CN112786738A - Solar cell and preparation method thereof - Google Patents

Solar cell and preparation method thereof Download PDF

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Publication number
CN112786738A
CN112786738A CN202110119879.1A CN202110119879A CN112786738A CN 112786738 A CN112786738 A CN 112786738A CN 202110119879 A CN202110119879 A CN 202110119879A CN 112786738 A CN112786738 A CN 112786738A
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layer
doped silicon
silicon
silicon substrate
film
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CN112786738B (en
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唐文帅
张俊兵
尹海鹏
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JA Solar Technology Yangzhou Co Ltd
Jingao Solar Co Ltd
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Ja Solar Co Ltd
JA Solar Technology Yangzhou Co Ltd
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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 System
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a solar cell and a preparation method thereof, wherein the preparation method comprises the following steps: forming a passivation layer on the surface of the silicon substrate; forming a first doped silicon film on the surface of the passivation layer opposite to the silicon substrate; forming a second layer of silicon film on the surface of the first doped silicon film, which is opposite to the silicon substrate, wherein the second layer of silicon film comprises a first part and a second part which are in contact with the first doped silicon film; carrying out second doping treatment on the first part, and removing the second part to expose the first doped silicon film; annealing the silicon substrate subjected to the second doping treatment to enable the second layer of silicon film to form a second doped silicon layer and enable the first doped silicon film to form a first doped silicon layer; and forming a metal electrode on the surface of the silicon substrate opposite to the second doped silicon layer, and enabling the metal electrode to be in ohmic contact with the second doped silicon layer to obtain the solar cell. The metal electrode of the solar cell prepared by the preparation method can not penetrate through the passivation layer and has good light transmittance.

Description

Solar cell and preparation method thereof
Technical Field
The invention relates to a solar cell and a preparation method thereof.
Background
In the field of solar cell manufacturing, a passivation layer is generally required to be formed on the surface of a silicon substrate to reduce the recombination rate of minority carriers on the surface of the solar cell, so that the solar cell has higher open-circuit voltage, short-circuit current and energy conversion efficiency. After the passivation layer is formed, a metal electrode needs to be prepared on the surface of the passivation layer to realize ohmic contact between the metal electrode and the silicon substrate, but the passivation layer is inevitably damaged, so that metal recombination is formed in the contact area of the passivation layer and the metal electrode, and the passivation effect on the surface of the solar cell is not facilitated.
The problem of metal recombination between the metal electrode and the passivation layer can be reduced by preparing the doped silicon layer on the surface of the passivation layer and making the metal electrode and the doped silicon layer in ohmic contact. However, when the thickness of the doped silicon layer is thin, it cannot be avoided that the metal electrode penetrates the doped silicon layer to contact the passivation layer. When the thickness of the doped silicon layer is thick, the light absorption rate of the solar cell is affected.
Disclosure of Invention
In view of this, the present invention provides a solar cell and a method for manufacturing the same, which can prevent a metal electrode from penetrating through a passivation layer and reduce light absorption loss caused by providing a doped silicon layer.
A first aspect of the present invention provides a method for manufacturing a solar cell, the method comprising:
forming a passivation layer on the surface of the silicon substrate;
forming a first doped silicon film on the surface of the passivation layer, which is opposite to the silicon substrate;
forming a second layer of silicon film on the surface of the first doped silicon film, which faces away from the silicon substrate, wherein the second layer of silicon film comprises a first part and a second part which are in contact with the first doped silicon film;
carrying out second doping treatment on the first part, and removing the second part to expose the first doped silicon film;
annealing the silicon substrate subjected to the second doping treatment to enable the second layer of silicon film to form a second doped silicon layer and enable the first doped silicon film to form a first doped silicon layer;
and forming a metal electrode on the surface of the silicon substrate opposite to the second doped silicon layer, and enabling the metal electrode to be in ohmic contact with the second doped silicon layer to obtain the solar cell.
According to the preparation method of the solar cell, the second layer of silicon film is formed on the surface, opposite to the silicon substrate, of the first doped silicon film, the first part of the second layer of silicon film is subjected to second doping treatment, the second part is removed, the first doped silicon film is exposed, the second layer of silicon film forms a second doped silicon layer after annealing treatment, and the first doped silicon film forms a first doped silicon layer. Therefore, when the metal electrode is formed on the surface of the silicon substrate opposite to the second doped silicon layer, the first doped silicon layer and the second doped silicon layer of the lamination provide larger sintering depth for the metal electrode, and the problem that the metal electrode penetrates through the first doped silicon layer and is compounded with the passivation layer is avoided, so that the passivation effect is ensured, and the short-circuit current and the open-circuit voltage of the solar cell are favorably improved. In addition, the light transmittance of the region without the second doped silicon layer is better, and the conversion efficiency of the solar cell is favorably improved.
A second aspect of the present invention provides a solar cell, comprising:
a silicon substrate;
the passivation layer is arranged on the surface of the silicon substrate;
the first doped silicon layer is arranged on the surface, back to the silicon substrate, of the passivation layer and comprises a third part and a fourth part;
the second doped silicon layer is arranged on the surface of the third part, which is back to the silicon substrate, and the second doped silicon layer is not arranged on the surface of the fourth part, which is back to the silicon substrate; and
and the metal electrode is in ohmic contact with the second doped silicon layer.
