WO2023160200A1 - 半导体衬底层的处理方法和太阳能电池的制备方法 - Google Patents

半导体衬底层的处理方法和太阳能电池的制备方法 Download PDF

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WO2023160200A1
WO2023160200A1 PCT/CN2022/141510 CN2022141510W WO2023160200A1 WO 2023160200 A1 WO2023160200 A1 WO 2023160200A1 CN 2022141510 W CN2022141510 W CN 2022141510W WO 2023160200 A1 WO2023160200 A1 WO 2023160200A1
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silicon wafer
crystal silicon
single crystal
layer
semiconductor substrate
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English (en)
French (fr)
Inventor
张良
张景
周锡伟
周肃
龚道仁
徐晓华
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Anhui Huasun Energy Co Ltd
Anhui Huasun Energy Co Ltd
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Anhui Huasun Energy Co Ltd
Anhui Huasun Energy Co Ltd
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Priority to JP2024523469A priority Critical patent/JP2024537419A/ja
Priority to US18/698,756 priority patent/US20240429339A1/en
Priority to EP22928443.5A priority patent/EP4394900A4/en
Publication of WO2023160200A1 publication Critical patent/WO2023160200A1/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
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/128—Annealing
    • 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
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/122—Active materials comprising only Group IV materials
    • 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
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6302—Non-deposition formation processes
    • H10P14/6304—Formation by oxidation, e.g. oxidation of the substrate
    • H10P14/6306—Formation by oxidation, e.g. oxidation of the substrate of the semiconductor materials
    • H10P14/6308—Formation by oxidation, e.g. oxidation of the substrate of the semiconductor materials of Group IV semiconductors
    • H10P14/6309—Formation by oxidation, e.g. oxidation of the substrate of the semiconductor materials of Group IV semiconductors of silicon in uncombined form, i.e. pure silicon
    • 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
    • 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 solar cell manufacturing, in particular to a method for processing a semiconductor substrate layer and a method for preparing a solar cell.
  • Solar cells have the advantages of clean and pollution-free, renewable, and stable working performance. According to the difference of solar cell structure, preparation process and materials used, solar cells are divided into different types. Including: silicon-based solar cells, multi-component compound thin-film solar cells, polymer multilayer modified electrode solar cells, organic solar cells, etc. Among them, silicon-based solar cells are the most mature, such as heterojunction solar cells. Taking heterojunction solar cells as an example, semiconductor layers, transparent conductive layers and metal electrodes are prepared on one or both sides of the N-type substrate to form cells, and then multiple cells are interconnected and packaged to form components, which generate electricity Then feed back to the grid through the inverter.
  • the N-type substrate is usually a single crystal silicon wafer, which is obtained by drawing a single crystal silicon rod and cutting it.
  • a plurality of single crystal silicon ingots are drawn, and in a single batch, the metal impurities in the post-drawn single crystal ingots are more than those in the front-drawn single crystal ingots.
  • Monocrystalline silicon wafers are used to prepare solar cells. Due to the presence of metal impurities, metal impurities and minority carriers will recombine, which will affect the photoelectric conversion efficiency, which in turn will affect the conversion efficiency of high-efficiency cells, and will also lead to a decrease in life.
  • Gettering is an important way to improve the crystal quality of single crystal silicon wafers. Through gettering, the content of metal impurities in single crystal silicon wafers can be reduced, making the quality of single crystal silicon wafers more consistent, so that the high-efficiency battery The conversion efficiency is more concentrated.
  • a main method is phosphoric acid chain spray gettering. Phosphoric acid is used as a diffusion liquid to spray onto the surface of monocrystalline silicon wafers. Phosphoric acid is naturally spread and then diffused and annealed to form a doped layer. The metal impurities in the doped layer are precipitated to the doped layer, and the doped layer is finally removed to achieve the purpose of impurity removal.
  • the present application provides a method for processing a semiconductor substrate layer and a method for preparing a solar cell, so as to solve the problem of uneven spreading of the diffusion liquid.
  • the present application provides a method for processing a semiconductor substrate layer, including the steps of providing a single crystal silicon wafer, the step of spraying a diffusion liquid on the surface of the single crystal silicon wafer and the step of annealing the single crystal silicon wafer, and
  • the method comprises the following steps: performing surface oxidation treatment on the single crystal silicon wafer before spraying the diffusion liquid on the surface of the single crystal silicon wafer, and the surface oxidation treatment is used to increase the lyophilicity of the surface of the single crystal silicon silicon wafer to the diffusion liquid , to increase the uniformity of the annealing treatment of monocrystalline silicon wafers.
  • the step of performing surface oxidation treatment includes: spraying oxygen-containing gas onto the surface of the single crystal silicon wafer.
  • the oxygen-containing gas includes ozone.
  • the concentration of the oxygen-containing gas is 50ppm-300ppm.
  • the injection rate of the oxygen-containing gas is 0.5slm ⁇ 5slm.
  • the time for spraying the oxygen-containing gas is 5 seconds to 30 seconds.
  • oxygen-containing gas is sprayed vertically toward the surface of the single crystal silicon wafer.
  • the surface oxidation treatment causes an oxide layer to be formed on the surface of the single crystal silicon wafer;
  • the method for processing the semiconductor substrate layer further includes: performing diffusion annealing treatment on the surface of the single crystal silicon wafer, diffusing the diffusion ions in the diffusion liquid into the partial thickness of the single crystal silicon wafer through the oxide layer, so as to form doped particles covered by the oxide layer in the partial thickness of the single crystal silicon wafer.
  • layer, and the diffusion annealing treatment is suitable for migrating impurities inside the single crystal silicon wafer into the doped layer.
  • the diffusion annealing treatment is a chain diffusion annealing treatment.
  • the surface oxidation treatment enables an oxide layer to be formed on the surface of the single crystal silicon wafer, and the thickness of the oxide layer is 0.5nm-20nm.
  • the material of the single crystal silicon wafer includes single crystal silicon
  • the material of the oxide layer includes silicon oxide
  • the step of performing diffusion annealing treatment on the surface of the single crystal silicon wafer includes: a heating process, a heat preservation process and a temperature reduction process carried out in sequence, the heat preservation process is suitable for diffusing diffusion ions into the single crystal silicon silicon wafer with a partial thickness, The cooling process is suitable for migrating impurities inside the monocrystalline silicon wafer to the doped layer.
  • the temperature of the heat preservation process is 800°C-900°C.
  • the thickness of the doped layer is 0.15 ⁇ m ⁇ 0.3 ⁇ m.
  • the diffusing fluid includes a phosphoric acid solution.
  • the mass concentration of the phosphoric acid solution is 2%-12%.
