CN102618937A - Texture etching technology of single crystalline silicon solar cell - Google Patents
Texture etching technology of single crystalline silicon solar cell Download PDFInfo
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Abstract
The invention discloses a texture etching technology of a single crystalline silicon solar cell. The texture etching technology comprises the following steps of: (1) placing a single crystalline silicon wafer in an alkalescence cleaning solution for washing, and removing the surface damage of the silicon wafer; (2) placing the cleaned single crystalline silicon wafer in a mixed liquor of potassium hydroxide and isopropyl alcohol, and forming a texture with pyramid structures on the surface of the silicon wafer; (3) placing the silicon wafer obtained in the step (2) in a mixed solution for texture etching so that the texture with porous pyramid structures is formed on the surface of the silicon wafer, wherein the mixed solution is the mixed liquor of a HF (Hydrogen Fluoride) solution, a AgNO3 solution and a H2CrO solution; and (4) cleaning the silicon wafer. Experiments prove that the surface reflectivity of the single crystalline silicon subjected to the final treatment can stabilize below 5% in the range of visible lights, and the obvious effect can be obtained.
Description
Technical field
The present invention relates to a kind of leather producing process of single crystal silicon solar cell, belong to technical field of solar.
Background technology
Along with the exhaustion day by day of petrochemical industry resource, the application of renewable energy source receives increasing concern.As the part of renewable energy source, Application of Solar Energy is just developing with swift and violent speed.The solar energy power generating overwhelming majority relies on crystal-silicon solar cell, because the photovoltaic generation cost is higher, is restricting the widespread use of solar cell, thereby, improve photoelectric transformation efficiency and become general trend to reduce cost.The reflection loss of incident light on the crystal-silicon solar cell surface is an importance in the photoelectric transformation efficiency loss, and existing way is to make matte to reach the purpose that reduces surface albedo at silicon chip surface.
The existing conventional leather producing process is that alkali reaction forms the pyramid suede structure, reduces reflectivity through incident light at the multiple reflection of pyramid structure.Experiment finds that for existing pyramid suede structure, in the visible light wave range scope, its average reflectance is generally more than 10%; And in optical wavelength during less than 350nm, reflectivity can reach more than 30%.This shows, as far as whole solar spectrum, after the conventional making herbs into wool reflection loss of silicon chip surface still bigger, the loss of particularly high-octane shortwave.
In order further to reduce the reflectivity of silicon chip surface, it is a reasonable alternatives that incident light is had the porous silicon of restriction.Disclose a kind of porous pyramid silicon face light trapping structure preparation method who is used for solar cell like Chinese invention patent application CN102299207A, its key step is following: a, cleaning silicon chip; B, employing alkaline etching prepare the pyramid structure surface; C, ion sputtering are silver-plated; D, employing noble metal nano particles catalysis etching; E, the residual silver of removal obtain silicon face porous pyramid light trapping structure; F, vacuumize drying, preserve in the moisture eliminator.
Though the surface albedo of the silicon chip that above-mentioned preparation method obtains is lower, there is following problem in it: certain damage can be caused to silicon chip because it has adopted the ion sputtering silver plating process in (1), can influence its electrical property; (2) ion sputtering is silver-plated is at silicon chip surface sputter one deck silver particle, has consumed a large amount of precious metals, has improved production cost; (3) mode of the silver-plated film of sputter may be introduced some detrimental impurity, and there is certain ununiformity in large-area preparation, with existing alkaline solution leather producing process poor compatibility.Therefore, develop a kind of leather producing process of new and single crystal silicon solar cell existing process compatible,, have active operation significance to improve the homogeneity of porous pyramid structure.
Summary of the invention
The object of the invention provides a kind of leather producing process of single crystal silicon solar cell.
