CN102270701A - One-step diffusion process of silicon solar cell with selective emitter - Google Patents
One-step diffusion process of silicon solar cell with selective emitter Download PDFInfo
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Abstract
The invention provides a one-step diffusion process of silicon solar cells with selective emitters. The process comprises the following steps of: printing silicon ink on a silicon wafer; introducing oxygen gas into a diffusion furnace to form silicon dioxide layers on the surfaces of the silicon wafer and the silicon ink; and introducing phosphorus oxychloride into the diffusion furnace for diffusion, to form a heavily-doped region in the area printed with the silicon ink and a lightly-doped zone in the area free of the silicon ink on the silicon wafer. The one-step diffusion process of silicon solar cells with selective emitters, provided by the invention, is suitable for large-scale industrial production, and has a simple technical process and a low cost.
Description
Technical field
The present invention relates to the selective emitter crystal silicon solar batteries and make the field, be specifically related to a kind of disposable diffusion technology of selective emitter crystal silicon solar batteries.
Background technology
High-performance, high efficiency solar battery sheet are the core developing goals of whole photovoltaic industry, and wherein the crystal silicon solar batteries of selective emitting electrode structure is the novel battery that has extensive Industry Promotion most.
Crystal silicon solar batteries for routine, emitter is the phosphorus-diffused layer on top layer, for the good electrode contact performance that has between the front metal gate electrode that ensures silk screen printing and the emitter, it is the lower square resistance of phosphorus-diffused layer that emitter needs higher surface doping concentration, yet the phosphorus-diffused layer of higher-doped concentration can cause the blue light absorption loss to combine loss again with the photo-generated carrier surface, be unfavorable for realizing high-photoelectric transformation efficiency, selective emitter is the effective technology that overcomes above-mentioned difficulties.
The basic structure and the conventional batteries of selective emitter crystal silicon solar batteries are similar, but need be to front metal gate electrode and silicon chip contact site and near the highly doped dark diffusion region of formation thereof, and other zones between the front metal gate electrode form low-doped shallow diffusion regions.It is compound that such structure can reduce the diffusion layer in zone between the front metal gate electrode, improve the short wave response of battery sheet, reduce the contact resistance of front metal gate electrode and emitter silicon layer simultaneously, make short circuit current, open circuit voltage and fill factor, curve factor all improve, thereby improve conversion efficiency.
But the key that realizes this structure is how to make the zone of two different levels of doping.Existing technology mainly contains two inferior diffusion methods and disposable diffusion method.Two times diffusion method need be carried out two zoness of different that twice thermal diffusion forms selective emitting electrode structure respectively, processing step more complicated and twice elevated temperature heat process hear rate are very big, the fire damage of bringing to silicon chip is bigger, and is especially even more serious for the polysilicon influence.Disposable diffusion method is to form this structure in a thermal diffusion, this needs at first to obtain in the zones of different of silicon chip surface the diffusion impurity source of different amounts, because the difference of diffusion impurity source will obtain different diffusion results, carry out just forming after the thermal diffusion doping of high-concentration and low-concentration, obtain selective emitting electrode structure.
The major programme that disposable diffusion method prepares selective emitter solar battery comprises: oxide layer mask diffusion print process, laser is coated with the source doping galvanoplastic, printing phosphorus source single step diffusion method etc.The technology that oxide layer mask diffusion print process relates to is too complicated, influence process efficiency, improved production cost, and laser is coated with the source doping galvanoplastic and need acquires large laser equipment, and the controllability that adopts uniformity that laser thermal effect mixes and follow-up galvanoplastic to make electrode does not solve fully yet; The accuracy rate that printing phosphorus source single step diffusion method is controlled phosphorus source diffusion depth is not high.Sometimes also can introduce metal ion in these preparation process, bring pollution to diffusion.So above method still has many difficult problems to overcome in Industry Promotion is used.
Summary of the invention
The object of the present invention is to provide a kind of disposable diffusion technology of selective emitter crystal silicon solar batteries, prepare the problem that selective emitter solar battery processing step complexity can not be carried out large-scale production to solve existing disposable diffusion method.