According to the solar cell provided by the invention, the second doped silicon layer is arranged on the surface of the third part of the first doped silicon layer, which is back to the passivation layer, and the second doped silicon layer is not arranged on the surface of the fourth part of the first doped silicon layer, which is back to the passivation layer, so that the metal electrode is in ohmic contact with the second doped silicon layer, the first doped silicon layer and the second doped silicon layer of the lamination layer provide a larger sintering depth for the metal electrode, the problem that the metal electrode penetrates through the first doped silicon layer and the passivation layer to generate metal recombination is avoided, the passivation effect is ensured, and the short-circuit current and the open-circuit voltage of the solar cell are favorably improved. In addition, the region without the metal electrode is not provided with the second doped silicon layer, so that the thickness of the doped silicon layer is reduced, the light transmittance of the region is improved, and the conversion efficiency of the solar cell is improved.
Drawings
Fig. 1 is a flow chart illustrating a method of fabricating a solar cell according to an exemplary embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating a structure for forming a passivation layer on a silicon substrate in accordance with an exemplary embodiment of the present invention;
FIG. 3 is a schematic structural diagram illustrating the formation of a first doped silicon thin film on a passivation layer in accordance with an exemplary embodiment of the present invention;
FIG. 4 is a schematic structural diagram illustrating the formation of a second silicon film on the first doped silicon film in accordance with an exemplary embodiment of the present invention;
FIG. 5 is a schematic structural view illustrating a second doping process performed on a first portion of a second silicon thin film in accordance with an exemplary embodiment of the present invention;
FIG. 6 is a schematic structural diagram illustrating a second portion of a second silicon thin film layer removed in accordance with an exemplary embodiment of the present invention;
fig. 7 is a schematic structural view illustrating the formation of a first doped silicon layer and a second doped silicon layer in accordance with an exemplary embodiment of the present invention;
FIG. 8 is a schematic structural diagram illustrating the formation of a passivated antireflective film in accordance with an exemplary embodiment of the present invention;
fig. 9 is a schematic structural diagram of a solar cell according to an exemplary embodiment of the present invention.
Reference numerals:
a silicon substrate 10;
a passivation layer 20;
a first doped silicon thin film 30; a first doped silicon layer 30';
a second silicon thin film 40; a first portion 41; a second portion 42; a second doped silicon layer 40';
a passivation antireflective film 50;
a metal electrode 60.
Detailed Description
First, the discovery of a technical problem solved by the technical means for obtaining the method for manufacturing a solar cell of the present invention will be described.
The passivation contact structure generally includes: an ultrathin passivation layer and a doped silicon layer prepared on the surface of the ultrathin passivation layer. The inventor researches and discovers that although the passivation contact structure effectively avoids metal recombination between the metal electrode and the passivation layer due to metallization, the doped silicon layer in the passivation contact structure directly reduces the light absorption efficiency of the solar cell. The light absorption loss of the solar cell is reduced along with the reduction of the thickness of the doped silicon layer, but the sintering depth required by the metal electrode in the sintering process cannot be met in the process of realizing metallization of the ultrathin doped silicon layer, so that the ultrathin passivation layer is damaged by burning through of the metal electrode, the passivation effect of the solar cell is greatly influenced, and the open-circuit voltage and the short-circuit current are reduced. After the inventor finds the technical problem, the technical scheme of the solar cell and the preparation method thereof is obtained through research. Hereinafter, the technical solution of the present invention will be described in detail.
A method for manufacturing a solar cell provided according to a first aspect of an embodiment of the present invention is described in detail below with reference to fig. 1. As can be seen from fig. 1, the preparation method of the solar cell includes the following steps:
step 1, forming a passivation layer on the surface of the silicon substrate. Wherein the surface of the silicon substrate may be a front surface or a back surface of the silicon substrate.
And 2, forming a first doped silicon film on the surface of the passivation layer, which faces away from the silicon substrate.
And 3, forming a second layer of silicon film on the surface of the first doped silicon film, which faces away from the silicon substrate, wherein the second layer of silicon film comprises a first part and a second part which are in contact with the first doped silicon film.
And 4, carrying out second doping treatment on the first part of the second layer of silicon film, and removing the second part to expose the first doped silicon film.
And 5, annealing the silicon substrate subjected to the second doping treatment to enable the second layer of silicon film to form a second doped silicon layer and enable the first doped silicon film to form a first doped silicon layer.
And 6, forming a metal electrode on the surface of the silicon substrate opposite to the second doped silicon layer, and enabling the metal electrode to be in ohmic contact with the second doped silicon layer to obtain the solar cell.
In an embodiment of the present invention, a first oxide layer is formed on a surface of the first doped silicon layer facing away from the silicon substrate, and a second oxide layer is formed on a surface of the second doped silicon layer facing away from the silicon substrate, where the method for manufacturing a solar cell provided in an embodiment of the present disclosure further includes: after the annealing treatment, the first oxide layer and the second oxide layer are removed by an acidic solution, which improves the conductive properties of the first doped silicon layer and the second doped silicon layer. Wherein the acidic solution may be an HF solution.
In the preparation method, after the second doping treatment is carried out on the first part of the second layer of silicon film in the step 4, the second part of the second layer of silicon film which is not subjected to the second doping treatment is removed, and then the annealing treatment in the step 5 is carried out, so that the second layer of silicon film forms a second doped silicon layer, and the first doped silicon film forms a first doped silicon layer. Thus, a portion of the first doped silicon layer is stacked with the second doped silicon layer, and another portion of the first doped silicon layer is exposed between adjacent second doped silicon layers. The first doped silicon layer and the second doped silicon layer of the lamination layer provide sintering depth for the metal electrode, so that the metal electrode can be prevented from burning through the first doped silicon layer to damage the passivation layer, the passivation effect is ensured, and further the open-circuit voltage and the short-circuit current of the solar cell are ensured. In addition, the region where the second doped silicon layer is not disposed has a high light absorption rate, thereby ensuring the conversion efficiency of the solar cell.