  • the monocrystalline silicon wafer before performing surface oxidation treatment on the monocrystalline silicon wafer, it also includes: removing the damaged layer on the surface of the monocrystalline silicon wafer; after removing the damaged layer on the surface of the monocrystalline silicon wafer, using a hydrophobic solution to treat the monocrystalline silicon Dehydration treatment is performed on the surface of the wafer; after the dehydration treatment, the monocrystalline silicon wafer is dried.
  • the etching solution used to remove the damaged layer on the surface of the single crystal silicon wafer is NaOH aqueous solution, KOH aqueous solution or a mixed solution of HF and HNO 3 .
  • the hydrophobic solution includes aqueous HF.
  • the mass concentration of the NaOH aqueous solution is 2%-15%.
  • the mass concentration of the KOH aqueous solution is 2%-15%.
  • the mixed solution of HF and HNO 3 is prepared from HF with a mass concentration of 45%-50% and HNO 3 with a mass concentration of 60%-70% in a volume ratio of 1:3-1:9.
  • the method further includes: removing the oxide layer; after removing the oxide layer, removing the doped layer.
  • the etching solution for removing the oxide layer is HCl aqueous solution, and the volume ratio of the HCl aqueous solution is 4%-5%.
  • the etching solution used for removing the doped layer is NaOH aqueous solution or KOH aqueous solution.
  • a mixed solution of HF and HNO 3 is used for removing the oxide layer and removing the doped layer.
  • the mass concentration of the NaOH aqueous solution is 2% to 15%;
  • the mass concentration of the KOH aqueous solution is 2% to 15%;
  • the mixed solution of HF and HNO 3 is prepared from HF with a mass concentration of 45%-50% and HNO 3 with a mass concentration of 60%-70% in a volume ratio of 1:3-1:9.
  • the method further includes: washing the monocrystalline silicon wafer with a neutralizing solution.
  • the neutralizing cleaning solution is a mixed solution of HF and HCl.
  • the present application also provides a method for preparing a solar cell, including the method for processing the semiconductor substrate layer provided in the present application.
  • the method for preparing the above-mentioned solar cell further includes the following steps: performing texturing treatment on the semiconductor substrate layer; A first intrinsic semiconductor layer is formed on one surface, and a second intrinsic semiconductor layer is formed on the other surface of the semiconductor substrate layer; a second intrinsic semiconductor layer is formed on the side of the first intrinsic semiconductor layer away from the semiconductor substrate layer.
  • a doped semiconductor layer forming a second doped semiconductor layer on the side of the second intrinsic semiconductor layer away from the semiconductor substrate layer; forming a second doped semiconductor layer on the side of the first doped semiconductor layer away from the semiconductor substrate layer forming a first transparent conductive film, forming a second transparent conductive film on the side of the second doped semiconductor layer away from the semiconductor substrate layer; and forming a second transparent conductive film on the side of the first transparent conductive film away from the semiconductor substrate layer
  • a first gate line electrode is formed, and a second gate line electrode is formed on the side of the second transparent conductive film away from the semiconductor substrate layer.
  • the single crystal silicon wafer is subjected to surface oxidation treatment before spraying the diffusion liquid.
  • surface oxidation treatment an oxide layer can be formed on the surface of single crystal silicon wafer in advance.
  • the oxide layer on the surface of the monocrystalline silicon wafer has a better lyophilic performance for the diffusion liquid, so the spreadability of the diffusion liquid is better during the spraying of the diffusion liquid, and the diffusion liquid has a faster spreading speed. Therefore, the spread of the diffusion liquid on the surface of the monocrystalline silicon wafer is more uniform.
  • the diffusion annealing treatment is suitable for migrating impurities inside the single crystal silicon wafer into the doped layer. Since the spreading of the diffusion liquid on the surface of the single crystal silicon wafer is more uniform, the distribution of diffused ions in the doped layer is more uniform, which makes the gettering effect of the doped layer more consistent in different regions, greatly improving the semiconductor substrate layer. performance.
  • FIG. 1 is a schematic flow diagram of a method for processing a semiconductor substrate layer in an embodiment of the present application
  • FIG. 2 is a detailed flow diagram of a method for processing a semiconductor substrate layer in an embodiment of the present application
  • 3 to 9 are structural schematic diagrams of the processing process of the semiconductor substrate layer in an embodiment of the present application.
  • 100 single crystal silicon wafer; 110, damaged layer; 120, oxide layer; 120', oxide layer; 130, doped layer; 200, semiconductor substrate layer.
  • the final photoelectric conversion efficiency and solar cell life may still be unsatisfactory.
  • the inventor's research has found that the specific reason is that phosphoric acid as a diffusion liquid has poor spreadability and a slow spreading speed in the process of phosphoric acid chain gettering, and the slow spreading speed of the diffusion liquid will easily lead to the formation of phosphoric acid on the surface of the single crystal silicon wafer. If the distribution is not uniform, there may be cases where gettering has been completed locally and will cause corrosion, but gettering has not been completed in other parts.
  • the application provides a method for processing a semiconductor substrate layer, including the step of providing a single crystal silicon wafer and the step of spraying the diffusion liquid on the surface of the single crystal silicon wafer, and also including The following steps: before spraying the diffusion liquid on the surface of the single crystal silicon wafer, perform surface oxidation treatment on the single crystal silicon wafer, the surface oxidation treatment is used to increase the lyophilicity of the single crystal silicon wafer to the diffusion liquid.
  • connection should be understood in a broad sense, for example, it can be a fixed connection or a detachable connection. Connected, or integrally connected; it can be mechanically or electrically connected; it can be directly connected, or indirectly connected through an intermediary, or it can be the internal communication of two components, which can be wireless or wired connect. Those of ordinary skill in the art can understand the specific meanings of the above terms in this application in specific situations.
  • the present embodiment provides a kind of processing method of semiconductor substrate layer, with reference to Fig. 1, comprises:
  • Step S1 providing monocrystalline silicon wafers
  • Step S2 performing surface oxidation treatment on the monocrystalline silicon wafer
  • Step S3 spraying the diffusion liquid on the surface of the monocrystalline silicon wafer
  • Step S4 Diffusion annealing treatment is performed on the surface of the single crystal silicon wafer.
  • the surface oxidation treatment is used to increase the lyophilicity of the single crystal silicon wafer to the diffusion liquid.
  • the diffusion liquid is used to form a doped layer in the diffusion annealing step, and get rid of metal impurities in the single crystal silicon wafer.
  • the surface oxidation treatment is carried out to the single crystal silicon silicon wafer before spraying the diffusion liquid.
  • an oxide layer can be formed on the surface of single crystal silicon wafer in advance.
