CN102800754A - Crystalline silicon solar cell and manufacturing method thereof - Google Patents
Crystalline silicon solar cell and manufacturing method thereof Download PDFInfo
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- CN102800754A CN102800754A CN2012103034481A CN201210303448A CN102800754A CN 102800754 A CN102800754 A CN 102800754A CN 2012103034481 A CN2012103034481 A CN 2012103034481A CN 201210303448 A CN201210303448 A CN 201210303448A CN 102800754 A CN102800754 A CN 102800754A
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Abstract
The invention provides a crystalline silicon solar cell and a manufacturing method thereof. The manufacturing method comprises the following steps of diffusion and knot making, etching, antireflection film deposition, printed electrode and sintering. The etching step comprises the following procedures of: (S1) etching the edge and the back face of the diffused and knotted silicon wafer by using the plasma etching method; (S2) treating the front face of the etched silicon wafer by using a first mixed acid liquid of nitric acid and hydrofluoric acid, wherein the mass ratio of HNO3 to HF in the first mixed acid liquid is 10:1-15:1, and the concentration of HF in the first mixed acid liquid is 10-80 g/L. In the etching step, the plasma etching method is firstly adopted to etch the edge and the back face of the silicon wafer, and the purpose of insulating the back face and the front face is realized; and then, the front face of the silicon wafer is treated by using the first mixed acid liquid containing nitrite acid and hydrofluoric acid, and phosphorosilicate glass or borosilicate glass formed in diffusion and a high-concentration phosphor-doped region or a high-concentration boron-doped region on the surface layer of the front face of the silicon wafer is removed.
Description
Technical field
The present invention relates to area of solar cell, in particular to a kind of crystal silicon solar batteries and preparation method thereof.
Background technology
Crystal silicon solar batteries is arrived every field by large-scale application, and its good stable property is the basis of its large-scale application with ripe technological process.The technological process of production of crystal silicon solar batteries is as shown in Figure 1, at first silicon chip is cleaned, and reaches through chemical cleaning the structuring of silicon chip surface is handled; Secondly the silicon chip after will cleaning carries out DIFFUSION TREATMENT, and silicon chip forms p-n junction through boron diffusion technology; Afterwards the silicon chip that forms p-n junction is carried out peripheral etching technics, to remove the formed conductive layer of silicon chip edge in diffusion technology; Pass through chemical cleaning technology then, to remove the glassy layer that in diffusion process, forms at silicon chip surface; Then through PECVD (plasma enhanced chemical vapor deposition method) process deposits antireflective coating-silicon nitride film; Obtain satisfactory crystal silicon solar batteries through making such as silk screen printing technology, sintering process successively more at last.
In the manufacturing process of above-mentioned crystal silicon solar batteries, through diffusion impurity on silicon chip, make the impurity concentration of silicon chip surface be higher than the inner impurity concentration of silicon chip, form concentration difference, and then diffusion of impurities is formed a N in silicon chip
+-N layer, such structure helps the preparation of subsequent electrode, because N
+Layer not only can form ohmic contact with metal electrode, reduces contact resistance, and obtaining good activity coefficient, and it is inner to prevent in the electrode production process that metallic atom is diffused into the silicon chip matrix, and then reduces the surface recombination loss that electrode brings.But too high doping forms " dead layer " easily, and good emitter region only needs certain doping content to get final product.Therefore, desirable p-n junction should have following structure: at the near surface of silicon chip matrix, except a heavily doped N is arranged under electrode
+Outside the district, remaining position all is the doping of general concentration.
Because the appearance of " dead layer " is inevitable; At present generally be through the nitrogen that reduces to carry impurity flow, or temperature, diffusion time and impurity concentration etc. during the control diffusion reduce the appearance of " dead layer " as far as possible, application number is that the method that 201110378576.8 Chinese patent adopts reduction source temperature (as the temperature of the POCl3 of impurity) to increase the flow of nitrogen has simultaneously obtained the lower solar cell of surface concentration.And similar with the research direction of above-mentioned patent, at present those skilled in the art generally are that the parameter being devoted to control diffusion technology is to obtain the lower solar cell of surface concentration.Inventor's of the present invention research thinking is different fully with above-mentioned research direction, and the electrode front that has diffuseed to form is handled, and has realized reducing the purpose of surface concentration.
