CN102703989A - Monocrystal-like solar battery texturing process - Google Patents

Monocrystal-like solar battery texturing process Download PDF

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Publication number
CN102703989A
CN102703989A CN2012101683552A CN201210168355A CN102703989A CN 102703989 A CN102703989 A CN 102703989A CN 2012101683552 A CN2012101683552 A CN 2012101683552A CN 201210168355 A CN201210168355 A CN 201210168355A CN 102703989 A CN102703989 A CN 102703989A
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silicon chip
solution
corrosion
silicon wafer
mixed acid
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CN102703989B (en
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高玲
段甜健
程曦
包崇彬
李质磊
盛雯婷
张凤鸣
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Baoding Tianwei Group Co Ltd
Tianwei New Energy Holdings Co Ltd
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Baoding Tianwei Group Co Ltd
Tianwei New Energy Holdings Co Ltd
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    • 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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Abstract

The invention discloses a monocrystal-like solar battery texturing process which comprises the following steps: placing a silicon wafer into a HNO3 and HF mixed acid solution for corrosion; taking out the treated silicon wafer from the mixed acid solution when the corrosion depth of the silicon wafer is up to 2-5 micrometers; carrying out water washing and drying treatment on the silicon wafer after acid corrosion; placing the dried silicon wafer into KOH or NaOH aqueous alkali with a single crystal for corrosion; taking out the silicon wafer from the aqueous alkali when the corrosion depth of the silicon wafer is up to 2-5 micrometers; and carrying out water washing and drying treatment on the silicon wafer after alkali corrosion. According to the process, the texturing treatment is carried out on the silicon wafer, a battery piece which is manufactured by the silicon wafer treated by using the process is small in reflectivity difference rate among crystalline grains with different sizes, and has better anti-damping performances.

