CN111106186A - Solar cell for all-black crystalline silicon photovoltaic module and preparation method thereof - Google Patents

Solar cell for all-black crystalline silicon photovoltaic module and preparation method thereof Download PDF

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CN111106186A
CN111106186A CN201911415174.3A CN201911415174A CN111106186A CN 111106186 A CN111106186 A CN 111106186A CN 201911415174 A CN201911415174 A CN 201911415174A CN 111106186 A CN111106186 A CN 111106186A
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layer
sinx
sioxny
thickness
siox
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杨苏平
周文远
尧海华
曾超
林纲正
陈刚
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Guangdong Aiko Technology 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
    • H01L31/02—Details
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    • 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
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the 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
    • H01L31/04—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 at least one potential-jump barrier or surface barrier
    • 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 at least one potential-jump barrier or surface barrier 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
    • H01L31/0682—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 at least one potential-jump barrier or surface barrier 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 back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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
    • H01L31/18—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
    • 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
    • Y02E10/546—Polycrystalline 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
    • 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 discloses a solar cell for a black crystalline silicon photovoltaic module and a preparation method thereof, wherein a front composite film is prepared by adopting tubular PECVD equipment and comprises a SiNx Hy layer, an SiOxNy layer and a SiOx layer, wherein the SiNx Hy layer is connected with an n-type doping layer, and the SiOx layer is connected with a front silver electrode; the SiNx Hy layer consists of 3-4 SiNx Hy layers with different refractive indexes and thicknesses; the SiOxNy layer consists of 2-3 SiOxNy layers with different refractive indexes and thicknesses; the SiOx layer is composed of 1-2 SiOx layers with different refractive indexes and thicknesses. By adopting the invention, the requirements of the all-black crystalline silicon photovoltaic module can be completely met, the appearance chromatic aberration of the black module can be obviously eliminated, and the black module can be applied to the traditional white back plate photovoltaic module.

Description

Solar cell for all-black crystalline silicon photovoltaic module and preparation method thereof
Technical Field
The invention relates to the field of manufacturing of solar cells, in particular to a solar cell for a black crystal silicon photovoltaic module and a preparation method thereof.
Background
Distributed photovoltaic systems are currently under rapid development, and have more stringent requirements for photovoltaic modules, for example, distributed rooftop photovoltaic systems are increasingly demanding the use of all-black photovoltaic modules based on aesthetic and light reflection reduction considerations. The black material is adopted as the back plate of the full-black photovoltaic module, and the slight color difference of the cell piece can show obvious uneven appearance under the support of the black back plate material, so that the full-black photovoltaic module provides higher requirements for the manufacturing technology of the photovoltaic cell piece.
At present, the tubular PERC solar cell has become a mainstream cell manufacturing technology in the photovoltaic industry due to the advantages of good back passivation effect, low equipment cost and high photoelectric conversion efficiency. The technology for manufacturing the PERC crystalline silicon solar cell usually adopts a multi-layer AlOx/SiOxNy/SiNx: Hy film as a back passivation film, and the AlOx/SiOxNy/SiNx: Hy back passivation layer of the PERC crystalline silicon solar cell is manufactured by a tubular PECVD (plasma Enhanced Chemical Vapor deposition)) device. Since the tubular PECVD equipment adopts the graphite boat as a silicon wafer bearing device, the silicon wafer vertically clings to the graphite boat piece, and in the process of plating the back passivation film layer, as the silicon wafer is thermally deformed and cannot be clung to the graphite boat piece, partial reaction gas migrates to the edge region of the front surface to react to generate a SiNx-Hy winding coating with a certain thickness, after the front film is plated, the difference of the thickness and the refractive index of the thin film between the edge region and the central region of the front film can be caused due to the existence of the winding coating, and after the battery piece is packaged into a black component, the obvious appearance unevenness and color difference can be presented.