For addressing the above problem, the present invention proposes a kind of disposable diffusion technology of selective emitter crystal silicon solar batteries, comprising: printing silicon China ink on silicon chip; Aerating oxygen in diffusion furnace makes the surface of described silicon chip and described silicon China ink all form silicon dioxide layer; Feed phosphorus oxychloride and spread in described diffusion furnace, make the zone that is printed with described silicon China ink form heavily doped region, the zone of not printing described silicon China ink on described silicon chip forms shallow doped region.
Preferably, feed in described diffusion furnace after phosphorus oxychloride spreads, elevated temperature makes phosphorus carry out high temperature in described silicon chip to distribute again.
Preferably, the time that described high temperature distributes again is 1000 seconds～3000 seconds, and technological temperature is 850 ℃～950 ℃.
Preferably, elevated temperature carries out after high temperature distributes again phosphorus in described silicon chip, and lowering the temperature distributes phosphorus again in silicon chip.
Preferably, cooling distributes phosphorus again in silicon chip time is 1000 seconds～2500 seconds, and technological temperature is 780 ℃～820 ℃.
Preferably, will on described silicon chip, print described silicon China ink by screen printing technique behind the described silicon chip cleaning and texturing.
Preferably, the technological temperature that forms described silicon dioxide layer is 780 ℃～820 ℃, and the oxygen flow of feeding is 500 cc/min～1000 cc/min.
Preferably, bring described phosphorus oxychloride in described diffusion furnace, under the acting in conjunction of oxygen, spread by low discharge nitrogen.
Preferably, the time of described diffusion is 800 seconds～1500 seconds, the temperature of diffusion is 780 ℃～820 ℃, and the flow of oxygen is 400 cc/min～800 cc/min, and the flow of described nitrogen is 800 cc/min～2500 cc/min.
Preferably, strengthen the flow of oxygen, form phosphorosilicate glass on the surface of described silicon chip.
Preferably, the time that forms described phosphorosilicate glass process is 500 seconds～1000 seconds, and technological temperature is 780 ℃～820 ℃, and the flow of oxygen is 6000 cc/min～13000 cc/min.
The disposable diffusion technology of selective emitter crystal silicon solar batteries provided by the invention, on silicon chip, print the silicon China ink earlier, the easier substituted for silicon atom of phosphorus atoms when described silicon China ink can make diffusion, afterwards form heavily doped region so that be printed with the zone of described silicon China ink, the zone of not printing described silicon China ink on described silicon chip forms shallow doped region.The selective emitter crystal silicon solar batteries that uses disposable diffusion technology provided by the invention to make has the weight doped region of obvious variable concentrations, the positive gate electrode contact area that later stage is formed has good Ohmic contact, and, improved the short wave response of solar cell because the photo-generated carrier surface recombination in doped regions reduces.The disposable diffusion technology of selective emitter crystal silicon solar batteries provided by the invention can be carried out large-scale industrial production, and technical process is simple, and cost is lower.
Further, after the feeding phosphorus oxychloride spreads in described diffusion furnace, elevated temperature makes phosphorus carry out high temperature in described silicon chip to distribute again, makes the CONCENTRATION DISTRIBUTION difference of the heavily doped region that forms on the silicon chip and light doping section more obvious, so that form darker doped region.
Further, elevated temperature carries out after high temperature distributes again phosphorus in described silicon chip, lowering the temperature distributes phosphorus again in silicon chip, and is more obvious with the CONCENTRATION DISTRIBUTION difference that further makes the heavily doped region that forms on the silicon chip and light doping section, and can eliminate lattice defect, realize the phosphorus gettering.
Further, bring described phosphorus oxychloride in described diffusion furnace by low discharge nitrogen, and spread under the acting in conjunction of oxygen, oxygen can promote that phosphorus oxychloride decomposites chlorine, so that finish diffusion process quickly, has saved the process time greatly.
Further, strengthen the flow of oxygen, form thicker phosphorosilicate glass on the surface of described silicon chip, the chlorine of avoiding decompositing with the formation resilient coating produces damage to silicon chip.
