CN114122190B - Transformation method for realizing monocrystalline PERC (PERC) thermal oxidation process by normal pressure diffusion equipment - Google Patents
Transformation method for realizing monocrystalline PERC (PERC) thermal oxidation process by normal pressure diffusion equipment Download PDFInfo
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- CN114122190B CN114122190B CN202111197168.2A CN202111197168A CN114122190B CN 114122190 B CN114122190 B CN 114122190B CN 202111197168 A CN202111197168 A CN 202111197168A CN 114122190 B CN114122190 B CN 114122190B
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000009792 diffusion process Methods 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 title claims abstract description 18
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 title claims abstract description 18
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000011426 transformation method Methods 0.000 title claims description 4
- 239000010453 quartz Substances 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000004140 cleaning Methods 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000009423 ventilation Methods 0.000 claims abstract description 7
- 238000010926 purge Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical group OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 239000012495 reaction gas Substances 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 12
- 239000007789 gas Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000002161 passivation Methods 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a production process of solar cell single crystal PERC. A modification method for achieving single crystal PERC hot oxygen process using atmospheric pressure diffusion equipment, which involves disassembling, cleaning, and reinstalling all quartz devices inside the atmospheric pressure diffusion equipment, closing the POCL3 source pipeline, and blowing the furnace tube, quartz boat, and ventilation pipeline; reducing the exhaust pressure value to 0.3-0.5mbar; the exhaust pressure is reduced to 0.3-0.5mbar from 1.1-1.5 mbar used in the diffusion process, the concentration of the effective components of the reaction gas in the furnace tube is improved, the quartz boat loads the cleaned silicon wafer (dummy wafer) after the silicon wafer is damaged, and the operation is repeatedly performed for more than 30 times according to the normal thermal oxidation process.
Description
Technical Field
The invention relates to a production process of solar cell single crystal PERC.
Background
The manufacturing process of the polycrystalline solar cell is almost the same as that of the monocrystalline silicon solar cell, but the photoelectric conversion efficiency of the polycrystalline solar cell is reduced by about 17-18%. Therefore, the polycrystalline solar cell production line can be modified into a single-crystal PERC solar cell production line when needed.
When the production line of the polycrystalline solar cell is required to be upgraded to the production line of the monocrystalline PERC solar cell, the monocrystalline PERC hot oxygen process can be carried out by using the original polycrystalline normal pressure diffusion equipment, and batch production is realized.
The thermal oxidation process of the single crystal PERC battery is that O is carried out under the high temperature condition 2 React with silicon atoms on the surface of the silicon wafer to form SiO 2 This layer of SiO 2 The film can reduce the surface recombination rate of minority carriers and the interface state density of the surface of the silicon wafer, thereby playing a passivation role and realizing solar energy electricityAnd improving the electrical performance of the cell. The low-pressure thermal oxidation process is mainly adopted in the thermal oxidation process used in the current monocrystalline PERC production line, namely O is introduced under the condition of vacuumizing in a furnace tube 2 And N 2 The process is carried out and equipment dedicated to the thermal oxygen process is used. The diffusion furnace body used in the technology is originally used for a polycrystalline diffusion process, a large amount of phosphorus-containing impurities are contained in the furnace body, on quartz boats and paddles, and phosphorus-containing oxides generated during a high-temperature hot-oxidation process can influence a front junction area, so that the influence of phosphorus-containing compounds needs to be thoroughly removed. Meanwhile, the process is debugged and optimized, the film forming uniformity of the hot oxygen process is improved under the normal pressure process condition, and the passivation effect of the normal pressure hot oxygen process is improved.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: how to realize the transformation of the normal pressure diffusion equipment of the existing production line of the polycrystalline solar cells to adapt to the single crystal PERC hot oxygen process.
The technical scheme adopted by the invention is as follows: a transformation method for realizing a monocrystalline PERC thermal oxidation process by normal pressure diffusion equipment comprises the following steps of
Step one, disassembling and cleaning all quartz devices in normal pressure diffusion equipment;
step two, closing POCL 3 The source pipeline is used for disassembling and cleaning a main air inlet pipeline and an air exhaust hose of the diffusion furnace body at the tail of the furnace and cleaning the silicon carbide paddle;
step three, all the components removed by the normal pressure diffusion equipment are installed, and POCL 3 The source pipeline is kept closed all the time, and the furnace tube, the quartz boat and the ventilation pipeline are purged;
step four, reducing the exhaust pressure value to 0.3-0.5mBar; the exhaust pressure is reduced to 0.3-0.5mBar from 1.1-1.5 mBar used in the diffusion process, and the concentration of the effective components of the reaction gas in the furnace tube is improved.