Description

Class monocrystalline solar cells leather producing process
Technical field
The present invention relates to the photovoltaic field, specifically type of being monocrystalline solar cells leather producing process.
Background technology
Type monocrystalline silicon piece is meant that monocrystalline is main mutually but contains the mixing crystalline phase silicon chip of local polycrystalline phase, and the grain-size of type monocrystalline is near monocrystalline, and quality is better than polycrystalline, and cost is near the ingot casting polysilicon, and the application of type monocrystalline in recent years more and more widely.Need pass through making herbs into wool when silicon chip is used to make solar cell handles; Polysilicon adopts the making herbs into wool of mixed acid solution low temperature at present; Obtain the porous matte after utilizing the isotropic etch of nitration mixture to silicon chip surface; Silicon single crystal adopts the making herbs into wool of alkaline solution high temperature, obtains the pyramid matte after utilizing the anisotropic etch of alkali to silicon chip surface.When the class monocrystalline silicon piece is used to make solar cell; People usually select different making herbs into wool modes according to the big chip area of class single-crystal surface in the shared ratio of silicon chip upper surface; Big crystal grain surpasses 50% o'clock people at the area of silicon chip upper surface and just adopts alkali making herbs into wool type of minimizing monocrystalline silicon piece difference in appearance and efficient discreteness, and big crystal grain is in the stability of the area of silicon chip upper surface when people just adopted sour making herbs into wool type of assurance monocrystalline to work less than 50% o'clock.Yet; Because a type monocrystalline silicon sheet surface grain size differs, impurity and crystal boundary skewness; Adopt the battery sheet energy conversion efficiency that silicon chip is processed after the sour making herbs into wool to reduce; Adopt after the alkali making herbs into wool difference of anisotropic etch to cause that different intercrystalline difference in reflectivity reach 16% or more, difference in appearance is bigger, the big and decay of efficient discreteness seriously.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; Can reduce the intercrystalline difference in reflectivity of silicon chip surface different size after a kind of making herbs into wool is provided, and can guarantee that the battery sheet that generates after the making herbs into wool has the class monocrystalline solar cells leather producing process of anti-decay property preferably.
The object of the invention is mainly realized through following technical scheme: type monocrystalline solar cells leather producing process may further comprise the steps:
Step a, silicon chip is put into HNO 3With corrode in the mixed acid solution of HF, and when the silicon slice corrosion degree of depth reaches 2~2.5 um, from mixed acid solution, take out, again the silicon chip after the acid corrosion is carried out washing and drying and handles;
Step b, dried silicon chip is put into KOH or NaOH alkaline solution with single crystalline catalyst corrode, and when the silicon slice corrosion degree of depth reaches 2~2.5 um, from alkaline solution, take out, again the silicon chip after the caustic corrosion is carried out washing and drying and handle.Involved in the present invention to depth of corrosion according to of poor quality the obtaining before and after the weighing silicon slice corrosion; Single face depth of corrosion=* etching factor constant of poor quality/2; Wherein, Etching factor constant=1/ (the wide * silicon of the long * of silicon chip density), depth of corrosion control can reach through methods such as control making herbs into wool time, Woolen-making liquid temperature, Woolen-making liquid concentration, the air drafts of adjusting environment.The present invention is when carrying out the caustic corrosion processing, and the single crystalline catalyst that adds in the alkaline solution can adopt the Virahol replacement, and the residue that perhaps produces through reaction carries out catalysis and do not add single crystalline catalyst and Virahol.The present invention's order of step a and step b when using can be changed.
The silicon chip that takes out from mixed acid solution among the said step a is in that to carry out washing and drying further comprising the steps of before handling: the silicon chip that will from mixed acid solution, take out is put into concentration after through washing and is lower than 5% KOH or NaOH solution and cleans, and then silicon chip is put into concentration again through washing and is lower than 10% HCl solution and concentration and is lower than 5% HF solution and cleans.Wherein, Concentration is KOH or NaOH dilute solution residual acid and the porous silicon of flush away silicon chip surface at normal temperatures below 5%; HCl concentration be lower than 10% with HF concentration be lower than dilute solution residual alkali of flush away silicon chip surface under normal temperature condition of 5%; Another effect of HCl is removed heavy metal and is promoted battery sheet efficient, and another effect of HF is removed the silicon chip surface oxide compound and reached hydrophobic interaction.
