CN112582485A - Solar cell and manufacturing method thereof - Google Patents
Solar cell and manufacturing method thereof Download PDFInfo
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- CN112582485A CN112582485A CN202011482067.5A CN202011482067A CN112582485A CN 112582485 A CN112582485 A CN 112582485A CN 202011482067 A CN202011482067 A CN 202011482067A CN 112582485 A CN112582485 A CN 112582485A
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- 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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
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- 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
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Abstract
The invention discloses a solar cell and a manufacturing method thereof, relates to the technical field of photovoltaics, and aims to reduce the formation of a boron-rich layer. The manufacturing method of the solar cell comprises the following steps: providing a silicon substrate, wherein a first surface of the silicon substrate is provided with a first boron doped layer and a first oxidation layer positioned on the first boron doped layer, the first oxidation layer is provided with a groove penetrating through the first oxidation layer, and a first area of the first boron doped layer is exposed in the groove; forming an oxide film at least in a first region of the first boron doped layer, wherein the thickness of the oxide film is smaller than that of the first oxide layer; forming a second boron doped layer in the first region under the mask of the first oxide layer; the doping concentration of the second boron doped layer is greater than the doping concentration of the first boron doped layer. The solar cell and the manufacturing method thereof provided by the invention are used for manufacturing the solar cell.
Description
Technical Field
The invention relates to the technical field of photovoltaics, in particular to a solar cell and a manufacturing method thereof.
Background
The selective emitter solar cell is a solar cell which is formed by heavily doping a contact part of a diffusion layer and a metal electrode on a silicon wafer and lightly doping other regions of the diffusion layer. The structure can not only reduce the composition of the diffusion layer of the silicon chip, but also reduce the contact resistance between the metal electrode and the silicon chip.
When the selective emitter solar cell is manufactured, a light doping treatment and a heavy doping treatment are required to be carried out.
Disclosure of Invention
The invention aims to provide a solar cell and a manufacturing method thereof, which aim to reduce the formation of a boron-rich layer.
In a first aspect, the present invention provides a method for fabricating a solar cell. The manufacturing method of the solar cell comprises the following steps:
providing a silicon substrate; the first surface of the silicon substrate is provided with a first boron doped layer and a first oxidation layer positioned on the first boron doped layer, the first oxidation layer is provided with a groove penetrating through the first oxidation layer, and a first area of the first boron doped layer is exposed in the groove;
forming an oxide film at least in a first region of the first boron doped layer, wherein the thickness of the oxide film is smaller than that of the first oxide layer;
forming a second boron doped layer in the first region; the doping concentration of the second boron doped layer is greater than the doping concentration of the first boron doped layer.
When the technical scheme is adopted, after the first boron doping treatment is carried out on the first surface of the silicon substrate to form the first boron doping layer, the oxide film is formed in the first area before the second boron doping treatment is carried out on the first area of the first boron doping layer to form the second boron doping layer.
When boron is used as an impurity to be doped in the doping treatment and the heavy doping treatment is performed, a Boron Rich Layer (BRL) is easily formed in the doped region. The boron-rich layer is enriched with inactive boron atoms, so that the part of the structure has more defects, the service life of minority carriers is influenced, and the performance of the battery is seriously influenced. In the process of manufacturing the solar cell, the boron-rich layer is not only difficult to remove, but also a great amount of impurities are easy to remain on the surface of the boron-rich layer during cleaning due to the non-hydrophobic characteristic, and the performance of the solar cell is seriously influenced. The oxide film has weak interception and blocking effects, and can ensure normal formation of the second boron doped layer and intercept and block excessive boron impurities in the process of carrying out second boron doping treatment, namely heavy doping treatment on the first region, so that the formation of a boron-rich layer in the first region can be reduced. Therefore, the manufacturing method of the solar cell can improve the performance of the solar cell.
In addition, when the second boron doping treatment is performed on the first region, the dopant is first brought into contact with the oxide film, and the oxide film can uniformly distribute the dopant. Therefore, the arrangement of the oxide film can ensure that each part of the first region is uniformly doped when the second boron doping layer is formed by the second boron doping treatment, so that the second boron doping layer with uniformly distributed boron impurities is formed. At this time, the conversion efficiency and performance of the solar cell may be improved.
