WO2023179021A1 - 一种浅结扩散发射极的晶硅太阳能电池的制备方法及其应用 - Google Patents

一种浅结扩散发射极的晶硅太阳能电池的制备方法及其应用 Download PDF

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WO2023179021A1
WO2023179021A1 PCT/CN2022/128187 CN2022128187W WO2023179021A1 WO 2023179021 A1 WO2023179021 A1 WO 2023179021A1 CN 2022128187 W CN2022128187 W CN 2022128187W WO 2023179021 A1 WO2023179021 A1 WO 2023179021A1
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temperature
diffusion
sccm
low
flow rate
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PCT/CN2022/128187
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English (en)
French (fr)
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任勇
何悦
任海亮
郭帅
王在发
李增彪
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横店集团东磁股份有限公司
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Priority to EP22933072.5A priority Critical patent/EP4386874A1/en
Publication of WO2023179021A1 publication Critical patent/WO2023179021A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/223—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a gaseous phase
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • 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
    • 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 Table
    • 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

Definitions

  • the present application relates to the field of photovoltaics, to the field of crystalline silicon solar cell manufacturing, and in particular to a preparation method and application of a crystalline silicon solar cell with a shallow junction diffused emitter.
  • Non-renewable energy is gradually depleting and global warming is becoming increasingly serious. It has become a global consensus to establish an energy system dominated by renewable energy and achieve green and sustainable development. At present, more than 130 countries and regions around the world have successively announced "carbon neutrality" goals, and some countries have adopted legislation to clarify "carbon neutrality" responsibilities to effectively respond to the crises and challenges brought about by climate change. At present, the penetration rate of global renewable energy is still at a low level, and there is broad room for development. Among them, photovoltaic power generation has obvious economic advantages. The cost of electricity is lower than that of coal power and will continue to decline in the future. Its development potential cannot be underestimated.
  • the junction depth of the diffused emitter is basically around 0.2um ⁇ 0.3um, and the absorption loss for short waves is obvious; and if you want to If a diffusion shallow junction of 0.1um to 0.2um is prepared through the traditional diffusion process, the diffusion resistance will be very high and the surface concentration will be low. This can easily cause problems with the alloy ohmic contact in the screen process, leading to the failure of solar cells.
  • the photoelectric conversion efficiency fails; therefore, it is very difficult to obtain a diffused shallow junction through the current traditional solar manufacturing process.
  • CN103943719A discloses a method for controlling the phosphorus doping concentration by using pre-oxidation combined with a low-temperature-high-temperature-low temperature variable temperature diffusion method.
  • the method includes pre-oxidation and a three-step temperature variable diffusion process of low temperature-high temperature-low temperature. The process is performed by changing the temperature.
  • Optimizing the gradient can accurately control the phosphorus doping concentration gradient, obtain good PN junction and sheet resistance uniformity, and improve the conversion efficiency of solar cells.
  • This invention mainly explains how to optimize and adjust the diffusion process, focusing on the temperature-changing diffusion method.
  • the method of controlling the phosphorus doping concentration is only limited to the optimization of a single diffusion process, and only achieves the optimization of the diffusion distribution of the ECV curve.
  • CN105280484A discloses a diffusion process for crystalline silicon high-efficiency and high-sheet resistance cells, which mainly includes the following steps: (1) entering the furnace; (2) low-temperature oxidation; (3) low-temperature gas reaction deposition; (4) heating up impurities and then Distribution; (5) high-temperature gas reaction deposition; (6) cooling impurity redistribution; (7) low-temperature gas reaction deposition; (8) low-temperature impurity redistribution; (9) release. Similar to CN103943719A, it only optimizes a single diffusion process, and the solar photoelectric conversion efficiency needs further improvement and breakthrough.
  • CN204905275U discloses a device based on a chain oxidation method to improve the resistance of solar cells to PID effects. It mainly includes: an ozone generator, a compressed air delivery pipe and a mixer; the ozone outlet of the ozone generator is connected to the mixer through an ozone delivery pipe.
  • the compressed air is connected to the mixer through the compressed air delivery pipe, and the mixer is connected to the mixed gas output end through the mixed gas delivery pipe.
  • the output end of the mixer is connected to the air inlet of the uniform flow plate; the uniform flow plate is hollow and has an air inlet at one end.
  • the flow uniformity plate is installed above the silicon wafer transfer track between the etching device and the PECVD device of the cell production equipment, with the air outlets facing the silicon wafer transfer track; ozone generator A device to control ozone production is installed on it.
  • This utility model can quickly grow a silicon oxide film on the surface of the silicon wafer before depositing the silicon nitride film, thereby improving the resistance of the photovoltaic cell to the PID effect and extending its service life.
  • this patent idea only considers the reliability of solar cells and does not improve the photoelectric conversion efficiency of solar cells under high temperature.
  • the purpose of this application is to provide a preparation method and application of a crystalline silicon solar cell with a shallow junction diffused emitter.
  • One of the purposes of this application is to provide a method for preparing a crystalline silicon solar cell with a shallow junction diffused emitter.
  • the preparation method includes a diffusion process and a chain oxidation process.
  • the diffusion process includes low-temperature diffusion and high-temperature advancement, and the chain oxidation process includes high-temperature chain oxidation.
  • this application analyzes the influencing factors: temperature, time, flow, formula, etc., and clarifies the key factors that change the ECV curve of the diffusion process, including surface concentration, emitter junction depth, co-error distribution and Gaussian distribution of doping distribution curve; secondly, through the principle understanding of high-temperature chain oxidation, and the impact on surface doping was explored during the experiment; finally, combined with the photovoltaic power generation principle of solar crystalline silicon cells, a creative application was made to combine the diffusion process and chain The oxygen process is combined to prepare a diffused emitter junction of about 0.15um, and achieves good ohmic alloy contact under high surface doping concentration, improves short-wave spectral absorption, and improves the photoelectric conversion efficiency of solar cells.
  • This application first prepares a low-doped diffusion shallow junction with a depth of 0.15um through the optimization of the diffusion process. At the same time, the photon thermal activation radiant energy of high-temperature chain oxidation is used to form a certain dose concentration of doping on the surface of the diffusion layer to solve the problem. The subsequent mismatch problem of alloy ohmic contact with silver paste is formed. Finally, a higher photoelectric conversion efficiency was achieved.
  • the diffusion process includes sequentially carrying out boat entry, first temperature rise, first constant temperature, vacuum stabilization, vacuum leak detection, oxidation, first low-temperature diffusion source, second low-temperature diffusion source, Second temperature rise, second constant temperature, high temperature advancement, first cooling, supplementary diffusion, purge, PSG deposition reaction, oxidation reaction, second cooling, nitrogen filling and boat release.
  • the low-temperature diffusion includes diffusing a constant source at a certain temperature.
  • the constant source is phosphorus oxychloride.
  • the low temperature diffusion includes a first low temperature diffusion source and a second low temperature diffusion source.
  • the temperature of the first low-temperature diffusion source is 770-790°C, where the temperature can be 770°C, 772°C, 774°C, 776°C, 778°C, 780°C, 782°C, 784°C, 786°C, 788°C or 790°C, etc., but are not limited to the listed values, other unlisted values within this range are also applicable.
  • the time of the first low-temperature diffusion source is 220 to 260s, where the time can be 220s, 225s, 230s, 235s, 240s, 245s, 250s, 255s or 260s, etc., but is not limited to those listed Value, other unlisted values within this value range are also applicable.
  • the small nitrogen flow rate of the first low-temperature diffusion source is 1000-1100 sccm, where the small nitrogen flow rate can be 1000 sccm, 1020 sccm, 1040 sccm, 1060 sccm, 1080 sccm or 1100 sccm, etc., but is not limited to the listed values, Other values within this range that are not listed are also applicable.
  • the oxygen flow rate of the first low-temperature diffusion source is 450-550 sccm, wherein the oxygen flow rate can be 450 sccm, 460 sccm, 470 sccm, 480 sccm, 490 sccm, 500 sccm, 510 sccm, 520 sccm, 530 sccm, 540 sccm or 550 sccm, etc., However, it is not limited to the listed values, and other unlisted values within this range of values are also applicable.
  • the maximum nitrogen flow rate of the first low-temperature diffusion source is 0 sccm.
  • the furnace tube pressure of the first low-temperature diffusion source is 50-60mbar, wherein the furnace tube pressure can be 50mbar, 51mbar, 52mbar, 53mbar, 54mbar, 55mbar, 56mbar, 57mbar, 58mbar, 59mbar or 60mbar etc., but not limited to the listed values, other unlisted values within this range are also applicable.
  • the temperature of the second low-temperature diffusion source is 790-810°C, where the temperature can be 790°C, 792°C, 794°C, 796°C, 798°C, 800°C, 802°C, 804°C, 806°C, 808°C or 810°C, etc., but are not limited to the listed values, other unlisted values within this range are also applicable.
  • the time of the second low-temperature diffusion source is 190 to 230s, where the time can be 190s, 195s, 200s, 205s, 210s, 215s, 220s, 225s or 230s, etc., but is not limited to those listed Value, other unlisted values within this value range are also applicable.
  • the small nitrogen flow rate of the second low temperature diffusion source is 1100-1200 sccm, where the small nitrogen flow rate can be 1100 sccm, 1120 sccm, 1140 sccm, 1160 sccm, 1180 sccm or 1200 sccm, etc., but is not limited to the listed values, Other values within this range that are not listed are also applicable.
  • the oxygen flow rate of the second low-temperature diffusion source is 550-650 sccm, wherein the oxygen flow rate can be 550 sccm, 560 sccm, 570 sccm, 580 sccm, 590 sccm, 600 sccm, 610 sccm, 620 sccm, 630 sccm, 640 sccm or 650 sccm, etc., However, it is not limited to the listed values, and other unlisted values within this range of values are also applicable.
  • the maximum nitrogen flow rate of the second low-temperature diffusion source is 0 sccm.
  • the furnace tube pressure of the second low-temperature diffusion source is 50-60mbar, where the furnace tube pressure can be 50mbar, 52mbar, 54mbar, 56mbar, 58mbar or 60mbar, etc., but is not limited to the listed values. Other values within this range that are not listed are also applicable.
