CN103346074A - Method for preparing crystalline silicon battery pieces through multistep gradient diffusion method - Google Patents
Method for preparing crystalline silicon battery pieces through multistep gradient diffusion method Download PDFInfo
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Abstract
The invention relates to the production technology of crystalline silicon battery pieces, in particular to the filed of crystalline silicon battery piece diffusion manufacturing procedures. A method for preparing the crystalline silicon battery pieces through a multistep gradient diffusion method specifically comprises the following steps: P type crystalline silicon is placed in a furnace tube at the preset temperature of 800 DEG C, then, nitrogen is blown into the furnace tube, and the temperature is kept constant for 600-900 seconds; the temperature inside the furnace tube is raised to 860 DEG C in two steps, and oxygen and the nitrogen are blown into the furnace tube at the same time; the temperature inside the furnace tube is kept constant at 860 DEG C, and the oxygen, the nitrogen and a phosphorus source are blown into the furnace tube at the same time; the temperature inside the furnace tube is gradually and slowly lowered to 852 DEG C, the phosphorus source, the oxygen and the nitrogen are blown into the furnace tube at the same time, and the time duration is 800 seconds; the temperature inside the furnace tube is directly lowered again to 800 DEG C, the oxygen and the nitrogen are blown into the furnace tube at the same time, and annealing is conducted after 300 seconds; after the annealing, the nitrogen is blown into the furnace tube, and a finished product is taken out of the furnace tube. Compared with the traditional technique, the method for preparing the crystalline silicon battery pieces through the multistep gradient diffusion method has increased the battery conversion rate by at least 0.25 percentage point.
Description
Technical field
The present invention relates to a kind of production technology of crystal silicon cell sheet, be specifically related to a kind of crystal silicon cell sheet diffusion process field.
Background technology
The production technology of conventional solar cell comprises: making herbs into wool, diffusion, etching, remove PSG, coated with antireflection film, silk screen printing, sintering.
The conventional diffusion technology of main flow is for once spreading or two step diffusion methods at present, and diffusion back minority carrier life time is relatively low, and the conversion efficiency of battery can not get tangible raising.
Summary of the invention
The object of the present invention is to provide a kind of employing multi-step gradient diffusion method to prepare the crystal silicon cell sheet, concrete steps are: adopt the gradient diffusion method to carry out the high temperature Doping Phosphorus at P type surface of crystalline silicon and obtain the N-type crystalline silicon, form the P-N knot.1) P type crystalline silicon is fed predefined 800 ℃ boiler tube, feed nitrogen, insulation 600-900s; 2) in two steps temperature in the boiler tube is warming up to 860 ℃, simultaneously aerating oxygen and nitrogen; 3) temperature constant temperature to 860 ℃ in the stove, aerating oxygen, nitrogen, phosphorus source simultaneously; 4) divided for four steps reduced temperature in the stove, be reduced to 852 ℃ gradually from 860 ℃, feed phosphorus source, oxygen, nitrogen simultaneously, the time is 800s; 5) directly furnace tube temperature is reduced to 800 ℃, while aerating oxygen, nitrogen, 300s after annealing from 850 ℃; 6) after the annealing, go out boat behind the feeding nitrogen 800s.
In the described step 1), P type crystalline silicon feeds boiler tube with the amount of 300-500PCS, and feeds nitrogen with the speed of 17.8-18.2L/min, insulation 600-900s.
Described step 2) in, temperature is warming up to 820 ℃ from 800 ℃ earlier in the stove, feeds nitrogen, oxygen simultaneously, and wherein nitrogen, oxygen feed in the stove with the speed of 18.0-18.6L/min, 0.8-1.0L/min respectively, and the feeding time is 250-350s; Be warming up to 860 ℃ from 820 ℃ again, feed nitrogen, oxygen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 17.8-18.2L/min, 0.8-1.1L/min respectively, and the feeding time is 800-1200s.
