CN110010721B - SE-based alkali polishing high-efficiency PERC battery process - Google Patents

SE-based alkali polishing high-efficiency PERC battery process Download PDF

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CN110010721B
CN110010721B CN201910221252.XA CN201910221252A CN110010721B CN 110010721 B CN110010721 B CN 110010721B CN 201910221252 A CN201910221252 A CN 201910221252A CN 110010721 B CN110010721 B CN 110010721B
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alkali
polishing
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silicon wafer
liquid supplementing
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CN110010721A (en
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郑云龙
张玉前
庞三凤
苏世杰
陈世琴
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Tongwei Solar Anhui Co Ltd
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Tongwei Solar Hefei Co Ltd
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    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses an alkaline polishing high-efficiency PERC battery process based on SE, which comprises the following steps of: performing alkali polishing on the silicon wafer by adopting the optimized alkali polishing formula; and (3) adding an additive and an alkali solution supplement used for alkali polishing according to a step mode: in the 1 st to 15 th batches, the additive liquid supplementing amount is 200-; in 16-30 batches, the additive liquid supplementing amount is 400ml, the alkali liquid supplementing amount is 1150ml and the pure water liquid supplementing amount is 8-10L; in 31-60 th batch, the additive liquid supplementing amount is 500ml, the alkali liquid supplementing amount is 1300ml and the pure water liquid supplementing amount is 9-11L. The invention adopts the optimized alkali polishing formula, and adopts a stepped replenishment mode as the replenishment mode of the additive and the alkali replenishment solution, thereby effectively prolonging the service life of the liquid medicine in the alkali polishing tank, achieving the yield improvement, greatly reducing the consumption of the additive and the alkali, and breaking through the capacity bottleneck of the alkali polishing SE.

Description

SE-based alkali polishing high-efficiency PERC battery process
Technical Field
The invention relates to the technical field of photovoltaic solar cells, in particular to an SE-based alkali polishing high-efficiency PERC cell process.
Background
The PERC cell technology has obvious performance and cost advantages, and promotes the application of the P-type solar-grade monocrystalline silicon wafer. Meanwhile, the development of the crystalline silicon solar cell is mainstream in the aspects of high efficiency, low cost and environmental protection. The PERC cell mainly forms a passivation film on the back surface, so that the back surface is required to have good flatness, and the alkali polishing equipment is mainly researched to polish the back surface, so that the problem of flatness of a plated film on the back surface is solved, an N-type diffusion layer on the back surface can be removed, a P + layer is promoted to be formed, the minority carrier lifetime is prolonged, and the reflectivity of the back surface is increased. Therefore, the introduction of a polishing process integrated into the existing production process of the PERC cell is an effective means for further improving the efficiency of the PERC cell.
The alkaline polishing cell is concerned by the photovoltaic market with simple equipment and process, unique process flow and high cell efficiency. The laser doping (SE) has the advantages of strong controllability, simple process, small laser-induced damage to materials and the like, and is an ideal technical choice for preparing the high-efficiency crystalline silicon solar cell. The selective emitter structure is prepared in the silicon-based solar cell by utilizing the characteristics of selective melting and diffusion of a laser doping process. In the structure, light doping is carried out in the light absorption region, so that surface minority carrier Auger recombination is reduced, and short-wave spectral response is good; heavy doping is carried out on the metal contact region, so that good ohmic contact is formed between the metal electrode and the battery emission region, and the short-circuit current, the open-circuit voltage, the filling factor and the conversion efficiency are high.
Aiming at the alkali polishing technology and the SE technology, the obvious defects of the PERC battery technology in the prior art can be obtained: the existing alkali polishing additive and alkali replenishing liquid formula and use mode are characterized in that 1-30 batches of the original formula are respectively added with the same amount of additive and alkali replenishing liquid, 300ml of additive is added in each batch, 1050ml of alkali replenishing liquid is added, and 9L of pure water replenishing liquid is adopted.