  • a constant source amount (phosphorus oxychloride) is introduced at about 800°C, that is, constant source diffusion.
  • the diffusion distribution curve at this time satisfies the residual error distribution.
  • the high-temperature pushing includes pushing the phosphorus source on the surface of crystalline silicon into the silicon matrix at high temperature.
  • the high-temperature advancement time is 350 to 370s, where the time can be 350s, 352s, 354s, 356s, 358s, 360s, 362s, 364s, 366s, 368s or 370s, etc., but is not limited to the listed ones. Value, other unlisted values within this value range are also applicable.
  • the temperature of the high-temperature propulsion is 800-900°C, where the temperature can be 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, 860°C, 870°C, 880°C, 890°C °C or 900 °C, etc., but are not limited to the listed values, and other unlisted values within this numerical range are also applicable.
  • the small nitrogen flow rate of high-temperature propulsion is 750-850 sccm, wherein the small nitrogen flow rate can be 750 sccm, 760 sccm, 770 sccm, 780 sccm, 790 sccm, 800 sccm, 810 sccm, 820 sccm, 830 sccm, 840 sccm or 850 sccm, etc., but not only Limited to the listed values, other unlisted values within this range are also applicable.
  • the oxygen flow rate for high-temperature propulsion is 0 sccm.
  • the large nitrogen flow rate of the high-temperature propulsion is 950-1050 sccm, wherein the large nitrogen flow rate can be 950 sccm, 960 sccm, 970 sccm, 980 sccm, 990 sccm, 1000 sccm, 1010 sccm, 1020 sccm, 1030 sccm, 1040 sccm or 1050 sccm, etc., but not only Limited to the listed values, other unlisted values within this range are also applicable.
  • the furnace tube pressure of the high-temperature propulsion is 50-60mbar, wherein the furnace tube pressure can be 50mbar, 51mbar, 52mbar, 53mbar, 54mbar, 55mbar, 56mbar, 57mbar, 58mbar, 59mbar or 60mbar, etc., but not only Limited to the listed values, other unlisted values within this range are also applicable.
  • the temperature starts to rise to about 850°C, and high-temperature advancement with a fixed doping source amount is carried out under certain conditions, that is, constant source diffusion.
  • the diffusion distribution curve at this time satisfies the Gaussian distribution.
  • the temperature of the PSG deposition reaction is 700-800°C, where the temperature can be 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C , 780°C, 790°C or 800°C, etc., but are not limited to the listed values, and other unlisted values within this numerical range are also applicable.
  • the time of the PSG deposition reaction is 700 to 800s, where the time can be 700s, 710s, 720s, 730s, 740s, 750s, 760s, 770s, 780s, 790s or 800s, etc., but is not limited to those listed value, other unlisted values within this value range are also applicable.
  • phosphorus oxychloride is introduced into the PSG deposition reaction.
  • the small nitrogen flow rate of the PSG deposition reaction is 1250-1350 sccm, wherein the small nitrogen flow rate can be 1250 sccm, 1260 sccm, 1270 sccm, 1280 sccm, 1290 sccm, 1300 sccm, 1310 sccm, 1320 sccm, 1330 sccm, 1340 sccm or 1350 sccm, etc. , but Not limited to the listed values, other unlisted values within this range are also applicable.
  • the oxygen flow rate of the PSG deposition reaction is 550-650 sccm, wherein the oxygen flow rate can be 550 sccm, 560 sccm, 570 sccm, 580 sccm, 590 sccm, 600 sccm, 610 sccm, 620 sccm, 630 sccm, 640 sccm or 650 sccm, etc., but is not limited to For the listed values, other unlisted values within the range are also applicable.
  • the maximum nitrogen flow rate of the PSG deposition reaction is 0 sccm.
  • the furnace tube pressure of the PSG deposition reaction is 55-65mbar, wherein the furnace tube pressure can be 55mbar, 56mbar, 57mbar, 58mbar, 59mbar, 60mbar, 61mbar, 62mbar, 63mbar, 64mbar or 65mbar, etc., but Not limited to the listed values, other unlisted values within this range are also applicable.
  • the furnace tube is evacuated.
  • the purge flow rate is 450 to 550 sccm, wherein the flow rate can be 450 sccm, 460 sccm, 470 sccm, 480 sccm, 490 sccm, 500 sccm, or 510 sccm , 520sccm, 530sccm, 540sccm or 550sccm, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
  • all gases are closed to keep the pressure of the furnace tube at 50-60mbar, where the pressure can be 50mbar, 51mbar, 52mbar, 53mbar, 54mbar, 55mbar, 56mbar, 57mbar, 58mbar , 59mbar or 60mbar, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
  • the oxidation includes protecting the growth of a silicon oxide layer on the surface of the crystalline silicon wafer.
  • the cut-off temperature of the second temperature rise is 830-870°C, where the cut-off temperature can be 830°C, 835°C, 840°C, 845°C, 850°C, 855°C, 860°C, 865°C or 870°C, etc., but are not limited to the listed values, and other unlisted values within this numerical range are also applicable.
  • nitrogen gas is passed through the second temperature rise to remove residual phosphorus oxychloride.
  • the maximum nitrogen flow rate in the second heating is 950 to 1050 sccm, wherein the maximum nitrogen flow rate can be 950 sccm, 960 sccm, 970 sccm, 980 sccm, 990 sccm, 1000 sccm, 1010 sccm, 1020 sccm, 1030 sccm, 1040 sccm or 1050 sccm, etc., but Not limited to the listed values, other unlisted values within this range are also applicable.
  • oxygen is introduced into the second constant temperature for further reaction of residual phosphorus oxychloride.
  • the oxygen flow rate in the second constant temperature is 550-650 sccm, wherein the oxygen flow rate can be 550 sccm, 560 sccm, 570 sccm, 580 sccm, 590 sccm, 600 sccm, 610 sccm, 620 sccm, 630 sccm, 640 sccm or 650 sccm, etc., but is not limited to For the listed values, other unlisted values within the range are also applicable.
  • the temperature of the first cooling is 750-810°C, where the temperature can be 750°C, 760°C, 770°C, 780°C, 790°C, 800°C or 810°C, etc., but Not limited to the listed values, other unlisted values within this range are also applicable.
  • the first cooling is used as the set temperature for supplementary diffusion.
  • the supplementary diffusion is used to repair defects of low doping in local areas of the crystalline silicon wafer caused by high-temperature advancement.
  • the purge removes residual phosphorus oxychloride in the furnace tube.
  • the oxidation reaction removes phosphorus oxychloride introduced in the PSG deposition reaction.
  • the second temperature reduction is used to repair lattice dislocation of the crystalline silicon wafer.
  • the nitrogen filling is used to restore the normal pressure state of the furnace tube.
  • the chain oxidation process includes high-temperature chain oxidation.
  • the temperature of the high-temperature chain oxidation is 660-670°C, where the temperature can be 660°C, 662°C, 664°C, 666°C, 668°C or 670°C, but is not limited to the listed values. , other unlisted values within this value range are also applicable.
  • the time of the high-temperature chain oxidation is 1 to 5 min, where the time may be 1 min, 2 min, 3 min, 4 min or 5 min, etc., but is not limited to the listed values, and other unlisted values outside the range of this value The same applies to numerical values.
  • the oxygen flow rate of the high-temperature chain oxidation is 95 to 105 slm, wherein the oxygen flow rate can be 95 slm, 96 slm, 97 slm, 98 slm, 99 slm, 100 slm, 101 slm, 102 slm, 103 slm, 104 slm or 105 slm, etc., but not only Limited to the listed values, other unlisted values within this range are also applicable.
  • the nitrogen flow rate of the high-temperature chain oxidation is 5 to 15slm, wherein the nitrogen flow rate can be 5slm, 6slm, 7slm, 8slm, 9slm, 10slm, 11slm, 12slm, 13slm, 14slm or 15slm, etc., but not only Limited to the listed values, other unlisted values within this range are also applicable.
  • This application prepares the diffusion curve doping distribution of this application by controlling the amount of low-temperature diffusion source and the high-temperature advancement time.
  • the surface doping concentration of the diffusion curve is low, which will cause the failure of the subsequent alloy ohmic contact. Therefore, High-temperature chain oxidation needs to be introduced to activate surface doping.
  • the high-temperature chain oxidation furnace is a heat treatment method with a very fast heating rate and a short holding time.
  • the heating rate can reach 10 to 100 degrees Celsius per second.
  • infrared halogen lamps are used for heating.
  • the current and power are very large during heating.
  • tungsten halogen lamp a large number of high-energy electrons are emitted.
  • the high-energy electrons bombard the silicon wafer, the irradiated electrons interact with the crystal lattice, destroying the position of the atoms in the crystal lattice, causing the atoms to have a displacement effect and forming holes and gaps.
  • Atom pairs; at the same time, phosphorus diffusion has two types: interstitial diffusion and substitution diffusion.
  • the bombardment of high-energy electrons reduces the difficulty of phosphorus diffusion.
  • the chain oxygen equipment uses a tungsten halogen lamp infrared lamp for heating.
  • the diffusion enhancement mechanism is triggered, resulting in the redistribution of the phosphorus source.
  • the preparation method includes in sequence:
  • Texturing process the diffusion process, laser doping process, the chain oxidation process, PSG removal process, alkali back polishing process, annealing process, ALD passivation process, front PECVD process, back PECVD process, laser grooving process , screen printing process and electric injection process.
  • the second object of the present application is to provide an application of a method for preparing a crystalline silicon solar cell with a shallow junction diffused emitter as described in the first object, and the preparation method is applied in the photovoltaic field.
  • the conversion rate of the solar cell prepared by this application is 0.1% higher than that of conventional solar cells.
  • Figure 1 is an ECV curve diagram of phosphorus diffusion impurity distribution in a specific embodiment of the present application.
  • Figure 2 is an ECV curve diagram of diffusion impurity distribution under two conditions in the specific embodiment of the present application.
  • Figure 3 is a structural diagram of a chain oxidation furnace in a specific embodiment of the present application.
  • Figure 4 is a high-temperature chain oxidation doping curve diagram (with/without PSG layer) in a specific embodiment of the present application.
  • FIG. 5 is a process flow diagram of a solar cell in a specific embodiment of the present application.
