CN114447147B - Method for improving texturing yield of silicon wafer for solar cell - Google Patents

Method for improving texturing yield of silicon wafer for solar cell Download PDF

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Publication number
CN114447147B
CN114447147B CN202111624966.9A CN202111624966A CN114447147B CN 114447147 B CN114447147 B CN 114447147B CN 202111624966 A CN202111624966 A CN 202111624966A CN 114447147 B CN114447147 B CN 114447147B
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texturing
tank
deionized water
solution
hours
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CN114447147A (en
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周海龙
张树德
钱洪强
荆蓉蓉
张俊巍
王展
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Suzhou Talesun Solar Technologies 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/08Etching
    • C30B33/10Etching in solutions or melts
    • 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
    • H01L31/02363Special surface textures of the semiconductor body itself, e.g. textured active layers

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  • Engineering & Computer Science (AREA)
  • Electromagnetism (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

The invention discloses a method for improving the texturing yield of a silicon wafer for a solar cell, which comprises the following steps of pre-cleaning a texturing groove of the silicon wafer: A. adding a first mixed solution of alkali liquor and hydrogen peroxide into the texturing tank, heating, bubbling for at least 10 hours, and adding hydrogen peroxide at intervals; B. evacuating the first mixed solution in the texturing tank, and adding deionized water for cleaning; C. adding a second mixed solution of alkali liquor and a texturing additive into the texturing groove, heating, and carrying out bubbling treatment for at least 10 hours; D. and (5) evacuating the second mixed solution in the texturing groove, and adding deionized water for cleaning. According to the invention, the silicon wafer texturing groove of the solar cell is pretreated, so that the texturing yield is improved, and the cell conversion efficiency is further improved.

