CN101931030A - Preparation technology of nano-modified polysilicon solar cell with high efficiency and low cost - Google Patents
Preparation technology of nano-modified polysilicon solar cell with high efficiency and low cost Download PDFInfo
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- CN101931030A CN101931030A CN2010102264400A CN201010226440A CN101931030A CN 101931030 A CN101931030 A CN 101931030A CN 2010102264400 A CN2010102264400 A CN 2010102264400A CN 201010226440 A CN201010226440 A CN 201010226440A CN 101931030 A CN101931030 A CN 101931030A
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Abstract
The invention discloses a preparation technology of a nano-modified polysilicon solar cell with high efficiency and low cost. The preparation technology comprises the following step: selecting a polycrystalline silicon wafer, preparing texture with a texture-preparing solution, diffusing and printing an electrode, wherein in the step of selecting the polycrystalline silicon wafer, a P-type polycrystalline silicon wafer with the life of more than or equal to 40mu s is selected; when the texture-preparing solution is used for texture-preparing, the mixed solution of HF and HNO3 is adopted, the mixed solution contains inorganic salt with nitrogen and dispersant; after the step of diffusing and before the step of printing the electrode, the nanometer modification technology is adopted to modify and clean the surface micro region, namely an alkaline aqueous solution with organic base and sizing agent is used to treat the diffused polycrystalline silicon wafer so as to remove microdefects and harmful impurities on the surface of the polycrystalline silicon wafer; and when the electrode is printed, the screen-printing technology is adopted to print the back electrode and the positive electrode which are sintered. By adopting the preparation technology of the invention, the ideal uniform texture with low reflectivity can be obtained, and the light absorption efficiency can be effectively improved.
Description
Technical field:
The present invention relates to a kind of polysilicon solar cell preparation technology.
Background technology:
The efficient of crystal-silicon solar cell depends primarily on three aspects---extinction amount, photoelectricity quantum efficiency and photoelectronic collection efficiency.Wherein, the photoelectricity quantum efficiency is to describe the ratio that the photon conversion that is absorbed by solar cell becomes electronics.The efficient that improves crystal-silicon solar cell then must improve extinction amount, photoelectric conversion efficiency and collection efficiency simultaneously.The matte preparation is to reduce the reflection of light rate, increase the effective means of extinction amount, eliminate the complex centre of PN junction and can effectively improve the photoelectricity quantum efficiency, and the characteristics of the defective of crystal silicon cell, impurity, resistivity and PN junction etc. there is material impact to the photoelectron collection efficiency.
The characteristics of polysilicon are to contain more crystal boundary.The existence of grain boundary is to making herbs into wool and the diffusion of road, back, and passivation and metallization all have very big influence.As in the matte preparation process, the defect and impurity of crystal boundary can be accelerated corrosion reaction speed, therefore is prone to excessive erosion at the crystal boundary place, causes decrease in yield and secondary defect (Cavitations).The diffusion coefficient of grain boundary place phosphorus causes the skewness of phosphorus concentration in entire cell thus much larger than crystal grain, will directly influence the ohmic contact of passivation and front-side metallization.
1. nano modification technical study
Diffusion is the core process of crystal-silicon solar cell opto-electronic conversion, and the microstructure of diffusion rear surface and the quality of PN junction characteristic be the quality of decision battery quality directly.The silicon chip surface microstructure comprises that the top layer matte rises and falls and top layer objectionable impurities and various defect state, and these defect and impurities can produce material impact to the local concentration and the distributing homogeneity of phosphorus in the diffusion process.Therefore, surface microstructure directly influences the form of PN junction, thereby influences battery quality and performance.
According to the concentration gradient notion, from the surface to the wafer bulk in certain depth, the concentration of phosphorus is from high to low.And be subjected to the influence of matte state, defect and impurity, the CONCENTRATION DISTRIBUTION of surperficial phosphorus is also inhomogeneous.The particularly inactive phosphorus of phosphorus of surface high concentration has very big influence to the performance of battery, mainly shows shortwave quantum difference in response.On the other hand, the phosphorus of higher concentration can improve the contact resistance of metallization processes, and the power loss of this part is reduced, and fill factor, curve factor improves.Therefore, surperficial phosphorus concentration is in the contradiction state.Experimental study shows that under the situation that does not change square resistance, the concentration of top layer regional area phosphorus objectionable impurities high more and the formation complex centre is many more, and then surface recombination is serious more, and short circuit current and open circuit voltage loss are big more, and photoelectric conversion efficiency is low more.Therefore, the modification on surface is handled become polysilicon solar cell one of the high efficiency development trend of marching toward.