According to the preparation method of the solar cell, the second layer of silicon film is formed on the surface, opposite to the silicon substrate, of the first doped silicon film, the first part of the second layer of silicon film is subjected to second doping treatment, the second part is removed, the first doped silicon film is exposed, the second layer of silicon film forms a second doped silicon layer after annealing treatment, and the first doped silicon film forms the first doped silicon layer. Therefore, when the metal electrode is formed on the surface of the silicon substrate opposite to the second doped silicon layer, the first doped silicon layer and the second doped silicon layer of the lamination provide larger sintering depth for the metal electrode, and the problem that the metal electrode penetrates through the first doped silicon layer and is compounded with the passivation layer is avoided, so that the passivation effect is ensured, and the short-circuit current and the open-circuit voltage of the solar cell are favorably improved. In addition, the light transmittance of the region without the second doped silicon layer is better, and the conversion efficiency of the solar cell is favorably improved.
The respective steps will be described in detail below.
As shown in fig. 2, a passivation layer 20 is formed on the surface of the silicon substrate 10 in step 1.
In embodiments of the present invention, the silicon substrate 10 may comprise P-type doped crystalline silicon and N-type doped crystalline silicon. In general, P-type doped crystalline silicon refers to crystalline silicon doped with an appropriate amount of a 3-valent element such as aluminum, indium, boron, or the like. N-type doped crystalline silicon means that a proper amount of 5-valent elements such as phosphorus or arsenic and the like are doped into crystalline silicon. The silicon substrate of the embodiment of the invention can be monocrystalline silicon or polycrystalline silicon.
In the embodiment of the present invention, the thickness of the passivation layer 20 may be 0.5nm to 2.5nm, and the passivation layer 20 having the thickness is an ultra-thin passivation layer in the art. For example, the thickness of the passivation layer 20 may be 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, 1.1nm, 1.2nm, 1.3nm, 1.4nm, 1.5nm, 1.6nm, 1.7nm, 1.8nm, 1.9nm, 2.0nm, 2.1nm, 2.2nm, 2.3nm, 2.4nm, 2.5nm, or the like. The passivation layer 20 may be a single layer film or a stacked layer film of silicon oxide, titanium oxide, silicon oxynitride, or the like. The passivation layer 20 may be grown and formed using a low temperature furnace oxidation process, a nitric acid oxidation process, an ozone oxidation process, or a deposition method. The Deposition method may include Atomic Layer Deposition (ALD), Low Pressure Chemical Vapor Deposition (LPCVD), Atmospheric Pressure Chemical Vapor Deposition (APCVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), and the like. The passivation layer can protect the silicon substrate, and in the subsequent doping step of the silicon film, doped elements are reduced or prevented from entering the silicon substrate.
As shown in fig. 3, in step 2, a first doped silicon thin film 30 is formed on the surface of the passivation layer 20 formed in the above step 1, which faces away from the silicon substrate 10.
In the embodiment of the present invention, step 2 may include: and forming a first silicon film on the surface of the passivation layer 20 opposite to the silicon substrate 10, and carrying out in-situ doping on the first silicon film by using a first doping agent to obtain a first doped silicon film 30. The first layer of silicon film and the first doping treatment may be performed simultaneously, or the first layer of silicon film may be formed first and then the first doping treatment may be performed on the first layer of silicon film. The first silicon film can be a single-layer film or a plurality of laminated films in a microcrystalline silicon film layer, an amorphous silicon film layer, a polycrystalline silicon film layer, a silicon oxide film layer, a silicon carbide film layer and the like. In the embodiment of the present invention, the first doped silicon thin film 30 may be obtained using silane and phosphine gases as reaction gases. The first doped silicon thin film 30 may be prepared by a chemical vapor deposition method, which may be a low pressure chemical vapor deposition method, a plasma enhanced chemical vapor deposition method, or an atmospheric pressure chemical vapor deposition method. The specific process conditions of the chemical vapor deposition method are not particularly limited in the present invention. For example, the pressure in the reaction chamber of the chemical vapor deposition method may be low pressure or normal pressure, the low pressure may be 0.1 to 0.5Torr, the temperature range may be 100 to 700 ℃, and the preferred temperature range is 500 to 700 ℃.
In the embodiment of the present invention, there is no particular limitation on the thickness of the first doped silicon thin film 30. The thickness of the first doped silicon thin film 30 may be 5nm to 200nm, and may be, for example, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, or 200 nm.
As shown in fig. 4, step 3, a second silicon film 40 is formed on the surface of the first doped silicon film 30 opposite to the silicon substrate 10, and the second silicon film 40 includes a first portion 41 and a second portion 42 contacting the first doped silicon film 30.
In the embodiment of the present invention, the material of the second silicon thin film 40 is the same as that of the first silicon thin film. For example, the first and second silicon thin films 40 may be a single-layer film or a stacked-layer film of a microcrystalline silicon thin film layer, an amorphous silicon thin film layer, a polycrystalline silicon thin film layer, a silicon oxide thin film layer, a silicon carbide thin film layer, or the like. In the embodiment of the present invention, the second silicon film 40 may be formed by a low pressure chemical vapor deposition method, a plasma enhanced chemical vapor deposition method, an atmospheric pressure chemical vapor deposition method, or the like. The specific process conditions of the chemical vapor deposition method are not particularly limited in the present invention, and for example, the pressure in the reaction chamber of the chemical vapor deposition method may be low pressure or normal pressure, the low pressure may be 0.1 to 0.5Torr, the temperature range is 100 to 700 ℃, and the preferable temperature range is 500 to 700 ℃. In the chemical vapor deposition method, silane may be used as a reaction gas.
In the embodiment of the present invention, the thickness of the second silicon thin film 40 is not particularly limited. The thickness of the second silicon thin film 40 may be between 5nm and 200nm, and may be, for example, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, or 200 nm.