Description of drawings
The flow chart of steps of the disposable diffusion technology of the selective emitter crystal silicon solar batteries that Fig. 1 provides for the embodiment of the invention.
Embodiment
Be described in further detail below in conjunction with the disposable diffusion technology of the drawings and specific embodiments the selective emitter crystal silicon solar batteries of the present invention's proposition.According to the following describes and claims, advantages and features of the invention will be clearer.It should be noted that accompanying drawing all adopts very the form of simplifying and all uses non-ratio accurately, only be used for conveniently, the purpose of the aid illustration embodiment of the invention lucidly.
Core concept of the present invention is, the disposable diffusion technology of the selective emitter crystal silicon solar batteries that provides, on silicon chip, print the silicon China ink earlier, the easier substituted for silicon atom of phosphorus atoms when described silicon China ink can make diffusion, afterwards form heavily doped region so that be printed with the zone of described silicon China ink, the zone of not printing described silicon China ink on described silicon chip forms shallow doped region.The selective emitter crystal silicon solar batteries that uses disposable diffusion technology provided by the invention to make has the weight doped region of obvious variable concentrations, the positive gate electrode contact area that later stage is formed has good Ohmic contact, and, improved the short wave response of solar cell because the photo-generated carrier surface recombination in doped regions reduces.The disposable diffusion technology of selective emitter crystal silicon solar batteries provided by the invention can be carried out large-scale industrial production, and technical process is simple, and cost is lower.
The flow chart of steps of the disposable diffusion technology of the selective emitter crystal silicon solar batteries that Fig. 1 provides for the embodiment of the invention.With reference to Fig. 1, the step of the disposable diffusion technology of selective emitter crystal silicon solar batteries comprises:
S11, on silicon chip printing silicon China ink;
S12, in diffusion furnace aerating oxygen, make the surface of described silicon chip and described silicon China ink all form silicon dioxide layer;
S13, feed phosphorus oxychloride spread in described diffusion furnace, make the zone that is printed with described silicon China ink form heavily doped region, the zone of not printing described silicon China ink on described silicon chip forms shallow doped region.
In step S11, utilize screen printing technique on silicon chip, to print the silicon China ink.Before carrying out silk screen printing, silicon chip is cleaned and conventional process for etching, those of ordinary skill in the art should the technical process of decorrelation, do not repeat them here.
Before carrying out diffusion technology, the quartz boat that will be mounted with the making herbs into wool monocrystalline silicon piece that has finished printing earlier advances in the diffusion furnace, in the present embodiment, the time of advancing the boat process was controlled at 480 seconds～680 seconds, can not cause silicon chip to break owing to the ambient temperature differences of entering the boat front and back makes silicon chip produce stress to guarantee silicon chip.The temperature of diffusion furnace is set in 780 ℃～820 ℃.The boat that advances from diffusion technology begins all will feed nitrogen constantly in diffusion furnace up to going out boat, to guarantee pure relatively diffusion furnace environment.When advancing boat, the flow control of the nitrogen of feeding is used the air in the nitrogen wash diffusion furnace that feeds in 18000 cc/min～25000 cc/min.
Refer step S12 forms oxygen-enriched environment in diffusion furnace, the surface oxidation of described silicon chip and described silicon China ink forms silicon dioxide layer.The oxygen flow that feeds is controlled at 500 cc/min～1000 cc/min, oxidizing process was controlled at 30 seconds～100 seconds, technological temperature is set in 780 ℃～820 ℃, and feed with the flow control that guarantees the nitrogen that pressure in the diffusion furnace is stable in 18000 cc/min～25000 cc/min.