For achieving the above object, the technical scheme that the present invention adopts is: a kind of leather producing process of single crystal silicon solar cell comprises the steps:
(1) monocrystalline silicon piece is put into the weakly alkaline scavenging solution and clean, remove the silicon chip surface damage;
(2) monocrystalline silicon piece after will cleaning is put into the mixed solution of Pottasium Hydroxide and Virahol, forms the matte of pyramid structure at silicon chip surface;
(3) silicon chip after step (2) completion is put into mixing solutions and carry out making herbs into wool, make its surface form the matte of porous pyramid structure;
Said mixing solutions is HF solution, AgNO
3Solution and H
2CrO
4The mixed solution of solution, three's concentration is respectively 5 ~ 15mol/L, 0.0001 ~ 0.0004mol/L and 0.05 ~ 0.5mol/L;
Reaction times is 5 ~ 20min, and temperature of reaction is 10 ~ 70 ℃;
(4) cleaning silicon chip.
In the technique scheme, in the said step (1), the weakly alkaline scavenging solution can be Trisodium Citrate or ammoniacal liquor.
In the technique scheme, in the said step (1), cleaning temperature is 70 ~ 90 ℃, and scavenging period is 5 ~ 20min.
In the technique scheme, in the said step (2), the mass concentration of Pottasium Hydroxide is 1 ~ 3%, and the volumetric concentration of Virahol is 3 ~ 8%.
In the technique scheme, the temperature of reaction of said step (2) is 70 ~ 85 ℃, and the reaction times is 20 ~ 60min.
The present invention utilizes HF/AgNO
3/ H
2CrO
4Mixing solutions prepare uniform porous silicon at silicon chip surface with pyramid structure, finally form the matte of porous pyramid structure.Wherein, the effect of the Silver Nitrate of lower concentration is to apply one deck dispersive silver particle at silicon chip surface, and the effect of chromic acid is an oxidized silicon chip, the SiO that final hydrofluoric acid generates silicon chip
2Form with silicofluoric acid is transported to the solution from silicon chip surface, and the silicon face of oxidizing reaction nidus contacts with oxygenant again and reacts like this, and then oxidation products is transported in the solution, thus the carrying out that reaction is gone round and begun again.Experiment showed, that final treated monocrystalline silicon surface reflectivity can be stabilized in below 5%, has obtained significant effect in visible-range.
Because the employing of technique scheme, compared with prior art, the present invention has following advantage:
1. the present invention has developed a kind of leather producing process of new single crystal silicon solar cell, experiment showed, that final treated monocrystalline silicon surface reflectivity can be stabilized in below 5% in visible-range, has obtained significant effect.
2. preparation method of the present invention is simple, and the treatment time is short, and is good with existing industrial manufacture process compatibility, is suitable for applying.
3. the present invention adopts the lower AgNO of concentration
3Solution carries out making herbs into wool, AgNO
3Solution can form finely dispersed silver-colored particle at silicon chip surface, thereby the homogeneity of the matte of the porous pyramid structure that makes is better, and stability is high.
Description of drawings
Fig. 1 is the SEM figure of monocrystalline silicon surface in the embodiment of the invention one;
Fig. 2 is the reflected light spectrogram of monocrystalline silicon suede in the embodiment of the invention one.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one
A kind of leather producing process of single crystal silicon solar cell comprises the steps:
1) be 180 ± 10 μ m with thickness, size is in 5% sodium citrate soln for the silicon chip input concentration of 20mm * 20mm, under 90 ℃ of conditions, reacts 5min, tentatively removes the dirty and damage of silicon chip surface;
2) silicon chip after will cleaning is put into the mixing solutions of KOH and Virahol, and wherein the concentration of KOH is 3%, and the volumetric concentration of Virahol is 8%, under 85 ℃ of conditions, reacts 30min, forms pyramid structure of uniform size at silicon chip surface;
3) will go up the silicon chip that obtains of step and put into the teflon seal container that mixing solutions is housed with pyramid structure, under 50 ℃, reaction 5min, said mixing solutions is 10mol/L HF+0.0001mol/L AgNO
3+ 0.2mol/L H
2CrO
4Mixed solution, form porous pyramid structure (seeing shown in Figure 1) on pyramid surface;
4) use the deionized water rinsing silicon chip surface at last, it is residual in the maroon of silicon chip surface to remove chromic acid solution.
