WO2024087838A1 - 一种太阳电池及其制备方法 - Google Patents

一种太阳电池及其制备方法 Download PDF

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WO2024087838A1
WO2024087838A1 PCT/CN2023/114589 CN2023114589W WO2024087838A1 WO 2024087838 A1 WO2024087838 A1 WO 2024087838A1 CN 2023114589 W CN2023114589 W CN 2023114589W WO 2024087838 A1 WO2024087838 A1 WO 2024087838A1
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doped region
silicon wafer
solar cell
type silicon
boron
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French (fr)
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徐文州
邢国强
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Tongwei Solar Meishan Co Ltd
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Tongwei Solar Meishan Co Ltd
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Priority to EP23844159.6A priority Critical patent/EP4383350A4/en
Priority to AU2023361984A priority patent/AU2023361984B2/en
Publication of WO2024087838A1 publication Critical patent/WO2024087838A1/zh
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • H10F77/315—Coatings for devices having potential barriers for photovoltaic cells the coatings being antireflective or having enhancing optical properties
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P32/00—Diffusion of dopants within, into or out of wafers, substrates or parts of devices
    • H10P32/10—Diffusion of dopants within, into or out of semiconductor bodies or layers
    • H10P32/12—Diffusion of dopants within, into or out of semiconductor bodies or layers between a solid phase and a gaseous phase
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P32/00—Diffusion of dopants within, into or out of wafers, substrates or parts of devices
    • H10P32/10—Diffusion of dopants within, into or out of semiconductor bodies or layers
    • H10P32/16—Diffusion of dopants within, into or out of semiconductor bodies or layers between a solid phase and a liquid phase
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P32/00—Diffusion of dopants within, into or out of wafers, substrates or parts of devices
    • H10P32/10—Diffusion of dopants within, into or out of semiconductor bodies or layers
    • H10P32/17—Diffusion of dopants within, into or out of semiconductor bodies or layers characterised by the semiconductor material
    • H10P32/171—Diffusion of dopants within, into or out of semiconductor bodies or layers characterised by the semiconductor material being group IV material
    • 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 photovoltaic cell preparation, and in particular, to a solar cell and a method for preparing the same.
  • Solar cells can convert light energy into electrical energy, which can help save energy and reduce emissions.
  • Solar cells can be divided into many types, such as TOPCon cells (Tunnel Oxide Passivated Contact solar cells), which are generally based on N-type silicon wafers, with good interface passivation layers on the front and back of the N-type silicon wafers, and electrodes that form good electrical connections with the N-type silicon wafers are also provided on the surface of the passivation layer.
  • TOPCon cells Tel Oxide Passivated Contact solar cells
  • the current TOPCon battery has a high square resistance, which can effectively reduce the occurrence of Auger recombination and increase the battery's opening voltage and current; but due to the high square resistance, the contact resistance between the electrode and the N-type silicon wafer is also large, which will affect the battery's fill factor and is not conducive to improving the battery's photoelectric conversion efficiency.
  • the purpose of the embodiments of the present application is to provide a solar cell and a method for preparing the same, wherein the solar cell can effectively reduce the contact resistance between the electrode and the N-type silicon wafer, thereby improving the cell efficiency.
  • the present invention provides a solar cell, which includes an N-type silicon wafer, an N-type silicon A doped region is arranged on the front side of the wafer, the doped region contains boron, the doped region is divided into a lightly doped region and a heavily doped region, the boron concentration in the lightly doped region is less than that in the heavily doped region, and the junction depth in the lightly doped region is less than that in the heavily doped region; a passivation layer and a first anti-reflection layer are sequentially stacked on the front side of the N-type silicon wafer; an electrode is arranged on the surface of the first anti-reflection layer in an area corresponding to the heavily doped region, and the electrode penetrates the first anti-reflection layer and the passivation layer to form an ohmic contact with the heavily doped region.
  • the doped region contains boron, so a PN junction is formed between the doped region and other regions of the N-type silicon wafer. After being irradiated by sunlight, the PN junction can generate carriers, and the electrode that forms an ohmic contact with the doped region can collect the carriers in the doped region, thereby outputting current to the outside.
  • the doped region is divided into a heavily doped region and a lightly doped region, wherein the electrode is located in the heavily doped region, and the boron concentration in the heavily doped region is greater than that in the lightly doped region, and the junction depth is greater than that in the lightly doped region, which is conducive to reducing the contact resistance between the N-type silicon wafer and the electrode, and can improve the battery efficiency.
  • the passivation layer can protect the N-type silicon wafer and the doped area on its surface, ensuring that the front side and doped area of the N-type silicon wafer are not easily oxidized; the first anti-reflection layer can reduce the light reflectivity of the solar cell, thereby improving the light absorption efficiency of the solar cell, which is beneficial to improving the cell efficiency.
  • the boron concentration of the lightly doped region is 10 18 cm ⁇ 3 to 10 19 cm ⁇ 3
  • the boron concentration of the heavily doped region is 10 19 cm ⁇ 3 to 10 20 cm ⁇ 3 .
  • the junction depth of the lightly doped region is 0.4-0.8 ⁇ m
  • the junction depth of the heavily doped region is 1.0-1.4 ⁇ m.
  • a polysilicon layer and a second anti-reflection layer are sequentially stacked on the back side of the N-type silicon wafer.
