CN103151428A - Method for realizing selective emitter of crystalline silicon solar cell - Google Patents
Method for realizing selective emitter of crystalline silicon solar cell Download PDFInfo
- Publication number
- CN103151428A CN103151428A CN2013100974555A CN201310097455A CN103151428A CN 103151428 A CN103151428 A CN 103151428A CN 2013100974555 A CN2013100974555 A CN 2013100974555A CN 201310097455 A CN201310097455 A CN 201310097455A CN 103151428 A CN103151428 A CN 103151428A
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- phosphorosilicate glass
- glass layer
- doped region
- selective emitter
- crystalline silicon
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Abstract
The invention relates to a method for realizing a selective emitter of a crystalline silicon solar cell. The method comprises three steps of pre-precipitating, removing a phosphorosilicate glass layer of an area which needs to be slightly doped and propelling, wherein a layer of phosphorosilicate glass and an n<+>-type emitter with low phosphate content can be formed on a p-type silicon slice surface through pre-precipitating; a phosphorosilicate glass layer of an area which needs to be slightly doped is removed through a chemical corrosion method; and finally, the emitter in the phosphorosilicate glass area is removed to redistribute phosphorus atoms through high-temperature propelling so as to realize slight doping, the emitter of the phosphorosilicate glass area is maintained to continuously propel the phosphorus atoms so as to realizing re-doping, and accordingly, a selective emitter structure is formed. According to the method, the phosphorosilicate glass layer of the light doping area is removed through chemical corrosion, the emitter is not damaged, and the method is easy to control; and the emitter uniformity is ensured, the selective emitter structure is perfect, and a selective emitter cell with high efficiency can be conveniently and stably obtained.
Description
Technical field
The invention belongs to technical field of solar cells, relate to a kind of manufacture method of crystalline silicon selective emitter solar battery, especially relate to a kind of implementation method of crystalline silicon solar battery selective emitter, be conducive to form perfect selective emitter.
Background technology
Along with an urgent demand to high-quality photovoltaic product of the day by day fierce and market of photovoltaic industry competition, the lifting efficiency of solar cell becomes the top priority of solar cell technological innovation.A kind of selective emitter technology that is derived from the conventional batteries technology is in the extensive attention that is subjected in the industry, and accomplishes scale production in the enterprise of part technological precedence, and produces good economic benefit and social benefit.
The core of selective emitter battery technology is the preparation of selective emitter.Compare with conventional emitter structure, selective emitter has the lightly doped characteristics of electrode zone heavy doping and effective light area.By this, reduce on the one hand Electrodes, to promote fill factor, curve factor; Reduce on the other hand the compound and emitter saturation current of emitter region, thereby improve open circuit voltage and short circuit current.
Nowadays, the method for preparing selective emitter has a lot, as the laser grooving mask method, and laser doping method, the chemical mask method of struggling against the corrosive influence, the printing nano-silicon method of the use of ink and water, printing phosphorus slurry method etc.But, these methods or exist the high-temperature process overlong time and cause substrate quality decline, the technical problem such as high energy laser is easily induced lattice damage, and the chemical corrosion uniformity is difficult to control, and the phosphorus source is volatile; Or there are technology transfer expense and the higher Cost Problems of auxiliary material price.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, propose a kind of implementation method of crystalline silicon selective emitter, be conducive to form perfect selective emitter, and do not need to pay high cost.
The technical scheme that the present invention takes for achieving the above object is:
A kind of implementation method of crystalline silicon selective emitter comprises: pre-deposition, removal need the lightly doped region phosphorosilicate glass layer and advance three steps, wherein:
Pre-deposition: under certain temperature conditions, at POCl
3, O
2And N
2In the atmosphere of mist, making, the p-type silicon chip surface of cleaning and texturing forms certain thickness phosphorosilicate glass layer and the low n of phosphorus content
+Type layer emitter;
Remove to need the lightly doped region phosphorosilicate glass layer: according to the selective emitting electrode structure design, by the method for chemical corrosion, need the phosphorosilicate glass layer of lightly doped region to remove with completing in the silicon chip of pre-deposition;
Advance: under higher temperature conditions, need the silicon chip of lightly doped region phosphorosilicate glass layer to be placed in N with removing
2Pure gas or O
2And N
2In the atmosphere of mist, remove the phosphorosilicate glass layer region in the situation that do not have the phosphorus source to replenish, carry out phosphorus atoms and distribute again, realize light dope; Keep the phosphorosilicate glass layer region take phosphorosilicate glass layer as the phosphorus source, proceed the diffusion of phosphorus atoms, realize heavy doping.
