CN102330154B - Acidic texturing solution for texturing of polycrystalline silicon chip and using method thereof - Google Patents
Acidic texturing solution for texturing of polycrystalline silicon chip and using method thereof Download PDFInfo
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- CN102330154B CN102330154B CN2011102125347A CN201110212534A CN102330154B CN 102330154 B CN102330154 B CN 102330154B CN 2011102125347 A CN2011102125347 A CN 2011102125347A CN 201110212534 A CN201110212534 A CN 201110212534A CN 102330154 B CN102330154 B CN 102330154B
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Abstract
The invention provides an acidic texturing solution for texturing of a polycrystalline silicon chip and a using method thereof. The acidic texturing solution is characterized in that: when the acidic texturing solution is used for surface texturing of the polycrystalline silicon chip for a solar cell, excellent texturing effect can be achieved. The technical problems of environmental pollution of the texturing solution and textured surface non-uniformity caused by instable states of the texturing solution and the process conditions in the prior art are solved.
Description
Technical field
The present invention relates to a kind of acid Woolen-making liquid and method of use thereof that is used for polycrystalline silicon texturing.
Background technology
Prepare in the process at solar cell piece; For performance and the efficient that improves solar cell; Need make matte at silicon chip surface, effectively suede structure can change the working direction of incident light in silicon so that the incident sunshine carries out multiple reflection and refraction at silicon chip surface.On the one hand, prolonged light path, thereby increased the specific absorption of silicon chip infrared light; On the other hand, make more photon be absorbed the generation photo-generated carrier near near the zone the pn knot, these photo-generated carriers are collected more easily, have therefore increased the collection effciency of photo-generated carrier.
For polycrystalline silicon solar cell, silicon chip surface making herbs into wool is the key link in its manufacturing processed.The effect of making herbs into wool has directly influenced the efficiency of conversion and the yield rate of final battery sheet.Because polysilicon chip is made up of the crystal grain of different crystal orientations, and the crystal orientation of each crystal grain arbitrarily distributes, and therefore, the wet-chemical etching methods of many employing acidic solutions are carried out making herbs into wool to the polysilicon chip surface in general leather producing process.This leather producing process forms similar pit shape matte based on the isotropic etch principle of acidic solution to silicon at the different grain surfaces of silicon chip, and the pattern of matte and grain orientation are irrelevant.
Chinese invention patent CN200410064831.1 discloses a kind of method for preparing polycrystalline silicon suede, yet the acid Woolen-making liquid that uses in this method comprises chromium trioxide or potassiumchromate, toxic and corrodibility, and can produce heavy metal contamination, the serious harm environment; Chinese invention patent CN200610065676.4 discloses a kind of acid etching solution and method of use thereof that is used to prepare polycrystalline silicon suede; But owing in etchant solution, used nitrate salt or nitrite; Therefore in the making herbs into wool process, can inevitably produce bubble; Thereby influence the homogeneity of matte, simultaneously can be nitrogen discharged in a large number, environment is polluted.In addition, use hypochlorite in the prior art in addition, like Youxiaolin and alcohol, like the ethanol preparation Woolen-making liquid.But because the oxidation capacity of chlorine in the hypochlorite is strong excessively, cause speed of response too fast, make the matte pyramid structure skewness on the crystal face of formation.These problems are present in the industrial production of present stage equally, solve the problems referred to above if can invent a kind of new acid Woolen-making liquid, will have great importance.
Summary of the invention
The present invention provides a kind of acid Woolen-making liquid and method of use thereof that is used for polycrystalline silicon texturing, it is characterized in that, utilizes acid Woolen-making liquid of the present invention that solar cell is carried out surface wool manufacturing with polysilicon chip, can reach excellent making herbs into wool effect.Overcome in the prior art technical problem such as the matte that Woolen-making liquid pollutes environment and the unsteady state of Woolen-making liquid itself and processing condition causes is inhomogeneous.