  • the oxide layer on the surface of the monocrystalline silicon wafer has a better lyophilic performance for the diffusion liquid, so the spreadability of the diffusion liquid is better during the spraying of the diffusion liquid, and the diffusion liquid has a faster spreading speed. In this way, the spread of the diffusion liquid on the surface of the single crystal silicon wafer is more uniform, so as to increase the uniformity of the annealing treatment of the single crystal silicon wafer and greatly improve the performance of the semiconductor substrate layer.
  • step A1 removing the damaged layer on the surface of the single crystal silicon wafer
  • step A2 removing the single crystal silicon wafer
  • step A3 after the dehydration treatment, the single crystal silicon wafer is dried.
  • step S5 after performing the diffusion annealing treatment, removing the doped layer.
  • a single crystal silicon wafer 100 is provided.
  • the material of the single crystal silicon wafer 100 includes single crystal silicon.
  • the material of the single crystal silicon wafer is other semiconductor materials, such as germanium or silicon germanium.
  • the material of the semiconductor substrate layer can also be other semiconductor materials.
  • the conductivity type of the single crystal silicon wafer 100 is N type
  • the conductivity type of the semiconductor substrate layer formed subsequently is N type
  • the semiconductor substrate layer is used for solar cells. It should be noted that, in other embodiments, the conductivity type of the single crystal silicon wafer is P type.
  • the surface of the single crystal silicon wafer 100 has a damaged layer 110 .
  • the single crystal silicon wafer 100 has a damaged layer 110 on both the front and back sides. The damaged layer 110 is caused during the process of cutting the single crystal raw material to form the single crystal silicon wafer 100 .
  • the damaged layer 110 on the surface of the single crystal silicon wafer 100 ( FIG. 3 ) is removed.
  • the process of removing the damaged layer 110 includes a wet etching process.
  • the etching solution used to remove the damaged layer 110 on the surface of the single crystal silicon wafer 100 is NaOH aqueous solution, KOH aqueous solution Or a mixed solution of HF and HNO 3 .
  • the mass concentration of the NaOH aqueous solution is 2% to 15%; when removing the damaged layer on the surface of the single crystal silicon wafer, the corrosion
  • the mass concentration of the KOH aqueous solution is 2% to 15%;
  • the etching solution used to remove the damaged layer on the surface of the monocrystalline silicon wafer is a mixed solution of HF and HNO 3 , it is HF and HNO 3
  • the mixed solution is prepared from HF with a mass concentration of 45% to 50% and HNO3 with a mass concentration of 60% to 70% in a volume ratio of 1:3 to 1:9.
  • the surface of the single crystal silicon wafer is dehydrated with a hydrophobic solution.
  • the hydrophobic solution includes aqueous HF.
  • the etching solution used to remove the damaged layer 110 is NaOH solution or KOH solution, before the dehydration treatment, it further includes: using a neutralization treatment solution to remove residual etching solution.
  • the neutralization treatment solution is a mixed solution of HF and HCl.
  • the single crystal silicon wafer 100 is dried.
  • surface oxidation treatment is performed on the single crystal silicon wafer 100 .
  • the surface oxidation treatment makes an oxide layer 120 formed on the surface of the single crystal silicon wafer 100 .
  • the surface oxidation treatment can improve the uniformity of spreading of the diffusion liquid on the surface of the initial semiconductor layer 100 during the subsequent process of spraying the diffusion liquid on the surface of the single crystal silicon wafer 100 .
  • the oxide layer 120 has a thickness of 0.5 nm ⁇ 20 nm, for example, 0.5 nm, 1 nm or 2 nm.
  • the oxide layer 120 itself is very thin, it will not affect the diffusion of diffusion ions in the diffusion liquid through the oxide layer 120 in the subsequent diffusion annealing step.
  • the material of the oxide layer 120 is silicon oxide.
  • the step of performing surface oxidation treatment includes: spraying oxygen-containing gas onto the surface of the single crystal silicon wafer 100 .
  • the oxygen-containing gas may be ozone, for example.
  • the oxidation ability of ozone is better.
  • the concentration of the oxygen-containing gas is 50 ppm ⁇ 300 ppm, for example, 50 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm or 300 ppm. If the concentration of the oxygen-containing gas is too small, the oxidation rate will be slow and the process efficiency will decrease; if the concentration of the oxygen-containing gas is too high, the oxidation rate will be too fast, and the oxidation process will be difficult to be well controlled.
  • the injection rate of the oxygen-containing gas is 0.5slm ⁇ 5slm (standard liter per minute, liter per minute under standard conditions), for example, it may be 0.5slm, 1slm, 2slm, 4slm or 5slm. If the injection rate of oxygen-containing gas is too small, the oxidation rate will be slow and the process efficiency will be reduced; if the injection rate of oxygen-containing gas is too fast, the oxidation rate will be too fast, the oxidation process will be difficult to be well controlled, and it will also cause oxygen-containing Insufficient utilization of the body leads to more waste.
  • the time for spraying the oxygen-containing gas is 5 seconds to 30 seconds, for example, 5 s, 10 s, 15 s, 20 s, 25 s or 30 s. If the time for spraying oxygen-containing gas is too little, the oxidation will be insufficient, the thickness of the oxide layer 120 will be too thin, the uniformity of the oxide layer 120 will be poor, and the degree of the uniformity of the spread of the diffusion liquid on the surface of the single crystal silicon wafer will be improved. Small; if the time for spraying oxygen-containing gas is too long, the oxide layer 120 is too thick, which is not conducive to the diffusion of diffusion ions in the diffusion liquid.
  • the oxygen-containing gas is preferably sprayed in a direction perpendicular to the single crystal silicon wafer 100 .
  • the oxygen-containing gas is sprayed onto opposite sides of the monocrystalline silicon wafer 100 to form the oxide layer 120 on both opposite sides of the monocrystalline silicon wafer 100 .
  • the surface of the monocrystalline silicon wafer 100 is sprayed with diffusion liquid; afterward, the surface of the monocrystalline silicon wafer 100 is subjected to diffusion annealing treatment, so that the diffusion ions in the diffusion liquid diffuse into the part through the oxide layer 120 thickness of the monocrystalline silicon wafer 100 to form a doped layer 130 covered by the oxide layer 120 in the partial thickness of the monocrystalline silicon wafer 100, the diffusion annealing treatment is suitable for the monocrystalline silicon wafer 100 Impurities inside the crystalline silicon wafer 100 migrate into the doped layer 130 .
  • the oxide layer 120 is also doped with diffused ions.
  • the oxide layer 120 is silicon oxide and the diffused ions are phosphorus ions, the oxide layer 120 is Then an oxide layer 120' doped with diffused ions is formed, and the oxide layer 120' is phosphosilicate glass (PSG).
  • the step of spraying the diffusion liquid on the surface of the monocrystalline silicon wafer is specifically: spraying phosphoric acid on the surface of the initial semiconductor layer, and the phosphoric acid spreads naturally on the surface of the initial semiconductor layer.