And fifthly, repeatedly operating the cleaned silicon wafer (dummy wafer) after the silicon wafer is damaged by the quartz boat according to a normal thermal oxidation process for more than 30 times, and cleaning the cleaned silicon wafer again by using an HF solution after 2 times of thermal oxidation process operation to optimize the stability of the furnace tube.
The quartz device in the first step comprises a quartz furnace tube, a quartz boat, a thermowell, a tail gas tube in the furnace, a quartz clamping ring and a condensation bottle.
The cleaning in the first step means cleaning with HF solution with concentration of 3-5% for 4-6 h. And removing residues such as metaphosphoric acid and the like on the quartz device.
The washing in the second step means washing with pure water and alcohol.
In the third step, the furnace tube, the quartz boat and N 2 、O 2 Purging the ventilation pipeline, and repeating the purging for more than three times, wherein each purging is performed at 700-900 ℃ with N 2 The flow is set to be 20-30slm, the purging is carried out for 20-40min, and then O is carried out 2 The flow rate is set to be 2000-2900sccm, N 2 The flow is set to be 2-6slm, and the purging is performed for more than 120 min.
The beneficial effects of the invention are as follows: the patent achieves the advantages of being superior to ozone (O) through the transformation and process debugging of the polycrystal normal pressure diffusion equipment 3 ) The passivation effect of the thermal oxidation process of the oxidation process realizes the batch production of the monocrystalline PERC thermal oxidation process.
Detailed Description
Because single crystals are produced at present with higher profits than polycrystal, solar cell manufacturers are required to modify part of the polycrystal solar production line into single crystal solar production line.
This embodiment only involves adapting the multicrystalline cell diffusion equipment to the single crystal cell thermal oxidation process.
The concrete transformation process is as follows
1. The method comprises the steps of disassembling additional components such as a quartz furnace tube, a quartz boat, a thermowell, an in-furnace tail gas tube, a quartz clasp, a condensation bottle and the like in polycrystalline battery diffusion equipment to be modified, then placing the components in a quartz tube cleaning tank, cleaning the components with HF solution with the concentration of 3-5%, and obtaining metaphosphoric acid (HPO) on a quartz piece 3 ) And cleaning the residues for 4-6 hours.
2. Turning off POCL 3 The through source pipeline (which is required to be thoroughly closed and can be closed by welding or locking after disassembly) is used for leading the diffusion furnace body at the tail of the furnaceThe air pipeline and the exhaust hose are disassembled (can be disassembled as far as possible), and are cleaned by pure water and alcohol in sequence. The silicon carbide paddle is dipped with pure water and alcohol in sequence by using dust-free cloth to wipe. Care was taken not to use HF solution for cleaning to prevent leakage after dissolution of the vessel wall.
3. Reinstalling cleaned and naturally dried quartz devices such as quartz furnace tubes, and cleaning the furnace tubes, quartz boat and N 2 、O 2 The ventilation pipeline is purged for more than three times. The specific process comprises the following steps: at 700-900 deg.C, N 2 The flow is set to be 20-30slm, the purging time is 20-40min, and then O is added 2 The flow rate is set to be 2000-2900sccm, N 2 The flow is set to be 2-6slm, and the purging time is more than 120 min; the process can remove residual metaphosphoric acid and water vapor on the quartz piece through high temperature on one hand, and can clean the ventilation pipeline and the furnace tube through ventilation and pumping. The purging process is important and subsequent purging failure can result in a large number of off-grade products.
4. Because the normal pressure furnace tube is not provided with a vacuum pump, the process is pumped and discharged through a furnace tail exhaust pipeline during operation, and N is introduced into the normal pressure diffusion process 2 Excessive amount of HPO 3 The byproducts are more, and the pumping pressure of the exhaust air is about 1.1 to 1.5. The quartz boat used by the equipment of the embodiment has the loading capacity of 500 sheets/boat, the flow of nitrogen and oxygen introduced in the normal pressure thermal oxygen process deposition step is smaller, and N is smaller 2 And O 2 The total flow of the water is 4 to 5slm. In order to maintain the air flow balance and ensure the concentration of the effective components in the furnace tube, the pumping pressure of the exhaust air is required to be greatly reduced (an exhaust pump of an exhaust pipeline can be used), and the exhaust pressure value is reduced to be 0.3-0.5 mBar. Additional installation of a vacuum pump is avoided by reducing the exhaust pressure value.
POCL after modification 3 The air inlet pipeline of the source is closed, and O is still reserved 2 And N 2 Pipeline, tail gas in the furnace is led into the condensation bottle through the tail gas pipe of the furnace mouth, and is pumped and discharged through the exhaust pipe connected with the condensation bottle, if the pumping and discharging pressure is too high, the effective concentration of the process gas is insufficient, so that the pumping and discharging pressure needs to be reduced, and the effective gas concentration in the furnace tube is improved (the exhaust pressure value is reducedThis value is important, from 0.3 to 0.5 mBar).