  • Figure 6 is a doping distribution curve diagram in a specific embodiment of the present application.
  • Figure 7 is a QE quantum efficiency diagram of Example 1 and Comparative Example 1 of the present application.
  • Figure 8 is an ECV doping concentration distribution curve diagram of Example 1 and Comparative Example 1 of the present application.
  • the present application provides a method for preparing a crystalline silicon solar cell with a shallow junction diffused emitter.
  • the preparation method includes a diffusion process and a chain oxidation process.
  • the diffusion process includes low-temperature diffusion and high-temperature advancement, and the chain oxidation process includes high-temperature chain oxidation.
  • the influencing factors are analyzed: temperature, time, flow rate, formula, etc., and the key factors that change the ECV curve of the diffusion process are clarified, including surface concentration, emitter junction depth, residual error distribution and Gaussian distribution of doping.
  • This application first prepares a low-doped diffusion shallow junction with a depth of 0.15um through the optimization of the diffusion process. At the same time, the photon thermal activation radiant energy of high-temperature chain oxidation is used to form a certain dose concentration of doping on the surface of the diffusion layer to solve the problem. The subsequent mismatch problem of alloy ohmic contact with silver paste is formed. Finally, a higher photoelectric conversion efficiency was achieved.
  • the diffusion process includes sequentially carrying out boat entry, first temperature increase, first constant temperature, vacuum stabilization, vacuum leak detection, oxidation, first low temperature diffusion source, second low temperature diffusion source, second temperature increase, and third temperature increase. 2. Constant temperature, high temperature advancement, first cooling, supplementary diffusion, purging, PSG deposition reaction, oxidation reaction, second cooling, nitrogen filling and boat release.
  • the low-temperature diffusion includes diffusing a constant source at a certain temperature.
  • the constant source is phosphorus oxychloride.
  • the low-temperature diffusion includes a first low-temperature diffusion source and a second low-temperature diffusion source.
  • the temperature of the first low-temperature diffusion source is 770-790°C.
  • the first low-temperature diffusion time is 220 to 260 seconds.
  • the small nitrogen flow rate of the first low-temperature diffusion source is 1000-1100 sccm.
  • the oxygen flow rate of the first low-temperature diffusion source is 450 to 550 sccm.
  • the maximum nitrogen flow rate of the first low-temperature diffusion source is 0 sccm.
  • furnace tube pressure of the first low-temperature diffusion source is 50-60 mbar.
  • the temperature of the second low-temperature diffusion source is 790 ⁇ 810°C.
  • the second low-temperature diffusion time is 190 to 230 seconds.
  • the small nitrogen flow rate of the second low-temperature diffusion source is 1100-1200 sccm.
  • the oxygen flow rate of the second low-temperature diffusion source is 550-650 sccm.
  • the maximum nitrogen flow rate of the second low-temperature diffusion source is 0 sccm.
  • furnace tube pressure of the second low-temperature diffusion source is 50-60 mbar.
  • a constant source amount (phosphorus oxychloride) is introduced at the temperature defined in this application, that is, constant source diffusion.
  • the diffusion distribution curve at this time satisfies the residual error distribution.
  • the impurity distribution curve of phosphorus diffusion doping is composed of low-temperature diffusion (co-error distribution) and high-temperature push (Gaussian distribution).
  • the impurity distribution curve of phosphorus diffusion doping is shown in Figure 1.
  • I in the figure is PSG layer doping. On the one hand, it promotes SE laser doping.
  • high-temperature chain thermal oxidation and thermal photon radiation can activate doping; II is surface layer doping.
  • high-concentration doping will cause dead layers caused by lattice mismatch and reduce short-wave response.
  • low-concentration doping will affect the ohmic contact conduction of subsequent meshes; III is junction conduction.
  • the deep curve on the one hand, affects the ohmic contact of the slurry; on the other hand, it is related to the photo-induced absorption.
  • the high-temperature pushing includes pushing the phosphorus source on the surface of the crystalline silicon into the silicon matrix at high temperature.
  • the high-temperature advancement time is 350 to 370 seconds.
  • the temperature of the high-temperature advancement is 800-900°C.
  • the small nitrogen flow rate for high-temperature propulsion is 750 to 850 sccm.
  • oxygen flow rate for high-temperature propulsion is 0 sccm.
  • the large nitrogen flow rate for high-temperature propulsion is 950 to 1050 sccm.
  • furnace tube pressure for high-temperature advancement is 50 to 60 mbar.
  • the temperature of the PSG deposition reaction is 700-800°C.
  • the PSG deposition reaction time is 700-800 s.
  • the small nitrogen flow rate of the PSG deposition reaction is 1250-1350 sccm.
  • oxygen flow rate of the PSG deposition reaction is 550-650 sccm.
  • the maximum nitrogen flow rate of the PSG deposition reaction is 0 sccm.
  • furnace tube pressure of the PSG deposition reaction is 55-65 mbar.
  • This application has prepared the diffusion curve doping distribution of this application by controlling the amount of low-temperature diffusion source and the high-temperature advancement time. As shown in Figure 2, it can be seen that this application has obtained the preparation of a shallow emitter of about 0.15um. But at the same time, the surface doping concentration of this diffusion curve is low, which will lead to the failure of subsequent alloy ohmic contacts. Therefore, high-temperature chain oxidation must be introduced to activate surface doping.
  • the chain oxidation process includes entering the oxidation chamber, high-temperature chain oxidation and exiting the oxidation chamber.
  • the temperature of the high-temperature chain oxidation is 660-670°C.
  • the high-temperature chain oxidation time is 1 to 5 minutes.
  • the oxygen flow rate of the high-temperature chain oxidation is 95 to 105 slm.
  • the nitrogen gas flow rate for the high-temperature chain oxidation is 5 to 15 slm.
  • This application uses chain alumina as shown in Figure 3 for heating.
  • the current is very large and the power is very high.
  • the tungsten halogen lamp a large number of high-energy electrons are emitted.
  • the high-energy electrons bombard the silicon wafer, the irradiated electrons interact with the crystal lattice, destroying the position of the atoms in the crystal lattice, causing the atoms to have a displacement effect and forming holes and gaps.
  • Atom pairs; at the same time, phosphorus diffusion has two types: interstitial diffusion and substitution diffusion.
  • the bombardment of high-energy electrons reduces the difficulty of phosphorus diffusion.
  • the chain oxygen equipment uses a tungsten halogen lamp infrared lamp for heating. When there is a constant source on the surface of the silicon wafer, the diffusion enhancement mechanism is triggered, resulting in the redistribution of the phosphorus source.
  • the PSG doped layer in Figure 1-I is a surface phosphorus-activated doping source under chain oxidation conditions. If the PSG layer is retained and the PSG layer is removed through chain oxidation, the surface concentration will change. Different changes, as shown in Figure 4, retain the PSG layer and remove the PSG layer.
  • the ECV doping curve test after high-temperature chain oxidation shows different surface doping concentrations, while retaining the high-temperature chain oxidation of the PSG layer. The final doping curve is the key factor in our quest to solve the alloy ohmic contact affected by surface layer doping.
  • preparation method includes as shown in Figure 5 in sequence:
  • Texturing process the diffusion process, laser doping process, the chain oxidation process, PSG removal process, alkali back polishing process, annealing process, ALD passivation process, front PECVD process, back PECVD process, laser grooving process , screen printing process and electric injection process.
  • the preparation method includes in sequence according to the process sequence, as shown in Figure 5:
  • Texturing process Texturing process, diffusion process, laser doping process, chain oxidation process, PSG removal process, alkali back polishing process, annealing process, ALD passivation process, front PECVD process, back PECVD process, laser grooving process, screen printing process and electro-injection process.
  • the diffusion process includes the following steps:
  • Vacuum leak detection check whether the furnace tube has cracks or poor sealing, which will cause the vacuum pressure to rise and fluctuate.
  • the time is set to 60s, the temperature is set to 770°C, all gas inlets are closed, and the furnace tube pressure Set to 55mbar;
  • the first phosphorus oxychloride diffusion doping reaction is carried out at a temperature of 775°C.
  • the time is set to 240s, the temperature is set to 775°C, and the small nitrogen flow rate is set to 1050sccm ( Phosphorus oxychloride is on), the oxygen flow is set to 500sccm, the maximum nitrogen flow is 0, and the furnace tube pressure is set to 55mbar;
  • the second low-temperature diffusion pass adjust the temperature to 795°C, and perform the second phosphorus oxychloride diffusion doping reaction.
  • the purpose is to activate the doping phosphorus source in the oxide layer through temperature-changing diffusion to make the diffusion reaction more efficient.
  • the time is set to 210s
  • the temperature is set to 795°C
  • the small nitrogen flow is set to 1150sccm (phosphorus oxychloride is turned on)
  • the oxygen flow is set to 600sccm
  • the large nitrogen flow is set to 0, and the furnace tube pressure is set to 55mbar ;
  • the second temperature rise is the process of raising the temperature from 795°C to 850°C in order to complete the subsequent high-temperature doping propulsion reaction.
  • a large amount of nitrogen gas is introduced to carry away part of the residual phosphorus oxychloride to avoid safety risks.
  • Time Set to 300s, the temperature to 850°C, the small nitrogen flow rate to 800 sccm (phosphorus oxychloride is off), the oxygen flow rate to 0 sccm, the large nitrogen flow rate to 1000 sccm, and the furnace tube pressure to 55 mbar;
  • the second constant temperature After the temperature rises to the set temperature, the constant temperature needs to be stabilized for a period of time. At the same time, a certain amount of oxygen is introduced to react the residual phosphorus oxychloride to avoid safety risks.
  • the time is set to 240s, and the temperature Set at 850°C, the small nitrogen flow is set to 500sccm (phosphorus oxychloride is turned off), the oxygen flow is set to 600sccm, the large nitrogen flow is set to 500sccm, and the furnace tube pressure is set to 55mbar;
  • the temperature is reduced to about 800°C.
  • the time is set to 1380s, the temperature is set to 790°C, and the small nitrogen flow rate is set to 800sccm (phosphorus oxychloride is turned off).