In the solar cell antireflection passivation film, the preparation method thereof and the solar cell sheet disclosed in prior art CN107068774A, the solar cell antireflection passivation film includes: the first layer is formed on a silicon chip substrate, and the first layer is a SiOx layer; the second layer is formed on the first layer and is a SiNx layer; a third layer formed on the second layer, the third layer being a SiONx layer; and the fourth layer is formed on the third layer and is a SiOx layer. The refractive index of the first layer is 1.6-2.3, the refractive index of the second layer is 1.9-2.3, the refractive index of the third layer is 1.9-2.1, and the refractive index of the fourth layer is 1.4-1.6. The film thickness of the first layer is 2-10 nm, the film thickness of the second layer is 45-55 nm, the film thickness of the third layer is 5-20 nm, and the film thickness of the fourth layer is 15-35 nm. The comparison document adopts a SiOx/SiNx/SiONx/SiOx laminated arrangement, a SiOx layer is in contact with a silicon wafer substrate, the refractive indexes of four layers of passivation films are increased and then decreased, and the four layers of passivation films are influenced by the film thickness, after a positive film is plated on a battery piece, the difference between the film thickness and the refractive index of the edge area and the central area of the positive film can be caused, and the color difference can present obvious uneven appearance under the support of a black back plate material.
At the present stage, the tubular PERC solar cell design cannot meet the requirements of the all-black photovoltaic module on the appearance, so that the development of a tubular PERC solar cell manufacturing technology capable of eliminating the appearance chromatic aberration of the black module is urgently needed
Disclosure of Invention
The invention aims to provide a solar cell for a black crystalline silicon photovoltaic module and a preparation method thereof, which can not only completely meet the requirements of the black crystalline silicon photovoltaic module and obviously eliminate the appearance chromatic aberration of the black module, but also can be applied to the traditional white back plate photovoltaic module.
In order to solve the technical problem, the invention provides a solar cell for a black crystalline silicon photovoltaic module, which sequentially comprises a back silver electrode, a back aluminum film, a back composite film, a p-type silicon wafer, an n-type doped layer, a front composite film and a front silver electrode from bottom to top, wherein the front composite film is prepared by adopting tubular PECVD equipment and comprises a SiNx Hy layer, an SiOxNy layer and a SiOx layer, the SiNx Hy layer is connected with the n-type doped layer, and the SiOx layer is connected with the front silver electrode;
the SiNx Hy layer consists of 3-4 SiNx Hy layers with different refractive indexes and thicknesses;
the SiOxNy layer consists of 2-3 SiOxNy layers with different refractive indexes and thicknesses;
the SiOx layer is composed of 1-2 SiOx layers with different refractive indexes and thicknesses.
As an improvement of the scheme, the SiNx and Hy layer sequentially comprises a first SiNx and Hy layer, a second SiNx and Hy layer, a third SiNx and Hy layer and a fourth SiNx and Hy layer from bottom to top, wherein the first SiNx and Hy layer is connected with the n-type doped layer;
the thickness of the first SiNx and Hy layer is 9-15 nm, and the refractive index is 2.2-2.3;
the thickness of the second SiNx-Hy layer is 9-15 nm, and the refractive index is 2.15-2.2;
the thickness of the Hy layer of the third SiNx is 10-17 nm, and the refractive index is 2.10-2.15;
the thickness of the fourth SiNx Hy layer is 8-14 nm, and the refractive index is 2.05-2.10.
As an improvement of the above scheme, the SiOxNy layer sequentially comprises a first SiOxNy layer, a second SiOxNy layer and a third SiOxNy layer from bottom to top, and the first SiOxNy layer is connected with the SiNx-Hy layer;
the thickness of the first SiOxNy layer is 7 nm-14 nm, and the refractive index is 1.95-2.0;
the thickness of the second SiOxNy layer is 6 nm-12 nm, and the refractive index is 1.90-1.95;
the third SiOxNy layer has a thickness of 5 to 10nm and a refractive index of 1.80 to 1.90.