In some possible implementations, the thickness of the oxide film is 0.1nm to 10 nm. When the second boron doping layer is formed through the second boron doping treatment, the blocking effect of the oxide film on the boron impurities is far smaller than that of the first oxide layer on the boron impurities, and therefore the doping concentration of the second boron doping layer can be guaranteed to be larger than that of the first boron doping layer. In addition, in the process of carrying out second boron doping treatment on the first region, when the thickness of the oxide film is 0.1 nm-10 nm, the oxide film is thinner, so that enough boron impurities can be ensured to enter the first region through the thinner oxide film, and a heavily doped second boron doping layer can be ensured to be formed.
In some possible implementations, forming an oxide film at least in a first region of the first boron doped layer includes: at least a first region of the first boron doped layer is treated with an oxidizing agent. In this case, the oxide film is formed by oxidizing the surface of the first region with the oxidizing agent, which not only has a simple process and can control the thickness of the oxide film by adjusting the amount of the oxidizing agent, but also can avoid the problem that the thickness, adhesiveness and density of the oxide film are difficult to control during film formation by a deposition process.
In some possible implementations, the oxidizing agent contains at least ozone. In this case, the ozone-containing oxidizing agent can form an oxide film in the first region, thereby improving the performance of the solar cell; and the first region to be subjected to the second boron doping treatment may be subjected to oxidation cleaning.
In some possible implementations, the pH of the oxidizing agent is less than 7. At this time, the oxidizing agent is in a solution state. When the pH value is less than 7, the oxidant is an acidic solution, and the solubility of ozone is higher, so that the oxidant can dissolve more ozone. Based on this, the acidic oxidant can more effectively infiltrate and oxidize the groove, thereby realizing a better cleaning function and forming an oxide film with better quality.
In some possible implementations, the ozone concentration of the oxidizing agent is less than or equal to 30 mg/L. In this case, the oxide film having the above thickness can be formed, and the problem of a low doping concentration of the second boron doped layer due to an excessively thick oxide film can be avoided.
In some possible implementations, the oxidizing agent further comprises hydrogen chloride. The pH value of the oxidant is 2-4. At this time, Cl-The ions can be combined with the metal ions and the transition metal ions through complexation, so that the metal ions and the transition metal ions in the groove can be effectively removed.
In some possible implementations, the groove is formed by laser film opening, and the laser pulse width of the laser film opening is less than 20 ns. At this time, the laser pulse width is small, that is, the time from laser excitation to stop is small. In this case, the laser energy is mainly concentrated on the first oxide layer for laser opening, so that only the first oxide layer can be removed, and damage to the first boron doped layer below the first oxide layer can be reduced.
In some possible implementations, the groove is formed by etching the film by the etching slurry.
In some possible implementations, the method of forming the first boron doped layer and the second boron doped layer are both thermal diffusion processes. At the moment, the second boron doping layer with uniformly doped boron can be formed by utilizing the oxide film on the first region, and when a thermal diffusion process is adopted, two steps of operations of doping and annealing can be completed by utilizing tubular diffusion equipment, so that the process is simple and the cost is low. Therefore, the thermal diffusion process can ensure the performance of the solar cell and reduce the cost.
In some possible implementations, after forming the second boron doped layer, the method for manufacturing a solar cell further includes: and forming a passivation contact structure on the second surface of the silicon substrate, and/or forming a passivation layer on the second surface of the silicon substrate. In this case, recombination loss of the solar cell can be reduced by the passivation contact structure or the passivation layer on the second surface, and the performance of the solar cell can be improved.
In a second aspect, the present invention provides a solar cell. The solar cell is manufactured by the manufacturing method of the solar cell described in the first aspect or any possible implementation manner of the first aspect.