  • the mass concentration of the phosphoric acid solution is 2% to 12%.
  • the diffusion liquid is sprayed on opposite sides of the single crystal silicon wafer 100 respectively, and the doped layer 130 is formed on both opposite sides of the single crystal silicon wafer 100 .
  • the steps of the diffusion annealing treatment include: a temperature rising process, a heat preservation process and a temperature drop process carried out in sequence, and the heat preservation process is suitable for diffusing the diffusion ions into the partial thickness of the single crystal silicon wafer, so The temperature reduction process is suitable for migrating impurities inside the single crystal silicon wafer to the doped layer.
  • the diffusion annealing treatment is a chain diffusion annealing treatment, which is performed in a chain diffusion annealing furnace.
  • the time of the heating process is 50s ⁇ 100s, for example, it may be 50s, 60s, 70s, 80s, 90s, 100s.
  • the heating process is from room temperature to 800°C to 900°C, for example, 800°C, 850°C, 900°C.
  • the temperature during the heat preservation process is maintained at 800°C to 900°C.
  • the time of the cooling process is 50s ⁇ 100s, for example, it may be 50s, 60s, 70s, 80s, 90s, 100s. During the cooling process, the temperature is lowered by 300°C to 500°C from the temperature during the heat preservation process.
  • the material of the initial semiconductor layer 100 is single crystal silicon
  • the doped layer 130 is a silicon layer doped with phosphorus.
  • the thickness of the doped layer 130 is 0.15 ⁇ m ⁇ 0.3 ⁇ m, for example, 0.15 ⁇ m, 0.2 ⁇ m, 0.25 ⁇ m, 0.3 ⁇ m.
  • the distribution of the diffused ions in the doped layer is more uniform, so that the gettering effect of the doped layer is more consistent in different regions.
  • the oxide layer 120' is removed; after removing the oxide layer 120', the doped layer 130 is removed to form a semiconductor substrate layer 200. Referring to FIG. 9, the oxide layer 120' is removed; after removing the oxide layer 120', the doped layer 130 is removed to form a semiconductor substrate layer 200. Referring to FIG. 9, the oxide layer 120' is removed; after removing the oxide layer 120', the doped layer 130 is removed to form a semiconductor substrate layer 200. Referring to FIG.
  • the etching solution for removing the oxide layer 120' is HCl aqueous solution, and the mass concentration of the HCl aqueous solution is 4%-5%, for example, 4% or 5%.
  • the process of removing the doped layer 130 includes a wet etching process.
  • the etching solution used for removing the doped layer 130 is NaOH aqueous solution or KOH aqueous solution.
  • the mass concentration of the NaOH aqueous solution is 2% to 15%; when the etching solution used to remove the doped layer 130 is a KOH aqueous solution, the mass concentration of the KOH aqueous solution is 2%. ⁇ 15%.
  • a mixed solution of HF and HNO 3 is used to remove the oxide layer 120 ′ and remove the doped layer 130 .
  • the etchant used is a mixed solution of HF and HNO 3
  • the mixed solution of HF and HNO 3 consists of HF with a mass concentration of 45% to 50% and a mass concentration of 60% to 70%
  • the % HNO 3 is prepared in a volume ratio of 1:3 to 1:9.
  • the impurity removal effect in the semiconductor substrate layer is better.
  • the method further includes: cleaning the monocrystalline silicon wafer with a neutralized cleaning solution.
  • the neutralization cleaning solution is a mixed solution of HF and HCl.
  • drying is performed to complete the processing of the semiconductor substrate layer 200 .
  • the relative values of the test results of the semiconductor substrate layer obtained by the processing method of this embodiment are as follows (with the non-oxidized single crystal silicon silicon wafer as the reference value) :
  • This embodiment provides a method for preparing a solar cell, including the method for processing a semiconductor substrate layer as provided in Embodiment 1.
  • the method for preparing a solar cell further includes the following steps after treating the semiconductor substrate layer: performing texturing treatment on the semiconductor substrate layer; A first intrinsic semiconductor layer is formed on one side surface; a second intrinsic semiconductor layer is formed on the other side surface of the semiconductor substrate layer; a second intrinsic semiconductor layer is formed on the side of the first intrinsic semiconductor layer away from the semiconductor substrate layer.
  • a doped semiconductor layer forming a second doped semiconductor layer on the side of the second intrinsic semiconductor layer away from the semiconductor substrate layer; forming a second doped semiconductor layer on the side of the first doped semiconductor layer away from the semiconductor substrate layer Forming a first transparent conductive film; forming a second transparent conductive film on the side of the second doped semiconductor layer away from the semiconductor substrate layer; forming a second transparent conductive film on the side of the first transparent conductive film away from the semiconductor substrate layer A first gate line electrode; a second gate line electrode is formed on the side of the second transparent conductive film away from the semiconductor substrate layer.
  • the solar cell finally formed by the solar cell manufacturing method in this embodiment has a higher photoelectric conversion efficiency and a longer service life.