As an improvement of the above scheme, the SiOx layer sequentially comprises a first SiOx layer and a second SiOx layer from bottom to top, and the first SiOx layer is connected with the SiOxNy layer;
the thickness of the first SiOx layer is 5 nm-10 nm, and the refractive index is 1.50-1.80;
the second SiOx layer has a thickness of 3 to 7nm and a refractive index of 1.40 to 1.55.
As an improvement of the scheme, the SiNx and Hy layer sequentially comprises a first SiNx and Hy layer, a second SiNx and Hy layer and a third SiNx and Hy layer from bottom to top, and the first SiNx and Hy layer is connected with the n-type doped layer;
the thickness of the first SiNx and Hy layer is 9-15 nm, and the refractive index is 2.2-2.3;
the thickness of the second SiNx-Hy layer is 9-15 nm, and the refractive index is 2.15-2.2;
the thickness of the third SiNx/Hy layer is 10-17 nm, and the refractive index is 2.10-2.15.
As an improvement of the above scheme, the SiOxNy layer sequentially comprises a first SiOxNy layer and a second SiOxNy layer from bottom to top, and the first SiOxNy layer is connected with the SiNx-Hy layer;
the thickness of the first SiOxNy layer is 7 nm-14 nm, and the refractive index is 1.95-2.0;
the thickness of the second SiOxNy layer is 6 nm-12 nm, and the refractive index is 1.90-1.95.
As an improvement of the above scheme, the SiOx layer sequentially comprises a first SiOx layer from bottom to top, and the first SiOx layer is connected with the SiOxNy layer;
the first SiOx layer has a thickness of 5nm to 10nm and a refractive index of 1.50 to 1.80.
As an improvement of the scheme, the back composite film is prepared by adopting tubular PECVD equipment and consists of AlOx/SiOxNy/SiNx: Hy multilayer films, the total thickness of the back composite film is 120-150 mu m, and the refractive index is 2.03-2.08.
As an improvement of the scheme, the p-type silicon wafer is a monocrystalline silicon wafer or a polycrystalline silicon wafer, the resistivity is 0.5-1.5 omega-cm, and the thickness is 170-190 mu m;
the height of the front silver electrode is 9-14 mu m;
the thickness of the back aluminum film is 15-30 μm;
the height of the back silver electrode is 3-8 μm.
Correspondingly, the invention discloses a preparation method of a solar cell for a black crystal silicon photovoltaic module, which comprises the following steps:
(1) selecting a p-type silicon wafer, and cleaning and texturing the silicon wafer;
(2) carrying out n-type layer diffusion on the silicon wafer after cleaning and texturing;
(3) carrying out an SE laser process on the front surface of the silicon wafer to form front surface selective doping;
(4) removing the n-type layer on the back and the edge of the silicon wafer and the redundant phosphorosilicate glass on the front by an etching process;
(5) preparing a back composite film by adopting tubular PERC equipment;
(6) preparing a front composite film by adopting tubular PERC equipment, wherein the front composite film comprises a SiNx Hy layer, a SiOxNy layer and a SiOx layer, and the SiNx Hy layer consists of 3-4 SiNx Hy layers with different refractive indexes and thicknesses; the SiOxNy layer consists of 2-3 SiOxNy layers with different refractive indexes and thicknesses; the SiOx layer is composed of 1-2 SiOx layers with different refractive indexes and thicknesses.
(7) Performing laser tapping treatment on the back surface of the silicon wafer so as to facilitate the silicon wafer to be in contact with a back aluminum film and a back electrode;
(8) preparing a back silver electrode, a back aluminum film and a front silver electrode by screen printing, and sintering;
(9) and (3) activating hydrogen in the battery by adopting light injection equipment through carrier injection, and passivating defects in the silicon wafer body.