  • the polysilicon layer on the back of the N-type silicon wafer has a good passivation effect and can reduce the metal contact composite current.
  • the second anti-reflection layer can not only reduce the light reflectivity of the solar cell, but also protect the back of the N-type silicon wafer from oxidation.
  • an embodiment of the present application provides a method for preparing a solar cell of the first aspect, comprising the following steps: performing a first boron diffusion on the front side of an N-type silicon wafer using a gas-phase boron source to form a lightly doped region and a borosilicate glass layer having a thickness of no more than 10 nm on the front side of the N-type silicon wafer; then coating a boron slurry on the surface of the borosilicate glass layer, and performing a second boron diffusion using the boron slurry to form a heavily doped region; thereafter removing the borosilicate glass layer, and sequentially forming a passivation layer and a first anti-reflection layer on the front side of the N-type silicon wafer, and printing an electrode on the surface of the first anti-reflection layer in an area corresponding to the heavily doped region, and the electrode penetrates the first anti-reflection layer and the passivation layer to form an oh
  • a BSG (Borosilicate glass) layer will inevitably be produced.
  • the BSG layer can protect the PN junction formed by the lightly doped region and the N-type silicon wafer from being oxidized; however, the BSG layer will also make it difficult to form a heavily doped region later, which is why it is difficult to reduce the contact resistance between the electrode and the N-type silicon wafer.
  • the applicant found that if the thickness of the BSG layer is controlled to be no more than 10nm during the process of forming the lightly doped region (i.e., the process of the first boron diffusion), and then a boron slurry is coated on the surface of the BSG layer no more than 10nm, and then a second boron diffusion is performed, a heavily doped region can be well formed on the surface of the N-type silicon wafer; and the formed BSG layer can still play the role of protecting the PN junction, ensuring that the PN junction is not easily oxidized.
  • the use of a gas-phase boron source is conducive to forming a BSG layer with a thickness of no more than 10nm; in the process of the second boron diffusion, the use of a boron slurry is conducive to forming a heavily doped region.
  • the temperature is 850-1000° C.
  • the gas-phase boron source is at least one of BCl 3 , BBr 3 , and BH 3 .
  • oxygen is first introduced and treated at 700-800°C for 30-60 min to remove impurities in the boron slurry; then the introduction of oxygen is stopped and the slurry is treated at 900-1100°C for 10-60 min under anaerobic conditions.
  • the passivation layer or the first anti-reflection layer is formed by vapor deposition.
  • the thickness of the passivation layer and the first anti-reflection layer can be accurately controlled by using a vapor deposition method.
  • the method further includes the following steps: forming a polysilicon layer and a second anti-reflection layer in sequence on the back side of the N-type silicon wafer.
  • FIG1 is a schematic diagram of the structure of a solar cell provided in an embodiment of the present application.
  • Icon 001-solar cell; 100-N-type silicon wafer; 110-doped region; 111-lightly doped region; 112-heavily doped region; 200-passivation layer; 300-first anti-reflection layer; 400-polysilicon layer; 500-second anti-reflection layer; 600-electrode.
  • the solar cell 001 and its preparation method according to the embodiment of the present application are described in detail below.
  • the structure of the solar cell 001 of this embodiment is as follows:
  • the structure of the solar cell 001 in the embodiment of the present application is based on an N-type silicon wafer 100, and a doped region 110 containing boron is arranged on the front of the N-type silicon wafer 100.
  • the doped region 110 is P-type and can form a PN junction with other regions of the N-type silicon wafer 100.
  • the PN junction can generate carriers after being irradiated by sunlight so that current can be output externally later.
  • the doped region 110 is divided into a lightly doped region 111 and a heavily doped region 112, wherein the boron concentration in the lightly doped region 111 is less than the boron concentration in the heavily doped region 112.
  • a passivation layer 200 and a first anti-reflection layer 300 are sequentially stacked on the front side of the N-type silicon wafer 100.
  • the passivation layer 200 can protect the N-type silicon wafer 100 and the doped region 110 on its surface, ensuring that the front side of the N-type silicon wafer 100 and the doped region 110 are not easily oxidized.
  • the material of the passivation layer 200 can be an oxide such as aluminum oxide (AlO x ) and silicon oxide.
  • AlO x aluminum oxide
  • the passivation layer 200 in this embodiment is aluminum oxide.
  • the first anti-reflection layer 300 can reduce the light reflectivity of the solar cell 001, thereby improving the light absorption efficiency of the solar cell 001, which is beneficial to improving the cell efficiency.
  • the material of the first anti-reflection layer 300 in this embodiment is silicon nitride (SiN x ).
  • An electrode 600 is provided on the surface of the first anti-reflection layer 300 in the area corresponding to the heavily doped area 112.
  • the material of the electrode 600 is usually silver. Since the first anti-reflection layer 300 and the passivation layer 200 are not conductive, the electrode 600 will penetrate the first anti-reflection layer 300 and the passivation layer 200 to form an ohmic contact with the heavily doped area 112, so that the electrode 600 can collect the carriers generated by the PN junction.
  • the boron concentration of the lightly doped area 111 is less than that of the heavily doped area 112, and the junction depth is also less than that of the heavily doped area 112.
  • the contact resistance will be significantly reduced, which is conducive to improving the battery efficiency, and will not significantly increase the occurrence of Auger recombination.