Disclosure of Invention
The invention aims to provide an alkaline polishing high-efficiency PERC battery process based on SE, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a SE-based alkaline polishing high efficiency PERC cell process comprising the steps of:
step S01, texturing: texturing the surface of a monocrystalline silicon wafer to obtain a textured structure;
step S02, diffusion: introducing phosphorus oxychloride and a silicon wafer for reaction to realize diffusion and junction preparation;
step S03, SE process: the selective emitter is arranged on a lightly doped silicon substrate, and impurity atoms are selectively and heavily doped by micron-sized laser beams;
step S04, hot oxygen: a high-temperature thermal oxidation process is added after the SE process, and a silicon dioxide protective layer is produced and deposited on the surface of the silicon wafer;
step S05, remove PSG: etching and removing the PN junction at the edge through PSG;
step S06, alkali polishing: performing alkali polishing on the silicon wafer by adopting the optimized alkali polishing formula;
step S07, annealing: annealing the silicon wafer after alkali polishing, and producing a deposited silicon dioxide film layer on the surface of the silicon wafer;
step S08, back passivation: depositing an aluminum oxide passivation film layer on the back of the silicon wafer in an ALD or PECVD mode;
step S09, back film: growing and depositing a silicon nitride film on the back of the silicon wafer;
step S10, positive film: growing and depositing a silicon nitride film on the front surface of the silicon wafer;
step S11, laser grooving: performing laser grooving on the back of the coated silicon wafer;
step S12, printing and sintering: finishing back and front printing through screen printing, and then performing a sintering process;
step S13, electrical injection: passing through a light attenuation furnace or an electric injection furnace;
step S14, test sorting: finally, battery testing and grading are carried out on the battery pieces;
the optimized alkali polishing formula comprises three alkali polishing liquids, wherein one alkali polishing liquid comprises 200-350ml of additive replenishing liquid, 300-1000ml of alkali replenishing liquid and 7-9L of pure water replenishing liquid; the two solutions comprise 250-400ml additive solution, 850-1150ml alkali solution and 8-10L pure water solution; the third step comprises 300-500ml additive solution, 1000-1300ml alkali solution and 9-11L pure water solution;
in step S06, the optimized alkali polishing formula used for alkali polishing is supplemented according to a stepwise manner:
in the 1 st to 15 th batches, the additive liquid supplementing amount is 200-;
in 16-30 batches, the additive liquid supplementing amount is 400ml, the alkali liquid supplementing amount is 1150ml and the pure water liquid supplementing amount is 8-10L;
in 31-60 th batch, the additive liquid supplementing amount is 500ml, the alkali liquid supplementing amount is 1300ml and the pure water liquid supplementing amount is 9-11L.
Preferably, the alkali solution is potassium hydroxide solution.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the optimized alkali polishing formula, and adopts a stepped replenishment mode as the replenishment mode of the additive and the alkali replenishment solution, thereby effectively prolonging the service life of the liquid medicine in the alkali polishing tank, achieving the yield improvement, greatly reducing the consumption of the additive and the alkali, and breaking through the capacity bottleneck of the alkali polishing SE.
Drawings
FIG. 1 is a flow diagram of a conventional process of the prior art;
FIG. 2 is a process flow diagram of the preparation method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-2, the present invention provides a technical solution:
a SE-based alkaline polishing high efficiency PERC cell process comprising the steps of:
step S01, texturing: the monocrystalline silicon wafer is subjected to surface texturing to obtain a good textured structure, so that the specific surface area is increased, more photons (energy) can be received, the reflection of incident light is reduced, residual liquid during texturing is cleaned, and the influence of acidic and alkaline substances on battery junction making is reduced.
Step S02, diffusion: phosphorus atoms are obtained by the reaction of phosphorus oxychloride and the silicon wafer, and after a certain period of time, the phosphorus atoms enter the surface layer of the silicon wafer and permeate and diffuse into the silicon wafer through gaps among the silicon atoms to form an interface of an N-type semiconductor and a P-type semiconductor, thereby completing the process of diffusion and junction making and realizing the conversion from light energy to electric energy.
Step S03, SE process: the selective emitter is a heavily doped region of impurity atoms selectively carried out on a lightly doped silicon substrate by micron-sized laser beams, so that a shallow junction process with low surface concentration is effectively formed, and simultaneously, ohmic contact of a printed grid line region can be ensured.
Step S04, hot oxygen: in order to prevent the damage of alkali polishing to the texture of the SE region, a post-SE thermal oxidation process is added, the temperature of thermal oxidation is 500-800 ℃, the appearance is good and is not damaged when observed under a SE region microscope, the PERC + SE efficiency can reach more than 22%, and a silicon dioxide protective layer is formed on a heavily doped region.