The advantages of the solar cell provided by the second aspect may refer to the advantages of the method for manufacturing a solar cell described in the first aspect or any possible implementation manner of the first aspect, which will not be further described herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural diagram of a solar cell according to an embodiment of the present invention;
fig. 2 to fig. 10 are schematic diagrams illustrating states of various stages of a method for manufacturing a solar cell according to an embodiment of the present invention.
In fig. 1 to 10, 10-substrate, 101-textured structure, 11-first boron doped layer, 111-first region, 112-second region, 12-first oxide layer, 121-groove, 13-oxide film, 14-second boron doped layer, 15-first passivation layer, 16-first electrode, 21-tunneling passivation layer, 22-doped semiconductor layer, 23-second passivation layer, and 24-second electrode.
Detailed Description
In order to facilitate clear description of technical solutions of the embodiments of the present invention, in the embodiments of the present invention, terms such as "first" and "second" are used to distinguish the same items or similar items having substantially the same functions and actions. Those skilled in the art will appreciate that the terms "first," "second," etc. do not denote any order or quantity, nor do the terms "first," "second," etc. denote any order or importance.
It is to be understood that the terms "exemplary" or "such as" are used herein to mean serving as an example, instance, or illustration. Any embodiment or design described herein as "exemplary" or "e.g.," is not necessarily to be construed as preferred or advantageous over other embodiments or designs. Rather, use of the word "exemplary" or "such as" is intended to present concepts related in a concrete fashion.
In the present invention, "at least one" means one or more, "a plurality" means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone, wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, at least one (one) of a, b, or c, may represent: a, b, c, a and b combination, a and c combination, b and c combination, or a, b and c combination, wherein a, b and c can be single or multiple.
The embodiment of the invention provides a solar cell. As shown in fig. 1, the solar cell comprises a substrate 10 having opposite first and second faces and first and second boron doped layers 11, 14. The first side of the substrate 10 comprises a first region 111 and a second region 112. The second region 112 forms the first boron doped layer 11 and the first region 111 forms the second boron doped layer 14. The second boron doped layer 14 is in contact with the first boron doped layer 11, and the doping concentration of the second boron doped layer 14 is greater than the concentration of the first boron doped layer 11. Of course, the solar cell may also include other structures, as described in more detail below.
The embodiment of the invention also provides a manufacturing method of the solar cell. As shown in fig. 2 to 10, the method for manufacturing a solar cell specifically includes the following steps.
As shown in fig. 2, a substrate 10 is provided. The substrate 10 may be an n-type semiconductor substrate or a p-type semiconductor substrate. The material of the substrate 10 may be silicon. The substrate 10 has opposing first and second sides. In practical applications, the first side may face the sun, or the second side may face the sun. The method of fabricating the solar cell will be described below by taking an n-type silicon semiconductor substrate as an example, with the first side of the substrate 10 facing the sun.
As shown in fig. 3, the substrate 10 is textured. Specifically, one side of the substrate 10 may be textured, or both sides of the substrate 10 may be textured. The following is a description of the double-sided texturing process.
As an example, the texturing process may be a double-sided texturing process using an alkaline solution. For example, by treating the substrate 10 with an alkaline solution having an additive, the textured structure 101 with a pyramid shape can be formed on the surface of the substrate 10. The texture structure 101 can play a role in trapping light, so that the reflection of the solar cell to sunlight is reduced, and the performance of the solar cell is improved.
Of course, in some solar cell fabrication methods, the texturing process may be omitted.
As shown in fig. 4, a first boron doping treatment is performed on a first surface of a substrate 10 to form a first boron doped layer 11 and a first oxide layer 12. During the first boron doping process, a wraparound doped layer and a wraparound oxidized layer are generated on the second face of the substrate 10. The first oxide layer 12 and the surrounding oxide layer are made of boron-containing silicon oxide (BSG).
The surface doping concentration of the first boron doped layer 11 is 1 × 1017～5×1021cm-3. The thickness of the first oxide layer 12 is greater than 50 nm. Specifically, the first boron doping treatment may adopt a single-sided doping process and a full-sided doping method for doping.