In described pre-deposition step, temperature conditions is 780 ~ 820 ℃, and the duration is 10 ~ 20min, takes source gas POCl by adjusting
3-N
2, reacting gas O
2Flow separately, the thickness that makes phosphorosilicate glass layer is 20 ~ 40nm, the surperficial phosphorus atoms concentration of emitter is 1 * 10
21~ 5 * 10
21/ cm
3, doping depth is 150nm ~ 250nm.
Described removal needs in lightly doped region phosphorosilicate glass layer step; chemical corrosion scheme one is: press selective emitting electrode structure design and printing or spraying and print one deck resist on the heavily doped region field surface; then silicon chip is placed in etchant solution a period of time; to not have the need lightly doped region phosphorosilicate glass layer of resist protection to remove by etchant solution, then with resist organic solution clean stripping.The resist main component that adopts is high molecular polymer.The organic solution that adopts is generally the alcohols solvents such as ethanol.The etchant solution that adopts only reacts with phosphorosilicate glass, and does not react with silicon substrate.
Described removal needs in lightly doped region phosphorosilicate glass layer step, chemical corrosion scheme two is: press selective emitting electrode structure design and printing or spraying and print the agent of one deck sour corrosion on the lightly doped region silicon chip surface, need remove by the lightly doped region phosphorosilicate glass layer by the sour corrosion agent, again silicon chip is placed in low concentration alkalescence cleaning solution a period of time, in order to corrosive agent is removed.The main component of the sour corrosion agent of adopting is phosphoric acid or ammonium acid fluoride.The sour corrosion agent of adopting only reacts with phosphorosilicate glass, and does not react with silicon substrate.
In described forward step, temperature conditions is 830 ~ 870 ℃, and the duration is 10 ~ 30min, and the surperficial phosphorus atoms concentration that forms lightly doped region is 5 * 10
19~ 2 * 10
20/ cm
3, doping depth is 300nm ~ 400nm; The surperficial phosphorus atoms concentration that forms heavily doped region is 4 * 10
20~ 6 * 10
20/ cm
3, doping depth is 500nm ~ 700nm.
As a kind of preferred, in described pre-deposition step, O
2With POCl
3-N
2Flow proportional be between 2 ~ 3:5.
As a kind of preferred, in described chemical corrosion scheme one, the etchant solution of employing is 1% ~ 5% low concentration HF solution, and etching time is 5 ~ 10min.
In the present invention, first pre-deposition is adopted in the making of crystalline silicon selective emitter, then removes the lightly doped region phosphorosilicate glass, the method that advances at last.Advantage of the present invention is:
The technology that forms selective emitting electrode structure from existing corrosion emitter is different, and the present invention only removes the phosphorosilicate glass layer of lightly doped region by chemical corrosion method, and emitter do not produced corrosion after pre-deposition is completed.The former easily causes that because of the inhomogeneous of corrosion emitter region is inhomogeneous, and the present invention can avoid the appearance of this problem.The former is easily wayward because of the change in concentration of etchant solution, and the present invention only need remove the lightly doped region phosphorosilicate glass fully, is easy to control.Therefore, the technology that proposes of the present invention is more stable realizes perfect selective emitter.In addition, the auxiliary material that comprises resist and corrosive agent that adopts is all conventional electronic industrial material, and cost is relatively low.
Description of drawings
Fig. 1 is the emitter phosphorus atoms doping curve after a kind of embodiment pre-deposition of the present invention.
Fig. 2 is the front surface structural representation after a kind of embodiment pre-deposition of the present invention, and in figure, 3 is the p-type silicon substrate, and 2 is n
+The type emitter, 1 is phosphorosilicate glass layer.
Fig. 3 is the front surface structural representation after a kind of embodiment of the present invention is removed the lightly doped region phosphorosilicate glass layer, and in figure, 3 is the p-type silicon substrate, and 2 is n
+The type emitter, the 4 phosphorosilicate glass zones for reservation.
Fig. 4 is the emitter phosphorus atoms doping curve after a kind of embodiment of the present invention advances.