Step S05, remove PSG: because the diffusion junction forms a short circuit channel at the edge of the silicon chip, photo-generated electrons collected by the front surface of the PN junction flow to the back surface of the PN junction along the region with phosphorus diffused at the edge, and short circuit is caused. The PN junction at the edge is removed by etching through PSG, so that short circuit caused by the edge is avoided. And then through the alkali polishing groove, the phosphorosilicate glass on the surface of the silicon wafer is removed, and the influence of the phosphorosilicate glass on the efficiency is reduced.
Step S06, alkali polishing: the PERC cell is mainly characterized in that an aluminum oxide passivation film layer 5 is prepared on the back surface, so that the back surface is required to have good flatness, and the current research mainly focuses on polishing the back surface, so that the problem of flatness of a plated film on the back surface is solved, an N-type diffusion layer on the back surface can be removed, a P + layer is promoted to be formed, the minority carrier lifetime is prolonged, and the reflectivity of the back surface is increased.
Therefore, the introduction of a KOH alkali polishing process into the conventional production process of the PERC cell is an effective means for further improving the efficiency of the PERC cell, and an additive and an alkali solution supplement used in alkali polishing are supplemented according to a step mode, wherein the additive is a Tuobang BP-170 reagent, and the alkali solution supplement is a potassium hydroxide solution:
the optimized alkali polishing formula comprises three alkali polishing liquids, wherein one alkali polishing liquid comprises 200-350ml of additive replenishing liquid, 300-1000ml of alkali replenishing liquid and 7-9L of pure water replenishing liquid; the two solutions comprise 250-400ml additive solution, 850-1150ml alkali solution and 8-10L pure water solution; the third step comprises 300-500ml additive solution, 1000-1300ml alkali solution and 9-11L pure water solution;
in batches 1 to 15, the additive fluid infusion amount is 200ml, the alkali fluid infusion amount is 300ml, and the pure water fluid infusion amount is 7L;
in 16 th to 30 th batches, the additive liquid supplementing amount is 250ml, the alkali liquid supplementing amount is 850ml, and the pure water liquid supplementing amount is 8L;
in 31 st to 60 th batches, the additive liquid supplementing amount is 300ml, the alkali liquid supplementing amount is 1000ml, and the pure water liquid supplementing amount is 9L.
Step S07, annealing: and (3) carrying out alkali polishing on the silicon wafer, and then annealing at 700 ℃, and producing a silicon dioxide layer on the surface of the cell through an oxygen high-temperature furnace.
Step S08, back passivation: and then laminating an aluminum oxide passivation film layer in an ALD or PECVD mode.
Step S09, back film: a silicon nitride film is laminated below the aluminum oxide passivation film layer, and the silicon nitride film on the back plays a role in protecting the aluminum oxide passivation film layer.
Step S10, positive film: the silicon nitride film on the front surface reduces reflection and passivation.
Step S11, laser grooving: and (4) laser grooving is carried out on the back of the coated silicon wafer.
Step S12, printing and sintering: and (4) finishing back and front printing by screen printing and then sintering.
Step S13, electrical injection: and the light attenuation of the battery cell is reduced through a light attenuation furnace or an electric injection furnace.
Step S14, test sorting: and finally, grading the battery test.