Carry out diffusion technology afterwards, integrating step S13 brings phosphorus oxychloride in the diffusion furnace into by the nitrogen of low discharge, under the acting in conjunction of oxygen, carry out diffusion process, oxygen can promote that phosphorus oxychloride decomposites chlorine, so that finish diffusion process quickly, has saved the process time greatly.Oxygen flow in the embodiment of the invention is controlled at 400 cc/min～800 cc/min, the time of diffusion process was controlled at 800 seconds～1500 seconds, the technological temperature of diffusion is 780 ℃～820 ℃, the flow control of the nitrogen of low discharge is in 800 cc/min～2500 cc/min, at this moment, feeding with the flow control that guarantees the nitrogen that pressure in the diffusion furnace is stable in 18000 cc/min～25000 cc/min.
In order to form thicker phosphorosilicate glass at silicon chip surface, the chlorine of avoiding decompositing with the formation resilient coating produces damage to silicon chip, strengthen the flow of oxygen, make the oxygen flow of feeding be controlled at 6000 cc/min～13000 cc/min, at this moment, feeding with the flow control of the nitrogen that guarantees ambient stable in 7000 cc/min～15000 cc/min.
Through diffusion process after a while, form heavily doped region in the zone that is printed with described silicon China ink, the zone of not printing described silicon China ink on described silicon chip forms shallow doped region, utilizes simple process steps to form the crystal silicon solar batteries with selective emitter.The selective emitter crystal silicon solar batteries that the disposable diffusion technology that the embodiment of the invention provides is made can effectively guarantee at the positive gate electrode contact area that the later stage forms good Ohmic contact is arranged, and be the zone that is not printed with the silicon China ink in other light areas, this region surface is compound to be reduced owing to low-doped meeting causes, and improves the short wave response of solar cell.
Preferably, for the CONCENTRATION DISTRIBUTION difference that makes the heavy and light doped region is more obvious, the temperature in the rising diffusion furnace is impelled phosphorus to carry out high temperature in silicon chip and is distributed, so that form darker doped region.Heat up again time of distributed process was controlled at 1000 seconds～3000 seconds, and temperature is set in 850 ℃～950 ℃, at this moment, feeding with the flow control that guarantees the nitrogen that pressure in the diffusion furnace is stable in 10000 cc/min～20000 cc/min.Then, lower the temperature to realize that phosphorus distributes again in silicon chip, more obvious with the CONCENTRATION DISTRIBUTION difference that further makes the heavy and light doped region, lower the temperature again time of distributed process was controlled at 1000 seconds～2500 seconds, temperature is set in 780 ℃～820 ℃, at this moment, feeding with the flow control that guarantees the nitrogen that pressure in the diffusion furnace is stable in 10000 cc/min～20000 cc/min.
At last, the quartz boat that loads silicon chip is withdrawed from from diffusion furnace, finish the disposable diffusion technology of selective emitter crystal silicon solar batteries, the time that goes out the boat process was controlled at 300 seconds～700 seconds, temperature is set in 780 ℃～820 ℃, at this moment, feeding with the flow control of the nitrogen that guarantees ambient stable in 18000 cc/min～25000 cc/min.
After the disposable diffusion technology of selective emitter crystal silicon solar batteries finished, check the CONCENTRATION DISTRIBUTION situation of high doped regions respectively by the square resistance of testing high low doped region, the concentration that high-doped zone mixes is high more, the square resistance that records in this zone is more little, the concentration that doped regions is mixed is low more, and the square resistance that records in this zone is high more.Concrete test result is referring to as following table 1, table 2.
Table 1
Table 2
Provide the resistance test result of the low doped region of the silicon chip after six disposable diffusion technologys of process are finished in the table 1, provided the resistance test result in the highly doped zone of the silicon chip after six disposable diffusion technologys of process are finished in the table 2.As can be seen from the table, the silicon chip that adopts technology of the present invention to finish, low doped region square resistance overall average is 82.92 Ω, highly doped regional square resistance overall average is 31.57 Ω.The numerical value of above-mentioned square resistance shows that diffusion result of the present invention can guarantee at the positive gate electrode contact area that the later stage forms good Ohmic contact to be arranged effectively, and be the zone that is not printed with the silicon China ink in other light areas, this region surface is compound to be reduced owing to low-doped meeting causes, and has improved the short wave response of solar cell.
Table 3 has provided the selective emitter solar battery that 400 embodiment of the invention provide and the characteristic parameter contrast of 400 conventional solar cells.