As shown in fig. 5 and 6, in step 4, a second doping process is performed on the first portion 41 of the second silicon thin film 40, and the second portion 42 of the second silicon thin film 40 is removed to expose the first doped silicon thin film 30.
In the embodiment of the present invention, step 4 includes: the surface of the first portion 41 facing away from the first doped silicon thin film 30 is subjected to a second doping treatment by using an ion implantation method, and the second doping treatment is performed, as shown in fig. 5, and the second portion 42 is removed by cleaning with an aqueous solution of ammonia gas, and the structure after the second portion 42 is removed by cleaning is shown in fig. 6. Wherein the position of the first portion 41 of the second silicon thin film 40 can be selected according to the position where the metal electrode is to be disposed. That is, the location of doping is the same as the location where the metal electrode is disposed. When the first portion 41 of the second silicon thin film 40 is subjected to the second doping treatment by the ion implantation method, the ion beam bombards the surface of the first portion 41 to a certain depth, so that a chemically inert layer is formed on the surface of the first portion 41 to protect the second silicon thin film 40 therebelow from being corroded by the aqueous solution of ammonia. After cleaning, a groove structure is formed as shown in fig. 6. In practice, the inner wall of the groove structure may be an arc-shaped surface structure, and fig. 6 is only shown as a schematic diagram and does not limit the present invention.
Wherein, the second layer of silicon thin film 40 is doped with a second dopant, and the second dopant can be a valence-3 element such as aluminum, indium or boron, or a valence-5 element such as phosphorus or arsenic.
In the embodiment of the present invention, the second dopant may be the same as the first dopant, and the valence of the doping element in the first doped silicon thin film 30 and the valence of the doping element in the second doped silicon thin film 40 in the same solar cell are the same, so as to avoid the influence on the conductivity of the solar cell caused by the formation of a PN junction between the formed first doped silicon layer and the second doped silicon layer.
As shown in fig. 7, step 5, annealing the silicon substrate 10 after the second doping treatment is performed, so that the second doped silicon layer 40 'is formed on the second silicon film 40, and the first doped silicon layer 30' is formed on the first doped silicon film 30.
In the embodiment of the present invention, the doping element (P or B) may be activated through an annealing process to improve the conductivity of the solar cell, and the first doped silicon thin film 30 and the second doped silicon thin film 40 in fig. 6 are subjected to a crystallization heat treatment to further improve the performance of the silicon thin films. It is considered that, under the high temperature condition, the doping element, for example, phosphorus atom is activated to enter each lattice structure of the polycrystalline silicon layer having the doping element and diffused in the lattice structure of the silicon thin film, so that the doping element, for example, phosphorus atom, is redistributed in the polycrystalline silicon thin film, thereby obtaining the doping effect of the silicon thin film. Wherein the temperature range of the annealing treatment can be between 600 and 900 ℃, and the time of the annealing treatment can be between 15 and 60 min.
In the embodiment of the present invention, the first dopant and the second dopant may include a phosphorus source, a boron source, and the like, the phosphorus source may be red phosphorus, a phosphane, and the like, and the boron source may be borane or boron bromide. The doping concentration of the doping element of the first dopant in the first doped silicon layer is 1.0E19atoms/cm3～2.0E21atoms/cm3For example, it may be 1.0E19atoms/cm3、2.0E19atoms/cm3 、3.0E19atoms/cm3、4.0E19atoms/cm3、5.0E19atoms/cm3、6.0E19atoms/cm3、7.0E19atoms/cm3、8.0E19atoms/cm3、9.0E19atoms/cm3、1.0E20atoms/cm3、2.0E20atoms/cm3、3.0E20atoms/cm3、4.0E20atoms/cm3、5.0E20atoms/cm3、6.0E20atoms/cm3、7.0E20atoms/cm3、8.0E20atoms/cm3、9.0E20atoms/cm3、1.0E21atoms/cm3Or 2.0E21atoms/cm3And the like. Wherein, 1.0E19atoms/cm3"means comprising 1.0 times 10 per cubic centimeter19The atoms, similar for other data, are not explained.
The doping concentration of the doping element of the second dopant in the second doped silicon layer may be 1.0E19atoms/cm3～2.0E21atoms/cm3For example, it may be 1.0E19atoms/cm3、2.0E19atoms/cm3、3.0E19atoms/cm3、4.0E19atoms/cm3、5.0E19atoms/cm3、6.0E19atoms/cm3、7.0E19atoms/cm3、8.0E19atoms/cm3、9.0E19atoms/cm3、1.0E20atoms/cm3、2.0E20atoms/cm3、3.0E20atoms/cm3、4.0E20atoms/cm3、5.0E20atoms/cm3、6.0E20atoms/cm3、7.0E20atoms/cm3、8.0E20atoms/cm3、9.0E20atoms/cm3、1.0E21atoms/cm3Or 2.0E21atoms/cm3And the like.
In an embodiment of the present invention, the doping concentration of the doping element of the first dopant in the first doped silicon layer 30 'is less than or equal to the doping concentration of the doping element of the second dopant in the second doped silicon layer 40'. Therefore, the light transmittance of the region without the metal electrode is improved, and the second doped silicon layer and the first doped silicon layer are beneficial to transmitting current to the metal electrode.
In the embodiment of the present invention, the doping concentration of the doping element in the first doped silicon layer 30 'is higher than that of the silicon substrate 10 itself, which has the effect of field effect, and thus facilitates the transmission of electrons from the silicon substrate to the first doped silicon layer 30', and further facilitates the collection of current by the metal electrode through the first doped silicon layer 30 'and the second doped silicon layer 40'. If the first doped silicon layer 30 'and the second doped silicon layer 40' are stacked only at the position of the metal electrode, the other regions where the metal electrode is not disposed are not provided with the doped silicon layer, which is not beneficial to the metal electrode to collect current.