  • the oxygen flow rate is set to 0 sccm, the maximum nitrogen flow rate is 1000 sccm, and the furnace tube pressure is set to 55 mbar;
  • the cooling in this step is to set the temperature to a very low value.
  • the purpose is to allow the crystalline silicon wafer to undergo a temperature change process after completion of diffusion. This process will promote the displacement of the crystal lattice. It will repair part of the lattice dislocation caused by high-temperature diffusion and further improve the quality of the diffusion reflector.
  • the time is set to 360s, the temperature is set to 700°C, the small nitrogen flow is set to 1000sccm (phosphorus oxychloride is turned off), and the oxygen
  • the flow rate is set to 0 sccm, the large nitrogen flow rate is 0 sccm, and the furnace tube pressure is set to 60 mbar;
  • the chain oxidation process includes the following steps:
  • the conveyor belt speed is set to 3.8m/min
  • the infrared halogen lamp temperature is set to 665°C
  • the oxygen flow rate is 100slm
  • the nitrogen flow rate is 10slm
  • the silicon wafers that have completed high-temperature chain oxidation activation are arranged as a whole to the unloading end through the conveyor belt, waiting to be sent into the carrier box;
  • step (8) in the diffusion process is replaced with: a first low-temperature diffusion source, and the first phosphorus oxychloride diffusion doping reaction is performed at a temperature of 770°C.
  • the time is set to 260s and the temperature is set to 770°C, the small nitrogen flow is set to 1000sccm (phosphorus oxychloride is on), the oxygen flow is set to 450sccm, the large nitrogen flow is 0, and the furnace tube pressure is set to 50mbar;
  • step (9) in the diffusion process with: a second low-temperature diffusion pass, adjust the temperature to 790°C, and perform a second phosphorus oxychloride diffusion doping reaction.
  • the purpose is to activate the doping in the oxide layer through temperature-changing diffusion. Mixed phosphorus source makes the diffusion reaction more uniform.
  • the time is set to 230s, the temperature is set to 790°C, the small nitrogen flow is set to 1100sccm (phosphorus oxychloride is turned on), the oxygen flow is set to 550sccm, and the large nitrogen flow is 0 , the furnace tube pressure is set to 50mbar;
  • step (12) in the diffusion process with: high-temperature advancement. After reaching the set high temperature and ensuring that there is no reaction gas in the furnace tube, perform doping advancement work at high temperature to move the phosphorus source on the surface of the crystalline silicon into the silicon matrix. Advancement, the time and temperature of this step are both critical, directly affecting the junction depth of the diffusion emitter. The time is set to 370s, the temperature is set to 800°C, the small nitrogen flow is set to 750sccm (phosphorus oxychloride is turned off), and the oxygen The flow rate is set to 0 sccm, the maximum nitrogen flow rate is 950 sccm, and the furnace tube pressure is set to 50 mbar;
  • step (16) in the diffusion process with: PSG deposition reaction.
  • the function of this step is to provide sufficient phosphorus source for the subsequent laser local doping.
  • the time is set to 800s, the temperature is set to 700°C, the small nitrogen flow is set to 1250sccm (phosphorus oxychloride is turned on), the oxygen flow is set to 550sccm, and the maximum The nitrogen flow rate is 0 sccm, and the furnace tube pressure is set to 55 mbar;
  • step (3) in the chain oxidation process with: entering the high-temperature oxidation furnace cavity, the conveyor belt speed is set to 3.8m/min, the infrared halogen lamp temperature is set to 660°C, the oxygen flow rate is 95slm, and the nitrogen flow rate is 5slm.
  • step (8) in the diffusion process is replaced with: a first low-temperature diffusion source, and the first phosphorus oxychloride diffusion doping reaction is performed at a temperature of 790°C.
  • the time is set to 220s and the temperature is set to 790°C, the small nitrogen flow is set to 1100sccm (phosphorus oxychloride is on), the oxygen flow is set to 550sccm, the large nitrogen flow is 0, and the furnace tube pressure is set to 60mbar;
  • step (9) in the diffusion process with: a second low-temperature diffusion pass, adjust the temperature to 810°C, and perform a second phosphorus oxychloride diffusion doping reaction.
  • the purpose is to activate the doping in the oxide layer through temperature-changing diffusion. Mixed phosphorus source makes the diffusion reaction more uniform.
  • the time is set to 190s, the temperature is set to 1200°C, the small nitrogen flow is set to 650sccm (phosphorus oxychloride is turned on), the oxygen flow is set to 650sccm, and the large nitrogen flow is 0 , the furnace tube pressure is set to 60mbar;
  • step (12) in the diffusion process with: high-temperature advancement. After reaching the set high temperature and ensuring that there is no reaction gas in the furnace tube, perform doping advancement at high temperature to move the phosphorus source on the surface of the crystalline silicon into the silicon matrix. Advancement, the time and temperature of this step are both critical, directly affecting the junction depth of the diffusion emitter. The time is set to 350s, the temperature is set to 900°C, the small nitrogen flow is set to 850sccm (phosphorus oxychloride is turned off), and the oxygen The flow rate is set to 0 sccm, the maximum nitrogen flow rate is 1050 sccm, and the furnace tube pressure is set to 60 mbar;
  • step (16) in the diffusion process with: PSG deposition reaction.
  • the function of this step is to provide sufficient phosphorus source for the subsequent laser local doping.
  • the time is set to 700s, the temperature is set to 800°C, the small nitrogen flow is set to 1350sccm (phosphorus oxychloride is turned on), the oxygen flow is set to 650sccm, and the large The nitrogen flow rate is 0 sccm, and the furnace tube pressure is set to 65 mbar;
  • step (3) in the chain oxidation process with: entering the high-temperature oxidation furnace cavity, the conveyor belt speed is set to 3.8m/min, the infrared halogen lamp temperature is set to 670°C, the oxygen flow rate is 105slm, and the nitrogen flow rate is 15slm.
  • the other conditions are the same as those in Embodiment 1 except that the temperature of the first low-temperature diffusion source in step (8) of the diffusion process is replaced by 700°C.
  • the other conditions are the same as those in Embodiment 1 except that the temperature in the high-temperature advancement in step (12) of the diffusion process is set to 950°C.
  • Example 1 the other conditions are the same as in Example 1 except that the temperature of the infrared halogen lamp in the high-temperature chain oxidation process is set from 665°C to 700°C.
  • Example 1 Several batch productions were carried out in Example 1 and Comparative Example 1 of the present application, and the results are shown in Table 1:
  • Example 1 and Comparative Example 1 in this application are shown in Figure 6, the quantum efficiency QE curve is shown in Figure 7, and the ECV (electrochemical corrosion) doping concentration distribution curve is shown in Figure 8.
  • Figure 7 Quantum efficiency QE curve, it can be clearly found that the short-wave spectral response at 300nm ⁇ 500nm, Example 1 is obviously higher than Comparative Example 1. From Figure 8, it can be known that the junction depth of Example 1 of the present application is 0.15um , the surface concentration is 1.0 ⁇ 10 21 cm -3 , both better than Comparative Example 1.
  • Example 1 0.0013 0.020 0.04 0.09
  • Example 2 0.0010 0.0130 0.16 0.101
  • Example 3 0.0011 0.0300 0.07 0.109
  • Example 4 -0.0007 -0.0099 0.00 -0.040
  • Example 5 -0.0004 -0.0250 0.00 -0.056
  • Example 6 -0.0004 -0.0100 -0.06 -0.047
  • Example 7 -0.0007 -0.0181 -0.08 -0.077
  • Example 8 -0.0010 -0.0230 0.02 -0.067
  • Comparative example 2 -0.0024 -0.0199 -0.16 -0.158
  • Comparative example 3 -0.0035 -0.0399 -0.10 -0.212
  • Example 4 replaces the first low-temperature diffusion source temperature with a lower temperature
  • Example 5 The high temperature in the diffusion process increases the temperature.
  • Example 6 further increases the temperature in the high-temperature chain oxidation process.
  • Example 7 removes the second low-temperature diffusion source.
  • the conversion efficiency decreased.
  • Comparative Example 1 the chain oxidation was replaced by high-temperature tubular oxidation.
  • Comparative Example 2 the high-temperature advancement process step was removed.
  • Comparative Example 3 the high-temperature chain oxidation was replaced by normal-temperature chain oxidation. It can be observed that the performance of the solar cell The light conversion efficiency further decreases.