In practical applications, the first boron doping process for forming the first boron doped layer 11 may be a thermal diffusion process, an ion implantation process, or a dopant source coating drive process. When the first boron doping treatment is performed by the thermal diffusion process, the impurity source of the first boron doping treatment may be BBr3Or BCl3. The apparatus for the first boron doping treatment may be a tubular thermal diffusion apparatus. The processing temperature of the first boron doping treatment may be 700 to 1100 ℃, and preferably, the processing temperature may be greater than or equal to 950 ℃.
It should be noted that, because oxygen can be introduced simultaneously during the first boron doping treatment, the first oxide layer 12 can be formed on the first boron-doped layer 11 during the first boron doping treatment, so that the process step of separately manufacturing the first oxide layer 12 can be omitted.
The first oxide layer 12 may be used as a diffusion mask layer in a second boron doping process described below to form a first boron doped layer 11 and a second boron doped layer 14 having a difference in doping concentration; on the other hand, the second side may be used as a mask layer for the spin-plating during the process of removing the spin-doped layer and the spin-plated oxide layer (the spin-plating generated by the first boron doping process and the second boron doping process) on the second side to prevent the damage to the first side of the substrate 10 during the spin-plating process. In addition, after the doped semiconductor layer 22 is formed on the second surface of the substrate 10, when the wraparound plating layer (wraparound plating generated by forming the doped semiconductor layer 22) on the first surface of the substrate 10 is removed, the first oxide layer 12 can be used as a protective layer to prevent the structure of the first surface of the substrate 10 from being damaged. When the second surface of the substrate 10 is formed with the n-type doped second surface doping layer, the first oxide layer 12 may be used as a diffusion mask layer on the first surface of the substrate 10 to avoid the co-doping problem of the first boron doping layer 11 and the second boron doping layer 14.
As shown in fig. 5, the first boron doped layer 11 has a first region 111 and a second region 112. In fig. 5, the portion of the first boron-doped layer 11 located inside the dashed line frame is a first region 111, and the portion located outside the dashed line frame is a second region 112. A portion of the first oxide layer 12 on the first region 111 is removed, and a portion of the first oxide layer 12 on the second region 112 is remained, thereby forming a recess 121 in the first oxide layer 12. The resulting structure may be defined as a silicon substrate. The first side of the silicon substrate has a first boron doped layer 11 and a first oxide layer 12 on the first boron doped layer 11. The first oxide layer 12 has a groove 121 penetrating the first oxide layer 12, and the first region 111 of the first boron doped layer 11 is exposed in the groove 121. It should be understood that, when manufacturing a solar cell, the substrate 10 may be used as a starting point for the process, or the silicon substrate defined in the embodiment of the present invention may be used as a starting point for the process.
The method for removing the portion of the first oxide layer 12 on the first region 111 may be laser film opening, or may be etching slurry etching. When the laser film opening process is adopted, the groove 121 is formed by laser film opening, and the laser pulse width of the laser film opening may be less than 20 ns. At this time, the laser pulse width is small, that is, the time from laser excitation to stop is small. In this case, the laser energy is mainly concentrated on the first oxide layer 12 where laser opening is performed, so that only the first oxide layer 12 can be removed, and damage to the first boron doped layer 11 below the first oxide layer 12 can be reduced. In practical applications, the laser pulse width may be less than 100ps in order to further reduce damage to the first boron doped layer 11. When the etching slurry etching process is used, the groove 121 is formed by etching the etching slurry to form a film. The etching paste may be an etching paste containing hydrofluoric acid. In a specific operation, an etching paste containing hydrofluoric acid may be printed on a portion of the first oxide layer 12 on the first region 111 by printing, so that the etching paste reacts with a portion of the first oxide layer 12 on the first region 111 to form the groove 121.