  • the boron concentration in the lightly doped region 111 is 10 18 cm -3 -10 19 cm -3 , and the junction depth is 0.4-0.8 ⁇ m; the boron concentration in the heavily doped region 112 is 10 19 cm -3 -10 20 cm -3 , and the junction depth is 1.0-1.4 ⁇ m.
  • a polysilicon layer 400 and a second anti-reflection layer 500 are sequentially stacked on the back side of the N-type silicon wafer 100 .
  • the polysilicon layer 400 has a good passivation effect and can reduce the metal contact composite current.
  • the second anti-reflection layer 500 can not only reduce the light reflectivity of the solar cell 001, but also protect the back of the N-type silicon wafer 100 from being easily oxidized; as an example, the material of the second anti-reflection layer 500 in this embodiment is the same as that of the first anti-reflection layer 300, both of which are silicon nitride.
  • an electrode 600 is also provided on the surface of the second anti-reflection layer 500, and the material is also silver. The electrode 600 on the surface of the second anti-reflection layer 500 will penetrate the second anti-reflection layer 500 and contact the polysilicon layer 400, and use the quantum tunneling effect to collect the carriers generated by the PN junction.
  • the above-mentioned cell is generally called TOPcon (Tunnel Oxide Passivated Contact solar cell).
  • a boron source is directly used to diffuse boron on the front side of the N-type silicon wafer 100 to form a doped region 110, which will inevitably form a thick BSG layer.
  • the BSG layer can protect the doped region 110 from being oxidized, it will prevent further diffusion of boron and fail to form a lightly doped region 111 and a heavily doped region 112 with different boron concentrations.
  • the present application also provides a method for preparing the above-mentioned solar cell 001, and the specific steps are as follows:
  • the alkali solution during texturizing is generally KOH or NaOH solution, and the concentration is generally 1%. After the texturizing is completed, the silicon wafer is cleaned with hydrogen peroxide and alkali solution.
  • a first boron diffusion is performed on the front side of the N-type silicon wafer 100 using a gas phase boron source to form a lightly doped region 111 and a BSG layer with a thickness of no more than 10 nm on the front side of the N-type silicon wafer 100.
  • the BSG layer with a thickness of no more than 10 nm can protect the lightly doped region 111 and ensure that it will not be oxidized during the production process, and will not hinder the subsequent second boron diffusion, so as to ensure that the heavily doped region 111 is formed on the front side of the N-type silicon wafer 100.
  • the gas phase boron source in this step can be at least one of BCl 3 , BBr 3 , and BH 3 , and the processing temperature in this step is generally 850 to 1000° C., and the processing time is generally 10 to 60 minutes.
  • This step is to coat the surface of the BSG layer with boron slurry and perform a second boron diffusion.
  • the use of boron slurry is conducive to the boron element passing through the BSG layer and penetrating into the front side of the N-type silicon wafer 100, thereby forming a heavily doped region 112.
  • the thickness of the BSG layer will increase to more than 100nm, which can prevent the subsequent cleaning (the cleaning process is detailed in the subsequent description) from causing over-engraving on the front side during the plating.
  • the slurry is first dried at a temperature of 150-300°C, and the drying time generally lasts 30-90 seconds. Then, oxygen is introduced and treated at 700-800°C for 30-60 minutes, which can remove impurities such as carbon in the boron slurry and convert them into carbon dioxide for discharge, solving the problem of impurity residues; then, the introduction of oxygen is stopped and treated at 900-1100°C for 10-60 minutes under anaerobic conditions, which is conducive to better pushing of the boron slurry and forming a deeper junction depth.
  • the boron is diffused on the front side of the N-type silicon wafer 100, not only a BSG layer is formed on the front side, but also a BSG layer and a doped region 110 are formed on the back side.
  • the BSG layer is a layer structure that is not needed for the subsequent formation of the solar cell 001, so it needs to be removed.
  • a chain HF machine is generally used to remove the BSG layer of the back side boron diffusion coating, and then a tank alkali polishing machine is used to remove the back side and edge p-n junction.
  • This step generally uses vapor deposition to deposit an amorphous silicon film on the back side of the N-type silicon wafer 100 , and then annealing is performed in a nitrogen or oxygen atmosphere to transform the amorphous silicon film into a polysilicon layer 400 .
  • the use of vapor deposition is beneficial to controlling the thickness of the film.
  • the vapor deposition method includes PEALD (Plasma Enhanced Atomic Layer Deposition) and PECVD (Plasma Enhanced Chemical Vapor Deposition) are used.
  • PEALD Pulsma Enhanced Atomic Layer Deposition
  • PECVD Pulsma Enhanced Chemical Vapor Deposition
  • the amorphous silicon film is deposited by PECVD.
  • the BSG layer is a layer structure that is not needed for the subsequent formation of the solar cell 001, so it needs to be removed.
  • This step is to remove the BSG layer on the front side of the N-type silicon wafer 100. Specifically, first use the RCA standard cleaning method for cleaning (the RCA standard cleaning method is a commonly used technology, and this application will not repeat it here); then use a chain HF machine to remove the BSG layer on the front side, and then use a tank alkali polishing machine to remove the residual boron paste printed on the front side.
  • the BSG layer is removed in this step in order to prevent contamination of the doping layer during the preparation process.
  • This step generally adopts a vapor deposition method to deposit the passivation layer 200 and the first anti-reflection layer 300 respectively, wherein the material of the passivation layer 200 is generally aluminum oxide, and the material of the first anti-reflection layer 300 is silicon nitride.