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Abstract

本申请提供一种浅结扩散发射极的晶硅太阳能电池的制备方法及其应用。所述制备方法包括扩散工艺和链式氧化工艺；所述扩散工艺包括低温扩散和高温推进，所述链式氧化工艺包括高温链式氧化。本申请首先通过扩散工艺的优化，制备了0.15um深的低掺杂扩散浅结，同时，利用高温链式氧化的光子热激活辐射能，在扩散层表面形成一定剂量浓度的掺杂，来解决后续与银浆形成合金欧姆接触的失配问题，最终获得了较高的光电转换效率提升。

Description

一种浅结扩散发射极的晶硅太阳能电池的制备方法及其应用 技术领域
本申请涉及光伏领域，涉及晶硅太阳能电池制造领域，尤其涉及一种浅结扩散发射极的晶硅太阳能电池的制备方法及其应用。
背景技术
非可再生能源逐渐枯竭，全球变暖日益严重，建立以可再生能源为主的能源系统，实现绿色可持续发展已成为全球共识。目前，全球已有130多个国家和地区相继宣布“碳中和”目标，部分国家更是采取立法形式明确“碳中和”责任，以有效应对气候变化带来的危机和挑战。目前，全球可再生能源渗透率仍处于低位，具有广阔发展空间，其中，光伏发电经济优势明显，度电成本已低于煤电，未来还将不断下降，发展潜力不容小觑。
在此基础上，提高太阳能电池的光电转换效率变的尤为重要；目前传统的高效电池，扩散发射极的结深，基本都在0.2um～0.3um左右，对于短波的吸收损失较明显；而想通过传统的扩散工艺方式，制备0.1um～0.2um的扩散浅结，扩散方阻会非常高，表面浓度会较低，这样非常容易引起，丝网工序的合金欧姆接触出现问题，导致太阳能电池的光电转换效率失效；因此，想通过目前传统的太阳能制造工艺获得扩散浅结，难度是非常大的。
CN103943719A公开了一种采用预氧结合低温一高温一低温的变温扩散方式对磷掺杂浓度进行控制的方法，该方法包含预氧化与低温一高温一低温三步变温扩散过程，该工艺通过对温度梯度进行优化，能精确控制磷掺杂浓度梯度，获得良好的PN结以及方阻均匀性，提高太阳能电池的转换效率，该发明主要阐述了如何通过扩散工艺的优化调整，重点说明了变温扩散方式对磷掺杂浓度进 行控制的方法，但是仅局限在扩散单个工序优化，并仅实现了ECV曲线的扩散分布优化。
CN105280484A公开了一种晶硅高效高方阻电池片的扩散工艺，其内容主要包括如下步骤：(1)进炉；(2)低温氧化；(3)低温气体反应沉积；(4)升温杂质再分布；(5)高温气体反应沉积；(6)降温杂质再分布；(7)低温气体反应沉积；(8)低温杂质再分布；(9)出炉。与CN103943719A相同仅仅是在扩散单个工序上进行优化，太阳能光电转换效率需要进一步改善突破。
CN204905275U公开了一种基于链式氧化法提升太阳电池抗PID效应的装置，其内容主要包括：臭氧发生器、压缩空气输送管道和混合器；臭氧发生器的臭氧出口通过臭氧输送管道连接混合器，压缩空气通过压缩空气输送管道连接混合器，混合器通过混合气输送管道连接混和气输出端混合器输出端连接在匀流板的进气口；匀流板内为空心，其一端开有进气口，下端壁上均匀开有多个出气孔；匀流板安装在电池片制作设备的刻蚀装置和PECVD装置之间的硅片传输轨道上方，出气孔正对硅片传输轨道；臭氧发生器上安装有控制臭氧产：生量的装置。该实用新型能够在沉积氮化硅薄膜之前于硅片表面迅速生长氧化硅薄膜，提升光伏电池抗PID效应，延长其使用寿命。但是该专利思路仅仅是考虑了太阳能电池的使用可靠性，并未从高温方式下改善提高太阳能电池的光电转换效率。
目前传统的太阳能电池光电转换效率已经接近瓶颈，如何通过工艺细节的进一步优化或者改善突破，成为技术工程师们日思夜想的一道道难题，我们需要寻找新的突破点。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的 保护范围。
本申请的目的在于提供一种浅结扩散发射极的晶硅太阳能电池的制备方法及其应用。
为达到此申请目的，本申请采用以下技术方案：
本申请的目的之一在于提供一种浅结扩散发射极的晶硅太阳能电池的制备方法，所述制备方法包括扩散工艺和链式氧化工艺。
所述扩散工艺包括低温扩散和高温推进，所述链式氧化工艺包括高温链式氧化。
本申请通过扩散工艺的DOE实验，分析影响因子：温度、时间、流量、配方等，明确改变扩散工艺ECV曲线的关键因子，包括表面浓度、发射极结深、余误差分布和高斯分布的掺杂分布曲线；其次，通过对高温链式氧化的原理性理解，以及实验过程中摸索出对表面掺杂的影响；最后，结合太阳能晶硅电池的光伏发电原理，创造性的申请出将扩散工艺和链氧工艺结合在一起，制备出了0.15um左右的扩散发射极结，并且实现了高表面掺杂浓度下，良好的欧姆合金接触，提高短波光谱吸收，提升了太阳能电池的光电转换效率。
本申请首先通过扩散工艺的优化，制备了0.15um深的低掺杂扩散浅结，同时，利用高温链式氧化的光子热激活辐射能，在扩散层表面形成一定剂量浓度的掺杂，来解决后续与银浆形成合金欧姆接触的失配问题。最终，获得了较高的光电转换效率提升。
作为本申请优选的技术方案，所述扩散工艺包括依次进行的进舟、第一升温、第一恒温、真空稳定、真空检漏、氧化、第一低温扩散通源、第二低温扩散通源、第二升温、第二恒温、高温推进、第一降温、补充扩散、吹扫、PSG沉积反应、氧化反应、第二降温、充氮气和出舟。
可选地，所述低温扩散包括在一定温度下进行扩散恒定源。
可选地，所述恒定源为三氯氧磷。
可选地，所述低温扩散包括第一低温扩散通源和第二低温扩散通源。
可选地，所述第一低温扩散通源的温度为770～790℃，其中所述温度可以是770℃、772℃、774℃、776℃、778℃、780℃、782℃、784℃、786℃、788℃或790℃等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第一低温扩散通源的时间为220～260s，其中所述时间可以是220s、225s、230s、235s、240s、245s、250s、255s或260s等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第一低温扩散通源的小氮流量为1000～1100sccm，其中所述小氮流量可以是1000sccm、1020sccm、1040sccm、1060sccm、1080sccm或1100sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第一低温扩散通源的氧气流量为450～550sccm，其中所述氧气流量可以是450sccm、460sccm、470sccm、480sccm、490sccm、500sccm、510sccm、520sccm、530sccm、540sccm或550sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第一低温扩散通源的大氮流量为0sccm。
可选地，所述第一低温扩散通源的炉管压力为50～60mbar，其中所述炉管压力可以是50mbar、51mbar、52mbar、53mbar、54mbar、55mbar、56mbar、57mbar、58mbar、59mbar或60mbar等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第二低温扩散通源的温度为790～810℃，其中所述温度可以是790℃、792℃、794℃、796℃、798℃、800℃、802℃、804℃、806℃、808℃或810℃等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第二低温扩散通源的时间为190～230s，其中所述时间可以是190s、195s、200s、205s、210s、215s、220s、225s或230s等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第二低温扩散通源的小氮流量为1100～1200sccm，其中所述小氮流量可以是1100sccm、1120sccm、1140sccm、1160sccm、1180sccm或1200sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第二低温扩散通源的氧气流量为550～650sccm，其中所述氧气流量可以是550sccm、560sccm、570sccm、580sccm、590sccm、600sccm、610sccm、620sccm、630sccm、640sccm或650sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第二低温扩散通源的大氮流量为0sccm。
可选地，所述第二低温扩散通源的炉管压力为50～60mbar，其中所述炉管压力可以是50mbar、52mbar、54mbar、56mbar、58mbar或60mbar等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请在低温扩散时，在800℃左右通入恒定的源量(三氯氧磷)，即恒定源扩散，这时的扩散分布曲线，满足余误差分布。
作为本申请优选的技术方案，所述高温推进包括高温下将晶硅表面的磷源向硅基体内推进。
可选地，所述高温推进的时间为350～370s，其中所述时间可以是350s、352s、354s、356s、358s、360s、362s、364s、366s、368s或370s等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述高温推进的温度为800～900℃，其中所述温度可以是800℃、810℃、820℃、830℃、840℃、850℃、860℃、870℃、880℃、890℃或900℃等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述高温推进的小氮流量为750～850sccm，其中所述小氮流量可以是750sccm、760sccm、770sccm、780sccm、790sccm、800sccm、810sccm、820sccm、830sccm、840sccm或850sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述高温推进的氧气流量为0sccm。
可选地，所述高温推进的大氮流量为950～1050sccm，其中所述大氮流量可以是950sccm、960sccm、970sccm、980sccm、990sccm、1000sccm、1010sccm、1020sccm、1030sccm、1040sccm或1050sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述高温推进的炉管压力为50～60mbar，其中所述炉管压力可以是50mbar、51mbar、52mbar、53mbar、54mbar、55mbar、56mbar、57mbar、58mbar、59mbar或60mbar等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请停止通入源量后开始升温至850℃左右，进行一定条件下，固定掺杂源量的高温推进，即恒量源扩散，这时的扩散分布曲线，满足高斯分布。