As shown in fig. 6, oxide film 13 is formed at least in first region 111 of first boron doped layer 11. It is to be understood that the oxide film 13 may be formed in other portions in the groove 121 than the first region 111. At this time, after the first boron doping treatment is performed on the first surface of the silicon substrate to form the first boron doped layer 11, the oxide film 13 is formed in the first region 111 of the first boron doped layer 11 before the second boron doping treatment is performed on the first region 111 to form the second boron doped layer 14. In view of the weak trapping and blocking effect of the oxide film 13, during the second boron doping treatment, i.e., heavily doping, on the first region 111, the oxide film 13 can not only ensure the normal formation of the second boron doped layer 14, but also trap and block excessive boron impurities, so that the formation of a boron-rich layer in the first region 111 can be reduced. Based on this, the method for manufacturing the solar cell provided by the embodiment of the invention can improve the performance of the solar cell.
In addition, when the second boron doping treatment is performed on the first region 111, the dopant first comes into contact with the oxide film 13, and the oxide film 13 can uniformly distribute the dopant. As can be seen, the oxide film 13 is provided to allow relatively uniform doping in the first region 111 when the second boron doping layer 14 is formed by the second boron doping treatment, thereby forming the second boron doping layer 14 in which boron impurities are uniformly distributed. At this time, the conversion efficiency and performance of the solar cell may be improved.
The thickness of the oxide film 13 is smaller than the thickness of the first oxide layer 12. When the second boron doping layer 14 is formed by the second boron doping treatment, since the thickness of the oxide film 13 is smaller than that of the first oxide layer 12, the blocking effect of the oxide film 13 on boron impurities is much smaller than that of the first oxide layer 12, and thus the doping concentration of the second boron doping layer 14 can be ensured to be greater than that of the first boron doping layer 11.
The material of the oxide film 13 may be silicon oxide. The thickness of the oxide film 13 may be 0.1nm to 10 nm. In the process of performing the second boron doping treatment on the first region 111, when the thickness of the oxide film 13 is 0.1nm to 10nm, the oxide film 13 is thin, so that sufficient boron impurities can be ensured to enter the first region 111 through the thin oxide film 13, and the formation of the heavily doped second boron doping layer 14 can be ensured. Illustratively, the thickness of the oxide film 13 may be 0.1nm, 0.3nm, 0.5nm, 0.6nm, 0.9nm, 1nm, 2nm, 5nm, 7nm, 8nm, 10nm, or the like.
The oxide film 13 may be formed by thin film deposition or by oxidizing the recess 121 with an oxidizing agent. When the oxide film 13 is formed by thin film deposition, the thickness of the oxide film 13 should be controlled by controlling the quality of the reactant, so as to avoid the problem of excessive thickness of the oxide film 13. When the oxide film 13 is formed by oxidizing with an oxidizing agent, the oxidizing agent may be an oxidizing gas or an oxidizing solution. The method of forming oxide film 13 at least in first region 111 of first boron doped layer 11 includes: at least the first region 111 of the first boron doped layer 11 is treated with an oxidizing agent. The oxidation film 13 is formed by oxidizing the surface of the first region 111 with the oxidant, so that the process is simple, the thickness of the oxidation film 13 can be controlled by adjusting the amount of the oxidant, and the problem that the thickness, adhesiveness and compactness of the oxidation film 13 are difficult to control in the deposition process of film making can be avoided.
The oxidizing agent contains at least ozone. In this case, the oxidizing agent containing ozone can form the oxide film 13 in the first region 111, thereby improving the performance of the solar cell; and the first region 111 to be subjected to the second boron doping treatment may be subjected to oxidation cleaning. To facilitate cleaning of the first region 111, i.e. the recess 121, the oxidizing agent may be an aqueous solution containing ozone.
The pH of the oxidizing agent may be less than 7. For example, the pH may be 1, 2, 3, 4, 5, 6, and the like. At this time, the oxidizing agent is in a solution state, and when the pH value is less than 7, the oxidizing agent is an acidic solution, and the solubility of ozone is greater, so that the oxidizing agent can dissolve more ozone. Based on this, the acidic oxidizing agent can more effectively infiltrate and oxidize the groove 121, thereby achieving a better cleaning function and forming the oxide film 13 with better quality.