In the described step 3), temperature to 860 ℃ in the constant stove, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 0.56-0.63L/min, 0.48-0.52L/min, 17.2-17.9L/min respectively, and the feeding time is 280-320s; Strengthen phosphorus source feeding amount, feed phosphorus source, nitrogen, oxygen again under 860 ℃, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 0.88-0.94L/min, 0.48-0.52L/min, 17.2-17.9L/min respectively, and the feeding time is 580-630s.
In the described step 4), temperature in the stove is reduced to 858 ℃ from 860 ℃, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 1.0-1.35L/min, 0.48-0.52L/min, 17.2-17.9L/min respectively, and the feeding time is 180-220s; Again temperature in the stove is reduced to 856 ℃ from 858 ℃, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 1.4-1.55L/min, 0.48-0.52L/min, 16.2-16.75L/min respectively, and the feeding time is 180-220s; Further temperature in the stove is reduced to 854 ℃ from 856 ℃, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 1.78-1.86L/min, 0.28-0.32L/min, 16.2-16.75L/min respectively, and the feeding time is 180-220s; Further temperature in the stove is reduced to 852 ℃ from 854 ℃, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 1.95-2.25L/min, 0.48-0.52L/min, 16.2-16.75L/min respectively, and the feeding time is 180-220s.
In the described step 5), directly furnace tube temperature is reduced to 800 ℃ from 850 ℃, aerating oxygen, nitrogen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 0.48-0.52L/min, 17.8-18.2L/min respectively, and the feeding time is 300s, annealing.
In the described step 6), after the annealing, continue to feed nitrogen with the speed of 17.8-18.2L/min, go out boat behind the feeding 800s.
Described phosphorus source is phosphorus oxychloride.
The invention has the advantages that: compare with other solar cell method of diffusion, because the PN that forms becomes shallow junction, mix lower near the PN junction district, minority carrier life time improves, the higher relatively conductivity with the battery grid line of the most surperficial phosphorus doping improves, thereby not only improved the solar cell short circuit current but also improved open circuit voltage, finally improved conversion efficiency.On battery conversion efficiency, can obviously improve short circuit current, guarantee higher open circuit voltage and fill factor, curve factor thereof.The raising of electric current and voltage proves that fully comparing final conversion efficiency of the present invention with the traditional handicraft method improves 0.25 percentage point at least.
Description of drawings
Fig. 1 is the open circuit voltage (UOC) of battery sheet and common batteries sheet among the embodiment 1;
Fig. 2 is the short circuit current (ISC) of battery sheet and common batteries sheet among the embodiment 1.
Embodiment
A kind of multi-step gradient diffusion method prepares the crystal silicon cell sheet, adopts the gradient diffusion method to carry out the high temperature Doping Phosphorus at P type surface of crystalline silicon and obtains the N-type crystalline silicon, forms the P-N knot, may further comprise the steps,
1) with the amount feeding predefined 800 ℃ boiler tube of P type crystalline silicon with 300PCS, the speed with 17.8-18.2L/min feeds nitrogen simultaneously, insulation 600s;
2) in two steps temperature in the boiler tube is warming up to 860 ℃, earlier temperature in the stove is warming up to 820 ℃ from 800 ℃, feed nitrogen, oxygen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 18.0L/min, 0.8L/min respectively, and the feeding time is 250s; Be warming up to 860 ℃ from 820 ℃ again, feed nitrogen, oxygen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 17.8L/min, 0.8L/min respectively, and the feeding time is 800s;
3) temperature to 860 ℃ in the constant stove feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, and wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 0.56L/min, 0.48L/min, 17.2L/min respectively, and the feeding time is 280s; Strengthen phosphorus oxychloride feeding amount, feed phosphorus oxychloride, nitrogen, oxygen again under 860 ℃, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 0.88L/min, 0.48L/min, 17.2L/min respectively, and the feeding time is 580s;
4) divided for four steps reduced temperature in the stove, earlier temperature in the stove is reduced to 858 ℃ from 860 ℃, feed phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.0L/min, 0.48L/min, 17.2L/min respectively, and the feeding time is 180s; Again temperature in the stove is reduced to 856 ℃ from 858 ℃, feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.4L/min, 0.48L/min, 16.2L/min respectively, and the feeding time is 180s; Further temperature in the stove is reduced to 854 ℃ from 856 ℃, feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.78L/min, 0.28L/min, 16.2L/min respectively, and the feeding time is 180s; Further temperature in the stove is reduced to 852 ℃ from 854 ℃, feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.95L/min, 0.48L/min, 16.2L/min respectively, and the feeding time is 180s;
5) directly furnace tube temperature is reduced to 800 ℃ from 850 ℃, aerating oxygen, nitrogen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 0.48L/min, 17.8L/min respectively, and the feeding time is 300s, annealing;
6) after the annealing, after the annealing, continue to feed nitrogen with the speed of 17.8L/min, go out boat behind the feeding 800s.