The thickness of the first doped silicon layer 30 'may be less than that of the second doped silicon layer 40' to ensure light transmittance of the region where the metal electrode is not disposed.
In the embodiment of the present invention, the first doped silicon layer 30 'forms a first oxide layer on the surface facing away from the silicon substrate 10, and the second doped silicon layer 40' forms a second oxide layer on the surface facing away from the silicon substrate 10, and after the annealing treatment, the first oxide layer and the second oxide layer may be removed by an acidic solution. For example, an HF chemical solution can be used to remove an oxide layer grown on the surface of the polysilicon after annealing, thereby effectively improving the light absorption rate of the solar cell. Wherein, the oxide layer can be a silicon oxide layer.
After step 5, the preparation method provided by the embodiment of the present invention further includes: as shown in fig. 8, a passivation antireflective film 50 is formed on the surface of the second doped silicon layer 40 ' facing away from the first doped silicon layer 30 ' and the surface of the first doped silicon layer 30 ' facing away from the silicon substrate.
In the embodiment of the present invention, the passivation anti-reflective film 50 may be a single layer film or a stacked layer film of a silicon oxide film, an aluminum oxide film, a titanium oxide film, a silicon oxynitride film, or the like. The thickness of the passivation anti-reflection film 50 may be 30 to 300nm, for example, 30nm, 50nm, 70nm, 90nm, 110nm, 130nm, 150nm, 170nm, 190nm, 210nm, 230nm, 250nm, 270nm, 290nm, or 300 nm. The refractive index of the passivation anti-reflective film 50 may be 1.2 to 2.8, and may be, for example, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, or 2.8.
The passivation anti-reflective film 50 can be formed by a Low Pressure Chemical Vapor Deposition (LPCVD), an Atmospheric Pressure Chemical Vapor Deposition (APCVD), a Plasma Enhanced Chemical Vapor Deposition (PECVD), or the like.
As shown in fig. 9, in step 6, a metal electrode 60 is formed on the surface of the silicon substrate 10 opposite to the second doped silicon layer 40 ', and the metal electrode 60 and the second doped silicon layer 40' are in ohmic contact, thereby obtaining a solar cell.
In the embodiment of the present invention, the electrode paste is printed on the surface of the second doped silicon layer 40' facing away from the silicon substrate 10 by a screen printing process; the silicon substrate 10 printed with the electrode paste is placed in a sintering furnace at 750 to 1000 ℃ for sintering treatment, so that the electrode paste forms a metal electrode 60 in ohmic contact with the second doped silicon layer 40'. Wherein the sintering temperature can be 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C or 1000 deg.C.
In the method for manufacturing a solar cell according to the embodiment of the present invention, as shown in fig. 5, a chemically inert layer may be formed on the surface of the first portion 41 of the second silicon thin film 40 in the second doping treatment, and the second portion 42 of the second silicon thin film 40 may be easily cleaned and removed by an ammonia aqueous solution. The thickness and the doping concentration of the first layer of silicon film and the second layer of silicon film 40 are easy to control, and the feasibility is relatively high. Meanwhile, according to the solar cell produced by the preparation method, the metal electrode 60 is arranged at the position where the first doped silicon layer 30 'and the second doped silicon layer 40' are laminated, so that the sintering depth of the metal electrode 60 can be ensured, the situation that the passivation layer 20 is damaged due to the fact that the metal electrode 60 burns through the first doped silicon layer 30 'and the second doped silicon layer 40' can be avoided, under the condition that good metal contact is ensured, the short-circuit current and the open-circuit voltage are effectively improved, and further the conversion efficiency of the solar cell is improved. In addition, only one second doped silicon layer 40' is formed in other regions of the metal electrode 60, which is beneficial to improving the light absorption rate of the solar cell, thereby ensuring the conversion efficiency of the solar cell.
The second aspect of the embodiments of the present invention also provides a solar cell, which is prepared by the preparation method provided in the embodiment of the first aspect. Referring to fig. 9, the solar cell includes: a silicon substrate 10, a passivation layer 20, a first doped silicon layer 30 ', a second doped silicon layer 40', and a metal electrode 60. The passivation layer 20 is provided on the surface of the silicon substrate 10. The first doped silicon layer 30 'is disposed on a surface of the passivation layer 20 facing away from the silicon substrate 10, and the first doped silicon layer 30' includes a third portion and a fourth portion. The second doped silicon layer 40 'is disposed on the surface of the third portion facing away from the silicon substrate 10, and the second doped silicon layer 40' is not disposed on the surface of the fourth portion facing away from the silicon substrate 10. The metal electrode 60 is in ohmic contact with the second doped silicon layer 40'.
In the embodiment of the present invention, the metal electrode 60 is also in ohmic contact with the first doped silicon layer 30 ', and the metal electrode 60 is prevented from penetrating into the passivation layer 20 and being metal-composited with the passivation layer 20 by the first doped silicon layer 30'.
In the solar cell provided by the embodiment of the invention, based on that the second doped silicon layer 40 'is disposed on the surface of the third portion of the first doped silicon layer 30' facing away from the passivation layer 20, and the second doped silicon layer 40 'is not disposed on the surface of the fourth portion of the first doped silicon layer 30' facing away from the passivation layer 20, in this way, the metal electrode 60 is in ohmic contact with the second doped silicon layer 40 ', the first doped silicon layer 30' and the second doped silicon layer 40 'of the stack provide a larger sintering depth for the metal electrode 60, so that the problem of metal recombination occurring when the metal electrode 60 penetrates between the first doped silicon layer 30' and the passivation layer 20 is avoided, a passivation effect is ensured, and the short-circuit current and the open-circuit voltage of the solar cell are improved. And, the second doped silicon layer 40' is not disposed in the region where the metal electrode is not disposed, which reduces the thickness of the doped silicon layer, and is beneficial to improving the light transmittance of the region, thereby improving the conversion efficiency of the solar cell.