The silicon chip that takes out from alkaline solution among the said step b is in that to carry out washing and drying further comprising the steps of before handling: the silicon chip that will from alkaline solution, take out is put into concentration after through washing and is lower than 10% HCl solution and concentration and is lower than 5% HF solution and cleans.Adopt concentration to be lower than 10% HCl solution and concentration among the step b and be lower than 5% HF solution silicon chip is cleaned, the effect of HCl solution and HF solution is identical among HCl solution and HF solution and the step a.
The volume ratio of HNO3 and HF is between 3:1~5:1 in said HNO3 and the HF mixed acid solution.
The KOH of corrosion of silicon or NaOH alkaline concentration are 1.0~2.0% among the said step b.
Said silicon chip is at HNO 3With in the HF mixed acid solution when corrosion mixed acid solution temperature be 5~10 ℃, KOH or NaOH alkaline solution temperature were 75~85 ℃ when said silicon chip corroded in KOH or NaOH alkaline solution.The present invention so can activate solution and can not cause solution evaporation too many again through mixed acid solution and the temperature of alkaline solution when silicon chip is corroded are set.
The present invention also needs the silicon chip after the making herbs into wool is carried out following processing: one, make the P-N knot through diffusion when making solar battery sheet; Two, remove back of the body knot and remove phosphorosilicate glass through etching; Three, the SixNy film that has reflection preventing ability through plasma reinforced chemical vapour deposition; Four, the silk screen printing back side and front slurry; Five, sintering forms ohmic contact; Six, test draws electrical performance data.
Compared with prior art, the present invention has following beneficial effect: the present invention includes silicon chip is put into HNO 3With corrode in the mixed acid solution of HF; And dried silicon chip is put into KOH or NaOH alkaline solution with single crystalline catalyst corrode; The present invention carries out isotropic etch through sour making herbs into wool and reduces silicon chip difference in appearance and efficient decay; And sour making herbs into wool can guarantee that the intercrystalline difference in reflectivity of silicon chip surface different size diminishes, and the anti-decay property of silicon chip improves; The present invention makes reflection efficiency lower through alkali making herbs into wool, has promoted the energy conversion efficiency of the battery sheet that silicon chip processes, and the isotropy reaction of sour making herbs into wool has further reduced different intercrystalline difference in reflectivity after the alkali making herbs into wool; The present invention can directly handle the class monocrystalline silicon piece, can avoid the shared manpower that per-cent caused of the big crystal grain of region class monocrystalline silicon sheet surface to expend, and saves manpower, reduces cost.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further detailed description, but embodiment of the present invention is not limited thereto.
Embodiment:
As shown in Figure 1, type monocrystalline solar cells leather producing process comprises two steps of sour making herbs into wool and alkali making herbs into wool, and wherein sour making herbs into wool comprises HNO 3With HF acid making herbs into wool-washing-alkali cleaning-washing-pickling-washing-drying; Alkali making herbs into wool comprises KOH or NaOH alkali making herbs into wool-washing-pickling-washing-drying.Wherein, the detailed process of sour making herbs into wool is: it is 5~10 ℃ HNO that silicon chip is put into temperature 3With corrode in the mixed acid solution of HF, and when the silicon slice corrosion degree of depth reaches 2~2.5 um, from mixed acid solution, take out; The silicon chip that will from mixed acid solution, take out is put into concentration after through washing and is lower than 5% KOH or NaOH solution and cleans, and then silicon chip is put into concentration again through washing and is lower than 10% HCl solution and concentration and is lower than 5% HF solution and cleans; At last the silicon chip after the acid corrosion being carried out washing and drying handles.Wherein, in HNO3 and the HF mixed acid solution volume ratio of HNO3 and HF between 3:1~5:1.
The detailed process of alkali making herbs into wool is: it is that 1.0~2.0% KOH or NaOH alkaline solution corrode that dried silicon chip is put into concentration; Add single crystalline catalyst in KOH or the NaOH alkaline solution; And the temperature of KOH or NaOH alkaline solution is set at 75~85 ℃, when the silicon slice corrosion degree of depth reaches 2~2.5 um, from alkaline solution, takes out; The silicon chip that will from alkaline solution, take out is put into concentration after through washing and is lower than 10% HCl solution and concentration and is lower than 5% HF solution and cleans; At last the silicon chip after the caustic corrosion being carried out washing and drying handles.
The depth of corrosion of acid making herbs into wool and alkali making herbs into wool is according to of poor quality the obtaining before and after the weighing silicon slice corrosion; Single face depth of corrosion=* etching factor constant of poor quality/2; Wherein, Etching factor constant=1/ (the wide * silicon of the long * of silicon chip density), depth of corrosion control can reach through methods such as control making herbs into wool time, Woolen-making liquid temperature, Woolen-making liquid concentration, the air drafts of adjusting environment.
As stated, then can well realize the present invention.