  • This step generally adopts a vapor deposition method to deposit the passivation layer 200 and the first anti-reflection layer 300 respectively.
  • the material of the second anti-reflection layer 500 is the same as that of the first anti-reflection layer 300, both of which are silicon nitride.
  • This step generally uses screen printing to print silver paste on the surface of the first anti-reflection layer 300 and the second anti-reflection layer 500, and then forms the electrode 600 after drying and sintering.
  • the electrode 600 on the surface of the first anti-reflection layer 300 is located in the area where the heavily doped region 112 is located, and the electrode 600 on the surface of the first anti-reflection layer 300 penetrates the first anti-reflection layer 300 and the passivation layer 200, and forms a European Mum contact.
  • This embodiment provides a solar cell 001, the preparation process of which includes the following steps:
  • Second boron diffusion a screen printer is used to print a boron paste with a concentration of 7% and a gate line height of 2 ⁇ m on the surface of the BSG layer, and the boron paste is baked at 200°C for 60 seconds. Thereafter, oxygen is introduced at 800°C for 30 minutes to remove carbon in organic matter. The temperature is then raised to 1000°C under oxygen-free conditions and maintained for 1800 seconds for oxygen-free push junction. A heavily doped region 112 is formed on the front side of the N-type silicon wafer 100, and a 120nm BSG layer is formed on the front side of the silicon wafer.
  • a tubular PECVD device is used to deposit an amorphous silicon film on the back of the silicon wafer, and then a tubular furnace is used for annealing, and nitrogen is used to convert the deposited amorphous silicon film into a polycrystalline silicon layer 400.
  • Cleaning the front side of the N-type silicon wafer 100 Use the RCA marking cleaning method to clean the front side of the N-type silicon wafer 100, then use a chain HF machine to remove the BSG layer on the front side, and then use a tank alkaline polishing machine to remove the residual boron paste printed on the front side.
  • Forming the passivation layer 200 and the first anti-reflection layer 300 Using the PECVD method, first deposit a layer of oxide on the front surface of the N-type silicon wafer 100 as the passivation layer 200, and then deposit A layer of silicon nitride is used as the first anti-reflection layer 300 .
  • Silicon nitride is deposited by PECVD to deposit a layer of silicon nitride on the surface of the polysilicon layer 400 as the second anti-reflection layer 500.
  • (9) Forming the electrode 600 Using screen printing, silver paste is printed on the surfaces of the first anti-reflection layer 300 and the second anti-reflection layer 500, respectively, and then the electrodes 600 are formed after drying and sintering.
  • the electrode 600 on the surface of the first anti-reflection layer 300 is located in the area where the heavily doped region 112 is located, and penetrates the first anti-reflection layer 300 and the passivation layer 200 to form an ohmic contact with the heavily doped region 112.
  • the electrode 600 on the surface of the second anti-reflection layer 500 penetrates the second anti-reflection layer 500 to form an electrical contact with the polysilicon layer 400.
  • This embodiment provides a solar cell 001, and the main differences of its preparation process compared with that of embodiment 1 are as follows:
  • step (3) oxygen is introduced at 700° C. for 30 minutes to remove carbon from the organic matter.
  • This embodiment provides a solar cell 001, and its preparation process has the following main differences compared with that of embodiment 1:
  • step (3) the temperature is raised to 980° C. under reduced pressure (700 Pa) to perform oxygen-free push-in, forming a heavily doped region 112 on the front side of the N-type silicon wafer 100, and forming a 120 nm BSG layer on the front side of the silicon wafer.
  • This embodiment provides a solar cell 001, and its preparation process is different from that of embodiment 1 in the following aspects:
  • step (3) oxygen-free push-in junction is performed under normal pressure and oxygen-free conditions at 1040° C. to form a heavily doped region 112 on the front side of the N-type silicon wafer 100, and a 120 nm BSG layer is formed on the front side of the silicon wafer.
  • This embodiment provides a solar cell 001, and its preparation process is different from that of embodiment 1 in the following aspects:
  • step (3) 1000 sccm of oxygen is introduced to form a 150 nm BSG layer on the front side of the N-type silicon wafer 100 .
  • This embodiment provides a solar cell 001, and its preparation process has the following main differences compared with that of embodiment 1:
  • step (2) BBr 3 is used as a boron source, the processing temperature is 950° C., and the processing time is 2400 s to form a lightly doped region 111 and a 9 nm BSG layer.
  • This comparative example provides a solar cell 001, and its preparation process is different from that of Example 1 in that:
  • step (2) boron slurry is used as a boron source, the processing temperature is 950° C., and the processing time is 2400 s to form a doped region 110 and a 20 nm BSG layer.
  • This comparative example provides a solar cell 001, and its preparation process is different from that of Example 1 in that:
  • step (2) the processing temperature is 980° C. and the processing time is 3600 s, forming a doped region 110 and a 30 nm BSG layer.
  • This comparative example provides a solar cell 001, and its preparation process is different from that of Example 1 in the following aspects:
  • the step (3) is not included, and in the step (9), the electrode 600 on the surface of the first anti-reflection layer 300 is penetrated
  • the first anti-reflection layer 300 and the passivation layer 200 form an ohmic contact with the lightly doped region 111 .