Summary of the invention
The present invention aims to provide a kind of crystal silicon solar batteries and preparation method thereof, to reduce the concentration of diffusing surface.
To achieve these goals; According to an aspect of the present invention; A kind of manufacture method of crystal silicon solar batteries is provided; Comprise to the silicon chip system of spreading knot, etching, deposition antireflection layer, print electrode and the step of sintering that the step of above-mentioned etching comprises: S1, the edge and the back side employing plasma etching method that will spread the silicon chip behind the system knot are carried out etching; S2, adopt the silicon chip front of first mix acid liquor after contain nitric acid and hydrofluoric acid to handle HNO in first mix acid liquor to etching
3With the mass ratio of HF be 10:1 ~ 15:1, and the concentration of HF is 10 ~ 80g/L in first mix acid liquor.
Further, HNO in above-mentioned first mix acid liquor
3With the mass ratio of HF be 10:1 ~ 12:1, the concentration of HF is 20 ~ 50g/L in first mix acid liquor.
Further, above-mentioned steps S2 comprises: S21, the silicon chip after the etching is soaked 40 ~ 80s in first mix acid liquor; S22, the silicon chip that will pass through immersion utilize high purity deionized water to clean.
Further, above-mentioned steps S1 comprises: second mix acid liquor that S11, employing contain nitric acid and hydrofluoric acid will spread edge and the back-etching of making the silicon chip after tying; S12, the silicon chip that adopts potassium hydroxide solution will pass through etching processing clean.
Further, HNO in above-mentioned second mix acid liquor
3Concentration be 400 ~ 600g/L, the concentration of HF is 20 ~ 50g/L, among the step S12 in the potassium hydroxide solution mass content of KOH be 3 ~ 10%.
According to a further aspect in the invention, a kind of crystal silicon solar batteries is provided also, this crystal silicon solar batteries obtains through above-mentioned manufacture method.
The present invention adopts two-step etching method, at first adopts the plasma etching method that etching is carried out at the edge and the back side of silicon chip, realizes the purpose of the back side with positive insulation; Then, adopt the mix acid liquor of nitric acid and hydrofluoric acid that the front of silicon chip is handled, in this process, hydrofluoric acid at first reacts with the silicon dioxide on surface and generates volatile six silicon fluorides, thereby removes the phosphorosilicate glass or the Pyrex of formation in the diffusion; Utilize the oxidation susceptibility of nitric acid to make the diffusion under phosphorosilicate glass or the Pyrex have the silicon oxidation of phosphorus or boron to form silicon dioxide then; Hydrofluoric acid in the mix acid liquor forms volatile six silicon fluorides with silicon dioxde reaction once more; Because diffusion has the silicon of phosphorus or boron to be corroded; Phosphorus or boron together are corroded owing to lose attachment, thereby have removed the high concentration phosphorus doped region or the high concentration boron doped region on the positive top layer of silicon chip.
Description of drawings
The Figure of description that constitutes the application's a part is used to provide further understanding of the present invention, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, do not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 shows the manufacture craft flow process of crystal silicon solar batteries in the prior art; And
Fig. 2 shows the manufacture craft flow process of crystal silicon solar batteries of the present invention.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the characteristic among the embodiment among the application can make up each other.Below with reference to accompanying drawing and combine embodiment to specify the present invention.
In a kind of typical embodiment of the present invention; A kind of manufacture method of crystal silicon solar batteries is provided; As shown in Figure 2; Comprise to the silicon chip system of spreading knot, etching, deposition antireflection layer, print electrode and the step of sintering that the step of above-mentioned etching comprises: S1, the edge and the back side employing plasma etching method that will spread the silicon chip behind the system knot are carried out etching; S2, adopt the silicon chip front of first mix acid liquor after contain nitric acid and hydrofluoric acid to handle HNO in first mix acid liquor to etching
3With the mass ratio of HF be 10:1 ~ 15:1, and the concentration of HF is 10 ~ 80g/L in first mix acid liquor.