The implementation of the invention has the following beneficial effects:
1. the invention provides a solar cell and a preparation method thereof, wherein the solar cell adopts a front composite film which is designed and superposed with different materials, different refractive indexes and different thicknesses, the front composite film comprises a SiNx Hy layer, a SiOxNy layer and a SiOx layer, the SiNx Hy layer consists of 3-4 SiNx and Hy layers with different refractive indexes and thicknesses, the SiOxNy layer consists of 2-3 SiOxNy layers with different refractive indexes and thicknesses, the SiOx layer consists of 1-2 SiOx layers with different refractive indexes and thicknesses, optical extinction and reflectivity reduction can be realized, after the SiOx layer is packaged into a black back panel photovoltaic module, the nonuniformity of the appearance of the module can be obviously eliminated, and the edge of a cell piece of the module does not appear blue;
2. the invention provides a solar cell and a preparation method thereof, wherein the front composite film of the solar cell can realize good passivation and reflectivity reduction effects, can meet the requirements of a full-black photovoltaic module on appearance, and can ensure that the photoelectric conversion efficiency of the cell is not lower than that of a cell prepared by the prior art, and the actual cell efficiency is improved by 0.15-0.2%;
3. the solar cell and the preparation method provided by the invention can be conveniently introduced into the existing tubular PERC crystalline silicon solar cell production line, no additional new equipment is required to be added, and the solar cell and the preparation method have the advantages of good compatibility, low cost and convenience in process.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a solar cell for an all-black-crystal-silicon photovoltaic module according to the present invention;
fig. 2 is a schematic diagram of another embodiment of a solar cell for an all-black-crystalline silicon photovoltaic module according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below.
With reference to fig. 1 and fig. 2, the solar cell for the all-black-crystal-silicon photovoltaic module provided by the invention sequentially comprises a back silver electrode 1, a back aluminum film 2, a back composite film 3, a p-type silicon wafer 4, an n-type doped layer 5, a front composite film 6 and a front silver electrode 7 from bottom to top, wherein the front composite film 6 comprises a SiNx hyy layer 61, an SiOxNy layer 62 and a SiOx layer 63, the SiNx hyy layer 61 is connected with the n-type doped layer 5, and the SiOx layer 63 is connected with the front silver electrode 7;
the SiNx Hy layer 61 is composed of 3-4 SiNx Hy layers with different refractive indexes and thicknesses;
the SiOxNy layer 62 consists of 2-3 SiOxNy layers with different refractive indexes and thicknesses;
the SiOx layer 63 is composed of 1-2 SiOx layers with different refractive indexes and thicknesses.
As a preferred embodiment of the present invention, as shown in fig. 1, the SiNx: Hy layer 61 sequentially includes, from bottom to top, a first SiNx: Hy layer 611, a second SiNx: Hy layer 612, a third SiNx: Hy layer 613, and a fourth SiNx: Hy layer 614, where the first SiNx: Hy layer 611 is connected to the n-type doped layer 5;
the thickness of the first SiNx/Hy layer 611 is 9-15 nm, and the refractive index is 2.2-2.3;
the thickness of the second SiNx/Hy layer 612 is 9-15 nm, and the refractive index is 2.15-2.2;
the thickness of the Hy layer 613 of the third SiNx is 10-17 nm, and the refractive index is 2.10-2.15;
the thickness of the fourth SiNx/Hy layer 614 is 8-14 nm, and the refractive index is 2.05-2.10.
The first SiNx Hy layer 611 has the function of passivating the surface of a silicon wafer with high refractive index, and the second SiNx Hy layer, the second SiNx Hy layer and the fourth SiNx Hy layer are designed with gradually-changed refractive indexes, so that the abrupt change difference of the interfaces of the thin film is reduced, the transition is stable, a better passivation effect is realized, and the integral uniformity is improved. The passivation effect of the first SiNx Hy layer and the second SiNx Hy layer is obvious, and the third SiNx Hy layer and the fourth SiNx Hy layer mainly reduce the reflectivity and improve the film color uniformity.