2. the additive matte prepares technology optimization
General ovalize of the matte of polysilicon or strip hole shape.Shallow and wealthy matte hole is higher to the reflectivity of light, is unfavorable for light absorption.Therefore desirable antiradar reflectivity (R%) polycrystalline silicon suede etch pit should have certain depth and long and narrow, and size is even.
Hydrofluoric acid, nitric acid and water (HF/HNO are used in the matte preparation of polysilicon usually
3/ H
2O) system.Main corrosion reaction is as follows:
Si+4HNO
3＝SiO
2+4NO
2+2H
2O (1)
SiO
2+6HF＝H
2SiF
6+2H
2O (2)
Oxidation reaction speed is slower, and HF acid corrosion reaction rate is very fast, wayward.Have only by regulation and control HF acid and participation process and the state of nitric acid in course of reaction, (1), (2) two reactions of vying each other can rationally be carried out, just can obtain ideal uniform corrosion matte.In addition, consider that the defective, impurity of crystal boundary all has considerable influence to matte preparation, diffusion and metallization, to avoid the excessive erosion of crystal boundary place simultaneously be important prerequisite and the basic assurance that reduces reflectivity, improves the photoelectricity quantum efficiency so effectively eliminate crystal boundary.
Summary of the invention:
The object of the present invention is to provide a kind of even matte of desirable antiradar reflectivity that obtains, effectively improve the preparation technology of nano-modified polysilicon solar cell with high efficiency and low cost of efficiency of light absorption.
Technical solution of the present invention is:
A kind of preparation technology of nano-modified polysilicon solar cell with high efficiency and low cost, comprise the selection polysilicon chip, use Woolen-making liquid making herbs into wool processing, diffusion, electrode printing, it is characterized in that: when selecting polysilicon chip, select the P type polysilicon chip of body life time for use more than or equal to 40 μ s, the polysilicon chip electrical resistivity range is 0.5～3 Ω cm, and thickness is 140～200 μ m; When handling, adopt HF and HNO with Woolen-making liquid making herbs into wool
3Mixed solution, HF and HNO
3Mixed solution in to contain percentage by weight be 0.05～0.1% inorganic salt containing nitrogen and percentage by weight smaller or equal to 0.1% dispersant, HF and HNO in the Woolen-making liquid
3Volume ratio be 1: 2～1: 6; After diffusion, before the electrode printing, also adopt nano modification technology to carry out surperficial microcell and modify and clean, promptly handle polysilicon chip after the diffusion, to remove the microdefect and the objectionable impurities on polysilicon chip surface with the alkaline aqueous solution that contains organic base and size; During the electrode printing, adopt silk-screen printing technique to carry out backplane and anodal printing, sintering.
The percentage by weight of dispersant is 0.01～0.1%; When selecting polysilicon chip, selecting body life time for use is the P type polysilicon chip of 40 μ s～60 μ s.
Described organic base is the alkylammonium class, and its weight percentage in alkaline aqueous solution is 0.1～10%; The weight percentage of size in alkaline aqueous solution is 0.01～0.1%, and the temperature when polysilicon chip is handled in alkaline aqueous solution is 25～85 ℃, and the time is 30 seconds～15 minutes.
Dispersant is one or more in polymethyl siloxane, polyether modified silicon oil, phosphate and higher alcohol, pure ether compound, the betaine; Size is one or more in polymethyl siloxane, polyether modified silicon oil, phosphate and higher alcohol, pure ether compound, the betaine.
The present invention is based on the nano modification technology that contains surfactant the silicon chip surface after spreading is carried out the selective modification processing, reduce the influence of surperficial phosphorus and other various impurity, improve the shortwave internal quantum efficiency of battery greatly the response of shortwave quantum.The present invention adopts advanced additive making herbs into wool technology, make the corrosion rate gentleness at crystal boundary place, avoid the excessive erosion phenomenon, obtain the even matte of desirable antiradar reflectivity, can effectively improve efficiency of light absorption (Isc raising), (Voc raising) reduced at the surface recombination center simultaneously.Cost of the present invention is low, has very wide application prospect.