5. Loading cleaned silicon wafer (hot oxygen and waste silicon wafer of the previous process section of hot oxygen) on a saturated quartz boat (which means that the purging process meets the requirement), cleaning an oxide layer and impurities on the surface of the silicon wafer by using HF solution, repeatedly operating for more than 30 times by using the production process, and carrying out HPO in the quartz tube 3 The residual substances are attached to the silicon wafer and carried away, and the silicon wafer after each 2 times of hot oxygen process operation is cleaned again by using HF solution.
Hydrophilicity is an important index for measuring film forming uniformity of a thermal oxidation process, and the testing method comprises the following steps: sucking pure water with a suction tube, dripping a drop of pure water onto the surface of the silicon wafer, and diffusing the water drop for more than 20cm within 15s to obtain the hydrophilic SiO 2 And the film forming property is qualified. Under the same production process, after the exhaust pressure of the furnace tube is reduced, the hydrophilicity of the modified process is effectively improved, and SiO is effectively improved 2 The film formation uniformity of (3) is effectively improved.
As can be seen from the table above, after a series of debugging, the film forming property of the hot oxygen process is improved, the efficiency gain is realized, the efficiency is 0.03% higher than that of the ozone process in the production line, and the open circuit voltage is obviously improved by 3mV. The hot oxygen process produces a good passivation effect, the ozone equipment is randomly deactivated, the hot oxygen process is started and mass production is performed.
Comparison of electrical properties of batteries produced by furnace tubes with different operation times
Technological tests are carried out on the furnace tubes debugged by the hot oxygen machine No. 5 and the hot oxygen machine No. 6, and the electric performance of each furnace tube is shown in the table. From the above electrical property data, the average efficiency of the battery is about 0.22% higher than the efficiency of the production process in which the silicon wafer is washed and then operated for more than 30 times. It can be seen that the more the number of times of operation of the thermal oxygen furnace tube is, the more thoroughly impurities in the furnace tube are taken away, the more stable the furnace tube operation state is, and the more excellent the electrical performance of the produced single crystal PERC battery is.
By cleaning the quartz devices in the furnace tube with HF solution, most of the phosphorus-containing impurities are removed. The high-temperature treatment of the furnace tube and the quartz boat further eliminates the phosphorus impurities, so that the production process is not affected. By reducing the exhaust pressure of the furnace tube, the air flow pressure balance of the furnace tube is regulated, the effective concentration of the process gas is increased, and the hydrophilicity is greatly improved. The influence of impurities is thoroughly removed through repeated process circulation of the dummy wafer, the process stability of the furnace tube is improved, and the electrical performance of the battery is effectively improved.
Claims (2)
1. A transformation method for realizing a monocrystalline PERC thermal oxidation process by normal pressure diffusion equipment is characterized by comprising the following steps of: the method comprises the following steps of
Step one, disassembling and cleaning all quartz devices in normal pressure diffusion equipment; the cleaning is to clean the quartz device for 4-6 hours by using an HF solution with the concentration of 3-5% to remove metaphosphoric acid residues on the quartz device;
step two, closing POCL 3 The source pipeline is used for disassembling and cleaning a main air inlet pipeline and an air exhaust hose of the diffusion furnace body at the tail of the furnace and cleaning the silicon carbide paddle; the cleaning herein means cleaning with pure water and alcohol;
step three, all components of normal pressure diffusion and equipment dismantling are installed, and POCL is adopted 3 The through source pipeline is always kept closed, and the furnace tube, the quartz boat and N are all closed 2 、O 2 Purging the ventilation pipeline, and repeating the purging for more than three times, wherein each purging is performed at 700-900 ℃ with N 2 The flow rate is set to be 20-30slm, the purging is carried out for 20-40min, and then O is carried out 2 The flow rate is set to 2000-2900sccm, N 2 The flow is set to be 2-6slm, and the purging is performed for more than 120min
Step four, reducing the exhaust pressure value to 0.3-0.5mBar;
and fifthly, repeatedly operating the cleaned silicon wafer after the silicon wafer is damaged by the quartz boat according to a normal thermal oxidation process for more than 30 times, and cleaning the silicon wafer again by using an HF solution after 2 times of operation of the thermal oxidation process to optimize the stability of the furnace tube.
2. The method for modifying a single crystal PERC thermal oxidation process by using an atmospheric diffusion device according to claim 1, wherein the method comprises the following steps: the quartz device in the first step comprises a quartz furnace tube, a quartz boat, a thermowell, a tail gas tube in the furnace, a quartz clamping ring and a condensation bottle.
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| CN202111197168.2A CN114122190B (en) | 2021-10-14 | 2021-10-14 | Transformation method for realizing monocrystalline PERC (PERC) thermal oxidation process by normal pressure diffusion equipment |
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