Description

Method for improving texturing yield of silicon wafer for solar cell
Technical Field
The invention belongs to the field of solar cell preparation, and relates to a method for improving the texturing yield of a silicon wafer for a solar cell.
Background
Under the large background of a double-carbon target, photovoltaics are increasingly paid attention to as a clean energy source, and the installed amount of photovoltaics is increasing in recent years, so that all photovoltaic enterprises are rapidly expanding. The texturing is the first procedure of the crystalline silicon solar cell manufacturing process, mainly plays roles of cleaning dirt on the surface of a silicon wafer, removing cutting loss on the surface of the silicon wafer and preparing a light trapping textured surface, and can improve the light utilization rate. In actual production, some silicon wafers are often poor in texturing, and if the silicon wafers with poor texturing flow are transferred to a finished product, the efficiency of the finished product battery piece is low. The original silicon wafer before texturing is shown in fig. 1a, the normal textured silicon wafer is shown in fig. 1b, and fig. 1c and 1d show two silicon wafers with abnormal textured appearance. The electrical properties of the battery plate with the texture defects and the normal battery plate efficiency test are shown in table 1.
TABLE 1
Eta Voc Isc FF Rs Rsh Irev2
Normal sheet 22.97% 0.683 11.370 81.09 1.64 840 0.07
Abnormal sheet 22.68% 0.680 11.307 80.86 1.74 413 0.35
Delta (Normal-abnormal) -0.29% -0.003 -0.063 -0.23 0.1 -427 0.27
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for improving the texturing yield of a silicon wafer for a solar cell, which improves the texturing yield by preprocessing a silicon wafer texturing groove of the solar cell, thereby improving the conversion efficiency of the cell.
The method for improving the texturing yield of the silicon wafer for the solar cell comprises the following steps of pre-cleaning a texturing groove of the silicon wafer:
A. Adding a first mixed solution of alkali liquor and hydrogen peroxide into the texturing tank, heating, bubbling for at least 10 hours, and adding hydrogen peroxide at intervals;
B. Evacuating the first mixed solution in the texturing tank, and adding deionized water for cleaning;
C. Adding a second mixed solution of alkali liquor and a texturing additive into the texturing groove, heating, and carrying out bubbling treatment for at least 10 hours;
D. and (5) evacuating the second mixed solution in the texturing groove, and adding deionized water for cleaning.
In one embodiment, the volume ratio of the alkali liquor, the hydrogen peroxide and the deionized water in the first mixed solution is 4:8:100-200, and the mass concentration of the alkali liquor is 40-50%.
Preferably, the mass concentration of the hydrogen peroxide is 30-35%.
In one embodiment, the volume ratio of the alkali liquor, the texturing additive and the deionized water in the second mixed solution is 4:2:100-200, and the mass concentration of the alkali liquor is 40-50%.
In one embodiment, the lye is NaOH solution.
In one embodiment, in the step a, the first mixed solution is further circulated in the texturing groove; and/or, in the step C, the second mixed solution is circulated in the texturing groove.
Preferably, the first mixed liquid or the second mixed liquid is circulated in the texturing tank by stirring.
In one embodiment, in the step B or the step D, after the deionized water is washed, the tank body and the cover plate of the texturing tank are washed by a water gun.
In one embodiment, step a is repeated after step B, and then step C is performed.
In a specific and preferred embodiment, the method is embodied as follows:
S101, adding 4L of NaOH solution with the mass concentration of 45%, 150L of deionized water and 8L of hydrogen peroxide solution with the mass concentration of 32% into a texturing tank, heating the texturing tank to 60 ℃, and opening bubbling and circulation functions, wherein 2L of hydrogen peroxide solution is added every 2 hours;
s102, after 12 hours, evacuating the solution in the texturing tank, filling the tank body with deionized water, opening the circulation function, evacuating the deionized water in the texturing tank after 15 minutes, and flushing the tank body and the cover plate with a water gun;
S103, adding 4L of 45% NaOH solution, 150L of deionized water and 8L of 32% hydrogen peroxide solution into the texturing tank, heating the texturing tank to 60 ℃, opening bubbling and circulation functions, adding 2L of hydrogen peroxide solution every 2 hours, and evacuating the solution in the texturing tank after 12 hours;
S104, adding 4L of NaOH solution with the mass concentration of 45%, 2L of texturing additive and 150L of deionized water into a texturing tank, raising the temperature of the texturing tank to 80 ℃, and opening bubbling and circulation functions;
And S105, after 12 hours, evacuating the solution in the texturing tank, filling the tank body with deionized water, opening the circulation function, evacuating the deionized water in the texturing tank body after 15 minutes, and flushing the tank body and the cover plate by using a water gun.
By adopting the technical scheme, the invention has the following advantages compared with the prior art:
According to the invention, the silicon wafer texturing groove of the solar cell is pretreated, firstly, the first mixed solution of alkali liquor and hydrogen peroxide is used for treating the texturing groove to fully remove greasy dirt, then, the second mixed solution of alkali liquor and texturing additive is used for treating to simulate the condition during texturing, and a small amount of pollutants which are possibly dissolved under the texturing condition are removed in advance, so that the pollution in the texturing groove can be completely removed, the yield of the texturing process is improved, the defective silicon wafers in texturing are prevented from flowing into a finished product, and the conversion efficiency of the finished battery piece is further improved.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the description below are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art, wherein:
FIG. 1a is a photograph of an original silicon wafer prior to texturing;
FIG. 1b is a photograph of a normal textured silicon wafer;
FIGS. 1c and 1d are photographs of two textured wafers with abnormal appearance, respectively;
FIG. 2a is a photograph of an apparent smudged textured silicon wafer;
FIG. 2b is a partial photomicrograph of an apparent dirty textured silicon wafer;
FIG. 3 is a graph showing the comparison trend of the yield of the wool production by two different methods of the examples and the comparative examples.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the attached drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In actual production, the inventor finds that the pile surface has low pile surface yield due to unknown oil pollution at abnormal parts through comparing and analyzing normal sheets and abnormal appearance and pile surface analysis, and the pile surface yield is as shown in fig. 2a and 2b, so that the appearance of the battery sheet after pile surface manufacture is abnormal, the post-finished battery light trapping effect is poor, the current is low, the compound serious open voltage is low, and the like, and the efficiency of the finished battery sheet is low. The pretreatment method is designed to completely remove the pollution in the texturing groove body, and improve the yield of the texturing process and the conversion efficiency of the battery.