Table 1. polycrystalline brick of the present invention solar cell electrical property statistical form
| Voc/mV | Isc?/mA | FF/％ | η/％ | |
| Reference group | 0 | 0 | 0 | 0 |
| Test group | +1.8 | +80 | -0.25 | +0.15 |
The aim of the selected chemicals of the present invention is environmentally friendly, small to the human injury, and it is not volatile, and do not change the matte pattern of silicon chip surface, square resistance there is not obvious influence yet, only be to remove the harmful substance that is difficult to remove in some common cleanings, and these materials generally all are in the nanoscale range scale, therefore are called the nano modification technology.
The invention will be further described below in conjunction with embodiment.
Embodiment:
Select the P type polysilicon chip of the about 50 μ s of body life time (or 40 μ s, 60 μ s) for use, electrical resistivity range 0.5～3 Ω cm (example 0.5 Ω cm, 2 Ω cm, 3 Ω cm), thickness 180 ± 20 μ m.Adopt a kind of additive making herbs into wool to optimize technology, the volume ratio of HF/HNO3 is 1: 2～1: 6 (example in the Woolen-making liquid, 1: 3,1: 4), dispersant is less than 0.1% (example 0.09%, 0.05%, 0.01%) corrosion temperature is 6～25 ℃ (6 ℃, 15 ℃, 25 ℃ of examples), about 4～5 μ m of silicon chip thinning single surface amount.Clean the back and adopt the tube furnace diffusion.After removing phosphorosilicate glass, adopt nano modification technology to carry out surperficial microcell and modify cleaning, nano modification technology is with the silicon chip after the alkaline aqueous solution processing diffusion that contains organic base and size, remove the microdefect and the objectionable impurities of silicon chip surface, organic base is the alkylammonium class, the weight percentage of organic base in the aqueous solution is 0.1～10% (example 0.1%, 5%, 10%); The weight percentage of size in the aqueous solution is less than 0.1% (example 0.09%, 0.05%, 0.01%).Temperature when silicon chip is handled in this alkaline solution is 25～85 ℃ (25 ℃, 55 ℃, 85 ℃ of examples), and the time is 30 seconds～15 minutes (example 30 seconds, 5 minutes, 15 minutes).Adopt method for printing screen to carry out backplane and anodal printing, sintering.
Dispersant is polymethyl siloxane (or in polyether modified silicon oil, phosphate and higher alcohol, pure ether compound, the betaine one or more); Size is polymethyl siloxane (or in polyether modified silicon oil, phosphate and higher alcohol, pure ether compound, the betaine one or more).
Claims (4)
1. preparation technology of nano-modified polysilicon solar cell with high efficiency and low cost, comprise the selection polysilicon chip, use Woolen-making liquid making herbs into wool processing, diffusion, electrode printing, it is characterized in that: when selecting polysilicon chip, select the P type polysilicon chip of body life time for use more than or equal to 40 μ s, the polysilicon chip electrical resistivity range is 0.5～3 Ω cm, and thickness is 140～200 μ m; When handling, adopt HF and HNO with Woolen-making liquid making herbs into wool
3Mixed solution, HF and HNO
3Mixed solution in to contain percentage by weight be 0.05～0.1% inorganic salt containing nitrogen and percentage by weight smaller or equal to 0.1% dispersant, HF and HNO in the Woolen-making liquid
3Volume ratio be 1: 2～1: 6; After diffusion, before the electrode printing, also adopt nano modification technology to carry out surperficial microcell and modify and clean, promptly handle polysilicon chip after the diffusion, to remove the microdefect and the objectionable impurities on polysilicon chip surface with the alkaline aqueous solution that contains organic base and size; During the electrode printing, adopt silk-screen printing technique to carry out backplane and anodal printing, sintering.
2. preparation technology of nano-modified polysilicon solar cell with high efficiency and low cost according to claim 1 is characterized in that: the percentage by weight of dispersant is 0.01～0.1%; When selecting polysilicon chip, selecting body life time for use is the P type polysilicon chip of 40 μ s～60 μ s.
3. preparation technology of nano-modified polysilicon solar cell with high efficiency and low cost according to claim 1 and 2 is characterized in that: described organic base is the alkylammonium class, and its weight percentage in alkaline aqueous solution is 0.1～10%; The weight percentage of size in alkaline aqueous solution is 0.01～0.1%, and the temperature when polysilicon chip is handled in alkaline aqueous solution is 25～85 ℃, and the time is 30 seconds～15 minutes.