作为本申请优选的技术方案，所述PSG沉积反应的温度为700～800℃，其中所述温度可以是700℃、710℃、720℃、730℃、740℃、750℃、760℃、770℃、 780℃、790℃或800℃等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述PSG沉积反应的时间为700～800s，其中所述时间可以是700s、710s、720s、730s、740s、750s、760s、770s、780s、790s或800s等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述PSG沉积反应中通入三氯氧磷。
可选地，所述PSG沉积反应的小氮流量为1250～1350sccm，其中所述小氮流量可以是1250sccm、1260sccm、1270sccm、1280sccm、1290sccm、1300sccm、1310sccm、1320sccm、1330sccm、1340sccm或1350sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述PSG沉积反应的氧气流量为550～650sccm，其中所述氧气流量可以是550sccm、560sccm、570sccm、580sccm、590sccm、600sccm、610sccm、620sccm、630sccm、640sccm或650sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述PSG沉积反应的大氮流量为0sccm。
可选地，所述PSG沉积反应的炉管压力为55～65mbar，其中所述炉管压力可以是55mbar、56mbar、57mbar、58mbar、59mbar、60mbar、61mbar、62mbar、63mbar、64mbar或65mbar等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
作为本申请优选的技术方案，所述第一升温和第一恒温中，对炉管进行抽真空处理。
可选地，所述第一恒温时通入小氮对管道进行吹扫，所述吹扫的流量为450～550sccm，其中所述流量可以是450sccm、460sccm、470sccm、480sccm、 490sccm、500sccm、510sccm、520sccm、530sccm、540sccm或550sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述真空稳定中压力稳定后关闭所有气体通入保持炉管的压力为50～60mbar，其中所述压力可以是50mbar、51mbar、52mbar、53mbar、54mbar、55mbar、56mbar、57mbar、58mbar、59mbar或60mbar等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述氧化包括在晶硅片表面进行一层氧化硅层的生长保护。
作为本申请优选的技术方案，所述第二升温的截至温度为830～870℃，其中所述截至温度可以是830℃、835℃、840℃、845℃、850℃、855℃、860℃、865℃或870℃等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第二升温中通入氮气用于去除残余的三氯氧磷。
可选地，所述第二升温中大氮流量为950～1050sccm，其中所述大氮流量可以是950sccm、960sccm、970sccm、980sccm、990sccm、1000sccm、1010sccm、1020sccm、1030sccm、1040sccm或1050sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述第二恒温中通入氧气用于进一步反应残余的三氯氧磷。
可选地，所述第二恒温中氧气流量为550～650sccm，其中所述氧气流量可以是550sccm、560sccm、570sccm、580sccm、590sccm、600sccm、610sccm、620sccm、630sccm、640sccm或650sccm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
作为本申请优选的技术方案，所述第一降温的温度为750～810℃，其中所述温度可以是750℃、760℃、770℃、780℃、790℃、800℃或810℃等，但不仅 限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请中第一降温作为补充扩散的设定温度。
可选地，所述补充扩散用于修复高温推进带来的晶硅片局部区域掺杂过低的缺陷。
可选地，所述吹扫将炉管内残余的三氯氧磷去除。
可选地，所述氧化反应将PSG沉积反应中通入的三氯氧磷去除。
可选地，所述第二降温用于修复晶硅片的晶格错位。
可选地，所述充氮气用于恢复炉管的常压状态。
作为本申请优选的技术方案，所述链式氧化工艺包括高温链式氧化。
可选地，所述高温链式氧化的温度为660～670℃，其中所述温度可以是660℃、662℃、664℃、666℃、668℃或670℃等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述高温链式氧化的时间为1～5min，其中所述时间可以是1min、2min、3min、4min或5min等，但不仅限于所列举的数值，该数值范围外其他未列举的数值同样适用。
可选地，所述高温链式氧化的氧气流量为95～105slm，其中所述氧气流量可以是95slm、96slm、97slm、98slm、99slm、100slm、101slm、102slm、103slm、104slm或105slm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
可选地，所述高温链式氧化的氮气流量为5～15slm，其中所述氮气流量可以是5slm、6slm、7slm、8slm、9slm、10slm、11slm、12slm、13slm、14slm或15slm等，但不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请通过对低温扩散源量的控制和高温推进时间的控制，制备出本申请的扩散曲线掺杂分布，但是扩散曲线的表面掺杂浓度较低，会导致后续合金欧姆接触的失效，因此，需要引入高温链式氧化来激活表面掺杂。
高温链式氧化炉是一种升温速度非常快的，保温时间很短的热处理方式。升温速率能达到10～100摄氏度每秒。一般采用红外卤素灯加热，加热时电流很大，功率很大。卤钨灯加热过程中，发射大量的高能电子，高能电子轰击硅片时，辐照电子与晶格相互作用，破坏原子在晶格中的位置，使原子产生位移效应，同时形成空穴-间隙原子对；同时磷扩散，有间隙扩散和替位扩散两种，高能电子的轰击就降低了磷扩散的难度。链氧设备，使用卤钨灯红外灯管加热，硅片表面有恒定源存在的情况下，触发了扩散增强机制，导致磷源再分布。
根据上述原理介绍，尝试了不同高温链式氧化的温度条件，发现温度越高，光子热激辐射的能力越强，有效扩散激活掺杂能力越高，薄层方块电阻的变化越大，不同链式氧化温度，对应的方阻变化差值，差值越大说明激活掺杂能力越强。因此，本申请采用高温光子热激辐射来激活磷掺杂。
作为本申请优选的技术方案，所述制备方法按照工艺顺序依次包括：
制绒工艺、所述扩散工艺、激光掺杂工艺、所述链式氧化工艺、去除PSG工艺、碱背抛工艺、退火工艺、ALD钝化工艺、正面PECVD工艺、背面PECVD工艺、激光开槽工艺、丝网印刷工艺和电注入工艺。
本申请除扩散工艺和链式氧化工艺外，其他工艺均采用常规工艺手段，在此不做过多赘述。
本申请的目的之二在于提供一种如目的之一所述的浅结扩散发射极的晶硅太阳能电池的制备方法的应用，所述制备方法应用于光伏领域。
相对于现有技术，本申请具有以下有益效果：
本申请制备的太阳能电池转换率较常规的太阳能电池达到了0.1％的提升。
附图说明
图1是本申请具体实施方式中磷扩散杂质分布ECV曲线图。
图2是本申请具体实施方式中两种条件下的扩散杂质分布ECV曲线图。
图3是本申请具体实施方式中链式氧化炉的结构图。
图4是本申请具体实施方式中高温链式氧化掺杂曲线图(有/无PSG层)。
图5是本申请具体实施方式中太阳能电池的工艺流程图。
图6是本申请具体实施方式中掺杂分布曲线图。
图7是本申请实施例1和对比例1的QE量子效率图。
图8是本申请实施例1和对比例1的ECV掺杂浓度分布曲线图。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
本申请提供一种浅结扩散发射极的晶硅太阳能电池的制备方法，所述制备方法包括扩散工艺和链式氧化工艺。
所述扩散工艺包括低温扩散和高温推进，所述链式氧化工艺包括高温链式氧化。
本申请中通过扩散工艺的DOE实验，分析影响因子：温度、时间、流量、配方等，明确改变扩散工艺ECV曲线的关键因子，包括表面浓度、发射极结深、余误差分布和高斯分布的掺杂分布曲线；其次，通过对高温链式氧化的原理性理解，以及实验过程中摸索出对表面掺杂的影响；最后，结合太阳能晶硅电池的光伏发电原理，创造性的申请出将扩散工艺和链氧工艺结合在一起，制备出了0.15um左右的扩散发射极结，并且实现了高表面掺杂浓度下，良好的欧姆合 金接触，提高短波光谱吸收，提升了太阳能电池的光电转换效率。
本申请首先通过扩散工艺的优化，制备了0.15um深的低掺杂扩散浅结，同时，利用高温链式氧化的光子热激活辐射能，在扩散层表面形成一定剂量浓度的掺杂，来解决后续与银浆形成合金欧姆接触的失配问题。最终，获得了较高的光电转换效率提升。
进一步地，所述扩散工艺包括依次进行的进舟、第一升温、第一恒温、真空稳定、真空检漏、氧化、第一低温扩散通源、第二低温扩散通源、第二升温、第二恒温、高温推进、第一降温、补充扩散、吹扫、PSG沉积反应、氧化反应、第二降温、充氮气和出舟。
进一步地，所述低温扩散包括在一定温度下进行扩散恒定源。
进一步地，所述恒定源为三氯氧磷。
进一步地，所述低温扩散包括第一低温扩散通源和第二低温扩散通源。
进一步地，所述第一低温扩散通源的温度为770～790℃。
进一步地，所述第一低温扩散通源的时间为220～260s。
进一步地，所述第一低温扩散通源的小氮流量为1000～1100sccm。
进一步地，所述第一低温扩散通源的氧气流量为450～550sccm。
进一步地，所述第一低温扩散通源的大氮流量为0sccm。
进一步地，所述第一低温扩散通源的炉管压力为50～60mbar。
进一步地，所述第二低温扩散通源的温度为790～810℃。
进一步地，所述第二低温扩散通源的时间为190～230s。
进一步地，所述第二低温扩散通源的小氮流量为1100～1200sccm。
进一步地，所述第二低温扩散通源的氧气流量为550～650sccm。
进一步地，所述第二低温扩散通源的大氮流量为0sccm。