Embodiment
Embodiment 1:
As shown in Figure 2,3 is the p-type silicon substrate, and 2 is n
+The type emitter, 1 is phosphorosilicate glass layer.P-type silicon substrate 3 in diffusion furnace tube, is warming up to 800 ℃ after conventional technique is carried out Wafer Cleaning, making herbs into wool, then pass into O
2And POCl
3-N
2, flow is respectively 500sccm and 1000sccm, continues pre-deposition 20min, obtains the n about 90 Ω/o
+Type emitter 2.Take 2.1mm as spacing, 0.2mm is width, sprays acidproof resist on silicon chip surface.Then silicon chip is placed in 5% HF solution, soaks 7min and remove with the need lightly doped region phosphorosilicate glass layer 1 that will there is no the resist protection, then with resist ethanolic solution clean stripping.Removal needs front surface structure such as the Fig. 3 after the lightly doped region phosphorosilicate glass layer, wherein the 4 phosphorosilicate glass zones for reservation.Silicon chip is after drying up, at the N of 830 ℃
2Protection advances 25min in atmosphere, completes the heavy doping that keeps the phosphorosilicate glass zone, completes simultaneously the light dope of removing the phosphorosilicate glass zone and distributes, forms selective emitter.The emitter phosphorus atoms doping curve of silicon chip after pre-deposition as shown in Figure 1; Emitter phosphorus atoms doping curve after propelling as shown in Figure 4.Follow-up successively by removing phosphorosilicate glass and edge isolation, deposition SiN
x: the techniques such as H deielectric-coating, electrode printing and sintering are completed the making of solar cell.
Embodiment 2:
As shown in Figure 2,3 is the p-type silicon substrate, and 2 is n
+The type emitter, 1 is phosphorosilicate glass layer.P-type silicon substrate 3 in diffusion furnace tube, is warming up to 810 ℃ after conventional technique is carried out Wafer Cleaning, making herbs into wool, then pass into O
2And POCl
3-N
2, flow is respectively 550sccm and 1000sccm, continues pre-deposition 15min, obtains the n about 100 Ω/o
+Type emitter 2.Take 0.25mm as spacing, 2.05mm is width, and the sour corrosion slurry of silk screen printing phosphoric acid is on silicon chip surface.Then silicon chip is placed in the drying oven of 350 ℃, drying time 90s is thoroughly removed the phosphorosilicate glass of corrosive slurry below by reaction.Subsequently, silicon chip is placed in the 0.1%NaOH solution of 40 ℃, ultrasonic cleaning 90s is to remove corrosive slurry.Removal needs front surface structure such as the Fig. 3 after the lightly doped region phosphorosilicate glass layer, wherein the 4 phosphorosilicate glass zones for reservation.Silicon chip is after drying up, at the N of 850 ℃
2Protection advances 20min in atmosphere, completes the heavy doping that keeps the phosphorosilicate glass zone, completes simultaneously the light dope of removing the phosphorosilicate glass zone and distributes, forms selective emitter.The emitter phosphorus atoms doping curve of silicon chip after pre-deposition as shown in Figure 1; Emitter phosphorus atoms doping curve after propelling as shown in Figure 4.Follow-up successively by removing phosphorosilicate glass and edge isolation, deposition SiN
x: the techniques such as H deielectric-coating, electrode printing and sintering are completed the making of solar cell.
Claims (9)
1. the implementation method of a crystalline silicon selective emitter, is characterized in that described method comprises pre-deposition, and removing needs the lightly doped region phosphorosilicate glass layer and advance three steps, wherein:
Pre-deposition: under certain temperature conditions, at POCl
3, O
2And N
2In the atmosphere of mist, making, the p-type silicon chip surface of cleaning and texturing forms certain thickness phosphorosilicate glass layer and the low n of phosphorus content
+Type layer emitter;
Remove to need the lightly doped region phosphorosilicate glass layer: according to the selective emitting electrode structure design, by the method for chemical corrosion, need the phosphorosilicate glass layer of lightly doped region to remove with completing in the silicon chip of pre-deposition;
Advance: under higher temperature conditions, need the silicon chip of lightly doped region phosphorosilicate glass layer to be placed in N with removing
2Pure gas or O
2And N
2In the atmosphere of mist, remove the phosphorosilicate glass layer region in the situation that do not have the phosphorus source to replenish, carry out phosphorus atoms and distribute again, realize light dope; Keep the phosphorosilicate glass layer region take phosphorosilicate glass layer as the phosphorus source, proceed the diffusion of phosphorus atoms, realize heavy doping.