Claims (6)

1. type monocrystalline solar cells leather producing process is characterized in that, may further comprise the steps:
Step a, silicon chip is put into HNO 3With corrode in the mixed acid solution of HF, and when the silicon slice corrosion degree of depth reaches 2~2.5 um, from mixed acid solution, take out, again the silicon chip after the acid corrosion is carried out washing and drying and handles;
Step b, dried silicon chip is put into KOH or NaOH alkaline solution with single crystalline catalyst corrode, and when the silicon slice corrosion degree of depth reaches 2~2.5 um, from alkaline solution, take out, again the silicon chip after the caustic corrosion is carried out washing and drying and handle.
2. according to claim 1 type of monocrystalline solar cells leather producing process; It is characterized in that; The silicon chip that takes out from mixed acid solution among the said step a is in that to carry out washing and drying further comprising the steps of before handling: the silicon chip that will from mixed acid solution, take out is put into concentration after through washing and is lower than 5% KOH or NaOH solution and cleans, and then silicon chip is put into concentration again through washing and is lower than 10% HCl solution and concentration and is lower than 5% HF solution and cleans.
3. according to claim 1 type of monocrystalline solar cells leather producing process; It is characterized in that the silicon chip that takes out from alkaline solution among the said step b is in that to carry out washing and drying further comprising the steps of before handling: the silicon chip that will from alkaline solution, take out is put into concentration after through washing and is lower than 10% HCl solution and concentration and is lower than 5% HF solution and cleans.
4. according to claim 1 type of monocrystalline solar cells leather producing process is characterized in that the volume ratio of HNO3 and HF is between 3:1~5:1 in said HNO3 and the HF mixed acid solution.
5. according to claim 1 type of monocrystalline solar cells leather producing process is characterized in that the KOH of corrosion of silicon or NaOH alkaline concentration are 1.0~2.0% among the said step b.
6. according to each described type of monocrystalline solar cells leather producing process of claim 1~5, it is characterized in that said silicon chip is at HNO 3With in the HF mixed acid solution when corrosion mixed acid solution temperature be 5~10 ℃, KOH or NaOH alkaline solution temperature were 75~85 ℃ when said silicon chip corroded in KOH or NaOH alkaline solution.
CN201210168355.2A 2012-05-28 2012-05-28 Class monocrystalline solar cells leather producing process Expired - Fee Related CN102703989B (en)

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Cited By (22)

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CN102931289A (en) * 2012-11-28 2013-02-13 山东力诺太阳能电力股份有限公司 Preparation method of flower piece solar cell
CN103021832A (en) * 2012-12-03 2013-04-03 天津中环领先材料技术有限公司 Processing technology of appearance improvement of silicon wafer corroded surface through alkali corrosion
CN103151423A (en) * 2013-02-28 2013-06-12 常州捷佳创精密机械有限公司 Texturing and cleaning process method of polysilicon wafer
CN103151425A (en) * 2013-03-18 2013-06-12 内蒙古日月太阳能科技有限责任公司 Polycrystalline silicon alkaline texturing method
CN103199005A (en) * 2013-03-11 2013-07-10 常州捷佳创精密机械有限公司 Cleaning process method of crystal silicon slice
CN103219428A (en) * 2013-04-12 2013-07-24 苏州大学 Textured structure of crystalline silicon solar cell and preparation method thereof
CN103361739A (en) * 2013-07-08 2013-10-23 浙江晶科能源有限公司 Method for implementing back polishing in crystalline silicon solar battery production
CN103367118A (en) * 2013-08-06 2013-10-23 中利腾晖光伏科技有限公司 High-temperature alkali washing method for polycrystalline texturing
CN103400901A (en) * 2013-08-12 2013-11-20 江苏宇兆能源科技有限公司 Etching technology of twice etching on surface of solar battery
CN103441070A (en) * 2013-08-22 2013-12-11 常州捷佳创精密机械有限公司 Texture surface making equipment of crystal silicon wafers and texture surface making method
CN103696021A (en) * 2013-12-23 2014-04-02 泰通(泰州)工业有限公司 Polycrystalline velvet additive-matched surface treatment technology after felting
CN103721968A (en) * 2012-10-15 2014-04-16 江苏天宇光伏科技有限公司 Texturing and cleaning method for improving battery conversion efficiency
CN103746044A (en) * 2014-01-29 2014-04-23 北京七星华创电子股份有限公司 Preparation method of single crystalline silicon solar cell with back polished structure
CN103924305A (en) * 2013-01-14 2014-07-16 东莞市长安东阳光铝业研发有限公司 Making method of quasi-monocrystalline silicon wafer suede
CN104218122A (en) * 2014-08-28 2014-12-17 奥特斯维能源(太仓)有限公司 Texturing method for decreasing polycrystalline silicon reflectivity during diamond wire cutting
CN104347756A (en) * 2013-08-08 2015-02-11 上海神舟新能源发展有限公司 One-sided polishing method for monocrystalline silicon wafer for solar battery
CN104752566A (en) * 2015-04-24 2015-07-01 中建材浚鑫科技股份有限公司 Polycrystalline silicon battery texturing process
CN106409658A (en) * 2016-09-22 2017-02-15 山西潞安太阳能科技有限责任公司 Cleaning process of monocrystalline silicon wafer
CN107658247A (en) * 2017-09-12 2018-02-02 北京旭日龙腾新能源科技有限公司 Preparation facilities of substrate surface light trapping structure and preparation method thereof
CN108987531A (en) * 2018-07-20 2018-12-11 通威太阳能(安徽)有限公司 One type monocrystalline PERC preparation method of solar battery
CN111769053A (en) * 2019-12-31 2020-10-13 保定光为绿色能源科技有限公司 Silicon crystal groove type wet-process texturing circulating filtration treatment method
CN114459946A (en) * 2022-01-29 2022-05-10 西安奕斯伟材料科技有限公司 Method and equipment for testing metal content of silicon wafer