进一步地，所述第二低温扩散通源的炉管压力为50～60mbar。
本申请在低温扩散时，在本申请限定的温度下通入恒定的源量(三氯氧磷)，即恒定源扩散，这时的扩散分布曲线，满足余误差分布。由低温扩散(余误差分布)和高温推进(高斯分布)组成磷扩散掺杂的杂质分布曲线。
其中，磷扩散掺杂的杂质分布曲线如图1所示，图中Ⅰ为PSG层掺杂，一方面促进SE激光掺杂，另一方面高温链式热氧化，热光子辐射可激活掺杂；Ⅱ为表层掺杂，一方面高浓度掺杂会带来晶格失配造成的死层，减少短波响应，另外一方面会如果低浓度掺杂会影响后续丝网的欧姆接触传导；Ⅲ为结深曲线，一方面影响浆料的欧姆接触；另一方面对光生吸收相关。
进一步地，所述高温推进包括高温下将晶硅表面的磷源向硅基体内推进。
进一步地，所述高温推进的时间为350～370s。
进一步地，所述高温推进的温度为800～900℃。
进一步地，所述高温推进的小氮流量为750～850sccm。
进一步地，所述高温推进的氧气流量为0sccm。
进一步地，所述高温推进的大氮流量为950～1050sccm。
进一步地，所述高温推进的炉管压力为50～60mbar。
进一步地，所述PSG沉积反应的温度为700～800℃。
进一步地，所述PSG沉积反应的时间为700～800s。
进一步地，所述PSG沉积反应中通入三氯氧磷。
进一步地，所述PSG沉积反应的小氮流量为1250～1350sccm。
进一步地，所述PSG沉积反应的氧气流量为550～650sccm。
进一步地，所述PSG沉积反应的大氮流量为0sccm。
进一步地，所述PSG沉积反应的炉管压力为55～65mbar。
本申请通过对低温扩散源量的控制和高温推进时间的控制，制备出了本申请的扩散曲线掺杂分布，如图2，可以得知，本申请获得了0.15um左右的浅发射极制备，但同时，该扩散曲线的表面掺杂浓度较低，这样会导致后续合金欧姆接触的失效，因此，必须引入高温链式氧化，激活表面掺杂。
进一步地，所述链式氧化工艺包括进氧化腔、高温链式氧化和出氧化腔。
进一步地，所述高温链式氧化的温度为660～670℃。
进一步地，所述高温链式氧化的时间为1～5min。
进一步地，所述高温链式氧化的氧气流量为95～105slm。
进一步地，所述高温链式氧化的氮气流量为5～15slm。
本申请采用如图3所示的链式氧化铝进行加热，加热时电流很大，功率很大。卤钨灯加热过程中，发射大量的高能电子，高能电子轰击硅片时，辐照电子与晶格相互作用，破坏原子在晶格中的位置，使原子产生位移效应，同时形成空穴-间隙原子对；同时磷扩散，有间隙扩散和替位扩散两种，高能电子的轰击就降低了磷扩散的难度。链氧设备，使用卤钨灯红外灯管加热，硅片表面有恒定源存在的情况下，触发了扩散增强机制，导致磷源再分布。
本申请通过实验发现，图1-Ⅰ的PSG掺杂层，是链式氧化条件下的表面磷激活掺杂来源，保留PSG层过链式氧化和去除PSG层过链式氧化，表面浓度发生了不同的变化，如图4所示，保留PSG层和去除PSG层，在高温链式氧化后的ECV掺杂曲线测试，表现出了不同的表面掺杂浓度，而保留PSG层的高温链式氧化后的掺杂曲线，正是我们寻求解决表层掺杂影响的合金欧姆接触的关键因素。
进一步地，所述制备方法按照工艺顺序依次包括如图5所示：
制绒工艺、所述扩散工艺、激光掺杂工艺、所述链式氧化工艺、去除PSG 工艺、碱背抛工艺、退火工艺、ALD钝化工艺、正面PECVD工艺、背面PECVD工艺、激光开槽工艺、丝网印刷工艺和电注入工艺。
为了更好的理解本申请中一种浅结扩散发射极的晶硅太阳能电池的制备方法，采用以下实施例和对比例进行说明：
实施例1
本实施例提供一种浅结扩散发射极的晶硅太阳能电池的制备方法：
所述制备方法按照工艺顺序依次包括，如图5所示：
制绒工艺、扩散工艺、激光掺杂工艺、链式氧化工艺、去除PSG工艺、碱背抛工艺、退火工艺、ALD钝化工艺、正面PECVD工艺、背面PECVD工艺、激光开槽工艺、丝网印刷工艺和电注入工艺。
其中，扩散工艺包括以下步骤：
(1)将需要扩散的晶硅片，整齐的插放到，等待进炉管的石英舟上；
(2)进舟，将晶硅片送入高温石英炉管里面，时间设定为630s，温度设定在770℃，通入氮气流量设定为2000sccm，压力设置在接近常压1000mbar；
(3)第一升温，等待炉管升温至设定的温度，时间设定为60s，温度设定为770℃，氮气流量设定为2000sccm，炉管的真空压力设定为700mbar，对炉管做一个预抽真空的动作；
(4)第一恒温，等待炉管稳定在我们设定的温度±5℃范围内，并且将炉管进行抽真空的动作，时间设定为180s，温度设定在770℃，通入氮气流量设定为2000sccm，炉管压力设定为55mbar，并且提前通入一部分小氮(三氯氧磷关闭)进行管道的吹扫，流量设定为500sccm；
(5)真空稳定，等待炉管内抽到设定真空压力，时间设定为60s，温度设 定在770℃，关闭所有气体通入，炉管压力设定为55mbar；
(6)真空检漏，查看炉管是否有裂纹和密封不好的情况出现，导致真空压力出现回升波动，时间设定为60s，温度设定在770℃，关闭所有气体通入，炉管压力设定为55mbar；
(7)氧化，在进入掺杂扩散前，需要对晶硅片表面进行一层氧化硅层的生长保护，防止后续三氯氧磷反应过程中，对晶硅片表面有腐蚀影响，时间设定为300s，温度设定在775℃，小氮流量设定为500sccm(三氯氧磷关闭)，氧气流量设定为900sccm，大氮流量为0，炉管压力设定为55mbar；
(8)第一低温扩散通源，在775℃温度下，进行第一次三氯氧磷扩散掺杂反应，时间设定为240s，温度设定在775℃，小氮流量设定为1050sccm(三氯氧磷开启)，氧气流量设定为500sccm，大氮流量为0，炉管压力设定为55mbar；
(9)第二低温扩散通源，将温度调整至795℃，进行第二次三氯氧磷扩散掺杂反应，目的是通过变温扩散，激活氧化层中的掺杂磷源，让扩散反应更加均匀，时间设定为210s，温度设定在795℃，小氮流量设定为1150sccm(三氯氧磷开启)，氧气流量设定为600sccm，大氮流量为0，炉管压力设定为55mbar；
(10)第二升温，将温度从795℃升高至850℃的过程，以便完成后续的高温掺杂推进反应，同时通入大量氮气携带走一部分残余的三氯氧磷，避免安全风险，时间设定为300s，温度设定在850℃，小氮流量设定为800sccm(三氯氧磷关闭)，氧气流量设定为0sccm，大氮流量为1000sccm，炉管压力设定为55mbar；
(11)第二恒温，温度升高至设定温度后，需要恒温稳定一段时间，同时通入一定量的氧气，反应掉残余的三氯氧磷，避免安全风险，时间设定为240s， 温度设定在850℃，小氮流量设定为500sccm(三氯氧磷关闭)，氧气流量设定为600sccm，大氮流量为500sccm，炉管压力设定为55mbar；
(12)高温推进，达到设定高温后，并且确保炉管内未有反应气体后，进行高温下的掺杂推进工作，将晶硅表层的磷源往硅基体内推进，这一步的时间和温度都很关键，直接影响扩散发射极的结深，时间设定为360s，温度设定在850℃，小氮流量设定为800sccm(三氯氧磷关闭)，氧气流量设定为0sccm，大氮流量为1000，炉管压力设定为55mbar；
(13)第一降温，温度降低至800℃左右，作为补充扩散的设定温度，时间设定为1380s，温度设定在790℃，小氮流量设定为800sccm(三氯氧磷关闭)，氧气流量设定为0sccm，大氮流量为1000sccm，炉管压力设定为55mbar；
(14)补充扩散，修复高温推进带来的晶硅片局部区域掺杂过低的现象，时间设定为90s，温度设定在790℃，小氮流量设定为1300sccm(三氯氧磷开启)，氧气流量设定为600sccm，大氮流量为0，炉管压力设定为60mbar；
(15)吹扫，扩散完成后，将炉管内的残余三氯氧磷通过氮气和抽真空去除干净，时间设定为120s，温度设定在780℃，小氮流量设定为800sccm(三氯氧磷关闭)，氧气流量设定为0sccm，大氮流量为1000sccm，炉管压力设定为60mbar；
(16)PSG沉积反应，这一步的作用是一方面为接下来的激光局部掺杂提供足够的磷源，另一方面就是本专利的关键发现，可以匹配后续的高温链式氧化激活磷源，形成表面高掺杂，时间设定为760s，温度设定在750℃，小氮流量设定为1300sccm(三氯氧磷开启)，氧气流量设定为600sccm，大氮流量为0sccm，炉管压力设定为60mbar；
(17)氧化反应，通入大量的氧气，将炉管内残余的三氯氧磷充分反应掉，避免接下来的开炉内造成泄漏风险，时间设定为180s，温度设定在700℃，小氮流量设定为500sccm(三氯氧磷关闭)，氧气流量设定为1500sccm，大氮流量为0，炉管压力设定为60mbar；
(18)第二降温，这一步骤的降温，是将温度设定到非常低的一个值，目的是让完成扩散后的晶硅片有一个变温的过程，这个过程会促进晶格的位移，会修复一部分高温扩散带来的晶格错位现象，进一步改善扩散反射极的品质，时间设定为360s，温度设定在700℃，小氮流量设定为1000sccm(三氯氧磷关闭)，氧气流量设定为0sccm，大氮流量为0sccm，炉管压力设定为60mbar；
(19)充氮气，将炉管通入大量氮气，恢复炉管的常压状态，以便为后续的开炉门取晶硅片做准备，时间设定为240s，温度设定在700℃，小氮流量设定为1000sccm(三氯氧磷关闭)，氧气流量设定为0sccm，大氮流量为3000sccm，炉管压力设定为1000mbar；
(20)出舟，开炉门，取石英舟，结束整个扩散工艺流程，时间设定为630s，温度设定在750℃，小氮流量设定为0sccm，氧气流量设定为0sccm，大氮流量为2000sccm，炉管压力设定为1000mbar
其中，链式氧化工艺包括以下步骤：
(1)放承载盒，将装有晶硅片的承载盒放置到自动化上料机上面；
(2)进氧化腔体准备，将晶硅片从承载盒里面推出，整齐排列至链式氧化炉腔前面的传送皮带上；
(3)进入高温氧化炉腔体内，传送带速度设定为3.8m/min，红外卤素灯温度设定为665℃，通入氧气流量为100slm，氮气流量为10slm；
(4)出氧化腔体，完成高温链式氧化激活的硅片，通过传送皮带，整体排列至下料端，等待送入承载盒内；
(5)装入承载盒，将完成氧化激活的晶硅片从传送皮带上依次推入承载盒内，完成装片后，送入下一道去PSG工序。
实施例2
本实施例将扩散工艺中步骤(8)替换为：第一低温扩散通源，在770℃温度下，进行第一次三氯氧磷扩散掺杂反应，时间设定为260s，温度设定在770℃，小氮流量设定为1000sccm(三氯氧磷开启)，氧气流量设定为450sccm，大氮流量为0，炉管压力设定为50mbar；
将扩散工艺中步骤(9)替换为：第二低温扩散通源，将温度调整至790℃，进行第二次三氯氧磷扩散掺杂反应，目的是通过变温扩散，激活氧化层中的掺杂磷源，让扩散反应更加均匀，时间设定为230s，温度设定在790℃，小氮流量设定为1100sccm(三氯氧磷开启)，氧气流量设定为550sccm，大氮流量为0，炉管压力设定为50mbar；