The cell texture on pyramid structure surface helps absorption of incident light, the surface albedo of the prepared monocrystalline silicon solar battery suede of present embodiment extremely low, and its average reflectance is 4.0% (see figure 2) in 400 ~ 800nm visible-range.
Embodiment two
A kind of leather producing process of single crystal silicon solar cell comprises the steps:
1) be 180 ± 10 μ m with thickness, size is that the silicon chip input concentration of 20 mm * 20 mm is in 5% sodium citrate soln, under 90 ℃ of conditions, reacts 5min, tentatively removes the dirty and damage of silicon chip surface;
2) silicon chip after will cleaning is put into the mixing solutions of KOH and Virahol, and wherein the concentration of KOH is 3%, and the volumetric concentration of Virahol is 8%, under 85 ℃ of conditions, reacts 30min, forms pyramid structure of uniform size at silicon chip surface;
3) with step 2) the silicon chip with pyramid structure put into the teflon seal container that mixing solutions is housed, under 10 ℃, the reaction 20min, said mixing solutions is 5mol/L HF+0.0002mol/L AgNO
3+ 0.5mol/L H
2CrO
4Mixed solution, form the porous pyramid structure on pyramid surface;
4) use the deionized water rinsing silicon chip surface at last, it is residual in the maroon of silicon chip surface to remove chromic acid solution.
The monocrystalline silicon solar battery suede of the prepared lower surface albedo of present embodiment, its average reflectance is 4.5% in 400 ~ 800nm visible-range.
Embodiment three
1) be 180 ± 10 μ m with thickness, size is that the silicon chip input concentration of 20 mm * 20 mm is in 5% ammoniacal liquor, under 80 ℃ of conditions, reacts 5min, tentatively removes the dirty and damage of silicon chip surface;
2) silicon chip after will cleaning is put into the mixing solutions of KOH and Virahol, and wherein the concentration of KOH is 3%, and the volumetric concentration of Virahol is 8%, under 85 ℃ of conditions, reacts 30min, forms pyramid structure of uniform size at silicon chip surface;
3) with step 2) the silicon chip with pyramid structure put into the teflon seal container that mixing solutions is housed, under 70 ℃, the reaction 8min, said mixing solutions is 15mol/L HF+0.0004mol/L AgNO
3+ 0.05mol/L H
2CrO
4Mixed solution, form the porous pyramid structure on pyramid surface;
4) use the deionized water rinsing silicon chip surface at last, it is residual in the maroon of silicon chip surface to remove chromic acid solution.
The monocrystalline silicon solar battery suede of the prepared lower surface albedo of present embodiment, its average reflectance is 4.3% in 400 ~ 800nm visible-range.
Claims (5)
1. the leather producing process of a single crystal silicon solar cell is characterized in that, comprises the steps:
(1) monocrystalline silicon piece is put into the weakly alkaline scavenging solution and clean, remove the silicon chip surface damage;
(2) monocrystalline silicon piece after will cleaning is put into the mixed solution of Pottasium Hydroxide and Virahol, forms the matte of pyramid structure at silicon chip surface;
(3) silicon chip after step (2) completion is put into mixing solutions and carry out making herbs into wool, make its surface form the matte of porous pyramid structure;
Said mixing solutions is HF solution, AgNO
3Solution and H
2CrO
4The mixed solution of solution, three's concentration is respectively 5 ~ 15mol/L, 0.0001 ~ 0.0004mol/L and 0.05 ~ 0.5mol/L;
Reaction times is 5 ~ 20min, and temperature of reaction is 10 ~ 70 ℃;
(4) cleaning silicon chip.