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CN103721968A (en) * 2012-10-15 2014-04-16 江苏天宇光伏科技有限公司 Texturing and cleaning method for improving battery conversion efficiency
CN102931289B (en) * 2012-11-28 2015-05-13 山东力诺太阳能电力股份有限公司 Preparation method of flower piece solar cell
CN102931289A (en) * 2012-11-28 2013-02-13 山东力诺太阳能电力股份有限公司 Preparation method of flower piece solar cell
CN103021832A (en) * 2012-12-03 2013-04-03 天津中环领先材料技术有限公司 Processing technology of appearance improvement of silicon wafer corroded surface through alkali corrosion
CN103924305A (en) * 2013-01-14 2014-07-16 东莞市长安东阳光铝业研发有限公司 Making method of quasi-monocrystalline silicon wafer suede
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CN103151423B (en) * 2013-02-28 2015-09-16 常州捷佳创精密机械有限公司 A kind of polycrystalline silicon texturing cleaning process
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CN103696021A (en) * 2013-12-23 2014-04-02 泰通(泰州)工业有限公司 Polycrystalline velvet additive-matched surface treatment technology after felting
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CN104218122A (en) * 2014-08-28 2014-12-17 奥特斯维能源(太仓)有限公司 Texturing method for decreasing polycrystalline silicon reflectivity during diamond wire cutting
CN104218122B (en) * 2014-08-28 2016-08-17 奥特斯维能源(太仓)有限公司 A kind of etching method of the polysilicon emitter rate reducing diamond wire cutting
CN104752566A (en) * 2015-04-24 2015-07-01 中建材浚鑫科技股份有限公司 Polycrystalline silicon battery texturing process
CN106409658A (en) * 2016-09-22 2017-02-15 山西潞安太阳能科技有限责任公司 Cleaning process of monocrystalline silicon wafer
CN107658247A (en) * 2017-09-12 2018-02-02 北京旭日龙腾新能源科技有限公司 Preparation facilities of substrate surface light trapping structure and preparation method thereof
CN108987531A (en) * 2018-07-20 2018-12-11 通威太阳能(安徽)有限公司 One type monocrystalline PERC preparation method of solar battery
CN111769053A (en) * 2019-12-31 2020-10-13 保定光为绿色能源科技有限公司 Silicon crystal groove type wet-process texturing circulating filtration treatment method
CN114459946A (en) * 2022-01-29 2022-05-10 西安奕斯伟材料科技有限公司 Method and equipment for testing metal content of silicon wafer

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