The present invention adopts aforesaid two-step etching method, at first adopts the plasma etching method that etching is carried out at the edge and the back side of silicon chip, realizes the purpose of the back side with positive insulation; Then, adopt the mix acid liquor of nitric acid and hydrofluoric acid that the front of silicon chip is handled, in this process, hydrofluoric acid at first reacts with the silicon dioxide on surface and generates volatile six silicon fluorides, thereby removes the phosphorosilicate glass or the Pyrex of formation in the diffusion; Utilize the oxidation susceptibility of nitric acid to make the diffusion under phosphorosilicate glass or the Pyrex have the silicon oxidation of phosphorus or boron to form silicon dioxide then; Hydrofluoric acid in the mix acid liquor forms volatile six silicon fluorides with silicon dioxde reaction once more; Because diffusion has the silicon of phosphorus or boron to be corroded; Phosphorus or boron together are corroded owing to lose attachment, thereby have removed the high concentration phosphorus doped region or the high concentration boron doped region on the positive top layer of silicon chip.
When the silicon chip front is handled, HNO in first mix acid liquor that is adopted
3With the preferred 10:1 ~ 12:1 of the mass ratio of HF, the preferred 20 ~ 50g/L of the concentration of HF in first mix acid liquor.According to first mix acid liquor that said ratio forms, can practice thrift the consumption of acid solution and can realize etching effect preferably again.
Above-mentioned steps S2 can adopt several different methods when utilizing mix acid liquor etching silicon chip positive, silicon chip is positive such as first mix acid liquor is sprayed, and perhaps adopts following steps: S21, the silicon chip after the etching is soaked 40 ~ 80s in first mix acid liquor; S22, the silicon chip that will pass through immersion utilize high purity deionized water to clean.Silicon chip after the etching is placed on the acid solution that has mixed, and silicon chip can be immersed in and can only guarantee also in the mix acid liquor that the positive of silicon chip all immerses in the mix acid liquor; Behind 40 ~ 80s silicon chip is taken out from mix acid liquor and then utilize high purity deionized water to wash the acid solution of silicon chip surface.
Also have multiple to the edge of the silicon chip after the diffusion and the method that etching is carried out at the back side at present; In a kind of preferred embodiment of the present invention, step S1 comprises: second mix acid liquor that S11, employing contain nitric acid and hydrofluoric acid will spread edge and the back-etching of making the silicon chip after tying; S12, the silicon chip that adopts potassium hydroxide solution will pass through etching processing clean.Identical with principle to the processing in the front of silicon chip, utilize nitric acid with the silicon chip back side and edge oxidation, form silicon dioxide, hydrofluoric acid and silicon dioxde reaction generate volatile six silicon fluorides, thereby reach the purpose of etching; Remove the porous silicon of silicon chip surface after the etching through potassium hydroxide solution, and the acid that does not wash down that will from the etching groove, carry removes, accomplish etching the silicon chip edge and the back side.
In the foregoing description, HNO in preferred second mix acid liquor
3Concentration be 400 ~ 600g/L, the concentration of HF is 20 ~ 50g/L, among the step S12 in the potassium hydroxide solution mass content of KOH be 3 ~ 10%.Select nitric acid, hydrofluoric acid and potassium hydroxide solution in the above-mentioned concentration range can make corrosion reaction under a stable reaction rate, carry out, reaction rate is easy to control, and corrosion evenly.
In the another kind of typical embodiment of the present invention, a kind of crystal silicon solar batteries also is provided, this crystal silicon solar batteries obtains through above-mentioned manufacture method.The diffusion into the surface concentration of the front electrode of the crystal silicon solar batteries that the above-mentioned manufacture method of process obtains is lower, has reduced the recombination rate of surperficial few son, and then has improved the photoelectric conversion efficiency of the crystal silicon solar batteries with it.