2. the leather producing process of single crystal silicon solar cell according to claim 1, it is characterized in that: in the step (1), said weakly alkaline scavenging solution is Trisodium Citrate or ammoniacal liquor.
3. the leather producing process of single crystal silicon solar cell according to claim 1, it is characterized in that: in the said step (1), cleaning temperature is 70 ~ 90 ℃, and scavenging period is 5 ~ 20min.
4. the leather producing process of single crystal silicon solar cell according to claim 1, it is characterized in that: in the said step (2), the mass concentration of Pottasium Hydroxide is 1 ~ 3%, and the volumetric concentration of Virahol is 3 ~ 8%.
5. the leather producing process of single crystal silicon solar cell according to claim 1, it is characterized in that: the temperature of reaction of said step (2) is 70 ~ 85 ℃, the reaction times is 20 ~ 60min.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337560A (en) * | 2013-07-08 | 2013-10-02 | 苏州大学 | Preparation method of three-dimensional silicon nano structure for solar cell |
| CN103474518A (en) * | 2013-10-10 | 2013-12-25 | 常州天合光能有限公司 | Multi-hole pyramid antireflection structure preparation method and HIT solar cell preparation technology |
| CN103806105A (en) * | 2012-11-02 | 2014-05-21 | 无锡尚德太阳能电力有限公司 | Coating source diffusion method capable of improving diffusion property |
| CN103882528A (en) * | 2014-03-28 | 2014-06-25 | 苏州阿特斯阳光电力科技有限公司 | Method for preparing polycrystalline silicon wafer texture surface |
| WO2014166256A1 (en) * | 2013-04-12 | 2014-10-16 | 苏州阿特斯阳光电力科技有限公司 | Crystalline silicon solar cell textured structure and manufacturing method for same |
| CN104393094A (en) * | 2014-09-26 | 2015-03-04 | 中国电子科技集团公司第四十八研究所 | N-type silicon chip cleaning texturing method for HIT battery |
| CN105428432A (en) * | 2015-11-06 | 2016-03-23 | 上海师范大学 | Preparation method for porous light-trapping structure on surface of silicon solar cell |
| CN105839193A (en) * | 2016-04-27 | 2016-08-10 | 宁波高新区夏远科技有限公司 | Textured monocrystalline silicon preparing method |
| CN106783670A (en) * | 2016-11-18 | 2017-05-31 | 梁叶青 | A kind of monocrystalline silicon battery production technology wafer thinning equipment |
| CN107316917A (en) * | 2017-06-06 | 2017-11-03 | 浙江师范大学 | A kind of method for the monocrystalline silicon suede structure for preparing antiradar reflectivity |
| CN107579124A (en) * | 2017-08-22 | 2018-01-12 | 江西展宇新能源股份有限公司 | A kind of microstructure for improving the black silicon photoelectric transformation efficiency of polycrystalline and component power |
| WO2018189131A1 (en) * | 2017-04-13 | 2018-10-18 | Rct Solutions Gmbh | Device and method for chemically treating a semiconductor substrate having a sawn surface structure |
| CN113707753A (en) * | 2020-05-06 | 2021-11-26 | 南京理工大学 | Preparation method of anti-reflection micro-nano structure material |
| CN114686989A (en) * | 2022-04-07 | 2022-07-01 | 锦州神工半导体股份有限公司 | Preparation method of micro-nano composite structure on surface of monocrystalline silicon wafer |
| CN117438502A (en) * | 2023-11-28 | 2024-01-23 | 江苏润阳世纪光伏科技有限公司 | Preparation method of monocrystalline silicon wafer textured surface with light conversion and full-angle light trapping |
| WO2024051175A1 (en) * | 2022-09-07 | 2024-03-14 | 中国科学院上海微系统与信息技术研究所 | Method for manufacturing flexible thin monocrystalline silicon solar cell |