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Abstract

本申请提供一种半导体衬底层的处理方法和太阳能电池的制备方法。半导体衬底层的处理方法包括提供单晶硅硅片的步骤、对所述单晶硅硅片的表面喷淋扩散液的步骤和对单晶硅硅片进行退火处理的步骤，还包括：在对单晶硅硅片的表面喷淋扩散液之前，对所述单晶硅硅片进行表面氧化处理，所述表面氧化处理用于增加所述单晶硅硅片的表面对所述扩散液的亲液性，以增加所述单晶硅硅片退火处理的均匀性。本申请提供的半导体衬底层的处理方法可解决扩散液铺展不均匀的问题，极大提高半导体衬底层的性能。

Description

半导体衬底层的处理方法和太阳能电池的制备方法
本申请要求在2022年2月28日提交中国专利局、申请号为202210189426.0、发明名称为“半导体衬底层的处理方法和太阳能电池的制备方法”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
本申请涉及太阳能电池制造领域，具体涉及一种半导体衬底层的处理方法和太阳能电池的制备方法。
背景技术
太阳能电池具有清洁无污染、可再生、工作性能稳定等优点。根据太阳能电池结构、制备工艺和使用材料的不同，太阳能电池划分为不同的类型。包括：硅基太阳能电池、多元化合物薄膜太阳能电池、聚合物多层修饰电极型太阳能电池、有机太阳能电池等，其中硅基太阳能电池是发展最成熟的，例如异质结太阳能电池等。以异质结太阳能电池作为示例，其在N型衬底的一侧或两侧制备半导体层、透明导电层和金属电极形成电池片，接着将多个电池片进行互联并封装形成组件，组件发电后通过逆变器回馈电网。
N型衬底通常为单晶硅硅片，单晶硅硅片通过拉制单晶硅晶棒切割后得到。在单晶硅晶棒拉制过程中，由于金属杂质的分凝系数非常小，单根晶棒头尾会存在金属含量的差异；尤其是现有技术通常采用连续投料拉制的方法，可以连续拉制出多根单晶硅晶棒，单批次中在后拉制的单晶棒中的金属杂质比在前拉制的单晶棒中的金属杂质更多。采用单晶硅硅片制备太阳能电池，由于金属杂质的存在，会发生金属杂质与少数载流子的复合，从而影响光电转化效率，进而影响高效电池的转换效率，还会导致寿命下降。
吸杂是改善单晶硅硅片晶体质量的一种重要方式，通过吸杂可以减少单晶硅硅片内的金属杂质含量，使得单晶硅硅片质量一致性更好，从而使得高效电池的转换效率集中度更高。目前一种主要的手段是磷酸链式喷淋吸杂，以磷酸作为扩散液喷淋至单晶硅硅片表面，磷酸自然铺展后经过扩散退火形成掺杂层，这个过程中单晶硅硅片中的金属杂质析出至掺杂层，最后去除掺杂层从而实现除杂目的。但是，对衬底的单晶硅硅片进行磷酸 链式喷淋吸杂的方法处理中，磷酸容易在单晶硅硅片表面铺展不均匀，可能导致最终的太阳能电池的寿命和光电转化效率不理想。因此需要一种方案来解决磷酸铺展不均匀的问题。
发明内容
本申请提供一种半导体衬底层的处理方法和太阳能电池的制备方法，以解决扩散液铺展不均匀的问题。
本申请提供一种半导体衬底层的处理方法，包括提供单晶硅硅片的步骤、对单晶硅硅片的表面喷淋扩散液的步骤和对单晶硅硅片进行退火处理的步骤，还包括以下步骤：在对单晶硅硅片的表面喷淋扩散液之前，对单晶硅硅片进行表面氧化处理，表面氧化处理用于增加单晶硅硅片的表面对扩散液的亲液性，以增加单晶硅硅片退火处理的均匀性。
可选的，进行表面氧化处理的步骤包括：向单晶硅硅片的表面喷射含氧气体。
可选的，含氧气体包括臭氧。
可选的，含氧气体的浓度为50ppm～300ppm。
可选的，含氧气体的喷射速率为0.5slm～5slm。
可选的，喷射含氧气体的时间为5秒～30秒。
可选的，在表面氧化处理的步骤中，含氧气体垂直向单晶硅硅片的表面喷射。
可选的，所述表面氧化处理使得在所述单晶硅硅片的表面形成氧化层；所述半导体衬底层的处理方法还包括：对所述单晶硅硅片的表面进行扩散退火处理，使得所述扩散液中的扩散离子通过所述氧化层扩散进入部分厚度的所述单晶硅硅片，以在部分厚度的所述单晶硅硅片中形成被所述氧化层覆盖的掺杂层，所述扩散退火处理适于将所述单晶硅硅片内部的杂质迁移至所述掺杂层中。
可选的，扩散退火处理为链式扩散退火处理。
可选的，表面氧化处理使得在单晶硅硅片的表面形成氧化层，氧化层的厚度为0.5nm～20nm。
可选的，单晶硅硅片的材料包括单晶硅，氧化层的材料包括氧化硅。
可选的，对单晶硅硅片的表面进行扩散退火处理的步骤包括：依次进行的升温过程、保温过程和降温过程，保温过程适于将扩散离子扩散进入部分厚度的单晶硅硅片，降温过程适于将单晶硅硅片内部的杂质迁移至掺杂层中。
可选的，保温过程的温度为800℃～900℃摄氏度。
可选的，掺杂层的厚度为0.15μm～0.3μm。
可选的，扩散液包括磷酸溶液。
可选的，磷酸溶液的质量浓度为2％～12％。
可选的，对单晶硅硅片进行表面氧化处理之前，还包括：去除单晶硅硅片表面的损伤层；去除单晶硅硅片表面的损伤层之后，采用疏水溶液对单晶硅硅片的表面进行脱水处理；进行脱水处理之后，对单晶硅硅片进行烘干处理。
可选的，去除单晶硅硅片表面的损伤层采用的腐蚀液为NaOH水溶液、KOH水溶液或HF与HNO 3的混合溶液。
可选的，疏水溶液包括HF水溶液。
可选的，NaOH水溶液的质量浓度为2％～15％。
可选的，KOH水溶液的质量浓度为2％～15％。
可选的，HF与HNO 3的混合溶液由质量浓度45％～50％的HF和质量浓度60％～70％的HNO 3按体积比1:3～1:9配制。
可选的，进行扩散退火处理之后，还包括：去除所述氧化层；去除所述氧化层之后，去除所述掺杂层。
可选的，去除所述氧化层的腐蚀液为HCl水溶液，HCl水溶液的体积比4％～5％。
可选的，去除掺杂层采用的腐蚀液为NaOH水溶液或KOH水溶液。可选的，去除所述氧化层和去除所述掺杂层均采用HF与HNO 3的混合溶液。
可选的，NaOH水溶液的质量浓度为2％～15％；
可选的，KOH水溶液的质量浓度为2％～15％；
可选的，HF与HNO 3的混合溶液由质量浓度45％～50％的HF和质量浓度60％～70％的HNO 3按体积比1:3～1:9配制。
可选的，在去除掺杂层之后，还包括：采用中和液清洗清洗所述单晶硅硅片。
可选的，中和清洗液为HF和HCl的混合溶液。
本申请还提供一种太阳能电池的制备方法，包括本申请提供的半导体衬底层的处理方法。
