CN102732886B - Matte manufacturing solution of solar energy single crystal silicon wafers and its preparation method - Google Patents
Matte manufacturing solution of solar energy single crystal silicon wafers and its preparation method Download PDFInfo
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- CN102732886B CN102732886B CN201110084611.5A CN201110084611A CN102732886B CN 102732886 B CN102732886 B CN 102732886B CN 201110084611 A CN201110084611 A CN 201110084611A CN 102732886 B CN102732886 B CN 102732886B
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- woolen
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Abstract
The invention relates to a matte manufacturing solution of solar energy single crystal silicon wafers and its preparation method. The method comprises the following steps: adding 18megohm water in a solvent preparation device, stirring and successively adding triethanolamine, tetramethyl ammonium hydroxide (TMAH), a surfactant and sodium silicate, stirring for 20-40 minutes, completely dissolving under the temperature of 5-25 DEG C, and filtering to obtain the finished product matte manufacturing solution. The surface of the single crystal silicon wafers forms a suede structure full of pyramids. The suede structure formed on the solar cells can reduce the reflectivity of the surface, form a light trap in the internal part of the cell, and increase the transition efficiency of the solar cell substantially.
Description
Technical field
The present invention relates to Woolen-making liquid of a kind of solar monocrystalline silicon slice and preparation method thereof.
Background technology
In recent years, photovoltaic industry rapid growth, within 2008, world's solar cell output reaches 6000MW, and within 2009, world's solar cell output breaks through 10GW.The annual average rate of increase of nearly 10 years solar cell/assemblies is 42.7%, the annual average rate of increase 51% of nearly 5 years, entered the epoch of selling the energy, the powerful market requirement is impelled the numerous and confused dilatation of each major company, and the solar cell industry of China has also obtained significant progress.Now main with NaOH, IPA and Na in domestic industry production process
2siO
3the alkaline solution of system carries out Surface Texture processing to monocrystalline silicon piece, and domestic silicon single crystal making herbs into wool technology is is also researched and developed based on this, but NaOH, IPA and Na
2siO
3in system, (1) must continue interpolation so IPA has very high volatility, this just makes this making herbs into wool system along with thereby the very large change of lasting generation of producing has influence on stability and the persistence of production, and in reaction process, easily form explosive mixed gas, there is potential safety hazard, IPA is expensive in addition, poisonous, contaminate environment, (2) NaOH is easily leaving residual outward appearance and the electricity conversion of affecting at monocrystalline silicon sheet surface in textured process.
Summary of the invention
In view of above-mentioned, object of the present invention aims to provide the solar monocrystalline silicon slice Woolen-making liquid of one " environmental protection, safety, stable, efficient ".
Another object of the present invention is to provide a kind of preparation method of solar monocrystalline silicon slice Woolen-making liquid, the method for the method utilization chemistry is carried out surface tissue processing to monocrystalline silicon piece, monocrystalline silicon sheet surface is formed and be covered with pyramidal suede structure.
The object of the invention is to be achieved through the following technical solutions:
A kind of solar monocrystalline silicon slice Woolen-making liquid, is characterized in that: it is the raw material by following weight proportioning: trolamine 1%～5%; Tetramethylammonium hydroxide (TMAH) 1%～10%; Series of surfactants 1～10%; Water glass 1.5%～6%, 18 megaohm water 69%～95.5% are made.
The molecular structural formula of above-mentioned tensio-active agent is:
The preparation method of solar monocrystalline silicon slice Woolen-making liquid
First 18 megaohm water are added in solvent orchestration processed, under agitation add successively trolamine, Tetramethylammonium hydroxide (TMAH), tensio-active agent, water glass, stir 20～40 minutes, it dissolved completely at 5-25 ℃, after filtering with 200 object filtering nets finished product Woolen-making liquid.
1. the physicochemical characteristic of Woolen-making liquid:
This Woolen-making liquid is micro-yellow, is alkaline liquid.
2. the ultimate principle of Woolen-making liquid is:
At higher temperature, there is following corrosion reaction in basic solution and crystalline silicon:
Si+6OH
-→SiO
3 2-+H
2O+4e
4H
++4e→2H
2↑
Total reaction equation is
Si+2OH
-+H
2O＝SiO
3 2-+2H
2↑
In silicon crystal, the different Siliciumatom arrangement pitches in crystal orientation has differently, and therefore alkaline solution is not identical to the corrosion speed in each crystal orientation yet, and anisotropic etch speed is except being determined by crystal orientation, also relevant with corrosive fluid type of the present invention, temperature, proportioning.