The method of fabricating the solar cell is further described below by way of specific examples.
Example 1
Embodiment 1 provides a method of manufacturing a solar cell, including:
1) preparing a suede: and (3) putting the silicon substrate into a tank filled with 3.2 mass percent of NaOH solution for texturing for 500s, so that the surface of the silicon substrate forms a textured surface.
2) Preparing a PN junction: placing the silicon substrate with the textured surface in a furnace tube, controlling the temperature of the furnace tube to be 900 ℃, and introducing nitrogen and BBr into the furnace tube3And oxygen, oxygen and BBr3Reacting and depositing on the suede of the silicon substrate, controlling the temperature of the furnace tube to be 1000 ℃, so that boron atoms are diffused in the silicon substrate to form a diffusion layer and a borosilicate glass layer, and forming a PN junction between the diffusion layer and the silicon substrate.
3) Wet etching: then, the silicon substrate was suspended in 7.2% by mass of HF and 30% by mass of HNO3In the mixed acid solution, the mixed acid solution is used for etching the back surface and the side surface of the silicon substrate for 1.5min so as to remove the borosilicate glass layer and the diffusion layer on the back surface and the side surface of the silicon substrate.
4) Preparing a passivation layer: controlling the temperature of an inner cavity of a low pressure chemical deposition (LPCVD) device to be 500 ℃, and introducing oxygen into the LPCVD device to form a silicon oxide layer with the thickness of 1.5nm on the back surface of the silicon substrate.
5) Preparing a first doped silicon film: setting the temperature of an inner cavity of the LPCVD equipment to be 610 ℃ and the pressure to be 0.2Torr, and introducing silane and phosphane into the LPCVD equipment to decompose the silane and the phosphane and deposit on the surface of the silicon oxide layer to form a first doped silicon film with the thickness of 40 nm.
6) Preparing a second silicon film: then, the temperature of the inner chamber of the LPCVD apparatus was controlled to 610 ℃ and the pressure was controlled to 0.2Torr, and silane was introduced into the LPCVD apparatus, so that the silane was decomposed and deposited on the surface of the first doped silicon thin film to form a second silicon thin film having a thickness of 60nm, the second silicon thin film including a first portion and a second portion in contact with the first doped silicon thin film.
7) Doping of the second silicon film: and implanting red phosphorus on the surface of the first part of the second layer of silicon film by using an ion implanter.
8) Removing the second part of the second layer of silicon film: and (3) placing the silicon substrate obtained in the step (7) in a cleaning machine, and cleaning by using a solution of ammonia gas with the mass percent of 22.4% to remove the second part of the second layer of silicon film so as to expose the first doped silicon film.
9) Annealing treatment: and (3) placing the silicon substrate treated in the step 8) into annealing equipment, controlling the temperature of the annealing equipment to be 900 ℃, and controlling the annealing time to be 200min, so that the second silicon film forms a second doped silicon layer, and the first doped silicon film forms a first doped silicon layer. Wherein the doping concentration of phosphorus element in the first doped silicon layer is 1E19atoms/cm3The doping concentration of the phosphorus element in the second doped silicon layer is 2E20atoms/cm3。
10) Removing an oxide layer: placing the silicon substrate treated in the step 9) in a cleaning machine, and removing the silicon oxide layer on the surface of the first doped silicon layer and the silicon oxide layer on the surface of the second doped silicon layer by adopting an HF solution with the mass percentage of 5%.
11) Preparing a silicon nitride anti-reflection film: placing the silicon substrate processed in the step 10) in a plate type PECVD device, controlling the temperature of an inner cavity of the PECVD device to be 450 ℃ and the pressure to be 1.75Torr, introducing ammonia gas and silane into the PECVD device, enabling the ammonia gas and the silane to form plasma, and carrying out reaction deposition on the front surface and the back surface of the silicon substrate to form a silicon nitride anti-reflection film with the thickness of 50 nm.
12) Preparing a metal electrode: and printing silver paste on the surface of the second doped silicon layer, which is back to the silicon substrate, through a screen printing process, printing the silver paste on the front surface of the silicon substrate, then placing the silicon substrate in sintering equipment, sintering the silver paste at 750 ℃ to form a metal electrode, enabling the metal electrode on the back surface of the silicon substrate to be in ohmic contact with the second doped silicon layer, and enabling the metal electrode on the front surface to be in ohmic contact with the diffusion layer, so that the solar cell is obtained.
Example 2
Embodiment 2 provides a method of manufacturing a solar cell, including:
1) preparing a suede: and (3) putting the silicon substrate into a tank filled with 3.2 mass percent of NaOH solution for texturing for 500s, so that the surface of the silicon substrate forms a textured surface.
2) Preparing a PN junction: placing the silicon substrate with the textured surface in a furnace tube, controlling the temperature of the furnace tube to 890 ℃, and introducing nitrogen and BBr into the furnace tube3And oxygen, oxygen and BBr3Reacting and depositing on the suede of the silicon substrate, controlling the temperature of the furnace tube to be 950 ℃, so that boron atoms are diffused in the silicon substrate to form a diffusion layer and a borosilicate glass layer, and forming a PN junction between the diffusion layer and the substrate of the silicon substrate.
3) Wet etching: then, the silicon substrate was suspended in 6.8% by mass of HF and 28% by mass of HNO3In the mixed acid solution, the mixed acid solution is used for etching the back surface and the side surface of the silicon substrate for 2min so as to remove the borosilicate glass layer and the diffusion layer on the back surface and the side surface of the silicon substrate.