Applicant of the present invention is through research for many years; Perchlorate a little less than finding to use oxidation capacity slightly; The hydrofluoric acid and the deionized water that cooperate certain content can effectively improve technical problems such as the unsteady state of Woolen-making liquid itself and processing condition causes in the prior art matte is inhomogeneous.Applicant of the present invention finds that through a large amount of experiments the content proportioning of strict control perchlorate, hydrofluoric acid and deionized water is to realize the key of technical purpose of the present invention.The content of perchlorate in Woolen-making liquid is low excessively, because contained active chlorine content is lower, can't effectively improve speed of reaction, causes the overlong time of whole making herbs into wool, and can't effectively remove the organic pollutant and the metallic impurity ion of silicon chip surface; The too high levels of perchlorate in Woolen-making liquid because contained active chlorine content is higher, accelerates the speed of response of making herbs into wool, is difficult to control.
Therefore; Applicant of the present invention proposes a kind of acid Woolen-making liquid that is used for polycrystalline silicon texturing; It is characterized in that the component that wherein comprises is: perchlorate, hydrofluoric acid and deionized water, wherein the content of perchlorate and hydrofluoric acid is respectively 5～30 mol and 1～20 mol.Perchlorate includes but not limited to sodium perchlorate, potassium perchlorate and ammoniumper chlorate.Content
Wherein, preferred, the content of perchlorate and hydrofluoric acid is respectively 10～25 mol and 5～15 mol.
Preferred, the content of perchlorate and hydrofluoric acid is respectively 15～18 mol and 10-12 mol.
Most preferred, the content of perchlorate and hydrofluoric acid is respectively 18 mol and 10 mol.
Can also add tensio-active agent in the Woolen-making liquid of the present invention, addition is 0.05%-02% (weight percent).Silica-based additive comprises but is not limited to silica-based surfactant, like polymethyl siloxane and verivate thereof; TX10 series is like polyoxyethylene octylphenol ether or polyoxyethylene nonylphenol.Through adding above-mentioned tensio-active agent, match with above-mentioned specific perchlorate and fluohydric acid content and ratio, homogeneity, the intercrystalline that can significantly improve making herbs into wool do not have obvious aberration.
A kind of method of use that is used for the acid Woolen-making liquid of polycrystalline silicon texturing is specially, and polysilicon chip is immersed in this acidity Woolen-making liquid, and during making herbs into wool, temperature is that 5-20 ℃, making herbs into wool time are 2-10min.
Employing should the acidity Woolen-making liquid and after method of use carries out making herbs into wool to the polysilicon chip surface, forms uniform pit shape matte at silicon chip surface, and the size of matte is about 1～5 μ m.
Under the condition of the content of specific perchlorate disclosed by the invention and hydrofluoric acid; Prepared acid Woolen-making liquid can be effectively to polycrystalline silicon surface wool manufacturing; Under the condition of this content proportioning, both overcome prior art and used the hypochlorite oxidisability strong excessively, cause reacting uncontrollable; Can overcome the lower defective of the oxidisability of perchlorate own again, can realize polysilicon ideal making herbs into wool effect.
In the prior art, two-step approach making herbs into wool is the conventional way that current solar cell enterprise is used for making herbs into wool, and in traditional making herbs into wool process, polysilicon chip at first will be removed affected layer, and then the preparation matte.And the application is through the perchlorate and the hydrofluoric acid of above-mentioned certain content and proportioning; Made full use of the gentle oxidation susceptibility of perchlorate; And cooperating hydrofluoric acid at polycrystalline silicon surface wool manufacturing, the process that affected layer is removed is exactly the making herbs into wool process, and polysilicon chip is placed in the Woolen-making liquid of the present invention; Corrode its surperficial affected layer, reach the purpose of making herbs into wool simultaneously.Both guaranteed that the reaction conditions gentleness was controlled, guaranteed simultaneously again that the reaction times was unlikely long.The unexpected technique effect that the present invention obtains, that is, outstanding feature shows:
1) the present invention is through a kind of novel Woolen-making liquid, makes the pyramid particulate size of matte can both be in an ideal scope (1-15 μ m), and arranges closely, and fraction of coverage is high:
2) the solar cell surface pyramid structure for preparing with this Woolen-making liquid is even, has increased the absorption area to sunshine greatly, has reduced the reflection loss of sunshine;
3) the own stable performance of Woolen-making liquid, speed of response is gentle, has avoided the control requirement to the harshness of speed of response;
4) simplified that two-step approach making herbs into wool is single stage method making herbs into wool in the prior art.