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Abstract

本申请实施例提供一种太阳电池及其制备方法，涉及光伏电池制备领域。太阳电池包括N型硅片，N型硅片的正面设置有掺杂区，掺杂区中含有硼，掺杂区分为轻掺杂区和重掺杂区，轻掺杂区中的硼浓度小于重掺杂区的硼浓度，轻掺杂区的结深小于重掺杂区的结深；N型硅片的正面还依次叠加设置有钝化层、第一减反射层；第一减反射层的表面对应重掺杂区的区域设置有电极，且电极穿透第一减反射层和钝化层与重掺杂区形成欧姆接触。本申请实施例的太阳电池能很好地降低电极与N型硅片的接触电阻，从而提升电池效率。

Description

一种太阳电池及其制备方法
本申请要求于2022年10月27日提交中国专利局、申请号为202211326548.6、发明名称为“一种太阳电池及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及光伏电池制备领域，具体而言，涉及一种太阳电池及其制备方法。
背景技术
太阳电池(又称“太阳能电池”)能将光能转化为电能，能起到节能减排的效果。太阳电池可以分为多个种类，例如TOPCon电池(Tunnel Oxide Passivated Contact solar cell，隧穿氧化层钝化接触太阳能电池)，其一般是以N型硅片为基底，在N型硅片的正面和背面均设置有良好的界面钝化层，而且在钝化层的表面还设置有与N型硅片形成良好的电性连接的电极。
目前的TOPCon电池方阻较高，能很好地减少俄歇复合的现象发生，可以提升电池开压及电流；但由于方阻较高，电极与N型硅片的接触电阻也很大，这会影响到电池的填充因子，不利于提升电池的光电转化效率。
发明内容
本申请实施例的目的在于提供一种太阳电池及其制备方法，该太阳电池能很好地降低电极与N型硅片的接触电阻，从而提升电池效率。
第一方面，本申请实施例提供了一种太阳电池，其包括N型硅片，N型硅 片的正面设置有掺杂区，掺杂区中含有硼，掺杂区分为轻掺杂区和重掺杂区，轻掺杂区中的硼浓度小于重掺杂区的硼浓度，轻掺杂区的结深小于重掺杂区的结深；N型硅片的正面还依次叠加设置有钝化层、第一减反射层；第一减反射层的表面对应重掺杂区的区域设置有电极，且电极穿透第一减反射层和钝化层与重掺杂区形成欧姆接触。
在上述技术方案中，掺杂区中含有硼，因此掺杂区和N型硅片的其它区域之间形成了PN结，在经过太阳光照射后，PN结能产生载流子，与掺杂区形成欧姆接触的电极能收集掺杂区内的载流子，从而对外输出电流。掺杂区分为重掺杂区和轻掺杂区，其中电极位于重掺杂区，而且重掺杂区的硼浓度大于轻掺杂区的浓度，结深大于轻掺杂区的结深，这样有利于降低N型硅片与电极的接触电阻，可以提升电池效率。
钝化层能起到保护N型硅片以及其表面的掺杂区的作用，保证N型硅片的正面和掺杂区不容易被氧化；第一减反射层能降低太阳电池的光反射率，从而提升太阳电池的吸光效率，有利于提升电池效率。
在一种可能的实现方式中，轻掺杂区的硼浓度为1018cm-3～1019cm-3，重掺杂区的硼浓度为1019cm-3～1020cm-3。
在一种可能的实现方式中，轻掺杂区的结深为0.4～0.8μm，重掺杂区的结深为1.0～1.4μm。
在一种可能的实现方式中，N型硅片的背面依次叠加设置有多晶硅层、第二减反射层。
在上述技术方案中，N型硅片背面的多晶硅层具有良好的钝化作用，能降低金属接触复合电流，第二减反射层不仅能降低太阳电池的光反射率，同时还能保护N型硅片的背面不容易发生氧化。
第二方面，本申请实施例提供了第一方面的太阳电池的制备方法，其包括以下步骤：使用气相硼源在N型硅片的正面进行第一次硼扩散，以在N型硅片的正面形成轻掺杂区和厚度不大于10nm的硼硅玻璃层；然后将硼浆涂覆在硼硅玻璃层的表面，并使用硼浆进行第二次硼扩散，以形成重掺杂区；之后除去硼硅玻璃层，并在N型硅片的正面依次形成钝化层、第一减反射层，并在第一减反射层的表面对应重掺杂区的区域印刷电极，且电极穿透第一减反射层和钝化层与重掺杂区形成欧姆接触。
现有的制备方法中，在硼扩散形成轻掺杂区的过程中，还会不可避免地产生BSG(Borosilicate glass，硼硅玻璃)层，BSG层能保护轻掺杂区和N型硅片形成的PN结不被氧化；但是BSG层同样也会导致后续很难形成重掺杂区，这也是电极与N型硅片的接触电阻很难降低的原因。
在上述技术方案中，申请人发现，若在形成轻掺杂区的过程中(即第一次硼扩散的过程)，控制BSG层的厚度不大于10nm，然后再在不大于10nm的BSG层的表面涂覆硼浆，再进行第二次硼扩散就能很好地在N型硅片的表面形成重掺杂区；而且形成的BSG层仍然可以起到保护PN结的效果，保证PN结不容易被氧化。而且在第一硼扩散的过程中，使用气相硼源有利于形成厚度不大于10nm的BSG层；在第二硼扩散的过程中，使用硼浆有利于形成重掺杂区。
在一种可能的实现方式中，在第一次硼扩散的步骤中，温度为850～1000℃。
在一种可能的实现方式中，在第一次硼扩散的步骤中，气相硼源为BCl3、BBr3、BH3中的至少一种。