2. the implementation method of a kind of crystalline silicon selective emitter according to claim 1, is characterized in that, in described pre-deposition step, temperature conditions is 780 ~ 820 ℃, and the duration is 10 ~ 20min, takes source gas POCl by adjusting
3-N
2, reacting gas O
2Flow separately, the thickness that makes phosphorosilicate glass layer is 20 ~ 40nm, the surperficial phosphorus atoms concentration of emitter is 1 * 10
21~ 5 * 10
21/ cm
3, doping depth is 150nm ~ 250nm.
3. the implementation method of a kind of crystalline silicon selective emitter according to claim 1; it is characterized in that; described removal needs in lightly doped region phosphorosilicate glass layer step; the chemical corrosion scheme can be: press selective emitting electrode structure design and printing or spraying and print one deck resist on the heavily doped region field surface; then silicon chip is placed in etchant solution a period of time; to not have the need lightly doped region phosphorosilicate glass layer of resist protection to remove by etchant solution, then with resist organic solution clean stripping.
4. the implementation method of a kind of crystalline silicon selective emitter according to claim 1, it is characterized in that, described removal needs in lightly doped region phosphorosilicate glass layer step, the method of chemical corrosion is: press selective emitting electrode structure design and printing or spraying and print the agent of one deck sour corrosion on the light doping section field surface, need remove by the lightly doped region phosphorosilicate glass layer by the sour corrosion agent, then corrosive agent is cleaned with low concentration alkalescence solution remove.
5. the implementation method of a kind of crystalline silicon selective emitter according to claim 1, is characterized in that, in described forward step, temperature conditions is 830 ~ 870 ℃, and the duration is 10 ~ 30min, and the surperficial phosphorus atoms concentration that forms lightly doped region is 5 * 10
19~ 2 * 10
20/ cm
3, doping depth is 300nm ~ 400nm; The surperficial phosphorus atoms concentration that forms heavily doped region is 4 * 10
20~ 6 * 10
20/ cm
3, doping depth is 500nm ~ 700nm.
6. the implementation method of a kind of crystalline silicon selective emitter according to claim 2, is characterized in that, described O
2With POCl
3-N
2Flow-rate ratio be 2 ~ 3:5.
7. the implementation method of a kind of crystalline silicon selective emitter according to claim 3, is characterized in that, described etchant solution only reacts with phosphorosilicate glass, and does not react with silicon substrate.
8. the implementation method of a kind of crystalline silicon selective emitter according to claim 3, is characterized in that, described etchant solution is 1% ~ 5% low concentration HF solution, and etching time is 5 ~ 10min.
9. the implementation method of a kind of crystalline silicon selective emitter according to claim 4, is characterized in that, described sour corrosion agent only reacts with phosphorosilicate glass, and does not react with silicon substrate.
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Cited By (7)
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| CN108258083A (en) * | 2018-01-19 | 2018-07-06 | 常州亿晶光电科技有限公司 | A kind of preparation process of silicon chip laser doping SE |
| CN109166794A (en) * | 2018-07-18 | 2019-01-08 | 常州大学 | A kind of multiple step format phosphorous doping methods of high efficiency, low cost crystal silicon battery |
| CN109888054A (en) * | 2019-01-16 | 2019-06-14 | 晶科能源科技（海宁）有限公司 | A kind of preparation method of the not damaged selective emitter of photovoltaic cell |
| CN111463322A (en) * | 2020-04-30 | 2020-07-28 | 常州时创能源股份有限公司 | P-type double-sided battery and preparation method thereof |
| CN111463323A (en) * | 2020-04-30 | 2020-07-28 | 常州时创能源股份有限公司 | P-type selective doping method |
| CN112599636A (en) * | 2020-12-07 | 2021-04-02 | 浙江晶科能源有限公司 | Preparation method of crystalline silicon solar cell and crystalline silicon solar cell |
| CN114497242A (en) * | 2021-06-01 | 2022-05-13 | 常州时创能源股份有限公司 | Preparation method and application of boron-doped selective emitter |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114497242A (en) * | 2021-06-01 | 2022-05-13 | 常州时创能源股份有限公司 | Preparation method and application of boron-doped selective emitter |
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Application publication date: 20130612 |