可选的，上述太阳能电池的制备方法在对所述半导体衬底层进行处理后，还包括以下步骤：对所述半导体衬底层进行制绒处理；进行制绒处理之后，在所述半导体衬底层的一侧表面形成第一本征半导体层，在所述半导体衬底层的另一侧表面形成第二本征半导体层；在所述第一本征半导体层背离所述半导体衬底层的一侧形成第一掺杂半导体层，在所述第二本征半导体层背离所述半导体衬底层的一侧形成第二掺杂半导体层；在所述第一掺杂半导体层背离所述半导体衬底层的一侧形成第一透明导电膜，在所述第 二掺杂半导体层背离所述半导体衬底层的一侧形成第二透明导电膜；以及在所述第一透明导电膜背离所述半导体衬底层的一侧形成第一栅线电极，在所述第二透明导电膜背离所述半导体衬底层的一侧形成第二栅线电极。
本申请的有益效果在于：
本申请提供的半导体衬底层的处理方法，在喷淋扩散液之前对单晶硅硅片进行表面氧化处理。通过表面氧化处理，可预先在单晶硅硅片表面形成氧化层。单晶硅硅片表面的氧化层对于扩散液具有更好的亲液性表现，因此喷淋扩散液的过程中扩散液的铺展性更好，且喷淋扩散液的过程中扩散液具有更快的铺展速度。从而使得扩散液在单晶硅硅片表面的铺展更加均匀。
进一步，对所述单晶硅硅片的表面进行扩散退火处理，使得扩散液中的扩散离子扩散进入部分厚度的所述单晶硅硅片，以在部分厚度的所述单晶硅硅片中形成掺杂层，所述扩散退火处理适于将所述单晶硅硅片内部的杂质迁移至所述掺杂层中。由于扩散液在单晶硅硅片表面的铺展更加均匀，因此使得掺杂层中扩散离子的分布较为均匀，这样使得掺杂层的吸杂效果在不同区域较为一致，极大提高半导体衬底层的性能。
附图说明
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，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的附图。
图1为本申请的一实施例中半导体衬底层的处理方法的流程示意图；
图2为本申请的一实施例中半导体衬底层的处理方法的详细流程示意图；
图3至图9为本申请的一实施例中的半导体衬底层的处理过程的结构示意图。
附图说明：
100、单晶硅硅片；110、损伤层；120、氧化层；120’、氧化层；130、掺杂层；200、半导体衬底层。
具体实施方式
正如背景技术所述，对衬底的单晶硅硅片进行链式磷酸吸杂的方法处理后，最终的光电转化效率和太阳能电池寿命可能仍不理想。经过发明人的研究发现，具体的原因在于：磷酸链式吸杂的过程中作为扩散液的磷酸铺展性较差且铺展速度较慢，扩散液铺展速度慢容易导致单晶硅硅片表面 磷酸的分布不均匀，可能产生局部已完成吸杂即将造成腐蚀，但仍有其他部位未完成吸杂的情况。
为解决上述扩散液铺展不均匀的问题，本申请提供一种半导体衬底层的处理方法，包括提供单晶硅硅片的步骤和对单晶硅硅片的表面喷淋扩散液的步骤，还包括以下步骤：在对所述单晶硅硅片的表面喷淋扩散液之前，对单晶硅硅片进行表面氧化处理，表面氧化处理用于增加单晶硅硅片对扩散液的亲液性。
下面将结合附图对本申请的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
在本申请的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
在本申请的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，还可以是两个元件内部的连通，可以是无线连接，也可以是有线连接。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本申请中的具体含义。
此外，下面所描述的本申请不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
实施例1
本实施例提供一种半导体衬底层的处理方法，参考图1，包括：
步骤S1：提供单晶硅硅片；
步骤S2：对单晶硅硅片进行表面氧化处理；
步骤S3：对单晶硅硅片的表面喷淋扩散液；
步骤S4：对单晶硅硅片的表面进行扩散退火处理。
在本申请中，所述表面氧化处理用于增加单晶硅硅片对扩散液的亲液性。扩散液用于在扩散退火步骤中形成掺杂层，吸除单晶硅硅片中的金属杂质。
本实施例的半导体衬底层的处理方法，在喷淋扩散液之前对单晶硅硅 片进行表面氧化处理。通过表面氧化处理，可预先在单晶硅硅片表面形成氧化层。单晶硅硅片表面的氧化层对于扩散液具有更好的亲液性表现，因此喷淋扩散液的过程中扩散液的铺展性更好，且喷淋扩散液的过程中扩散液具有更快的铺展速度。从而使得扩散液在单晶硅硅片表面的铺展更加均匀，以增加单晶硅硅片退火处理的均匀性，极大提高半导体衬底层的性能。
本实施例中，参考图2，对所述单晶硅硅片进行表面氧化处理之前，还包括：步骤A1：去除所述单晶硅硅片表面的损伤层；步骤A2：去除所述单晶硅硅片表面的损伤层之后，采用疏水溶液对所述单晶硅硅片的表面进行脱水处理；步骤A3：进行所述脱水处理之后，对所述单晶硅硅片进行烘干处理。
本实施例中，参考图2，还包括：步骤S5：进行扩散退火处理之后，去除掺杂层。
下面结合参考图3至图9进行详细的说明。
参考图3，提供单晶硅硅片100。
所述单晶硅硅片100的材料包括单晶硅。在其他实施例中，所述单晶硅硅片的材料为其他的半导体材料，如锗或者硅锗。所述半导体衬底层的材料还可以为其他的半导体材料。
本实施例中，所述单晶硅硅片100的导电类型为N型，后续形成的半导体衬底层的导电类型为N型，半导体衬底层用于太阳能电池。需要说明的是，在其他实施例中，单晶硅硅片的导电类型为P型。
本实施例中，所述单晶硅硅片100的表面具有损伤层110。在一个具体的实施例中，所述单晶硅硅片100的正面和背面均具有损伤层110。所述损伤层110是由于在切割单晶原料以形成单晶硅硅片100的过程中造成的。
参考图4，去除所述单晶硅硅片100表面的损伤层110(图3)。
本实施例中，去除损伤层110的工艺包括湿法刻蚀工艺，在一个具体的实施例中，去除所述单晶硅硅片100表面的损伤层110采用的腐蚀液为NaOH水溶液、KOH水溶液或HF与HNO 3的混合溶液。当去除所述单晶硅硅片表面的损伤层采用的腐蚀液为NaOH水溶液时，NaOH水溶液的质量浓度为2％～15％；当去除所述单晶硅硅片表面的损伤层采用的腐蚀液为KOH水溶液时，KOH水溶液的质量浓度为2％～15％；当去除所述单晶硅硅片表面的损伤层采用的腐蚀液为HF与HNO 3的混合溶液时，为HF与HNO 3的混合溶液由质量浓度45％～50％的HF和质量浓度60％～70％的HNO 3按体积比1:3～1:9配制。
参考图5，去除所述单晶硅硅片100表面的损伤层110之后，采用疏水溶液对所述单晶硅硅片的表面进行脱水处理。