4) Preparing a passivation layer: controlling the temperature of an inner cavity of a low pressure chemical deposition (LPCVD) device to be 510 ℃, and introducing oxygen into the LPCVD device to form a silicon oxide layer with the thickness of 1.5nm on the back surface of the silicon substrate.
5) Preparing a first doped silicon film: placing the silicon substrate processed in the step 4) in Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment, controlling the temperature of an inner cavity of the PECVD equipment to be 610 ℃, and setting the pressure to be 0.2Torr, and introducing silane and phosphorane into the PECVD equipment to decompose the silane and the phosphorane and deposit on the surface of the silicon oxide layer to form a first doped silicon film with the thickness of 30 nm.
6) Preparing a second silicon film: and then controlling the temperature of the inner cavity of the PECVD equipment to be 610 ℃, and introducing silane into the PECVD equipment to decompose the silane and form a second silicon film with the thickness of 70nm on the surface of the first doped silicon film.
7) Doping of the second silicon film: and implanting red phosphorus on the surface of the first part of the second layer of silicon film by using an ion implanter.
8) Removing the second part of the second layer of silicon film: and (3) placing the silicon substrate obtained in the step (7) in a cleaning machine, and cleaning by using a solution of ammonia gas with the mass percent of 22.4% to remove the second part of the second layer of silicon film so as to expose the first doped silicon film.
9) Annealing treatment: and (3) placing the silicon substrate treated in the step 8) into annealing equipment, controlling the temperature of the annealing equipment to be 1000 ℃, and setting the time of annealing treatment to be 200min, so that the second silicon film forms a second doped silicon layer, and the first doped silicon film forms a first doped silicon layer. Wherein the doping concentration of phosphorus element in the first doped silicon layer is 2E20atoms/cm3The doping concentration of phosphorus element in the second doped silicon layer is 5E20atoms/cm3。
10) Removing an oxide layer: placing the silicon substrate treated in the step 9) in a cleaning machine, and removing the silicon oxide layer on the surface of the first doped silicon layer and the silicon oxide layer on the surface of the second doped silicon layer by adopting an HF solution with the mass percentage of 5%.
11) Preparing a silicon oxynitride antireflection film: placing the silicon substrate processed in the step 10) in a plate type PECVD device, controlling the temperature of an inner cavity of the PECVD device to be 450 ℃, the radio frequency power to be 15KW and the pressure to be 1.75Torr, introducing ammonia gas and silane into the PECVD device to enable the ammonia gas and the silane to form plasma, and forming a silicon nitride antireflection film with the thickness of 50nm by reaction and deposition on the front surface and the back surface of the silicon substrate.
12) Preparing a metal electrode: and printing silver paste on the surface of the second doped silicon layer, which is back to the silicon substrate, through a screen printing process, printing the silver paste on the front surface of the silicon substrate, then placing the silicon substrate in sintering equipment, sintering the silver paste at 750 ℃ to form a metal electrode, enabling the metal electrode on the back surface of the silicon substrate to be in ohmic contact with the second doped silicon layer, and enabling the metal electrode on the front surface to be in ohmic contact with the diffusion layer, so that the solar cell is obtained.
Example 3
Embodiment 3 provides a method of manufacturing a solar cell, including:
1) preparing a suede: and (3) putting the silicon substrate into a groove filled with 2.5 mass percent of NaOH solution for texturing for 550s, so that the surface of the silicon substrate forms a textured surface.
2) Preparing a PN junction: and placing the silicon substrate with the textured surface in a furnace tube, controlling the temperature of the furnace tube to be 820 ℃, introducing nitrogen, phosphorane and oxygen into the furnace tube, reacting the oxygen and the phosphorane and depositing on the textured surface of the silicon substrate, controlling the temperature of the furnace tube to be 960 ℃, diffusing phosphorus atoms in the silicon substrate to form a diffusion layer and a phosphorosilicate glass layer, and forming a PN junction between the diffusion layer and the silicon substrate.
3) Wet etching: then, the silicon substrate was suspended in 7.2% by mass of HF and 30% by mass of HNO3In the mixed acid solution, the mixed acid solution is used for etching the back surface and the side surface of the silicon substrate for 1.5min so as to remove the phosphosilicate glass layer and the diffusion layer on the back surface and the side surface of the silicon substrate.
4) Preparing a passivation layer: controlling the temperature of an inner cavity of a low pressure chemical deposition (LPCVD) device to be 500 ℃, and introducing oxygen into the LPCVD device to form a silicon oxide layer with the thickness of 1.5nm on the back surface of the silicon substrate.
5) Preparing a first doped silicon film: the temperature of the inner chamber of the LPCVD apparatus was set to 610 ℃, the pressure was set to 0.2Torr, and silane and borane were introduced into the LPCVD apparatus, so that the silane and the borane were decomposed and deposited on the surface of the silicon oxide layer to form a first doped silicon thin film having a thickness of 30 nm.
6) Preparing a second silicon film: then controlling the temperature of the inner cavity of the LPCVD equipment to be 610 ℃ and the pressure to be 0.2Torr, and introducing silane into the LPCVD equipment, so that the silane is decomposed and a second silicon film with the thickness of 70nm is deposited on the surface of the first doped silicon film, wherein the second silicon film comprises a first part and a second part which are in contact with the first doped silicon film.
7) Doping of the second silicon film: and implanting borane into the surface of the first part of the second layer of silicon film by using an ion implanter.
8) Removing the second part of the second layer of silicon film: and (3) placing the silicon substrate obtained in the step (7) in a cleaning machine, and cleaning by using a solution of ammonia gas with the mass percent of 22.4% to remove the second part of the second layer of silicon film so as to expose the first doped silicon film.