Below with reference to embodiment and Comparative Examples, further specify beneficial effect of the present invention.
Embodiment 1
The silicon chip that will pass through phosphorous diffusion system knot places HNO
3Concentration be that the concentration of 400g/L and HF is that the front of silicon chip is more than liquid level in second mix acid liquor of 30g/L; Taking-up employing mass concentration is 5% potassium hydroxide solution drip washing 30s behind the 108s; Then silicon chip is placed HNO
3With the mass ratio of HF be that the concentration of HF is 10g/L in first mix acid liquor in first mix acid liquor of 10:1, take out behind the 40s and utilize high purity deionized water to wash the acid solution of silicon chip surface again.
Embodiment 2
The silicon chip that will pass through phosphorous diffusion system knot places HNO
3Concentration be that the concentration of 500g/L and HF is that the front of silicon chip is more than liquid level in second mix acid liquor of 40g/L; Taking-up employing mass concentration is 3% potassium hydroxide solution drip washing 30s behind the 108s; Then silicon chip is placed HNO
3With the mass ratio of HF be that the concentration of HF is 80g/L in first mix acid liquor in first mix acid liquor of 15:1, take out behind the 40s and utilize high purity deionized water to wash the acid solution of silicon chip surface again.
Embodiment 3
The silicon chip that will pass through phosphorous diffusion system knot places HNO
3Concentration be that the concentration of 600g/L and HF is that the front of silicon chip is more than liquid level in second mix acid liquor of 50g/L; Taking-up employing mass concentration is 10% potassium hydroxide solution drip washing 30s behind the 108s; Then silicon chip is placed HNO
3With the mass ratio of HF be that the concentration of HF is 50g/L in first mix acid liquor in first mix acid liquor of 12:1, take out behind the 40s and utilize high purity deionized water to wash the acid solution of silicon chip surface again.
Embodiment 4
The silicon chip that will pass through phosphorous diffusion system knot places HNO
3Concentration be that the concentration of 500g/L and HF is that the front of silicon chip is more than liquid level in second mix acid liquor of 40g/L; Taking-up employing mass concentration is 7% potassium hydroxide solution drip washing 30s behind the 108s; Then silicon chip is placed HNO
3With the mass ratio of HF be that the concentration of HF is 20g/L in first mix acid liquor in first mix acid liquor of 11:1, take out behind the 40s and utilize high purity deionized water to wash the acid solution of silicon chip surface again.
Embodiment 5
The silicon chip that will pass through phosphorous diffusion system knot places HNO
3Concentration be that the concentration of 350g/L and HF is that the front of silicon chip is more than liquid level in second mix acid liquor of 60g/L; Taking-up employing mass concentration is 3% potassium hydroxide solution drip washing 30s behind the 108s; Then silicon chip is placed HNO
3With the mass ratio of HF be that the concentration of HF is 40g/L in first mix acid liquor in first mix acid liquor of 13:1, take out behind the 40s and utilize high purity deionized water to wash the acid solution of silicon chip surface again.
Embodiment 6
With placing HNO through the silicon chip after phosphorous diffusion system knot, edge and the surface etching treatment successively
3With the mass ratio of HF be that the concentration of HF is 40g/L in first mix acid liquor in first mix acid liquor of 13:1, take out behind the 50s and utilize high purity deionized water to wash the acid solution of silicon chip surface again.