The beneficial effect of advantage of the present invention and generation is:
1, the present invention can make monocrystalline silicon sheet surface formation be covered with uniform pyramid suede structure.The suede structure forming at solar battery surface not only can reduce surperficial reflectivity, but also can form light trapping in the inside of battery, thereby improves significantly the efficiency of conversion of solar cell.
2, the present invention adopts macromolecule organic to make tensio-active agent, has overcome the large problem of IPA volatility.This promoting agent is amphoterics, plays the effect that reduces silicon chip surface tension force, increases silicon chip wetting property and help bubble hydrogen desorption.Experimental study shows: the effect of promoting agent is not only to increase silicon chip wetting property, improves pyramidal homogeneity, and promoting agent also has very large impact to pyramid structure.
3, the present invention adopts organic mixed base corrosion system of trolamine and Tetramethylammonium hydroxide (TMAH) composition.Organic mixed base replaces NaOH to be difficult for forming remained on surface on silicon chip
In sum, corrosive fluid, the tensio-active agent that the present invention adopts forms the novel making herbs into wool system of one " environmental protection, safety, stable, efficient ".
Accompanying drawing explanation
Fig. 1 forms pyramid suede structure high power electron-microscope scanning figure at monocrystalline silicon sheet surface.
Fig. 2 forms pyramid suede structure low power electron-microscope scanning figure at monocrystalline silicon sheet surface.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is described in any further:
Embodiment 1
First 85g18 megaohm water is added in solvent orchestration processed, adding while stirring 2g trolamine, 2.5g Tetramethylammonium hydroxide (TMAH), 8gR is CH
3(manufacturer of tensio-active agent is Baise of Guangxi distant mountain company limited to tensio-active agent, and rank is technical grade.), 2.5g water glass, stir 35 minutes, it is dissolved completely at 25 ℃, after filtering with 200 object filtering nets clear liquid, be Woolen-making liquid.
Getting P type (100) vertical pulling solar monocrystalline silicon slice carries out putting into after surface cleaning the plastics reactor that fills Woolen-making liquid and carries out chemical corrosion (surface-texturing is also called surface wool manufacturing), the temperature of controlling making herbs into wool is 80 ℃, react after 25 minutes and take out, after cleaning with 18 megaohm water, making herbs into wool finishes, the suede structure obtaining after making herbs into wool as depicted in figs. 1 and 2, form pyramid suede structure at monocrystalline silicon sheet surface as seen from the figure, fraction of coverage is very high, and size is substantially even.
Making herbs into wool be solar cell make first technique, claim again " surface-texturing ", for silicon single crystal, making herbs into wool is to utilize the anisotropic etch of alkali to monocrystalline silicon surface, form countless four sides side's cones at silicon face, monocrystalline silicon sheet surface is formed and be covered with pyramidal suede structure.The surface area ratio plane of pyramid pyramid has improved 1.732 times.Desirable matte effect, should be that pyramid size is even, covers whole surface.The height of gold tower, between 3-5 μ m, does not have space between adjacent pyramid, so just can have lower surface albedo.
Embodiment 2:
First 80.0g18 megaohm water is added in solvent orchestration processed, adding while stirring 5.0g trolamine, 2.0g Tetramethylammonium hydroxide (TMAH), 10.0gR is C
2h
5tensio-active agent, 3g water glass, stir 25 minutes, it dissolved completely at 15 ℃, after filtering with 200 object filtering nets finished product Woolen-making liquid.
Get P type (100) vertical pulling solar monocrystalline silicon slice carry out putting into after surface cleaning aforesaid method system Woolen-making liquid, take out react 25 minutes at 90 ℃ of temperature after, clean making herbs into wool afterwards with 18 megaohm water and finish.
Embodiment 3:
First 90g18 megaohm water is added in solvent orchestration processed, add while stirring tensio-active agent, 5g water glass that 1g trolamine, 2.0g Tetramethylammonium hydroxide (TMAH), 2gR are H, stir 35 minutes, at 5 ℃, it is dissolved completely, after filtering with 200 object filtering nets, obtain finished product Woolen-making liquid.
Get P type (100) vertical pulling solar monocrystalline silicon slice carry out putting into after surface cleaning aforesaid method system Woolen-making liquid, under temperature 70 C, react after 20 minutes and take out, clean making herbs into wool afterwards with 18 megaohm water and finish.