Hy thickness and refractive index are specially limited, the passivation effect is improved, the color uniformity of the battery film is ensured under the condition of reducing front light reflection, the requirements of black components are met, and meanwhile, the overall reliability of the battery such as PID is also considered.
Hy structure gradual change design of multilayer SiNx, because adopt different gas flow ratio, compare the individual layer membrane, can promote passivation effect simultaneously reduce reflectivity again, let incident light effectively reach the PN junction in order to promote efficiency, in addition, this kind of gradual change design is favorable to reducing positive membrane colour difference and satisfies black subassembly light trapping structure demand.
The SiOxNy layer 62 sequentially comprises a first SiOxNy layer 621, a second SiOxNy layer 622 and a third SiOxNy layer 623 from bottom to top, wherein the first SiOxNy layer 621 is connected with the SiNx-Hy layer 61;
the thickness of the first SiOxNy layer 621 is 7 nm-14 nm, and the refractive index is 1.95-2.0;
the thickness of the second SiOxNy layer 622 is 6nm to 12nm, and the refractive index is 1.90 to 1.95;
the third SiOxNy layer 623 has a thickness of 5 to 10nm and a refractive index of 1.80 to 1.90.
SiOxNy has excellent passivation permeability-increasing characteristics, and the components of a film layer can be changed by changing the gas flow ratio of required special gas, so that a preferable optical characteristic structure is formed. The first SiOxNy layer and the second SiOxNy layer contain a large amount of H for passivating the silicon nitride layer and the front surface of the silicon wafer, the reflection effect of the front surface of the silicon wafer is reduced, the reflectivity of the film can be reduced to a greater extent by the design of the gradient film, and the reliability of the battery piece is improved. The third SiOxNy layer is used as a transition layer, the content of O and N in the third SiOxNy layer is adjusted to gradually change to the required optical characteristic requirement, and the optical characteristic required by the appearance of the black component is overlapped with the later SiOx layer.
The SiOx layer 63 sequentially includes a first SiOx layer 631 and a second SiOx layer 632 from bottom to top, and the first SiOx layer 631 is connected to the SiOxNy layer 632;
the thickness of the first SiOx layer 631 is 5 nm-10 nm, and the refractive index is 1.50-1.80;
the second SiOx layer 632 has a thickness of 3 to 7nm and a refractive index of 1.40 to 1.55.
The first SiOx layer is connected with a SiOxNy layer, the film component of the first SiOx layer can meet the requirements of passivation and reflectivity reduction, and can also meet the optical characteristics of a black component battery, and the second SiOx layer can reduce the reflectivity of the front side and improve the uniformity of the film color of the composite film. While the second SiOx layer also serves to protect the first SiOx layer.
As another preferred embodiment of the present invention, as shown in fig. 2, the SiNx: Hy layer 61 sequentially includes a first SiNx: Hy layer 611, a second SiNx: Hy layer 612, and a third SiNx: Hy layer 613 from bottom to top, where the first SiNx: Hy layer 611 is connected to the n-type doped layer 5;
the thickness of the first SiNx/Hy layer 611 is 9-15 nm, and the refractive index is 2.2-2.3;
the thickness of the second SiNx/Hy layer 612 is 9-15 nm, and the refractive index is 2.15-2.2;
the thickness of the third SiNx/Hy layer 613 is 10-17 nm, and the refractive index is 2.10-2.15.
The first SiNx Hy layer 611 has the function of passivating the surface of a silicon wafer with high refractive index, and the second SiNx Hy layer, the second SiNx Hy layer and the third SiNx Hy layer are designed with gradually-changed refractive indexes, so that the abrupt change difference of the interfaces of the thin film is reduced, the transition is stable, a better passivation effect is realized, and the integral uniformity is improved. The first SiNx Hy layer and the second SiNx Hy layer have obvious passivation effects, and the third SiNx Hy layer mainly reduces reflectivity and improves film color uniformity.