The silicon chip of test phosphorous diffusion system knot and respectively through the surface concentration and side's resistance of the silicon chip after embodiment 1 to the 6 positive etching, test result is seen table 1
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Side's resistance (Ω) of the silicon chip of phosphorous diffusion system knot | 64.42 | 64.42 | 64.42 | 64.42 | 64.42 | 64.42 |
| Side's resistance (Ω) of the silicon chip after the positive etching | 65.63 | 66.86 | 70.71 | 81.53 | 102.05 | 73.6 |
| Surface concentration (the 1/cm of the silicon chip of phosphorous diffusion system knot 3） | 9.5x10 20 | 9.5x10 20 | 9.5x10 20 | 9.5x10 20 | 9.5x10 20 | 9.5x10 20 |
| Surface concentration (the 1/cm of the silicon chip after the positive etching 3） | 7.0x10 20 | 5.8x10 20 | 4.1x10 20 | 2.5x10 20 | 2.1x10 20 | 3.34x10 20 |
Data from table 1 can find out that the phosphorus doped polycrystal silicon surface concentration that embodiment 1 to 6 adopts lithographic method of the present invention to handle obviously reduces, and side's resistance is obviously increased.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. the manufacture method of a crystal silicon solar batteries comprises the silicon chip system of spreading knot, etching, deposition antireflection layer, prints electrode and the step of sintering, it is characterized in that the step of said etching comprises:
S1, adopt the plasma etching method to carry out etching at the edge and the back side of the silicon chip behind the said diffusion system knot;
S2, adopt the silicon chip front of first mix acid liquor after contain nitric acid and hydrofluoric acid to handle HNO in said first mix acid liquor to etching
3With the mass ratio of HF be 10:1 ~ 15:1, and the concentration of HF is 10 ~ 80g/L in said first mix acid liquor.
2. manufacture method according to claim 1 is characterized in that, HNO in said first mix acid liquor
3With the mass ratio of HF be 10:1 ~ 12:1, the concentration of HF is 20 ~ 50g/L in said first mix acid liquor.
3. manufacture method according to claim 1 is characterized in that, said step S2 comprises:
S21, the silicon chip after the said etching is soaked 40 ~ 80s in said first mix acid liquor;
S22, the silicon chip that will pass through immersion utilize high purity deionized water to clean.
4. manufacture method according to claim 1 is characterized in that, said step S1 comprises:
S11, adopt the edge and the back-etching of the silicon chip of second mix acid liquor after contain nitric acid and hydrofluoric acid with said diffusion system knot;
S12, the silicon chip that adopts potassium hydroxide solution will pass through etching processing clean.
5. manufacture method according to claim 4 is characterized in that, HNO in said second mix acid liquor
3Concentration be 400 ~ 600g/L, the concentration of HF is 20 ~ 50g/L, among the said step S12 in the potassium hydroxide solution mass content of KOH be 3 ~ 10%.
6. a crystal silicon solar batteries is characterized in that, said crystal silicon solar batteries obtains through each described manufacture method in the claim 1 to 5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104505431A (en) * | 2014-12-11 | 2015-04-08 | 东方日升新能源股份有限公司 | Process method for reducing use level of solar battery cell etching acid |
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|---|---|---|---|---|
| JPH01265521A (en) * | 1988-04-15 | 1989-10-23 | Fujitsu Ltd | Cleaning of semiconductor substrate |
| CN101369612A (en) * | 2008-10-10 | 2009-02-18 | 湖南大学 | Production method for implementing selective emitter solar battery |
| CN101783374A (en) * | 2010-01-25 | 2010-07-21 | 宁波太阳能电源有限公司 | Method for manufacturing silicon solar cell |
| CN102386284A (en) * | 2011-11-29 | 2012-03-21 | 苏州阿特斯阳光电力科技有限公司 | Preparation method of crystalline silicon solar cell |
-
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- 2012-08-23 CN CN2012103034481A patent/CN102800754A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01265521A (en) * | 1988-04-15 | 1989-10-23 | Fujitsu Ltd | Cleaning of semiconductor substrate |
| CN101369612A (en) * | 2008-10-10 | 2009-02-18 | 湖南大学 | Production method for implementing selective emitter solar battery |
| CN101783374A (en) * | 2010-01-25 | 2010-07-21 | 宁波太阳能电源有限公司 | Method for manufacturing silicon solar cell |
| CN102386284A (en) * | 2011-11-29 | 2012-03-21 | 苏州阿特斯阳光电力科技有限公司 | Preparation method of crystalline silicon solar cell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104505431A (en) * | 2014-12-11 | 2015-04-08 | 东方日升新能源股份有限公司 | Process method for reducing use level of solar battery cell etching acid |
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Application publication date: 20121128 |