The ozone concentration of the above-mentioned oxidizing agent may be less than or equal to 30 mg/L. For example, the ozone concentration of the oxidizing agent can be 30mg/L, 25mg/L, 20mg/L, 17mg/L, 14mg/L, 10mg/L, 9mg/L, or 5mg/L, and the like. In this case, oxide film 13 having a thickness of 0.1nm to 10nm can be formed, and the problem of low doping concentration of second boron doped layer 14 due to excessive thickness of oxide film 13 can be avoided.
The oxidizing agent may further contain hydrogen chloride. At this time, Cl of hydrogen chloride-The ions can be combined with the metal ions and the transition metal ions through complexation, so that the metal ions and the transition metal ions in the groove 121 can be effectively removed. Moreover, the hydrogen chloride can provide hydrogen ions for the oxidant, so that the pH value of the oxidant is in a range of 2-4, and the solubility of ozone is improved.
As shown in fig. 7, a second boron doping treatment is performed under the mask of the first oxide layer 12 to form a second boron doped layer 14 in the first region 111. The doping concentration of the second boron doped layer 14 is greater than the doping concentration of the first boron doped layer 11. The surface doping concentration of the second boron doped layer 14 is 2 × 1017～5×1021cm-3。
The process of forming the second boron doped layer 14 is a thermal diffusion process. The impurity source of the second boron doping treatment may be BBr3Or BCl3. The equipment for the second boron doping treatment can be the same as the equipment for the first boron doping treatment, and tubular thermal diffusion equipment is adopted, so that the equipment cost can be reduced, and the process can be simplified. The processing temperature of the second boron doping treatment may be the same as that of the first boron doping treatment.
During the second boron doping process to form the second boron doped layer 14, oxygen may be introduced to grow a boron-containing silicon oxide (BSG) layer on the surface of the first side of the substrate 10, i.e., on the first oxide layer 12 and the second boron doped layer 14. At this time, the thickness of the BSG layer located on the first region 111 is greater than 30 nm. At the same time, the first oxide layer 12 on the second region 112 is further increased in thickness, so that the thickness is greater than 50 nm. The thickness of the surrounding oxide layer on the second side of the substrate 10 is also increased. In addition, the boron impurity in the first oxide layer 12 located on the second region 112 is further redistributed, and a part of the boron impurity enters the first boron doped layer 11 again.
The method for forming the first boron doped layer 11 and the second boron doped layer 14 can better realize the doping concentration difference between the first boron doped layer 11 and the second boron doped layer 14 in an industrialized mode, thereby being beneficial to improving the efficiency of the solar cell. The method for forming the first boron doped layer 11 and the second boron doped layer 14 is simple in process and easy to implement.
Further, the second boron doped layer 14 having a higher doping concentration is used for electrical contact with the first electrode 16 described below. The contact resistance of the second boron doped layer 14 with the first electrode 16 is small due to the high doping concentration. In addition, the second boron doped layer 14 with higher doping concentration can effectively shield the high surface recombination rate brought by the metal electrode, thereby improving the conversion efficiency of the solar cell. The doping concentration of the first boron doping layer 11 is low, so that surface recombination can be reduced, and the conversion efficiency of the solar cell is improved. Therefore, the conversion efficiency of the solar cell can be effectively improved by the selective emitter structure formed by combining the first boron doped layer 11 and the second boron doped layer 14.
As shown in fig. 8, a passivation contact structure is formed on the second side of the silicon substrate. The passivation contact structure includes a tunneling passivation layer 21 and a doped semiconductor layer 22 sequentially formed on the second surface of the silicon substrate.
The tunneling passivation layer 21 is made of a dielectric material. The material of the tunneling passivation layer 21 may be one or more of self-hydrogenated amorphous silicon, silicon oxynitride, silicon carbide, silicon nitride, aluminum oxide, and silicon oxide. The thickness of the tunneling passivation layer 21 is 0.5nm-5 nm.
The formation process of the tunnel passivation layer 21 may be a physical vapor deposition process or a chemical vapor deposition process. To simplify the process, the silicon substrate may be directly oxidized to form silicon oxide as the tunnel passivation layer 21.