在一种可能的实现方式中，在第二次硼扩散的步骤时，先通入氧气并在700～800℃下处理30～60min以除去硼浆中的杂质；之后停止通入氧气，在无氧条件下于900～1100℃处理10～60min。
在一种可能的实现方式中，采用气相沉积的方式形成钝化层或第一减反射层。
在上述技术方案中，采用气相沉积的方式能精确地控制钝化层和第一减反射层的厚度。
在一种可能的实现方式中，在形成重掺杂区之后，其还包括以下步骤：在N型硅片的背面依次形成多晶硅层、第二减反射层。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本申请的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本申请实施例提供的一种太阳电池的结构示意图。
图标：001-太阳电池；100-N型硅片；110-掺杂区；111-轻掺杂区；112-重掺杂区；200-钝化层；300-第一减反射层；400-多晶硅层；500-第二减反射层；600-电极。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚，下面将对本申请实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
下面对本申请实施例的太阳电池001及其制备方法进行具体说明。
请参看图1，本实施例的太阳电池001的结构如下：
本申请实施例中的太阳电池001的结构是以N型硅片100为基底，在N型硅片100的正面设置有含有硼的掺杂区110，掺杂区110为P型，能和N型硅片100的其它区域形成PN结，PN结在经过太阳光照射后能产生载流子，以便后续能对外输出电流。掺杂区110分为轻掺杂区111和重掺杂区112，其中轻掺杂区111中的硼浓度小于重掺杂区112的硼的浓度。
在N型硅片100的正面依次叠加设置有钝化层200、第一减反射层300，钝化层200能起到保护N型硅片100以及其表面的掺杂区110的作用，保证N型硅片100的正面和掺杂区110不容易被氧化，钝化层200的材质可以是氧化铝(AlOx)、氧化硅等氧化物，作为示例性地，本实施例中的钝化层200是氧化铝。第一减反射层300能降低太阳电池001的光反射率，从而提升太阳电池001的吸光效率，有利于提升电池效率。作为示例性的，本实施例中的第一减反射层300的材质为氮化硅(SiNx)。
在第一减反射层300的表面对应重掺杂区112的区域设置有电极600，电极600的材质通常为银；由于第一减反射层300和钝化层200不导电，因此电极600会穿透第一减反射层300和钝化层200与重掺杂区112形成欧姆接触，这样电极600才能收集到PN结产生的载流子。轻掺杂区111的硼浓度小于重掺杂区112的浓度，结深也小于重掺杂区112的浓度，因此重掺杂区112在与电极600形成欧姆接触时，接触电阻会明显降低，这有利于提升电池效率，而且还不会明显增加俄歇复合的现象发生。作为示例性的，本实施例中轻掺杂区111中的硼浓度为1018cm-3～1019cm-3，结深为0.4～0.8μm；重掺杂区112的硼浓度为1019cm-3～1020cm-3，结深为1.0～1.4μm。
在N型硅片100的背面依次叠加设置有多晶硅层400、第二减反射层500。 多晶硅层400具有良好的钝化作用，能降低金属接触复合电流。第二减反射层500不仅能降低太阳电池001的光反射率，同时还能保护N型硅片100的背面不容易发生氧化；作为示例性的，本实施例中的第二减反射层500的材质和第一减反射层300的材质相同，都是氮化硅。另外，本实施例在第二减反射层500的表面也设置有电极600，材质也为银。第二减反射层500表面的电极600会穿透第二减反射层500与多晶硅层400接触，并利用量子隧穿效应收集PN结产生的载流子。
上述的电池一般被称为TOPcon(Tunnel Oxide Passivated Contact solar cell，隧穿氧化层钝化接触太阳能电池)。目前在制备该类电池时，都会直接使用硼源在N型硅片100的正面进行硼扩散，以形成掺杂区110，会不可避免地形成厚的BSG层，BSG层虽然能保护掺杂区110不会被氧化，但是会阻止硼进一步扩散，无法形成硼浓度不同的轻掺杂区111和重掺杂区112。
因此，本申请还提供了上述的太阳电池001的制备方法，其具体步骤如下：
S100、制绒。
取N型硅片100，使用碱液对N型硅片100的正面和背面进行制绒，以使得N型硅片100的表面形成金字塔型的绒面，有利于增加N型硅片100的吸光率，制绒时碱液一般为KOH或NaOH溶液，浓度一般为1％。制绒完成之后再使用双氧水和碱液清洗硅片。
S200、第一次硼扩散。
使用气相硼源在N型硅片100的正面进行第一次硼扩散，以在N型硅片100的正面形成轻掺杂区111和厚度不大于10nm的BSG层，厚度不大于10nm的BSG层既能够起到保护轻掺杂区111的作用，保证其在生产过程中不会被氧化，还不会阻碍后续的第二次硼扩散，能保证后续在N型硅片100的正面形成重掺 杂区112。
作为示例性地，本步骤中的气相硼源可以是BCl3、BBr3、BH3中的至少一种，而且本步骤的处理温度一般为850～1000℃，时间一般为10～60min。