5) adopt acid Woolen-making liquid of the present invention and method of use, can obtain the matte that good uniformity, intercrystalline do not have obvious aberration, the matte size is tiny evenly.Acidic solution of the present invention produces bubble at making herbs into wool process middle part, therefore helps obtaining uniform matte.In addition, heavy metal, high concentration N etc. have been eliminated in the discharging waste liquid to the harm of environment.The configuration of this Woolen-making liquid and use technology are simple, cheap device, good reproducibility.
Description of drawings
Fig. 1 is the ESEM plane photo of the polysilicon chip surface matte that obtains of embodiment 1.
Embodiment
Embodiment 1
Take following process step: 1) dispose acid Woolen-making liquid: with the hydrofluoric acid dissolution of the sodium perchlorate of 5 mol and 1 mol in deionized water; 2) solar cell is immersed in the solution with polysilicon chip carry out surface wool manufacturing, the making herbs into wool temperature is 7 ℃, and the making herbs into wool time is 8min.
Fig. 1 has provided the ESEM plane photo of the polysilicon chip surface matte that obtains, and from figure, can see the uniform pit shape matte that forms at silicon chip surface, and the matte size is about 1～5 μ m.
Embodiment 2
Take following process step: 1) dispose acid Woolen-making liquid: the polymethyl siloxane of the hydrofluoric acid, 0.05% (weight percent) of the sodium perchlorate of 30 mol and 20 mol is dissolved in the deionized water; 2) solar cell is immersed in the solution with polysilicon chip carry out surface wool manufacturing, the making herbs into wool temperature is 10 ℃, and the making herbs into wool time is 5min.
Embodiment 3
Take following process step: 1) dispose acid Woolen-making liquid: the polyoxyethylene octylphenol ether of the hydrofluoric acid, 0.2% (weight percent) of the sodium perchlorate of 10 mol and 5 mol is dissolved in the deionized water: 2) solar cell is immersed in the solution with polysilicon chip and carry out surface wool manufacturing; The making herbs into wool temperature is 10 ℃, and the making herbs into wool time is 5min.
Embodiment 4
Take following process step: 1) dispose acid Woolen-making liquid: with the hydrofluoric acid dissolution of the sodium perchlorate of 25 mol and 15 mol in deionized water; 2) solar cell is immersed in the solution with polysilicon chip carry out surface wool manufacturing, the making herbs into wool temperature is 10 ℃, and the making herbs into wool time is 5min.
Embodiment 5
Take following process step: 1) dispose acid Woolen-making liquid: with the hydrofluoric acid dissolution of the sodium perchlorate of 15 mol and 10 mol in deionized water; 2) solar cell is immersed in the solution with polysilicon chip carry out surface wool manufacturing, the making herbs into wool temperature is 10 ℃, and the making herbs into wool time is 2min.
Embodiment 6
Take following process step: 1) dispose acid Woolen-making liquid: with the hydrofluoric acid dissolution of the sodium perchlorate of 18 mol and 12 mol in deionized water; 2) solar cell is immersed in the solution with polysilicon chip carry out surface wool manufacturing, the making herbs into wool temperature is 10 ℃, and the making herbs into wool time is 5min.
Embodiment 7
Take following process step: 1) dispose acid Woolen-making liquid: with the hydrofluoric acid dissolution of the sodium perchlorate of 18 mol and 10 mol in deionized water: 2) solar cell immersed in the solution with polysilicon chip carry out surface wool manufacturing; The making herbs into wool temperature is 10 ℃, and the making herbs into wool time is 10min.
Embodiment 8 (comparative example)
Take following process step: 1) dispose acid Woolen-making liquid: with the hydrofluoric acid dissolution of the Youxiaolin of 18 mol and 12 mol in deionized water; 2) solar cell is immersed in the solution with polysilicon chip carry out surface wool manufacturing, the making herbs into wool temperature is 10 ℃, and the making herbs into wool time is 5min.