9) Annealing treatment: and (3) placing the silicon substrate treated in the step 8) into annealing equipment, controlling the temperature of the annealing equipment to be 1000 ℃, and setting the time of annealing treatment to be 200min, so that the second silicon film forms a second doped silicon layer, and the first doped silicon film forms a first doped silicon layer. Wherein the doping concentration of boron element in the first doped silicon layer is 1E19atoms/cm3The doping concentration of boron element in the second doped silicon layer is 4E19atoms/cm2。
10) Removing an oxide layer: placing the silicon substrate treated in the step 9) in a cleaning machine, and removing the silicon oxide layer on the surface of the first doped silicon layer and the silicon oxide layer on the surface of the second doped silicon layer by adopting an HF solution with the mass percentage of 5%.
11) Preparing a silicon oxynitride antireflection film: placing the silicon substrate processed in the step 10) in a plate type PECVD device, controlling the temperature of an inner cavity of the PECVD device to be 450 ℃, the radio frequency power to be 15KW and the pressure to be 1.75Torr, introducing ammonia gas and silane into the PECVD device to enable the ammonia gas and the silane to form plasma, and forming a silicon nitride antireflection film with the thickness of 50nm by reaction and deposition on the front surface and the back surface of the silicon substrate.
12) Preparing a metal electrode: and printing silver paste on the surface of the second doped silicon layer, which is back to the silicon substrate, through a screen printing process, printing the silver paste on the front surface of the silicon substrate, then placing the silicon substrate in sintering equipment, sintering the silver paste at 750 ℃ to form a metal electrode, enabling the metal electrode on the back surface of the silicon substrate to be in ohmic contact with the second doped silicon layer, and enabling the metal electrode on the front surface to be in ohmic contact with the diffusion layer, so that the solar cell is obtained.
The foregoing is directed to embodiments of the present invention, and it is understood by those skilled in the art that various changes, modifications and improvements may be made without departing from the spirit and scope of the invention.

Claims (10)

1. A method of fabricating a solar cell, the method comprising:
forming a passivation layer on the surface of the silicon substrate;
forming a first doped silicon film on the surface of the passivation layer, which is opposite to the silicon substrate;
forming a second layer of silicon film on the surface of the first doped silicon film, which faces away from the silicon substrate, wherein the second layer of silicon film comprises a first part and a second part which are in contact with the first doped silicon film;
carrying out second doping treatment on the first part, and removing the second part to expose the first doped silicon film;
annealing the silicon substrate subjected to the second doping treatment to enable the second layer of silicon film to form a second doped silicon layer and enable the first doped silicon film to form a first doped silicon layer;
and forming a metal electrode on the surface of the silicon substrate opposite to the second doped silicon layer, and enabling the metal electrode to be in ohmic contact with the second doped silicon layer to obtain the solar cell.
2. The method of claim 1, wherein the performing a second doping process on the first portion and removing the second portion comprises:
performing the second doping treatment on the surface of the first part, which is opposite to the first doped silicon film, by an ion implantation method;
the second portion is removed by washing with an aqueous solution of ammonia.
3. The method for preparing the silicon substrate as claimed in claim 1, wherein the forming of the first doped silicon thin film on the surface of the passivation layer opposite to the silicon substrate comprises:
forming a first layer of silicon film on the surface of the passivation layer, which is opposite to the silicon substrate, and carrying out in-situ doping on the first layer of silicon film through a first doping agent to obtain a first doped silicon film;
the first dopant comprises a phosphorous source or a boron source;
the second doping treatment is performed by a second dopant, which is the same as the first dopant.
4. The method according to claim 3, wherein a doping concentration of a doping element of the first dopant in the first doped silicon layer is less than or equal to a doping concentration of a doping element of the second dopant in the second doped silicon layer.
5. The method according to claim 3, wherein the doping concentration of the doping element of the first dopant in the first doped silicon layer is 1.0E19atoms/cm3～2.0E21atoms/cm3(ii) a And/or
The doping concentration of the doping element of the second dopant in the second doped silicon layer is 1.0E19atoms/cm3～2.0E21atoms/cm3。
6. The method according to claim 3, wherein a material of the first silicon thin film is the same as a material of the second silicon thin film.
7. The method of claim 1, wherein the first doped silicon layer forms a first oxide layer on a surface facing away from the silicon substrate, and the second doped silicon layer forms a second oxide layer on a surface facing away from the silicon substrate, the method further comprising:
after the annealing treatment, the first oxide layer and the second oxide layer are removed by an acidic solution.
8. The method according to claim 1, wherein the forming a metal electrode on a surface of the silicon substrate opposite to the second doped silicon layer to make ohmic contact with the second doped silicon layer comprises:
printing electrode slurry on the surface of the second doped silicon layer, which faces away from the silicon substrate, through a screen printing process;
and placing the silicon substrate printed with the electrode paste into a sintering furnace at 750-1000 ℃ for sintering treatment, so that the electrode paste forms a metal electrode in ohmic contact with the second doped silicon layer.
9. A solar cell, comprising:
a silicon substrate;
the passivation layer is arranged on the surface of the silicon substrate;
the first doped silicon layer is arranged on the surface, back to the silicon substrate, of the passivation layer and comprises a third part and a fourth part;
the second doped silicon layer is arranged on the surface of the third part, which is back to the silicon substrate, and the second doped silicon layer is not arranged on the surface of the fourth part, which is back to the silicon substrate; and
and the metal electrode is in ohmic contact with the second doped silicon layer.
10. The solar cell of claim 9, wherein the metal electrode is also in ohmic contact with the first doped silicon layer.
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