S300、第二次硼扩散。
本步骤是将硼浆涂覆在BSG层的表面并进行第二次硼扩散，使用硼浆有利于硼元素穿过BSG层并渗透在N型硅片100的正面，从而形成重掺杂区112的形成，而且在第二次硼扩散的过程中，BSG层的厚度会增加到100nm以上，这样能防止后续清洗(清洗过程详见后续说明)绕镀时造成正面过刻。
具体的，本步骤中，会先在150～300℃的温度下烘干浆料，烘干时间一般持续30～90s。之后再通入氧气在700～800℃下处理30～60min，这样能除去硼浆中的碳之类的杂质，使其转化成二氧化碳排出，解决了杂质残留问题；之后停止通入氧气，在无氧条件下于900～1100℃处理10～60min，这样有利于硼浆更好地推结，形成更深的结深。
S400、清理N型硅片100的背面。
在对N型硅片100的正面进行硼扩散的同时，不仅会在正面形成BSG层，还会在背面形成BSG层和掺杂区110。BSG层是后续形成太阳电池001不需要的层结构，因此需要除去。本步骤一般都是采用链式HF机去除背面硼扩绕镀的BSG层，再采用槽式碱抛机去除背面和边缘p-n结。
S500、形成多晶硅层400。
本步骤一般是采用气相沉积的方式在N型硅片100的背面沉积非晶硅薄膜，然后再通过退火的方式，在氮气或氧气的氛围下使得非晶硅薄膜转化形成多晶硅层400。
采用气相沉积的方式有利于控制薄膜的厚度，气相沉积的方式有PEALD (Plasma Enhanced Atomic Layer Deposition，等离子体增强原子层沉积)和PECVD(Plasma Enhanced Chemical Vapor Deposition，等离子体增强化学气相沉积法)等方式，作为示例性地，本实施例中是通过PECVD的方式沉积非晶硅薄膜。
S600、清理N型硅片100的正面。
正如步骤S400中的，BSG层是后续形成太阳电池001不需要的层结构，因此需要除去。该步骤是将N型硅片100的正面的BSG层除去。具体为：先使用RCA标准清洗法进行清洗(RCA标准清洗法为现有常用的技术，本申请在此不再赘述)；然后再用链式HF机去除正面的BSG层，再采用槽式碱抛机去除正面印刷残余的硼浆。
在该步骤才将BSG层除去，目的是为了防止制备过程中对掺杂层造成污染。
S700、形成钝化层200和第一减反射层300。
本步骤一般也是采用气相沉积的方式分别沉积钝化层200和第一减反射层300，其中钝化层200的材质一般为氧化铝，第一减反射层300的材质为氮化硅。
S800、形成第二减反射层500。
本步骤一般也是采用气相沉积的方式分别沉积钝化层200和第一减反射层300，而且在本实施例中，第二减反射层500的材质和第一减反射层300的材质相同，都是氮化硅。
S900、形成电极600。
该步骤一般使用丝网印刷的方式，分别在第一减反射层300和第二减反射层500的表面印刷银浆，然后经过烘干烧结形成电极600。其中在第一减反射层300表面的电极600是位于重掺杂区112所在的区域，而且第一减反射层300表面的电极600穿透了第一减反射层300和钝化层200，并与重掺杂区112形成欧 姆接触。
以下结合实施例对本申请的特征和性能作进一步的详细描述。
实施例1
本实施例提供了一种太阳电池001，其制备工艺包括如下步骤：
(1)制绒：采用N型硅片100，采用1％的NaOH溶液对N型硅片100进行制绒，之后分别使用双氧水和碱液清洗制绒后的N型硅片100。
(2)第一次硼扩散：以BCl3作为硼源，在管式硼扩散炉中对N型硅片100的正面进行第一次硼扩散，处理温度为950℃，处理时间为1800s，形成轻掺杂区111和5nm的BSG层。
(3)第二次硼扩散：采用丝网印刷机在BSG层表面印刷浓度7％、栅线高度为2μm的硼浆，并将硼浆在200℃温度下烘60s；之后在800℃条件下通入氧气30min，去除有机物中的碳，再在无氧条件下升温至1000℃并维持1800s进行无氧推结，在N型硅片100的正面形成重掺杂区112，并在硅片正面形成120nm的BSG层。
(4)清理N型硅片100的背面：采用链式HF机去除背面硼扩绕镀BSG，再采用槽式碱抛机去除背面和边缘p-n结。
(5)形成多晶硅层400：采用管式PECVD设备在硅片背面沉积非晶硅薄膜，然后采用管式炉退火，利用氮气使沉积的非晶硅薄膜转化成多晶硅层400。
(6)清理N型硅片100的正面：使用RCA标注清洗法清洗N型硅片100的正面，然后采用链式HF机去除正面的BSG层，再采用槽式碱抛机去除正面印刷残余的硼浆。
(7)形成钝化层200和第一减反射层300：采用PECVD的方式，先在N型硅片100的正面沉积一层氧化作为钝化层200，然后在钝化层200的表面沉积 一层氮化硅作为第一减反射层300。
(8)形成第二减反射层500：采用PECVD的方式沉积氮化硅，在多晶硅层400的表面沉积一层的氮化硅层作为第二减反射层500。
(9)形成电极600：使用丝网印刷的方式，分别在第一减反射层300和第二减反射层500的表面印刷银浆，然后经过烘干烧结形成电极600。其中第一减反射层300表面的电极600位于重掺杂区112所在的区域，且穿透了第一减反射层300和钝化层200与重掺杂区112形成欧姆接触。第二减反射层500的表面的电极600穿透第二减反射层500与多晶硅层400形成电性接触。