所述疏水溶液包括HF水溶液。
在其他一些实施例中，当去除损伤层110时采用的腐蚀液为NaOH溶液或KOH溶液时，在脱水处理之前还包括：使用中和处理液去除残留的腐蚀液。中和处理液为HF与HCl的混合溶液。
参考图6，进行所述脱水处理之后，对所述单晶硅硅片100进行烘干处理。
参考图7，对单晶硅硅片100进行表面氧化处理。所述表面氧化处理使得在所述单晶硅硅片100的表面形成氧化层120。表面氧化处理能提高在后续对单晶硅硅片100的表面喷扩散液的过程中扩散液在初始半导体层100表面铺展的均匀程度。
在一个实施例中，所述氧化层120的厚度为0.5nm～20nm，例如可以为0.5nm、1nm或2nm。
由于氧化层120本身很薄，因此不会影响后续的扩散退火步骤中扩散液中的扩散离子的扩散通过氧化层120。
当所述单晶硅硅片的材料为单晶硅时，所述氧化层120的材料为氧化硅。
进行表面氧化处理的步骤包括：向单晶硅硅片100的表面喷射含氧气体。
具体的，含氧气体例如可以为臭氧。臭氧的氧化能力较好。
在一个实施例中，含氧气体的浓度为50ppm～300ppm，例如可以为50ppm、100ppm、150ppm、200ppm、250ppm或300ppm。若含氧气体的浓度过小，则氧化速率较慢，工艺效率降低；若含氧气体的浓度过大，则氧化速度过快，氧化过程难以得到较好的控制。
在一个实施例中，含氧气体的喷射速率为0.5slm～5slm(standard liter per minute，标况下升每分钟)，例如可以为0.5slm、1slm、2slm、4slm或5slm。若含氧气体的喷射速率过小，则氧化速率较慢，工艺效率降低；若含氧气体的喷射速率过快，则氧化速度过快，氧化过程难以得到较好的控制，还会造成含氧气体利用不充分而导致较多的浪费。
在一个实施例中，喷射含氧气体的时间为5秒～30秒，例如可以为5s、10s、15s、20s、25s或30s。若喷射含氧气体的时间过少，则氧化不充分，氧化层120的厚度过薄，氧化层120的均匀性较差，扩散液在单晶硅硅片的表面的铺展均匀性的提高的程度较小；若喷射含氧气体的时间过长，氧化层120过厚，不利于扩散液中的扩散离子的扩散。
喷射含氧气体较佳为垂直单晶硅硅片100的方向喷射。
在一些实施例中，向单晶硅硅片100的相对两侧表面均喷射含氧气体， 在单晶硅硅片100的相对两侧均形成氧化层120。
参考图8，对单晶硅硅片100的表面喷淋扩散液；之后对单晶硅硅片100表面进行扩散退火处理，使得所述扩散液中的扩散离子通过所述氧化层120扩散进入部分厚度的所述单晶硅硅片100，以在部分厚度的所述单晶硅硅片100中形成被所述氧化层120覆盖的掺杂层130，所述扩散退火处理适于将所述单晶硅硅片100内部的杂质迁移至所述掺杂层130中。
掺杂层130对于金属杂质的固溶度相比于初始半导体层有所增加，因此金属杂质会自初始半导体层中未形成掺杂层130的部分逐渐向掺杂层130中迁移。本实施例中，进行所述扩散退火处理之后，氧化层120中也掺杂有扩散离子，当氧化层120的材料为氧化硅，扩散离子为磷离子时，氧化层120在所述扩散退火处理之后形成掺杂有扩散离子的氧化层120’,氧化层120’为磷硅玻璃(PSG)。
在本实施例中，对单晶硅硅片的表面喷淋扩散液的步骤具体为：对初始半导体层表面喷淋磷酸，磷酸在初始半导体层表面自然铺展。其中磷酸溶液的质量浓度为2％～12％。
在一些实施例中，在单晶硅硅片100的相对两侧表面分别喷淋扩散液，在单晶硅硅片100的相对两侧均形成掺杂层130。
在本实施例中，扩散退火处理的步骤包括：依次进行的升温过程、保温过程和降温过程，所述保温过程适于将所述扩散离子扩散进入部分厚度的所述单晶硅硅片，所述降温过程适于将所述单晶硅硅片内部的杂质迁移至所述掺杂层中。在本实施例中，扩散退火处理为链式扩散退火处理，在链式扩散退火炉中进行。
其中，升温过程的时间为50s～100s，例如可以为50s、60s、70s、80s、90s、100s。升温过程为从室温升温至800℃～900℃，例如可以为800℃、850℃、900℃。保温过程中的温度保持为800℃～900℃。降温过程的时间为50s～100s，例如可以为50s、60s、70s、80s、90s、100s。降温过程中温度从保温过程中的温度降低300℃～500℃。
在本实施例中，初始半导体层100的材料为单晶硅，掺杂层130为掺杂磷的硅层。掺杂层130的厚度为0.15μm～0.3μm，例如可以为0.15μm、0.2μm、0.25μm、0.3μm。
由于扩散液在单晶硅硅片表面的铺展更加均匀，因此使得掺杂层中扩散离子的分布较为均匀，这样使得掺杂层的吸杂效果在不同区域较为一致。
参考图9，去除所述氧化层120’；去除所述氧化层120’之后，去除所述掺杂层130，以形成半导体衬底层200。
本实施例中，去除所述氧化层120’的腐蚀液为HCl水溶液，HCl水溶 液的质量浓度为4％～5％，例如为4％或5％。本实施例中，去除掺杂层130的工艺包括湿法刻蚀工艺。在一个具体的实施例中，去除掺杂层130采用的腐蚀液为NaOH水溶液或KOH水溶液。当去除掺杂层130采用的腐蚀液为NaOH水溶液时，NaOH水溶液的质量浓度为2％～15％；当去除掺杂层130采用的腐蚀液为KOH水溶液时，KOH水溶液的质量浓度为2％～15％。
在其他实施例中，去除所述氧化层120’和去除所述掺杂层130均采用HF与HNO 3的混合溶液。当去除氧化层120和去除掺杂层130采用的腐蚀液为HF与HNO 3的混合溶液时，为HF与HNO 3的混合溶液由质量浓度45％～50％的HF和质量浓度60％～70％的HNO 3按体积比1:3～1:9配制。
由于掺杂层的吸杂效果在不同区域较为一致，去除掺杂层之后，半导体衬底层中杂质去除效果更好。
在其他一些实施例中，在去除掺杂层之后，还包括：采用中和清洗液清洗单晶硅硅片。其中，中和清洗液为HF和HCl的混合溶液。
最后进行干燥，以完成半导体衬底层200的处理。
以未经氧化处理的单晶硅硅片作为对比组，采用本实施例的处理方法得到的半导体衬底层的测试结果的相对值如下(以未经氧化处理的单晶硅硅片作为基准值)：
组别 平均少子寿命 少子寿命最小值 少子寿命最大值 电池效率
经氧化处理组 +10％ +30％ +2％ +0.08％
未经氧化处理组 1 1 1 1
可见，经氧化处理后，半导体衬底层的平均少子寿命、少子寿命最小值均得到了极大改善，少子寿命最大值和制得的电池效率也得到了一定程度的提高。
实施例2