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Cited By (20)
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| CN103806105A (en) * | 2012-11-02 | 2014-05-21 | 无锡尚德太阳能电力有限公司 | Coating source diffusion method capable of improving diffusion property |
| WO2014166256A1 (en) * | 2013-04-12 | 2014-10-16 | 苏州阿特斯阳光电力科技有限公司 | Crystalline silicon solar cell textured structure and manufacturing method for same |
| CN103337560A (en) * | 2013-07-08 | 2013-10-02 | 苏州大学 | Preparation method of three-dimensional silicon nano structure for solar cell |
| CN103337560B (en) * | 2013-07-08 | 2015-10-28 | 苏州大学 | For the preparation method of the three-dimensional silicon nano structure of solar cell |
| CN103474518A (en) * | 2013-10-10 | 2013-12-25 | 常州天合光能有限公司 | Multi-hole pyramid antireflection structure preparation method and HIT solar cell preparation technology |
| CN103474518B (en) * | 2013-10-10 | 2015-09-09 | 常州天合光能有限公司 | Multi-hole pyramid anti-reflection structure preparation method and HIT solar cell preparation technology |
| CN103882528A (en) * | 2014-03-28 | 2014-06-25 | 苏州阿特斯阳光电力科技有限公司 | Method for preparing polycrystalline silicon wafer texture surface |
| CN104393094A (en) * | 2014-09-26 | 2015-03-04 | 中国电子科技集团公司第四十八研究所 | N-type silicon chip cleaning texturing method for HIT battery |
| CN105428432A (en) * | 2015-11-06 | 2016-03-23 | 上海师范大学 | Preparation method for porous light-trapping structure on surface of silicon solar cell |
| CN105839193A (en) * | 2016-04-27 | 2016-08-10 | 宁波高新区夏远科技有限公司 | Textured monocrystalline silicon preparing method |
| CN106783670A (en) * | 2016-11-18 | 2017-05-31 | 梁叶青 | A kind of monocrystalline silicon battery production technology wafer thinning equipment |
| CN106783670B (en) * | 2016-11-18 | 2019-11-05 | 安徽省凤阳县前力玻璃制品有限公司 | A kind of monocrystalline silicon battery production technology wafer thinning equipment |
| WO2018189131A1 (en) * | 2017-04-13 | 2018-10-18 | Rct Solutions Gmbh | Device and method for chemically treating a semiconductor substrate having a sawn surface structure |
| CN107316917A (en) * | 2017-06-06 | 2017-11-03 | 浙江师范大学 | A kind of method for the monocrystalline silicon suede structure for preparing antiradar reflectivity |
| CN107579124A (en) * | 2017-08-22 | 2018-01-12 | 江西展宇新能源股份有限公司 | A kind of microstructure for improving the black silicon photoelectric transformation efficiency of polycrystalline and component power |
| CN113707753A (en) * | 2020-05-06 | 2021-11-26 | 南京理工大学 | Preparation method of anti-reflection micro-nano structure material |
| CN114686989A (en) * | 2022-04-07 | 2022-07-01 | 锦州神工半导体股份有限公司 | Preparation method of micro-nano composite structure on surface of monocrystalline silicon wafer |
| WO2024051175A1 (en) * | 2022-09-07 | 2024-03-14 | 中国科学院上海微系统与信息技术研究所 | Method for manufacturing flexible thin monocrystalline silicon solar cell |
| CN117438502A (en) * | 2023-11-28 | 2024-01-23 | 江苏润阳世纪光伏科技有限公司 | Preparation method of monocrystalline silicon wafer textured surface with light conversion and full-angle light trapping |
| CN117438502B (en) * | 2023-11-28 | 2024-05-28 | 江苏润阳世纪光伏科技有限公司 | Preparation method of monocrystalline silicon wafer textured surface with light conversion and full-angle light trapping |
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Application publication date: 20120801 |