueous slkali;
4) silicon chip is immersed in step 1) in preparation making herbs into wool pretreatment fluid in, pretreatment fluid temperature is 60 DEG C -80 DEG C, pretreatment time 60s~300s;Silicon chip is immersed in deionized water after completing by pretreatment, and water temperature is Room temperature, washing time is 60s-300s;Step 3 is joined after having washed) in the Woolen-making liquid prepared, making herbs into wool Temperature is 70 DEG C-90 DEG C, making herbs into wool time 600s~1500s.
2. a kind of monocrystalline silicon piece as claimed in claim 1 is without alcohol process for etching, it is characterised in that: described Step 1) in, oxidant is one or more in sodium hypochlorite, hypochlorous acid and hydrogen peroxide;Described alkali Be dilute sodium hydroxide, dilute potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia and organic base one therein or Several.
3. a kind of monocrystalline silicon piece as claimed in claim 1 is without alcohol process for etching, it is characterised in that: described Step 3) in, described aqueous slkali be mass fraction be sodium hydroxide or the potassium hydroxide solution of 0.1%-5%.
4. monocrystalline silicon piece as claimed in claim 1 is without the flocking additive used in alcohol process for etching, It is characterized in that: the component of flocking additive includes: sodium lignin sulfonate, tetramethylolmethane, triethanolamine with And deionized water;Each constituent mass degree is: tetramethylolmethane 0.05wt%-5wt%, triethanolamine 0.1wt%-5wt%, sodium lignin sulfonate 0.01wt%-5wt%, surplus is deionized water.
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CN105113009A (en) * 2015-08-21 2015-12-02 合肥中南光电有限公司 Environment-friendly monocrystalline silicon piece texturing liquid and preparation method thereof
CN105133025A (en) * 2015-08-21 2015-12-09 合肥中南光电有限公司 High-efficiency monocrystalline silicon slice texturing solution and preparation method thereof
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CN105133030A (en) * 2015-08-25 2015-12-09 合肥中南光电有限公司 Long-acting silicon wafer texture-etchant and preparation method therefor
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CN107287597A (en) * 2016-03-30 2017-10-24 杭州聚力氢能科技有限公司 Wool-making agent of monocrystalline silicon surface processing and preparation method thereof and application method
CN107523880A (en) * 2016-06-20 2017-12-29 杭州聚力氢能科技有限公司 For the processing method of bad after Wool-making agent of bad processing and preparation method thereof after monocrystalline silicon making herbs into wool and monocrystalline silicon making herbs into wool
CN107858752A (en) * 2017-11-03 2018-03-30 通威太阳能(安徽)有限公司 A kind of crystal silicon Woolen-making liquid and preparation method thereof
CN108660510A (en) * 2018-05-10 2018-10-16 天津赤霄科技有限公司 A kind of manufacture of novel fine-hair maring using monocrystalline silicon slice additive and simple etching method
CN111509077B (en) * 2019-01-31 2022-01-18 嘉兴尚能光伏材料科技有限公司 Monocrystalline silicon piece texturing method
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CN110846721A (en) * 2019-10-12 2020-02-28 湖南理工学院 Monocrystalline silicon texturing additive formula containing polyalcohol and PEG
CN110922970A (en) * 2019-11-29 2020-03-27 南京纳鑫新材料有限公司 PERC battery back polishing additive and technology
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