Hy thickness and refractive index are specially limited, the passivation effect is improved, the color uniformity of the battery film is ensured under the condition of reducing front light reflection, the requirements of black components are met, and meanwhile, the overall reliability of the battery such as PID is also considered.
Hy structure gradual change design of multilayer SiNx, because adopt different gas flow ratio, compare the individual layer membrane, can promote passivation effect simultaneously reduce reflectivity again, let incident light effectively reach the PN junction in order to promote efficiency, in addition, this kind of gradual change design is favorable to reducing positive membrane colour difference and satisfies black subassembly light trapping structure demand.
The SiOxNy layer 62 sequentially comprises a first SiOxNy layer 621 and a second SiOxNy layer 622 from bottom to top, wherein the first SiOxNy layer 621 is connected with the SiNx-Hy layer 622;
the thickness of the first SiOxNy layer 621 is 7 nm-14 nm, and the refractive index is 1.95-2.0;
the thickness of the second SiOxNy layer 622 is 6nm to 12nm, and the refractive index is 1.90 to 1.95.
SiOxNy has excellent passivation permeability-increasing characteristics, and the components of a film layer can be changed by changing the gas flow ratio of required special gas, so that a preferable optical characteristic structure is formed. The first SiOxNy layer and the second SiOxNy layer contain a large amount of H for passivating the silicon nitride layer and the front surface of the silicon wafer, the reflection effect of the front surface of the silicon wafer is reduced, the reflectivity of the film can be reduced to a greater extent by the design of the gradient film, and the reliability of the battery piece is improved. At the same time, the second SiOxNy layer may serve as the optical characteristic required for the subsequent SiOx layer to superpose the transition to the appearance of a black component.
The SiOx layer 63 sequentially includes a first SiOx layer 631 from bottom to top, and the first SiOx layer 631 is connected to the SiOxNy layer 62;
the first SiOx layer 631 has a thickness of 5nm to 10nm and a refractive index of 1.50 to 1.80.
The first SiOx layer is connected with a SiOxNy layer, and the composition of the SiOx layer can meet the requirements of passivation and reflectivity reduction and also meet the optical characteristics of a black component battery.
The front composite film 6 is prepared by adopting tubular PECVD equipment, the back composite film 3 is prepared by adopting tubular PECVD equipment, wherein the back composite film 3 is composed of AlOx/SiOxNy/SiNx-Hy multilayer films, the total thickness of the back composite film is 120-150 mu m, and the refractive index is 2.03-2.08.
The p-type silicon wafer 4 is a monocrystalline silicon wafer or a polycrystalline silicon wafer, the resistivity is 0.5-1.5 omega-cm, and the thickness is 170-190 mu m.
The n-type doped layer 5 is formed by phosphorus doping, and can be performed by gas phase diffusion or ion implantation, and the sheet resistance after diffusion is 160 Ω/sq.
The front silver electrode 7 is prepared by adopting screen printing front silver paste sintering, and the height of the front silver electrode is 9-14 um.
The back aluminum film 2 is prepared by adopting screen printing back silver paste sintering, and the thickness of the aluminum film is 15-30 um.
The back silver electrode 1 is prepared by adopting screen printing back silver paste sintering, and the height of the back electrode is 3-8 um.
The back silver electrode 1, the back aluminum film 2, the back composite film 3, the p-type silicon wafer 4, the n-type doped layer 5, the front composite film 6 and the front silver electrode 7 are sequentially stacked, so that the requirement of a full black crystal silicon photovoltaic module can be completely met, the appearance chromatic aberration of the black module is remarkably eliminated, and the black module can be applied to a traditional white back plate photovoltaic module.