The battery sheet open circuit voltage (UOC) that the present invention produces is than 0.05 volt of common batteries sheet mean height; Short circuit current (ISC) mean height 0.2A.
A kind of multi-step gradient diffusion method prepares the crystal silicon cell sheet, adopts the gradient diffusion method to carry out the high temperature Doping Phosphorus at P type surface of crystalline silicon and obtains the N-type crystalline silicon, forms the P-N knot, may further comprise the steps,
1) with the amount feeding predefined 800 ℃ boiler tube of P type crystalline silicon with 400PCS, the speed with 18L/min feeds nitrogen simultaneously, insulation 800s;
2) in two steps temperature in the boiler tube is warming up to 860 ℃, earlier temperature in the stove is warming up to 820 ℃ from 800 ℃, feed nitrogen, oxygen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 18L/min, 0.9L/min respectively, and the feeding time is 300s; Be warming up to 860 ℃ from 820 ℃ again, feed nitrogen, oxygen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 18L/min, 0.9L/min respectively, and the feeding time is 900s;
3) temperature to 860 ℃ in the constant stove feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, and wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 0.6L/min, 0.5L/min, 17.9L/min respectively, and the feeding time is 300s; Strengthen phosphorus oxychloride feeding amount, feed phosphorus oxychloride, nitrogen, oxygen again under 860 ℃, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 0.9L/min, 0.5L/min, 17.9L/min respectively, and the feeding time is 600s;
4) divided for four steps reduced temperature in the stove, earlier temperature in the stove is reduced to 858 ℃ from 860 ℃, feed phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.2L/min, 0.5L/min, 17.9L/min respectively, and the feeding time is 200s; Again temperature in the stove is reduced to 856 ℃ from 858 ℃, feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.5L/min, 0.5L/min, 16.5L/min respectively, and the feeding time is 200s; Further temperature in the stove is reduced to 854 ℃ from 856 ℃, feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.8L/min, 0.3L/min, 16.5L/min respectively, and the feeding time is 200s; Further temperature in the stove is reduced to 852 ℃ from 854 ℃, feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 2.0L/min, 0.5L/min, 16.5L/min respectively, and the feeding time is 200s;
5) directly furnace tube temperature is reduced to 800 ℃ from 850 ℃, aerating oxygen, nitrogen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 0.5L/min, 18L/min respectively, and the feeding time is 300s, annealing;
6) after the annealing, after the annealing, continue to feed nitrogen with the speed of 18L/min, go out boat behind the feeding 800s.
The battery sheet open circuit voltage (UOC) that the present invention produces is than 0.07 volt of common batteries sheet mean height; Short circuit current (ISC) mean height 0.25A.