Table 1
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Pyramid size degree of uniformity | More even | Evenly | More even |
| Whether pyramid covers whole surface | Be | Be | Be |
| The altitude range of gold tower | 3.5-4.9μm | 3.3-4.8μm | 3.1-5.0μm |
Table 1 is the comparison that on embodiment 1 embodiment 2 embodiment 3 solar monocrystalline silicon slices, whether pyramid size degree of uniformity, pyramid cover the altitude range of whole surface, gold tower.Relatively can find out from embodiment 1 embodiment 2 embodiment 3, the making herbs into wool effect of the solar monocrystalline silicon slice of embodiment 2 is best.Can find out at monocrystalline silicon sheet surface and form pyramid suede structure by Fig. 1 of embodiment 2, fraction of coverage is very high as seen from Figure 2, size is substantially even, the height of the gold tower of solar monocrystalline silicon slice is between 3-5 μ m, between adjacent pyramid, there is no space, its reason is that the proportioning of each material is moderate, reaches optimum value, just can have lower surface albedo like this through the monocrystalline silicon sheet surface of making herbs into wool.
Claims (2)
1. a solar monocrystalline silicon slice Woolen-making liquid, is characterized in that: it is the raw material by following weight proportioning: trolamine 1%～5%; Tetramethylammonium hydroxide 1%～10%; Tensio-active agent 1～10%; Water glass 1.5%～6%, 18 megaohm water 69%～95.5% are made, and the molecular structural formula of tensio-active agent is:
In formula,
R：CH
3，C
2H
5，C
3H
7，H
n：100-300 。
2. implement the claims a kind of method of preparing solar monocrystalline silicon slice Woolen-making liquid described in 1, the steps include: first 18 megaohm water to be added in solvent orchestration processed, under agitation add successively trolamine, Tetramethylammonium hydroxide, tensio-active agent, water glass, stir 20～40 minutes, at 5-25 ℃ of temperature, it is dissolved completely, after filtering with 200 object filtering nets, obtain finished product Woolen-making liquid.
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| CN201110084611.5A CN102732886B (en) | 2011-04-01 | 2011-04-01 | Matte manufacturing solution of solar energy single crystal silicon wafers and its preparation method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106118926A (en) * | 2016-06-16 | 2016-11-16 | 深圳市唯特偶新材料股份有限公司 | A kind of used in electronic industry is entirely without halogen VOC free aqueous cleaning agent |
| CN106012027B (en) * | 2016-07-05 | 2018-06-26 | 常州大学 | A kind of list polysilicon chain type soda acid one making herbs into wool and preparation method thereof |
| CN107046072A (en) * | 2017-04-20 | 2017-08-15 | 通威太阳能（合肥）有限公司 | A kind of polycrystalline process for etching for improving the solar panel matte uniformity |
| CN113284978A (en) * | 2021-04-20 | 2021-08-20 | 山西潞安太阳能科技有限责任公司 | Wet-process texturing process suitable for P-type and N-type solar cells |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323955A (en) * | 2008-02-27 | 2008-12-17 | 苏州苏电微电子信息化学品研发中心有限公司 | Wool-making agent for monocrystalline silicon solar cell surface treatment and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009032816A (en) * | 2007-07-25 | 2009-02-12 | Asahi Kasei Chemicals Corp | Sodium hydroxide aqueous solution for silicon wafer etching |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323955A (en) * | 2008-02-27 | 2008-12-17 | 苏州苏电微电子信息化学品研发中心有限公司 | Wool-making agent for monocrystalline silicon solar cell surface treatment and manufacturing method thereof |
Non-Patent Citations (7)
| Title |
|---|
| JP特开2009-32816A 2009.02.12 |
| Micro-fabrication of crystalline silicon by controlled alkali etching;Yuan Fulong et.al;《Journal of Materials Processing Technology》;20041231;第149卷;567-572 * |
| TMAH 腐蚀液制作硅微结构的研究;张建辉等;《传感技术学报》;20060630;第19卷(第3期);593-596 * |
| Yuan Fulong et.al.Micro-fabrication of crystalline silicon by controlled alkali etching.《Journal of Materials Processing Technology》.2004,第149卷567-572. |
| 壳聚糖类表面活性剂的研究进展;杜经武等;《中国洗涤用品工业》;20081231(第1期);71-72 * |
| 张建辉等.TMAH 腐蚀液制作硅微结构的研究.《传感技术学报》.2006,第19卷(第3期),593-596. |
| 杜经武等.壳聚糖类表面活性剂的研究进展.《中国洗涤用品工业》.2008,(第1期),71-72. |
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