Correspondingly, the invention discloses a preparation method of a solar cell for a black crystal silicon photovoltaic module, which comprises the following steps:
(1) selecting a p-type silicon wafer, and cleaning and texturing the silicon wafer;
specifically, a low-reflectivity suede is prepared on the surface of a silicon wafer by adopting methods such as alkali texturing or ion etching, and the reflectivity of the front side after texturing is 8.5% -11.0%;
(2) carrying out n-type layer diffusion on the silicon wafer after cleaning and texturing;
specifically, gas phase diffusion or ion implantation is adopted, and the sheet resistance after diffusion is 100-150 omega/sq;
(3) carrying out an SE laser process on the front surface of the silicon wafer to form front surface selective doping;
specifically, the n-type diffusion layer is processed by adopting front laser to form front selective doping, and the sheet resistance of a selective doping area is 70-100 omega/sq;
(4) removing the n-type layer on the back and the edge of the silicon wafer and the redundant phosphorosilicate glass on the front by an etching process;
specifically, an etching process is used for removing the n-type layer on the back surface and the edge of the silicon wafer and redundant phosphorosilicate glass on the front surface, the flatness of the back surface of the silicon wafer is improved, and the reflectivity of the back surface after etching is 22% -32%;
(5) preparing a back composite film by adopting tubular PERC equipment;
and preparing the AlOx/SiOxNy/SiNx/Hy structure composite passivation film layer by adopting tubular PECVD. Loading the silicon wafers processed by the steps into a graphite boat, wherein the front surfaces of the silicon wafers are tightly attached to the graphite boat sheets, then conveying the graphite boat loaded with the silicon wafers to a tubular PECVD equipment reaction chamber, wherein the deposition temperature of the reaction chamber is 260-500 ℃, the pressure of the reaction chamber is 700-1600 mtorr, the power of a radio frequency power supply is 3000-14000 w, and Silane (SiH)4) Gas flow rate of 300-1200 sccm, ammonia gas (NH)3) Gas flow rate of 2000-8000 sccm, laughing gas (N)2O) gas flow rate of 3000 sccm-7000 sccm, Trimethylaluminum (TMA) gas flow rate of 60 sccm-100 sccm, and deposition time of 50 s-850 s.
(6) Preparing a front composite film by adopting tubular PERC equipment, wherein the front composite film comprises a SiNx Hy layer, a SiOxNy layer and a SiOx layer, and the SiNx Hy layer consists of 3-4 SiNx Hy layers with different refractive indexes and thicknesses; the SiOxNy layer consists of 2-3 SiOxNy layers with different refractive indexes and thicknesses; the SiOx layer is composed of 1-2 SiOx layers with different refractive indexes and thicknesses.
Loading the silicon wafer processed by the steps into a graphite boat, wherein the back surface of the silicon wafer is tightly attached to the graphite boat sheet, then conveying the graphite boat loaded with the silicon wafer to a tubular PECVD equipment reaction chamber, wherein the deposition temperature of the reaction chamber is 400-500 ℃, the pressure of the reaction chamber is 1000-1800 mtorr, the power of a radio frequency power supply is 5000-14000 w, and Silane (SiH)4) Gas flow rate of 300-1200 sccm, ammonia gas (NH)3) Gas flow rate of 2000-8000 sccm, laughing gas (N)2O) the gas flow rate is 4000sccm to 9000sccm, and the deposition time is 50s to 500 s.
(7) Performing laser tapping treatment on the back surface of the silicon wafer so as to facilitate the silicon wafer to be in contact with a back aluminum film and a back electrode;
specifically, a back passivation film is processed by laser ablation so that a silicon wafer can be in contact with a back aluminum film and a back electrode, wherein the back laser power is 14 w-20 w, and the diameter of a laser opening is 25 um-45 um;
(8) preparing a back silver electrode, a back aluminum film and a front silver electrode by screen printing, and sintering;
specifically, a back silver electrode, a back aluminum film and a front silver electrode are respectively prepared through screen printing equipment, and the front silver electrode and the back silver electrode are formed through a chain type sintering furnace, wherein the temperature of a drying area is set to be 200-400 ℃, the temperature of a pre-sintering area is set to be 400-750 ℃, and the temperature of a sintering area is set to be 790-870 ℃;
(9) and (3) activating hydrogen in the battery by adopting light injection equipment through carrier injection, and passivating defects in the silicon wafer body.