Comparative experiment:
comparison group: carrying out alkali polishing on the silicon wafer on the production line by adopting the liquid medicine of the original formula in the background technology;
experimental groups: carrying out alkali polishing on the silicon wafer on the production line by adopting the optimized formula liquid medicine;
the fluid infusion modes of the control group and the experimental group are shown in the following table 1:
Figure GDA0002621130240000061
TABLE 1
According to the data in the table 1, compared with the liquid supplementing mode of the original formula, the mode of adopting the optimized formula to carry out stepped liquid supplementing has the beneficial effects on different batches of silicon wafers on the production line: the production capacity of the whole liquid medicine period of the alkali polishing is improved from 10800 tablets to 22000 tablets, the liquid medicine period is improved from 30 batches to 60 batches, and the unit consumption of the additive is reduced from 18.5 liters/ten thousand tablets to 12.6 liters/ten thousand tablets.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (2)

1. A SE-based alkaline polishing high efficiency PERC cell process comprising the steps of:
step S01, texturing: texturing the surface of a monocrystalline silicon wafer to obtain a textured structure;
step S02, diffusion: introducing phosphorus oxychloride and a silicon wafer for reaction to realize diffusion and junction preparation;
step S03, SE process: the selective emitter is arranged on a lightly doped silicon substrate, and impurity atoms are selectively and heavily doped by micron-sized laser beams;
step S04, hot oxygen: a high-temperature thermal oxidation process is added after the SE process, and a silicon dioxide protective layer is produced and deposited on the surface of the silicon wafer;
step S05, remove PSG: etching and removing the PN junction at the edge through PSG;
step S06, alkali polishing: performing alkali polishing on the silicon wafer by adopting the optimized alkali polishing formula;
step S07, annealing: annealing the silicon wafer after alkali polishing, and producing a deposited silicon dioxide film layer on the surface of the silicon wafer;
step S08, back passivation: depositing an aluminum oxide passivation film layer on the back of the silicon wafer in an ALD or PECVD mode;
step S09, back film: growing and depositing a silicon nitride film on the back of the silicon wafer;
step S10, positive film: growing and depositing a silicon nitride film on the front surface of the silicon wafer;
step S11, laser grooving: performing laser grooving on the back of the coated silicon wafer;
step S12, printing and sintering: finishing back and front printing through screen printing, and then performing a sintering process;
step S13, electrical injection: passing through a light attenuation furnace or an electric injection furnace;
step S14, test sorting: finally, battery testing and grading are carried out on the battery pieces;
the method is characterized in that: the optimized alkali polishing formula comprises three alkali polishing liquids, wherein one alkali polishing liquid comprises 200-350ml of additive replenishing liquid, 300-1000ml of alkali replenishing liquid and 7-9L of pure water replenishing liquid; the two solutions comprise 250-400ml additive solution, 850-1150ml alkali solution and 8-10L pure water solution; the third step comprises 300-500ml additive solution, 1000-1300ml alkali solution and 9-11L pure water solution;
in step S06, the optimized alkali polishing formula used for alkali polishing is supplemented according to a stepwise manner:
in the 1 st to 15 th batches, the additive liquid supplementing amount is 200-;
in 16-30 batches, the additive liquid supplementing amount is 400ml, the alkali liquid supplementing amount is 1150ml and the pure water liquid supplementing amount is 8-10L;
in 31-60 th batch, the additive liquid supplementing amount is 500ml, the alkali liquid supplementing amount is 1300ml and the pure water liquid supplementing amount is 9-11L.
2. The SE-based alkaline polishing PERC cell process as claimed in claim 1, wherein: the alkali solution is potassium hydroxide solution.
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CN110176522A (en) * 2019-06-13 2019-08-27 常州时创能源科技有限公司 A kind of alkaline etching technique of SE solar battery
CN110459646A (en) * 2019-08-07 2019-11-15 山西潞安太阳能科技有限责任公司 A kind of novel process for throwing laser selective emitter suitable for alkali
CN110416368A (en) * 2019-08-21 2019-11-05 常州时创能源科技有限公司 A kind of production line of laser SE battery
CN110752271A (en) * 2019-09-26 2020-02-04 无锡琨圣科技有限公司 Processing method of PERC battery
CN110922970A (en) * 2019-11-29 2020-03-27 南京纳鑫新材料有限公司 PERC battery back polishing additive and technology
CN111403552B (en) * 2020-03-24 2022-07-22 浙江爱旭太阳能科技有限公司 Multi-light-source composite passivation method for reducing crystalline silicon solar cell attenuation
CN111584687A (en) * 2020-06-09 2020-08-25 山西潞安太阳能科技有限责任公司 Novel method for realizing LDSE (laser direct ion exchanger) by alkali throwing
CN115132876A (en) * 2021-03-22 2022-09-30 黄河水电西宁太阳能电力有限公司 Efficient PERC battery preparation process based on SE back alkali polishing
CN114032035B (en) * 2021-10-28 2022-06-07 常州时创能源股份有限公司 Additive for alkali polishing of silicon wafer and application thereof
CN115494887B (en) * 2022-11-16 2023-02-17 合肥新晶集成电路有限公司 Etching liquid supplementing method, etching liquid supplementing device and etching equipment

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