将扩散工艺中步骤(12)替换为：高温推进，达到设定高温后，并且确保炉管内未有反应气体后，进行高温下的掺杂推进工作，将晶硅表层的磷源往硅基体内推进，这一步的时间和温度都很关键，直接影响扩散发射极的结深，时间设定为370s，温度设定在800℃，小氮流量设定为750sccm(三氯氧磷关闭)，氧气流量设定为0sccm，大氮流量为950sccm，炉管压力设定为50mbar；
将扩散工艺中步骤(16)替换为：PSG沉积反应，这一步的作用是一方面为接下来的激光局部掺杂提供足够的磷源，另一方面就是本专利的关键发现，可以匹配后续的高温链式氧化激活磷源，形成表面高掺杂，时间设定为800s， 温度设定在700℃，小氮流量设定为1250sccm(三氯氧磷开启)，氧气流量设定为550sccm，大氮流量为0sccm，炉管压力设定为55mbar；
将链式氧化工艺中步骤(3)替换为：进入高温氧化炉腔体内，传送带速度设定为3.8m/min，红外卤素灯温度设定为660℃，通入氧气流量为95slm，氮气流量为5slm。
其他条件均与实施例1相同。
实施例3
本实施例将扩散工艺中步骤(8)替换为：第一低温扩散通源，在790℃温度下，进行第一次三氯氧磷扩散掺杂反应，时间设定为220s，温度设定在790℃，小氮流量设定为1100sccm(三氯氧磷开启)，氧气流量设定为550sccm，大氮流量为0，炉管压力设定为60mbar；
将扩散工艺中步骤(9)替换为：第二低温扩散通源，将温度调整至810℃，进行第二次三氯氧磷扩散掺杂反应，目的是通过变温扩散，激活氧化层中的掺杂磷源，让扩散反应更加均匀，时间设定为190s，温度设定在1200℃，小氮流量设定为650sccm(三氯氧磷开启)，氧气流量设定为650sccm，大氮流量为0，炉管压力设定为60mbar；
将扩散工艺中步骤(12)替换为：高温推进，达到设定高温后，并且确保炉管内未有反应气体后，进行高温下的掺杂推进工作，将晶硅表层的磷源往硅基体内推进，这一步的时间和温度都很关键，直接影响扩散发射极的结深，时间设定为350s，温度设定在900℃，小氮流量设定为850sccm(三氯氧磷关闭)，氧气流量设定为0sccm，大氮流量为1050sccm，炉管压力设定为60mbar；
将扩散工艺中步骤(16)替换为：PSG沉积反应，这一步的作用是一方面 为接下来的激光局部掺杂提供足够的磷源，另一方面就是本专利的关键发现，可以匹配后续的高温链式氧化激活磷源，形成表面高掺杂，时间设定为700s，温度设定在800℃，小氮流量设定为1350sccm(三氯氧磷开启)，氧气流量设定为650sccm，大氮流量为0sccm，炉管压力设定为65mbar；
将链式氧化工艺中步骤(3)替换为：进入高温氧化炉腔体内，传送带速度设定为3.8m/min，红外卤素灯温度设定为670℃，通入氧气流量为105slm，氮气流量为15slm。
其他条件均与实施例1相同。
实施例4
本实施例除将扩散工艺中步骤(8)中第一低温扩散通源的温度替换为700℃外，其他条件均与实施例1相同。
实施例5
本实施例除将扩散工艺中步骤(12)中高温推进中的温度设定为950℃外，其他条件均与实施例1相同。
实施例6
本实施例除将高温链式氧化工序中红外卤素灯温度设定为665℃替换为700℃外，其他条件均与实施例1相同。
实施例7
本实施例除将扩散工艺步骤(9)第二低温扩散通源去掉外，其他条件均与实施例1相同。
实施例8
本实施例除将扩散工艺步骤(16)PSG沉积反应去掉外，其他条件均与实施例1相同。
对比例1
本对比例除将链式氧化替换为常规的高温管式氧化外，其他条件均与实施例1相同。
对比例2
本对比例除将扩散工艺步骤(12)高温推进步骤去掉外，其他条件均与实施例1相同。
对比例3
本实施例除将链式氧化工序替换为常温链式氧化工序外，其他条件均与实施例1相同。
对本申请实施例1和对比例1中进行几次批量生产，结果如表1所示：
表1
Figure PCTCN2022128187-appb-000001
通过上述表格可以看出，通过本申请制备浅结扩散发射极，获得了晶硅太 阳能电池转换效率0.1％的提升，主要提升了开路电压Uoc和短路电流Isc。
其中，本申请中实施例1与对比例1掺杂分布曲线如图6所示，量子效率QE曲线图如图7所示，ECV(电化学腐蚀)掺杂浓度分布曲线图8所示，通过图7量子效率QE曲线图，能明显发现在300nm～500nm的短波光谱响应，实施例1明显要高于对比例1，从图8中可以得知，本申请实施例1的结深在0.15um，表面浓度在1.0×10 21cm -3，均优于对比例1。
对实施例1-8和对比例1-3中的太阳能电池进行产线生产，测试结果如表2所示。
表2
  ΔUOC/A ΔIsc/A ΔFF ΔNcell/％
实施例1 0.0013 0.020 0.04 0.09
实施例2 0.0010 0.0130 0.16 0.101
实施例3 0.0011 0.0300 0.07 0.109
实施例4 -0.0007 -0.0099 0.00 -0.040
实施例5 -0.0004 -0.0250 0.00 -0.056
实施例6 -0.0004 -0.0100 -0.06 -0.047
实施例7 -0.0007 -0.0181 -0.08 -0.077
实施例8 -0.0010 -0.0230 0.02 -0.067
对比例1 -0.0022 -0.0169 -0.02 -0.108
对比例2 -0.0024 -0.0199 -0.16 -0.158
对比例3 -0.0035 -0.0399 -0.10 -0.212
通过上述表格可以得到，实施例1-3的效率提升是较明显，并且效率提升0.1％左右，结果较一致；实施例4将第一低温扩散通源温度替换为较低温度，实施例5将扩散工艺中的高温推进温度提升，实施例6将高温链式氧化工序中的温度进一步提升，实施例7将第二低温扩散通源去掉，与实施例1相比，实施例4-6的光转换效率均下降，对比例1将链式氧化替换为高温管式氧化，对比例2去掉高温推进工艺步骤，对比例3将高温链式氧化替换为常温链式氧化，可以观察到，太阳能电池的光转换效率进一步下降。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。

Claims (10)

  1. 一种浅结扩散发射极的晶硅太阳能电池的制备方法，其中，所述制备方法包括扩散工艺和链式氧化工艺；
    所述扩散工艺包括低温扩散和高温推进，所述链式氧化工艺包括高温链式氧化。
  2. 根据权利要求1所述的制备方法，其中，所述扩散工艺包括依次进行的进舟、第一升温、第一恒温、真空稳定、真空检漏、氧化、第一低温扩散通源、第二低温扩散通源、第二升温、第二恒温、高温推进、第一降温、补充扩散、吹扫、PSG沉积反应、氧化反应、第二降温、充氮气和出舟；
    可选地，所述低温扩散包括在一定温度下进行扩散恒定源；
    所述恒定源为三氯氧磷；
    可选地，所述低温扩散包括第一低温扩散通源和第二低温扩散通源；
    所述第一低温扩散通源的温度为770～790℃；
    所述第一低温扩散通源的时间为220～260s；
    所述第一低温扩散通源的小氮流量为1000～1100sccm；
    所述第一低温扩散通源的氧气流量为450～550sccm；
    所述第一低温扩散通源的大氮流量为0sccm；
    所述第一低温扩散通源的炉管压力为50～60mbar；
    所述第二低温扩散通源的温度为790～810℃；
    所述第二低温扩散通源的时间为190～230s；
    所述第二低温扩散通源的小氮流量为1100～1200sccm；
    所述第二低温扩散通源的氧气流量为550～650sccm；
    所述第二低温扩散通源的大氮流量为0sccm；
    所述第二低温扩散通源的炉管压力为50～60mbar。
  3. 根据权利要求1或2所述的制备方法，其中，所述高温推进包括高温下将晶硅表面的磷源向硅基体内推进；
    所述高温推进的时间为350～370s；
    所述高温推进的温度为800～900℃；
    所述高温推进的小氮流量为750～850sccm；
    所述高温推进的氧气流量为0sccm；
    所述高温推进的大氮流量为950～1050sccm；
    所述高温推进的炉管压力为50～60mbar。
  4. 根据权利要求2或3任一项所述的制备方法，其中，所述PSG沉积反应的温度为700～800℃；
    所述PSG沉积反应的时间为700～800s；
    所述PSG沉积反应中通入三氯氧磷；
    所述PSG沉积反应的小氮流量为1250～1350sccm；
    所述PSG沉积反应的氧气流量为550～650sccm；
    所述PSG沉积反应的大氮流量为0sccm；
    所述PSG沉积反应的炉管压力为55～65mbar。
  5. 根据权利要求2-4任一项所述的制备方法，其中，所述第一升温和第一恒温中，对炉管进行抽真空处理；
    可选地，所述第一恒温时通入小氮对管道进行吹扫，所述吹扫的流量为450～550sccm；
    可选地，所述真空稳定中压力稳定后关闭所有气体通入保持炉管的压力为50～60mbar；
    可选地，所述氧化包括在晶硅片表面进行一层氧化硅层的生长保护。
  6. 根据权利要求2-5任一项所述的制备方法，其中，所述第二升温的截至温度为830～870℃；
    所述第二升温中通入氮气用于去除残余的三氯氧磷；
    所述第二升温中大氮流量为950～1050sccm；
    可选地，所述第二恒温中通入氧气用于进一步反应残余的三氯氧磷；
    所述第二恒温中氧气流量为550～650sccm。
  7. 根据权利要求2-6任一项所述的制备方法，其中，所述第一降温的温度为750～810℃；
    可选地，所述补充扩散用于修复高温推进带来的晶硅片局部区域掺杂过低的缺陷；
    可选地，所述吹扫将炉管内残余的三氯氧磷去除；
    可选地，所述氧化反应将PSG沉积反应中通入的三氯氧磷去除；
    可选地，所述第二降温用于修复晶硅片的晶格错位；
    可选地，所述充氮气用于恢复炉管的常压状态。
  8. 根据权利要求1-7任一项所述的制备方法，其中，所述链式氧化工艺包括高温链式氧化；
    所述高温链式氧化的温度为660～670℃；
    所述高温链式氧化的时间为1～5min；
    所述高温链式氧化的氧气流量为95～105slm；
    所述高温链式氧化的氮气流量为5～15slm。
  9. 根据权利要求1-8任一项所述的制备方法，其中，所述制备方法按照工艺顺序依次包括：
    制绒工艺、所述扩散工艺、激光掺杂工艺、所述链式氧化工艺、去除PSG 工艺、碱背抛工艺、退火工艺、ALD钝化工艺、正面PECVD工艺、背面PECVD工艺、激光开槽工艺、丝网印刷工艺和电注入工艺。
  10. 一种如权利要求1-9任一项所述的浅结扩散发射极的晶硅太阳能电池的制备方法的应用，其中，所述制备方法应用于光伏领域。
PCT/CN2022/128187 2022-03-24 2022-10-28 一种浅结扩散发射极的晶硅太阳能电池的制备方法及其应用 WO2023179021A1 (zh)

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