A kind of multi-step gradient diffusion method prepares the crystal silicon cell sheet, adopts the gradient diffusion method to carry out the high temperature Doping Phosphorus at P type surface of crystalline silicon and obtains the N-type crystalline silicon, forms the P-N knot, may further comprise the steps,
1) with the amount feeding predefined 800 ℃ boiler tube of P type crystalline silicon with 500PCS, the speed with 18.2L/min feeds nitrogen simultaneously, insulation 900s;
2) in two steps temperature in the boiler tube is warming up to 860 ℃, earlier temperature in the stove is warming up to 820 ℃ from 800 ℃, feed nitrogen, oxygen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 18.6L/min, 1.0L/min respectively, and the feeding time is 350s; Be warming up to 860 ℃ from 820 ℃ again, feed nitrogen, oxygen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 18.2L/min, 1.1L/min respectively, and the feeding time is 1200s;
3) temperature to 860 ℃ in the constant stove feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, and wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 0.63L/min, 0.52L/min, 17.9L/min respectively, and the feeding time is 320s; Strengthen phosphorus oxychloride feeding amount, feed phosphorus oxychloride, nitrogen, oxygen again under 860 ℃, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 0.94L/min, 0.52L/min, 17.9L/min respectively, and the feeding time is 630s;
4) divided for four steps reduced temperature in the stove, earlier temperature in the stove is reduced to 858 ℃ from 860 ℃, feed phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.35L/min, 0.52L/min, 17.2-17.9L/min respectively, and the feeding time is 220s; Again temperature in the stove is reduced to 856 ℃ from 858 ℃, feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.55L/min, 0.52L/min, 16.75L/min respectively, and the feeding time is 220s; Further temperature in the stove is reduced to 854 ℃ from 856 ℃, feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 1.86L/min, 0.32L/min, 16.75L/min respectively, and the feeding time is 220s; Further temperature in the stove is reduced to 852 ℃ from 854 ℃, feeds phosphorus oxychloride, nitrogen, oxygen simultaneously, wherein phosphorus oxychloride, nitrogen, oxygen feed in the stove with the speed of 2.25L/min, 0.52L/min, 16.75L/min respectively, and the feeding time is 220s;
5) directly furnace tube temperature is reduced to 800 ℃ from 850 ℃, aerating oxygen, nitrogen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 0.52L/min, 18.2L/min respectively, and the feeding time is 300s, annealing;
6) after the annealing, after the annealing, continue to feed nitrogen with the speed of 18.2L/min, go out boat behind the feeding 800s.
The battery sheet open circuit voltage (UOC) that the present invention produces is than 0.06 volt of common batteries sheet mean height; Short circuit current (ISC) mean height 0.22A.
Claims (8)
1. method that adopts the multi-step gradient diffusion method to prepare the crystal silicon cell sheet, adopt the gradient diffusion method to carry out the high temperature Doping Phosphorus at P type surface of crystalline silicon and obtain the N-type crystalline silicon, form the P-N knot, it is characterized in that: may further comprise the steps, 1) P type crystalline silicon is fed predefined 800 ℃ boiler tube, feed nitrogen, insulation 600-900s; 2) in two steps temperature in the boiler tube is warming up to 860 ℃, simultaneously aerating oxygen and nitrogen; 3) temperature constant temperature to 860 ℃ in the stove, aerating oxygen, nitrogen, phosphorus source simultaneously; 4) divided for four steps reduced temperature in the stove, be reduced to 852 ℃ gradually from 860 ℃, feed phosphorus source, oxygen, nitrogen simultaneously, the time is 800s; 5) directly furnace tube temperature is reduced to 800 ℃, while aerating oxygen, nitrogen, 300s after annealing from 852 ℃; 6) after the annealing, feed nitrogen, go out boat behind the 800s.
2. multi-step gradient diffusion method according to claim 1 prepares the method for crystal silicon cell sheet, it is characterized in that: in the step 1), 300-500 P type crystalline silicon fed boiler tube, and feed nitrogen with the speed of 17.8-18.2L/min, insulation 600-900s.