The material of the doped semiconductor layer 22 may be polysilicon or the like. The dopant impurity may be a group VA element, such as phosphorus. The doping concentration of the doped semiconductor layer 22 is 1 × 1018～5×1021cm-3. The thickness of the doped semiconductor layer 22 may be 20nm to 500 nm.
The forming process of the doped semiconductor layer 22 may be an in-situ doping process or an ex-situ doping process. The in-situ doping process is to complete the doping of the semiconductor layer while forming the semiconductor layer on the substrate 10, and form the doped semiconductor layer 22 after the annealing treatment. The temperature of the annealing treatment may be 700-1000 ℃. The ex-situ doping process is to form an intrinsic semiconductor layer, and then perform doping treatment on the intrinsic semiconductor layer to form a doped semiconductor layer 22. The difference between the two is that the doping is performed simultaneously with the formation of the semiconductor layer or after the formation of the semiconductor layer.
The thin film forming process for forming the intrinsic or doped semiconductor layer 22 may be a physical vapor deposition Process (PVD) or a chemical vapor deposition Process (PVD), regardless of the in-situ doping process or the ex-situ doping process. Specifically, the physical vapor deposition process may be magnetron sputtering. The chemical vapor deposition process may be any one of a low pressure vapor deposition process (LPCVD), an enhanced plasma chemical vapor deposition Process (PECVD), an atmospheric pressure vapor deposition process (APCVD), and a hot wire chemical vapor deposition process (HWCVD).
When the doped semiconductor layer 22 is formed by the in-situ doping process, a dopant source gas may be introduced while the semiconductor layer is formed by the above-described thin film forming process. The dopant source gas may be PH3And the like. When the doped semiconductor layer 22 is formed by the ex-situ doping process, any one of a tubular thermal diffusion method, an annealing method after ion implantation, and a doping source coating advancing method may be selected to dope the intrinsic semiconductor layer. The dopant source may be POCl3And the like. To simplify the process, the preparation of the doped semiconductor layer 22 and the tunnel passivation layer 21 may be done in a tubular thermal diffusion apparatus.
It should be appreciated that the second side of the silicon substrate should be subjected to a cleaning process to remove the wraparound diffusion layer and the wraparound oxide layer located on the second side of the silicon substrate before the passivation contact structure is formed. Specifically, the mixed solution of hydrofluoric acid, nitric acid and sulfuric acid can be used to perform single-side cleaning treatment on the second surface, and the plating-around diffusion layer, the plating-around oxidation layer and a part of the substrate 10 of the second surface are removed, so that the second surface of the substrate 10 is flat, and the reflectivity of the second surface to light is greater than 20%.
As shown in fig. 9, a first side of the silicon substrate is passivated to form a first passivation layer 15; the second side of the silicon substrate is passivated to form a second passivation layer 23.
The material of the first passivation layer 15 may include one or more of silicon nitride, silicon oxide, silicon oxynitride, aluminum oxide, silicon carbide, and amorphous silicon. The material of the second passivation layer 23 may include one or more of silicon nitride, silicon oxide, silicon oxynitride, aluminum oxide, silicon carbide, and amorphous silicon. The first passivation layer 15 and the second passivation layer 23 may be made of the same material or different materials.
The process of forming the first passivation layer 15 and the second passivation layer 23 may be one of an enhanced plasma chemical vapor deposition process and an atomic layer deposition process.
It will be appreciated that prior to the passivation process, the first and second sides of the silicon substrate should be subjected to a cleaning process to remove the first oxide layer 12 on the first side and the wraparound layer produced during the fabrication of the passivated contact structures, and to remove the oxide layer on the second side produced during the fabrication of the passivated contact structures.
In practical applications, the passivation contact structure formed on the second side of the silicon substrate may be omitted. At this time, a second-side doping layer may be formed on the second side. The second surface-doped layer is doped with a group VA element such as phosphorus, with a doping type different from that of the first boron-doped layer 11. Specifically, POCl can be used3And forming the second surface doping layer by any one of thermal diffusion, phosphorus ion implantation annealing and APCVD phosphorosilicate glass heating propulsion. The second surface doping layer may not only function to laterally transport carriers but also reduce contact resistance when the second surface of the substrate 10 is in contact with an electrode.