The making herbs into wool the key technical indexes of Woolen-making liquid of the present invention is referring to table 1
Table 1
Claims (10)
1. acid Woolen-making liquid that is used for polycrystalline silicon texturing, it is characterized in that the component that wherein comprises is: perchlorate, hydrofluoric acid and deionized water, wherein the content of perchlorate and hydrofluoric acid is respectively 5～30 mol and 1～20 mol.
2. acid Woolen-making liquid according to claim 1, wherein, the content of perchlorate and hydrofluoric acid is respectively 10～25 mol and 5～15 mol.
3. acid Woolen-making liquid according to claim 2, wherein, the content of perchlorate and hydrofluoric acid is respectively 15～18 mol and 10～12 mol.
4. acid Woolen-making liquid according to claim 3, the content of perchlorate and hydrofluoric acid are respectively 18 mol and 10 mol.
5. according to the described acid Woolen-making liquid of one of claim 1-4, add tensio-active agent, addition is 0.05%-0.2% (weight percent).
6. acid Woolen-making liquid according to claim 5, tensio-active agent are silica-based surfactant or TX10 series.
7. acid Woolen-making liquid according to claim 6, tensio-active agent are polymethyl siloxane and verivate thereof.
8. acid Woolen-making liquid according to claim 6, tensio-active agent are polyoxyethylene octylphenol ether or polyoxyethylene nonylphenol.
9. according to any described acid Woolen-making liquid of claim 1-8, wherein perchlorate is sodium perchlorate, potassium perchlorate or ammoniumper chlorate.
10. a method of using any described acid Woolen-making liquid making herbs into wool of claim 1-9 is characterized in that, polysilicon chip is immersed in this acidity Woolen-making liquid; During making herbs into wool; Temperature is 5-20 ℃, and the making herbs into wool time is 2-10min, after making herbs into wool is accomplished; Form uniform pit shape matte at silicon chip surface, matte is of a size of 1～5 μ m.
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| CN104342702A (en) * | 2013-08-05 | 2015-02-11 | 南京科乃迪科环保科技有限公司 | Auxiliary chemical composition for monocrystalline silicon or polycrystalline silicon acidic wool making |
| CN103409808B (en) * | 2013-09-04 | 2015-10-21 | 常州时创能源科技有限公司 | Polycrystalline silicon texturing additive and using method thereof |
| CN104195645B (en) * | 2014-08-06 | 2020-03-17 | 深圳市石金科技股份有限公司 | Acidic texturing solution for etching solar cell silicon wafer, texturing method, solar cell and manufacturing method thereof |
| CN104404628B (en) * | 2014-11-14 | 2017-01-04 | 大连理工大学 | One class is for the surfactant blend of polysilicon making herbs into wool, the Woolen-making liquid containing this compound and etching method |
| CN105839192A (en) * | 2016-04-28 | 2016-08-10 | 吕铁铮 | Wet texturization method for pretreated silicon wafer |
| CN107217306B (en) * | 2017-05-19 | 2023-07-07 | 湖州三峰能源科技有限公司 | Chemical composition of polycrystalline silicon wafer acid texturing optimizing agent and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1614789A (en) * | 2004-09-30 | 2005-05-11 | 无锡尚德太阳能电力有限公司 | Method for preparing polycrystalline silicon suede |
| CN1983645A (en) * | 2005-12-13 | 2007-06-20 | 上海太阳能科技有限公司 | Production of polycrystalline silicon solar battery suede |
| WO2007107053A1 (en) * | 2006-03-21 | 2007-09-27 | Wuxi Suntech Power Co., Ltd. | An acid corrosion soluton for preparing polysilicon suede and the applied method of it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1614789A (en) * | 2004-09-30 | 2005-05-11 | 无锡尚德太阳能电力有限公司 | Method for preparing polycrystalline silicon suede |
| CN1983645A (en) * | 2005-12-13 | 2007-06-20 | 上海太阳能科技有限公司 | Production of polycrystalline silicon solar battery suede |
| WO2007107053A1 (en) * | 2006-03-21 | 2007-09-27 | Wuxi Suntech Power Co., Ltd. | An acid corrosion soluton for preparing polysilicon suede and the applied method of it |
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