实施例2
本实施例提供了一种太阳电池001，其制备工艺相比于实施例1，主要区别为：
步骤(3)中，在700℃条件下通入氧气30min，去除有机物中的碳。
实施例3
本实施例提供了一种太阳电池001，其制备工艺相比于实施例1，主要具有如下区别：
步骤(3)中，在减压(700pa)条件下升温至980℃进行无氧推结，在N型硅片100的正面形成重掺杂区112，并在硅片正面形成120nm的BSG层。
实施例4
本实施例提供了一种太阳电池001，其制备工艺相比于实施例1，主要区别如下：
步骤(3)中，在1040℃的常压无氧条件下进行无氧推结，在N型硅片100的正面形成重掺杂区112，并在硅片正面形成120nm的BSG层。
实施例5
本实施例提供了一种太阳电池001，其制备工艺相比于实施例1，主要区别有：
步骤(3)中，通入1000sccm的氧在N型硅片100的正面形成150nm的BSG层。
实施例6
本实施例提供了一种太阳电池001，其制备工艺相比于实施例1，主要具有以下区别：
步骤(2)中，以BBr3作为硼源，处理温度为950℃，处理时间为2400s，形成轻掺杂区111和9nm的BSG层。
对比例1
本对比例提供了一种太阳电池001，其制备工艺相比于实施例1，主要区别为：
步骤(2)中，以硼浆作为硼源，处理温度为950℃，处理时间为2400s，形成掺杂区110和20nm的BSG层。
对比例2
本对比例提供了一种太阳电池001，其制备工艺相比于实施例1，主要区别是：
步骤(2)中，处理温度为980℃，处理时间为3600s，形成掺杂区110和30nm的BSG层。
对比例3
本对比例提供了一种太阳电池001，其制备工艺相比于实施例1，主要区别如下：
不含有步骤(3)，且在步骤(9)中，第一减反射层300表面的电极600穿 透第一减反射层300和钝化层200与轻掺杂区111形成欧姆接触。
应用例
使用Halm测试机对实施例1～实施例6和对比例1～对比例3中的太阳电池001的性能进行测试，具体结果如下表所示：
表1实施例1～6和对比例1～3的太阳能电池性能
以上仅为本申请的实施例而已，并不用于限制本申请的保护范围，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (10)

  1. 一种太阳电池，其特征在于，其包括N型硅片，所述N型硅片的正面设置有含有硼的掺杂区，所述掺杂区分为轻掺杂区和重掺杂区，所述轻掺杂区中的硼浓度小于所述重掺杂区的硼浓度，所述轻掺杂区的结深小于所述重掺杂区的结深；
    所述N型硅片的正面还依次叠加设置有钝化层、第一减反射层；所述第一减反射层的表面对应所述重掺杂区的区域设置有电极，且所述电极穿透所述第一减反射层和所述钝化层与所述重掺杂区形成欧姆接触。
  2. 根据权利要求1所述的太阳电池，其特征在于，所述轻掺杂区的硼浓度为1018cm-3～1019cm-3，所述重掺杂区的硼浓度为1019cm-3～1020cm-3。
  3. 根据权利要求1～2任一项所述的太阳电池，其特征在于，所述轻掺杂区的结深为0.4～0.8μm，所述重掺杂区的结深为1.0～1.4μm。
  4. 根据权利要求1～3任一项所述的太阳电池，其特征在于，所述N型硅片的背面依次叠加设置有多晶硅层、第二减反射层。
  5. 一种权利要求1～4任一项所述的太阳电池的制备方法，其特征在于，其包括以下步骤：
    使用气相硼源在N型硅片的正面进行第一次硼扩散，以在所述N型硅片的正面形成轻掺杂区和厚度不大于10nm的硼硅玻璃层；
    将硼浆涂覆在所述硼硅玻璃层的表面，并使用所述硼浆进行第二次硼扩散，以形成重掺杂区；
    除去所述硼硅玻璃层，并在所述N型硅片的正面依次形成钝化层、第一减反射层，并在所述第一减反射层的表面对应所述重掺杂区的区域印刷电极，且所述电极穿透所述第一减反射层和所述钝化层与所述重掺杂区形成欧姆接触。
  6. 根据权利要求5所述的太阳电池的制备方法，其特征在于，在所述第一次硼扩散的步骤中，温度为850～1000℃。
  7. 根据权利要求5～6任一项所述的太阳电池的制备方法，其特征在于，在所述第一次硼扩散的步骤中，所述气相硼源为BCl3、BBr3、BH3中的至少一种。
  8. 根据权利要求5～7任一项所述的太阳电池的制备方法，其特征在于，在所述第二次硼扩散的步骤时，先通入氧气并在700～800℃下处理30～60min以除去所述硼浆中的杂质；之后停止通入氧气，在无氧条件下于900～1100℃处理10～60min。
  9. 根据权利要求5～8任一项所述的太阳电池的制备方法，其特征在于，采用气相沉积的方式形成所述钝化层或所述第一减反射层。
  10. 根据权利要求5～9任一项所述的太阳电池的制备方法，其特征在于，在形成所述重掺杂区之后，其还包括以下步骤：
    在所述N型硅片的背面依次形成多晶硅层、第二减反射层。
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