As shown in fig. 10, a first electrode 16 is formed on the first side of the silicon substrate, the first electrode 16 being in contact with the second boron doped layer 14. A second electrode 24 is formed on the second side of the silicon substrate.
The material of each of the first electrode 16 and the second electrode 24 may include one or more of silver, copper, aluminum, nickel, titanium, tungsten, tin. In practice, the first electrode 16 and the second electrode 24 may be formed using a metallization process. Specifically, the metallization process may be one or more of a PVD process, a screen printing process, an electroplating process, an electroless plating process, a laser transfer process, and a spraying process.
In forming the first electrode 16 and the second electrode 24, a process combining a plurality of processes may be employed. For example, a paste containing silver or copper may be printed using a screen printing process, and then electrode preparation may be completed by a sintering process or an annealing process at 500 to 900 ℃. For another example, a seed layer may be prepared by a PVD process, patterned, and then an electrode may be prepared by an electroplating method, and then an electrode may be formed by annealing. For another example, an electroless plating process may be used to form a seed layer, followed by thickening using an electroplating method, and finally annealing to complete the electrode preparation. It should be noted that when forming the first electrode 16, the first electrode 16 should be fabricated on the surface of the second boron doped layer 14 in alignment with the second boron doped layer 14.
It should be noted that, in the embodiment of the present invention, the specific structure of the second surface of the substrate 10 is not limited to the above structure. In the embodiment of the present invention, the second surface of the substrate 10 may form a passivation contact structure, a point contact structure, or a local diffusion structure of the second surface. When the first surface of the silicon substrate is doped in an n-type mode, the second surface of the silicon substrate can also form a second surface aluminum alloy contact structure.
While the invention has been described in connection with various embodiments, other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed invention, from a review of the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other elements or steps, and the word "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
While the invention has been described in conjunction with specific features and embodiments thereof, it will be evident that various modifications and combinations can be made thereto without departing from the spirit and scope of the invention. Accordingly, the specification and figures are merely exemplary of the invention as defined in the appended claims and are intended to cover any and all modifications, variations, combinations, or equivalents within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method for manufacturing a solar cell, comprising:
providing a silicon substrate, wherein a first surface of the silicon substrate is provided with a first boron doped layer and a first oxidation layer positioned on the first boron doped layer, the first oxidation layer is provided with a groove penetrating through the first oxidation layer, and a first area of the first boron doped layer is exposed in the groove;
forming an oxide film at least in a first region of the first boron doped layer, wherein the thickness of the oxide film is smaller than that of the first oxide layer;
and forming a second boron doped layer in the first region, wherein the doping concentration of the second boron doped layer is greater than that of the first boron doped layer.
2. The method of claim 1, wherein the oxide film has a thickness of 0.1nm to 10 nm.
3. The method of claim 1, wherein forming an oxide film at least in the first region of the first boron-doped layer comprises:
treating at least a first region of the first boron doped layer with an oxidizing agent.
4. The method of claim 1, wherein the oxidant comprises at least ozone.
5. The method of claim 4, wherein the oxidant has a pH of less than 7 and/or an ozone concentration of less than or equal to 30 mg/L.
6. The method for manufacturing a solar cell according to claim 4, wherein the oxidizing agent further contains hydrogen chloride, and the pH value of the oxidizing agent is 2 to 4.
7. The method for manufacturing the solar cell according to any one of claims 1 to 6, wherein the groove is formed by laser film opening, the laser pulse width of the laser film opening is less than 20ns, or the groove is formed by etching the film opening with etching slurry.
8. The method according to any one of claims 1 to 6, wherein the first boron doped layer and the second boron doped layer are formed by a thermal diffusion process.
9. The method according to any one of claims 1 to 6, wherein after the forming of the second boron doped layer, the method further comprises:
forming a passivation contact structure on a second side of the silicon substrate, and/or,
and forming a passivation layer on the second surface of the silicon substrate.
10. A solar cell produced by the method for producing a solar cell according to any one of claims 1 to 9.
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