Examples
The method for improving the texturing yield of the silicon wafer for the solar cell is divided into two steps of degreasing cleaning and soaking cleaning, and takes about 48 hours in total.
The degreasing cleaning reagents are shown in Table 2.
TABLE 2
Degreasing and cleaning NaOH(45%) DI water 2O2(32%) Heating Bubbling device Circulation Remarks
Texturing groove 4L 150L 8L 60℃ Opening device Opening device Every 2 hours add 2L-H2O2
The specific implementation is as follows:
1-1) 4LNaOH solution (45% mass fraction), 150L deionized water and 8L H 2O2 solution (32% mass fraction) were added to the texturing tank. Raising the temperature of the texturing tank to 60 ℃ and opening bubbling and circulation functions, wherein the bubbling is regulated to a proper size, and the bubbles are visible but cannot be excessively large so as to cause the solution to splash out of the tank. Since H 2O2 is decomposed, 2LH 2O2 solution is added every 2 hours. The NaOH solution, the deionized water and the H 2O2 solution can be increased or decreased in the same proportion according to the different volumes of the texturing groove bodies of different machines.
1-2) After 12 hours, evacuating the solution in the texturing tank body, filling the tank body with deionized water, opening the circulation function, evacuating the deionized water in the texturing tank body after 15 minutes, and flushing the tank body and the cover plate by a water gun.
1-3) Repeating the steps 1-1, and evacuating the solution in the texturing groove after 12 hours.
The reagents used for the soak cleaning are shown in Table 3.
TABLE 3 Table 3
Soaking and cleaning NaOH(45%) Additive agent DI water Heating Bubbling device Circulation
Texturing groove 4L 2L 150L 80℃ Opening device Opening device
2-1) Into the texturing tank was added 4LNaOH solution (45% mass fraction), 2L of texturing additive (purchased from additive manufacturer) and 150L of deionized water. Raising the temperature of the texturing tank to 80 ℃ and opening bubbling and circulation functions, wherein the bubbling is regulated to a proper size, and the bubbles are visible but cannot be excessively large so as to cause the solution to splash out of the tank. The NaOH solution, the deionized water and the H 2O2 solution can be increased or decreased in the same proportion according to the different volumes of the texturing groove bodies of different machines.
2-2) After 12 hours, evacuating the solution in the texturing tank body, filling the tank body with deionized water, opening the circulation function, evacuating the deionized water in the texturing tank body after 15 minutes, and flushing the tank body and the cover plate by a water gun.
The method of the embodiment comprises two steps of degreasing cleaning and soaking cleaning: the mixed solution of NaOH and H 2O2 is adopted for degreasing and cleaning, so that pollutants can be fully removed; the mixed solution of NaOH and a texturing additive is adopted for soaking and cleaning, the condition during texturing is simulated, and a small amount of pollutants which are possibly dissolved under the texturing condition are removed in advance; thereby ensuring the cleanliness of the texturing groove body during mass production and improving the yield of the texturing process and the conversion efficiency of the battery. The device can completely remove the pollution in the texturing groove body, improve the yield of the texturing process and the conversion efficiency of the battery, and not only can be applied to cleaning of the texturing groove body of a new machine, but also can be applied to cleaning of the texturing groove body of a polluted machine.
Comparative example
Adding deionized water into the texturing tank, raising the temperature of the texturing tank to 60 ℃, and opening bubbling and circulation functions, wherein the bubbling is regulated to a proper size, and the bubbles are visible but cannot be excessively large to cause the solution to splash out of the tank. And (3) after 12 hours, the tank body is filled with ionized water in the empty texturing tank body, the circulation function is opened, deionized water in the texturing tank body is emptied after 15 minutes, and the tank body and the cover plate are washed by a water gun. The above steps were repeated once.
And filling deionized water into the texturing tank again, raising the temperature of the texturing tank to 80 ℃, and opening bubbling and circulation functions, wherein the bubbling is regulated to a proper size, and the bubbles are visible but cannot be excessively large so as to cause the solution to splash out of the tank. And (3) after 12 hours, the tank body is filled with ionized water in the empty texturing tank body, the circulation function is opened, deionized water in the texturing tank body is emptied after 15 minutes, and the tank body and the cover plate are washed by a water gun.
And (5) wool making yield evaluation:
for both examples and comparative examples, the yield of the wool making was measured with tracking, and fig. 3 shows the comparative trend of the yield of the wool making for different cleaning methods, where the ordinate is the yield of the wool making, the abscissa is time, and D2, D3, D4 represent days. The following data of the yield of the wool making groove are obtained: the yield rate of the method of the comparative example drops sharply after 12 hours of wool making, and the yield rate of the wool making of the comparative example drops below 92% compared with the method of the example; for the abnormal tank, the yield rate after the chemical tank washing treatment is continuously carried out by adopting the method of the embodiment is raised to be the same as that of the normal tank body, as shown in figure 3.
In the description of the present invention, it should be noted that the positional or positional relationship indicated by the terms such as "upper", "lower", "left", "right", "vertical", "horizontal", etc. are based on the positional or positional relationship shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or element in question must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
As used herein, the terms "comprises," "comprising," and "includes" are intended to cover merely the inclusion of a stated step or element that is not an exclusive list of steps or elements but may include other steps or elements as well. The term "and/or" as used herein includes any combination of one or more of the associated listed items.
The above-described embodiments are provided for illustrating the technical concept and features of the present invention, and are intended to be preferred embodiments for those skilled in the art to understand the present invention and implement the same according to the present invention, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (9)