4. preparation technology of nano-modified polysilicon solar cell with high efficiency and low cost according to claim 1 and 2 is characterized in that: dispersant is one or more in polymethyl siloxane, polyether modified silicon oil, phosphate and higher alcohol, pure ether compound, the betaine; Size is one or more in polymethyl siloxane, polyether modified silicon oil, phosphate and higher alcohol, pure ether compound, the betaine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181940A (en) * | 2011-04-08 | 2011-09-14 | 光为绿色新能源有限公司 | Preparation method of multicrystalline silicon texture |
| CN102373474A (en) * | 2011-10-31 | 2012-03-14 | 合肥晶澳太阳能科技有限公司 | Method for recycling wool making/etching solution |
| CN102496569A (en) * | 2011-12-31 | 2012-06-13 | 英利集团有限公司 | Texturing method of monocrystal N type solar cell slice |
| CN106129139A (en) * | 2016-07-08 | 2016-11-16 | 合肥中南光电有限公司 | A kind of monocrystaline silicon solar cell sheet surface texture liquid containing soybean oligo saccharide and preparation method thereof |
| CN114267751A (en) * | 2021-12-22 | 2022-04-01 | 晋能清洁能源科技股份公司 | Polycrystalline silicon wafer wet-method texturing method for solar cell |
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| US20040094510A1 (en) * | 2002-11-08 | 2004-05-20 | 3M Innovative Properties Company | Fluorinated surfactants for aqueous acid etch solutions |
| US20050133084A1 (en) * | 2003-10-10 | 2005-06-23 | Toshio Joge | Silicon solar cell and production method thereof |
| CN101409313A (en) * | 2008-11-19 | 2009-04-15 | 张根发 | Method for preparing silicon solar battery pile face in magnetic field |
| CN101667602A (en) * | 2009-09-23 | 2010-03-10 | 中轻太阳能电池有限责任公司 | Polysilicon solar cell and preparation method thereof |
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2010
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Patent Citations (4)
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| US20040094510A1 (en) * | 2002-11-08 | 2004-05-20 | 3M Innovative Properties Company | Fluorinated surfactants for aqueous acid etch solutions |
| US20050133084A1 (en) * | 2003-10-10 | 2005-06-23 | Toshio Joge | Silicon solar cell and production method thereof |
| CN101409313A (en) * | 2008-11-19 | 2009-04-15 | 张根发 | Method for preparing silicon solar battery pile face in magnetic field |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181940A (en) * | 2011-04-08 | 2011-09-14 | 光为绿色新能源有限公司 | Preparation method of multicrystalline silicon texture |
| CN102373474A (en) * | 2011-10-31 | 2012-03-14 | 合肥晶澳太阳能科技有限公司 | Method for recycling wool making/etching solution |
| CN102496569A (en) * | 2011-12-31 | 2012-06-13 | 英利集团有限公司 | Texturing method of monocrystal N type solar cell slice |
| CN106129139A (en) * | 2016-07-08 | 2016-11-16 | 合肥中南光电有限公司 | A kind of monocrystaline silicon solar cell sheet surface texture liquid containing soybean oligo saccharide and preparation method thereof |
| CN114267751A (en) * | 2021-12-22 | 2022-04-01 | 晋能清洁能源科技股份公司 | Polycrystalline silicon wafer wet-method texturing method for solar cell |
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| CN101931030B (en) | 2012-06-20 |
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Application publication date: 20101229 Assignee: Jiangsu Linyang Solarfun Co., Ltd. Assignor: Jiangsu Linyang Solar Battery and Applied Engineering Technology Research Center Co., Ltd. Contract record no.: 2014320010140 Denomination of invention: Preparation technology of nano-modified polysilicon solar cell with high efficiency and low cost Granted publication date: 20120620 License type: Exclusive License Record date: 20140714 |
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Effective date of registration: 20200720 Address after: 226200 888 Lin Yang Road, Qidong Economic Development Zone, Nantong, Jiangsu Patentee after: HANWHA SOLARONE (QIDONG) Co.,Ltd. Address before: Qidong City, Jiangsu province 226200 Nantong City Economic Development Zone No. 888 Lin Yang Lu Patentee before: JIANGSU HANWHA SOLAR CELL AND APPLIED ENGINEERING TECHNOLOGY RES CT Co.,Ltd. |
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