3. multi-step gradient diffusion method according to claim 1 prepares the method for crystal silicon cell sheet, it is characterized in that: step 2) in, temperature is warming up to 820 ℃ from 800 ℃ earlier in the stove, feed nitrogen, oxygen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 18.0-18.6L/min, 0.8-1.0L/min respectively, and the feeding time is 250-350s; Be warming up to 860 ℃ from 820 ℃ again, feed nitrogen, oxygen simultaneously, wherein nitrogen, oxygen feed in the stove with the speed of 17.8-18.2L/min, 0.8-1.1L/min respectively, and the feeding time is 800-1200s.
4. multi-step gradient diffusion method according to claim 1 prepares the method for crystal silicon cell sheet, it is characterized in that: in the step 3), temperature to 860 ℃ in the constant stove, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 0.56-0.63L/min, 0.48-0.52L/min, 17.2-17.9L/min respectively, and the feeding time is 280-320s; Strengthen phosphorus source feeding amount, feed phosphorus source, nitrogen, oxygen again under 860 ℃, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 0.88-0.94L/min, 0.48-0.52L/min, 17.2-17.9L/min respectively, and the feeding time is 580-630s.
5. multi-step gradient diffusion method according to claim 1 prepares the method for crystal silicon cell sheet, it is characterized in that: in the step 4), temperature in the stove is reduced to 858 ℃ from 860 ℃, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 1.0-1.35L/min, 0.48-0.52L/min, 17.2-17.9L/min respectively, and the feeding time is 180-220s; Again temperature in the stove is reduced to 856 ℃ from 858 ℃, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 1.4-1.55L/min, 0.48-0.52L/min, 16.2-16.75L/min respectively, and the feeding time is 180-220s; Further temperature in the stove is reduced to 854 ℃ from 856 ℃, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 1.78-1.86L/min, 0.28-0.32L/min, 16.2-16.75L/min respectively, and the feeding time is 180-220s; Further temperature in the stove is reduced to 852 ℃ from 854 ℃, feed phosphorus source, nitrogen, oxygen simultaneously, wherein phosphorus source, nitrogen, oxygen feed in the stove with the speed of 1.95-2.25L/min, 0.48-0.52L/min, 16.2-16.75L/min respectively, and the feeding time is 180-220s.
6. multi-step gradient diffusion method according to claim 1 prepares the method for crystal silicon cell sheet, it is characterized in that: in the step 5), directly furnace tube temperature is reduced to 800 ℃ from 850 ℃, while aerating oxygen, nitrogen, wherein nitrogen, oxygen feed in the stove with the speed of 0.48-0.52L/min, 17.8-18.2L/min respectively, the feeding time is 300s, annealing.
7. multi-step gradient diffusion method according to claim 1 prepares the crystal silicon cell sheet, it is characterized in that: in the step 6), after the annealing, continue to feed nitrogen with the speed of 17.8-18.2L/min, go out boat behind the feeding 800s.
8. prepare the crystal silicon cell sheet according to any described multi-step gradient diffusion method among the claim 1-7, it is characterized in that: the phosphorus source is phosphorus oxychloride.
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| CN104485391A (en) * | 2014-12-25 | 2015-04-01 | 中利腾晖光伏科技有限公司 | Preparation method of crystalline silicon solar cell PN junction |
| CN108728901A (en) * | 2018-06-15 | 2018-11-02 | 常州亿晶光电科技有限公司 | A kind of maintenance method of diffusion furnace tube |
| CN114823983A (en) * | 2022-05-16 | 2022-07-29 | 一道新能源科技(衢州)有限公司 | Diffusion annealing process of perc battery |
| WO2023088173A1 (en) * | 2021-11-17 | 2023-05-25 | 拉普拉斯新能源科技股份有限公司 | Gas diffusion method |
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