本实施例提供一种太阳能电池的制备方法，包括如实施例1中提供的半导体衬底层的处理方法。
本实施例中，太阳能电池的制备方法在对所述半导体衬底层进行处理后，还包括以下步骤：对所述半导体衬底层进行制绒处理；进行制绒处理之后，在所述半导体衬底层的一侧表面形成第一本征半导体层；在所述半导体衬底层的另一侧表面形成第二本征半导体层；在所述第一本征半导体层背离所述半导体衬底层的一侧形成第一掺杂半导体层；在所述第二本征半导体层背离所述半导体衬底层的一侧形成第二掺杂半导体层；在所述第一掺杂半导体层背离所述半导体衬底层的一侧形成第一透明导电膜；在所述第二掺杂半导体层背离所述半导体衬底层的一侧形成第二透明导电膜；在所 述第一透明导电膜背离所述半导体衬底层的一侧形成第一栅线电极；在所述第二透明导电膜背离所述半导体衬底层的一侧形成第二栅线电极。
由于半导体衬底层的杂质去除效果更好，因此使得本实施例中的太阳能电池的制备方法最终形成的太阳能电池光电转化效率更高，寿命更长。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本申请的保护范围之中。

Claims (11)

  1. 一种半导体衬底层的处理方法，包括提供单晶硅硅片的步骤、对所述单晶硅硅片的表面喷淋扩散液的步骤和对单晶硅硅片进行退火处理的步骤，其特征在于，还包括以下步骤：
    在对所述单晶硅硅片的表面喷淋扩散液之前，对所述单晶硅硅片进行表面氧化处理，所述表面氧化处理用于增加所述单晶硅硅片的表面对所述扩散液的亲液性，以增加所述单晶硅硅片退火处理的均匀性。
  2. 根据权利要求1所述的半导体衬底层的处理方法，其特征在于，进行所述表面氧化处理的步骤包括：向所述单晶硅硅片的表面喷射含氧气体；
    优选的，所述含氧气体包括臭氧；
    优选的，所述含氧气体的浓度为50ppm～300ppm；
    优选的，所述含氧气体的喷射速率为0.5slm～5slm；
    优选的，喷射所述含氧气体的时间为5秒-30秒；
    优选的，在所述表面氧化处理的步骤中，所述含氧气体垂直向所述单晶硅硅片的表面喷射。
  3. 根据权利要求1所述的半导体衬底层的处理方法，其特征在于，所述表面氧化处理使得在所述单晶硅硅片的表面形成氧化层；
    所述对所述单晶硅硅片的表面进行扩散退火处理的步骤，使得所述扩散液中的扩散离子通过所述氧化层扩散进入部分厚度的所述单晶硅硅片，以在部分厚度的所述单晶硅硅片中形成被所述氧化层覆盖的掺杂层，所述扩散退火处理适于将所述单晶硅硅片内部的杂质迁移至所述掺杂层中；
    优选的，所述扩散退火处理为链式扩散退火处理。
  4. 根据权利要求3所述的半导体衬底层的处理方法，其特征在于，所述氧化层的厚度为0.5nm～20nm；
    优选的，所述单晶硅硅片的材料包括单晶硅，所述氧化层的材料包括氧化硅。
  5. 根据权利要求3所述的半导体衬底层的处理方法，其特征在于，对所述单晶硅硅片的表面进行扩散退火处理的步骤包括：依次进行的升温过程、保温过程和降温过程，所述保温过程适于将所述扩散离子扩散进入部分厚度的所述单晶硅硅片，所述降温过程适于将所述单晶硅硅片内部的杂质迁移至所述掺杂层中；
    优选的，所述保温过程的温度为800℃～900℃摄氏度；
    优选的，所述掺杂层的厚度为0.15μm～0.3μm。
  6. 根据权利要求1至5任意一项所述的半导体衬底层的处理方法，其特征在于，所述扩散液包括磷酸溶液；
    优选的，所述磷酸溶液的质量浓度为2％～12％。
  7. 根据权利要求1至5任意一项所述的半导体衬底层的处理方法，其特征在于，对所述单晶硅硅片进行表面氧化处理之前，还包括：去除所述单晶硅硅片表面的损伤层；去除所述单晶硅硅片表面的损伤层之后，采用疏水溶液对所述单晶硅硅片的表面进行脱水处理；进行所述脱水处理之后，对所述单晶硅硅片进行烘干处理；
    优选的，去除所述单晶硅硅片表面的损伤层采用的腐蚀液为NaOH水溶液、KOH水溶液或HF与HNO 3的混合溶液；
    优选的，所述疏水溶液包括HF水溶液；
    优选的，所述NaOH水溶液的质量浓度为2％～15％；
    优选的，所述KOH水溶液的质量浓度为2％～15％；
    优选的，所述HF与HNO 3的混合溶液由质量浓度45％～50％的HF和质量浓度60％～70％的HNO 3按体积比1:3～1:9配制。
  8. 根据权利要求3所述的半导体衬底层的处理方法，其特征在于，进行所述扩散退火处理之后，还包括：去除所述氧化层；去除所述氧化层之后，去除所述掺杂层；
    优选的，去除所述氧化层的腐蚀液为HCl水溶液，HCl水溶液中HCl的质量浓度为4％～5％；
    优选的，去除所述掺杂层采用的腐蚀液为NaOH水溶液或KOH水溶液；
    优选的，去除所述氧化层和去除所述掺杂层均采用HF与HNO 3的混合溶液；
    优选的，所述NaOH水溶液的质量浓度为2％～15％；
    优选的，所述KOH水溶液的质量浓度为2％～15％；
    优选的，所述HF与HNO 3的混合溶液由质量浓度45％～50％的HF和质量浓度60％～70％的HNO 3按体积比1:3～1:9配制。
  9. 根据权利要求8所述的半导体衬底层的处理方法，其特征在于，
    在去除所述掺杂层之后，还包括：采用中和清洗液清洗所述单晶硅硅片；
    优选的，所述中和清洗液为HF和HCl的混合溶液。
  10. 一种太阳能电池的制备方法，其特征在于，包括权利要求1至9任意一项所述的半导体衬底层的处理方法。
  11. 根据权利要求10所述的太阳能电池的制备方法，其特征在于，在对所述半导体衬底层进行处理后，还包括以下步骤：
    对所述半导体衬底层进行制绒处理；
    进行制绒处理之后，在所述半导体衬底层的一侧表面形成第一本征半 导体层，在所述半导体衬底层的另一侧表面形成第二本征半导体层；
    在所述第一本征半导体层背离所述半导体衬底层的一侧形成第一掺杂半导体层，在所述第二本征半导体层背离所述半导体衬底层的一侧形成第二掺杂半导体层；
    在所述第一掺杂半导体层背离所述半导体衬底层的一侧形成第一透明导电膜，在所述第二掺杂半导体层背离所述半导体衬底层的一侧形成第二透明导电膜；以及
    在所述第一透明导电膜背离所述半导体衬底层的一侧形成第一栅线电极，在所述第二透明导电膜背离所述半导体衬底层的一侧形成第二栅线电极。
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