1. The method for improving the texturing yield of the silicon wafer for the solar cell is characterized by comprising the following steps of pre-cleaning a texturing groove of the silicon wafer:
A. Adding a first mixed solution of alkali liquor and hydrogen peroxide into the texturing tank, heating, bubbling for at least 10 hours, and adding hydrogen peroxide at intervals;
B. Evacuating the first mixed solution in the texturing tank, and adding deionized water for cleaning;
C. Adding a second mixed solution of alkali liquor and a texturing additive into the texturing groove, heating, and carrying out bubbling treatment for at least 10 hours;
D. Evacuating the second mixed solution in the texturing tank, and adding deionized water for cleaning;
wherein, step A is repeated after step B, and then step C is performed.
2. The method according to claim 1, wherein the volume ratio of the alkali liquor, the hydrogen peroxide and the deionized water in the first mixed solution is 4:8:100-200, and the mass concentration of the alkali liquor is 40-50%.
3. The method according to claim 2, wherein the mass concentration of the hydrogen peroxide is 30-35%.
4. The method according to claim 1, wherein the volume ratio of the alkali liquor, the texturing additive and the deionized water in the second mixed solution is 4:2:100-200, and the mass concentration of the alkali liquor is 40-50%.
5. The process according to any one of claims 1 to 4, wherein the lye is a NaOH solution.
6. The method of claim 1, wherein in step a, the first mixed liquor is also circulated in the texturing tank; and/or, in the step C, the second mixed solution is circulated in the texturing groove.
7. The method of claim 6, wherein the first mixed liquor or the second mixed liquor is circulated in the texturing tank by stirring.
8. The method according to claim 1, wherein in step B or step D, after the deionized water is washed, the tank body and the cover plate of the texturing tank are washed with a water gun.
9. The method according to claim 1, characterized in that it is implemented as follows:
S101, adding 4L of NaOH solution with the mass concentration of 45%, 150L of deionized water and 8L of hydrogen peroxide solution with the mass concentration of 32% into a texturing tank, heating the texturing tank to 60 ℃, and opening bubbling and circulation functions, wherein 2L of hydrogen peroxide solution is added every 2 hours;
s102, after 12 hours, evacuating the solution in the texturing tank, filling the tank body with deionized water, opening the circulation function, evacuating the deionized water in the texturing tank after 15 minutes, and flushing the tank body and the cover plate with a water gun;
S103, adding 4L of 45% NaOH solution, 150L of deionized water and 8L of 32% hydrogen peroxide solution into the texturing tank, heating the texturing tank to 60 ℃, opening bubbling and circulation functions, adding 2L of hydrogen peroxide solution every 2 hours, and evacuating the solution in the texturing tank after 12 hours;
s104, adding 4L of NaOH solution with the mass concentration of 45%, 2L of texturing additive and 150L of deionized water into a texturing tank, raising the temperature of the texturing tank to 80 ℃, and opening bubbling and circulation functions;
And S105, after 12 hours, evacuating the solution in the texturing tank, filling the tank body with deionized water, opening the circulation function, evacuating the deionized water in the texturing tank body after 15 minutes, and flushing the tank body and the cover plate by using a water gun.
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US6185777B1 (en) * 1998-06-16 2001-02-13 Al Siamon Systems and methods for cleaning
CN101350380A (en) * 2008-09-01 2009-01-21 上海联孚新能源科技有限公司 Method for preparing monocrystalline silicon solar battery pile fabrics in magnetic field
CN101409312A (en) * 2008-10-20 2009-04-15 宁海县日升电器有限公司 Method for fine-hair maring using monocrystalline silicon slice
CN101719530A (en) * 2009-08-31 2010-06-02 上海科伟达超声波科技有限公司 Polysilicon solar battery slice etching device
CN102181934A (en) * 2010-08-09 2011-09-14 苏州晶瑞化学有限公司 Environment-friendly biological texture etch solution and application method thereof
CN106367815A (en) * 2016-09-12 2017-02-01 英利能源(中国)有限公司 Cleaning method of texture surface making equipment for single crystal silicon
CN106601862A (en) * 2015-10-15 2017-04-26 钧石(中国)能源有限公司 Texturing method for reducing reflectivity of monocrystalline silicon heterojunction solar cell

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6185777B1 (en) * 1998-06-16 2001-02-13 Al Siamon Systems and methods for cleaning
CN101350380A (en) * 2008-09-01 2009-01-21 上海联孚新能源科技有限公司 Method for preparing monocrystalline silicon solar battery pile fabrics in magnetic field
CN101409312A (en) * 2008-10-20 2009-04-15 宁海县日升电器有限公司 Method for fine-hair maring using monocrystalline silicon slice
CN101719530A (en) * 2009-08-31 2010-06-02 上海科伟达超声波科技有限公司 Polysilicon solar battery slice etching device
CN102181934A (en) * 2010-08-09 2011-09-14 苏州晶瑞化学有限公司 Environment-friendly biological texture etch solution and application method thereof
CN106601862A (en) * 2015-10-15 2017-04-26 钧石(中国)能源有限公司 Texturing method for reducing reflectivity of monocrystalline silicon heterojunction solar cell
CN106367815A (en) * 2016-09-12 2017-02-01 英利能源(中国)有限公司 Cleaning method of texture surface making equipment for single crystal silicon

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