Table 3
Adopt open circuit voltage, the short circuit current of the selective emitter solar battery of the embodiment of the invention that certain lifting has all been arranged, thereby make the mean value of the power of solar cell bring up to 2.88 watts by 2.73 watts, conversion efficiency mean value has brought up to 18.62% by 17.64%.This shows, adopt disposable diffusion technology of the present invention can effectively improve the conversion efficiency and the power output of crystal silicon solar batteries.
In the present embodiment, the material of described silicon chip is a monocrystalline silicon, and the specification of monocrystalline silicon piece is 125mm * 125mm.Will be understood by those skilled in the art that the material of described solar cell can be monocrystalline silicon, polysilicon, can also be nano material, low-dimensional materials etc.
Obviously, those skilled in the art can carry out various changes and modification to invention and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (11)
1. the disposable diffusion technology of a selective emitter crystal silicon solar batteries is characterized in that, comprising:
Printing silicon China ink on silicon chip;
Aerating oxygen in diffusion furnace makes the surface of described silicon chip and described silicon China ink all form silicon dioxide layer;
Feed phosphorus oxychloride and spread in described diffusion furnace, make the zone that is printed with described silicon China ink form heavily doped region, the zone of not printing described silicon China ink on described silicon chip forms shallow doped region.
2. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 1 is characterized in that, feeds in described diffusion furnace after phosphorus oxychloride spreads, and elevated temperature makes phosphorus carry out high temperature in described silicon chip to distribute again.
3. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 2 is characterized in that, the time that described high temperature distributes again is 1000 seconds～3000 seconds, and technological temperature is 850 ℃～950 ℃.
4. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 2 is characterized in that, elevated temperature carries out after high temperature distributes again phosphorus in described silicon chip, and lowering the temperature distributes phosphorus again in silicon chip.
5. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 4 is characterized in that, cooling distributes phosphorus again in silicon chip time is 1000 seconds～2500 seconds, and technological temperature is 780 ℃～820 ℃.
6. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 1 is characterized in that, will print described silicon China ink by screen printing technique on described silicon chip behind the described silicon chip cleaning and texturing.
7. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 1, it is characterized in that, the technological temperature that forms described silicon dioxide layer is 780 ℃～820 ℃, and the oxygen flow of feeding is 500 cc/min～1000 cc/min.
8. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 1 is characterized in that, brings described phosphorus oxychloride in described diffusion furnace by nitrogen, spreads under the acting in conjunction of oxygen.
9. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 8, it is characterized in that, the time of described diffusion is 800 seconds～1500 seconds, the temperature of diffusion is 780 ℃～820 ℃, the flow of oxygen is 400 cc/min～800 cc/min, and the flow of described low discharge nitrogen is 800 cc/min～2500 cc/min.
10. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 9 is characterized in that, strengthens the flow of oxygen, forms phosphorosilicate glass on the surface of described silicon chip.
11. the disposable diffusion technology of selective emitter crystal silicon solar batteries as claimed in claim 10, it is characterized in that, the time that forms described phosphorosilicate glass process is 500 seconds～1000 seconds, technological temperature is 780 ℃～820 ℃, and the flow of oxygen is 6000 cc/min～13000 cc/min.
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| CN104409562A (en) * | 2014-10-30 | 2015-03-11 | 广东爱康太阳能科技有限公司 | Preparation method and preparation system of selective emitter electrode solar cell |
| CN105017848A (en) * | 2014-04-27 | 2015-11-04 | 巨力新能源股份有限公司 | Silicon ink, preparing method of silicon ink and method for preparing crystalline silicon battery emitting electrode |
| CN106653954A (en) * | 2017-02-27 | 2017-05-10 | 常州亿晶光电科技有限公司 | Preparation process of silicon dioxide passivation layer for polycrystalline silicon solar cell |
| CN114447140A (en) * | 2020-10-30 | 2022-05-06 | 山西潞安太阳能科技有限责任公司 | Diffusion process of single crystal solar cell |
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Application publication date: 20111207 |