Specifically, a light injection device is adopted, hydrogen in a battery is activated through carrier injection, defects in a silicon wafer body are passivated, and power attenuation of the battery piece is reduced, wherein the temperature of a light injection preheating zone is 200-300 ℃, the power of an LED light source is set to be 70-95%, and the transmission speed is set to be 6.5-11 m/min.
The invention is further illustrated by the following specific examples
Example 1
A solar cell for a black crystal silicon photovoltaic component comprises a back silver electrode, a back aluminum film, a back composite film, a p-type silicon wafer, an n-type doping layer, a front composite film and a front silver electrode from bottom to top in sequence,
the front composite film comprises a SiNx Hy layer, a SiOxNy layer and a SiOx layer, wherein the SiNx Hy layer is connected with an n-type doping layer, and the SiOx layer is connected with a front silver electrode;
the SiNx Hy layer consists of 4 SiNx and Hy layers with different refractive indexes and thicknesses and sequentially comprises a first SiNx and Hy layer, a second SiNx and Hy layer, a third SiNx and Hy layer and a fourth SiNx and Hy layer from bottom to top; the thickness of the first SiNx/Hy layer is 10nm, and the refractive index is 2.3; the thickness of the second SiNx/Hy layer is 12nm, and the refractive index is 2.16; the thickness of the third SiNx-Hy layer is 15nm, and the refractive index is 2.12; the fourth SiNx: Hy layer has a thickness of 9nm and a refractive index of 2.08.
The SiOxNy layer consists of 3 SiOxNy layers with different refractive indexes and thicknesses, and sequentially comprises a first SiOxNy layer, a second SiOxNy layer and a third SiOxNy layer from bottom to top, wherein the first SiOxNy layer is connected with a SiNx/Hy layer; the thickness of the first SiOxNy layer is 10nm, and the refractive index is 2.0; the thickness of the second SiOxNy layer is 8nm, and the refractive index is 1.93; the third SiOxNy layer has a thickness of 7nm and a refractive index of 1.85.
The SiOx layer consists of 2 SiOx layers with different refractive indexes and thicknesses, and sequentially comprises a first SiOx layer and a second SiOx layer from bottom to top, wherein the first SiOx layer is connected with an SiOxNy layer; the thickness of the first SiOx layer is 8nm, and the refractive index is 1.70; the second SiOx layer has a thickness of 5nm and a refractive index of 1.50.
The back composite film is prepared by adopting tubular PECVD equipment and consists of AlOx/SiOxNy/SiNx: Hy multilayer films, the total thickness of the back composite film is 130 mu m, and the refractive index is 2.05.
The back aluminum film is prepared by adopting screen printing back silver paste sintering, and the thickness of the aluminum film is 15 microns;
the back silver electrode is prepared by adopting screen printing back silver paste sintering, and the height of the back electrode is 5 mu m;
the front silver electrode is prepared by adopting screen printing front silver paste after sintering, and the height of the front silver electrode is 9 mu m.
Example 2
A solar cell for a black crystal silicon photovoltaic component comprises a back silver electrode, a back aluminum film, a back composite film, a p-type silicon wafer, an n-type doping layer, a front composite film and a front silver electrode from bottom to top in sequence,
the front composite film comprises a SiNx Hy layer, a SiOxNy layer and a SiOx layer, wherein the SiNx Hy layer is connected with an n-type doping layer, and the SiOx layer is connected with a front silver electrode;
the SiNx Hy layer consists of 3 SiNx Hy layers with different refractive indexes and thicknesses and sequentially comprises a first SiNx Hy layer, a second SiNx Hy layer and a third SiNx Hy layer from bottom to top; the thickness of the first SiNx/Hy layer is 12nm, and the refractive index is 2.25; the thickness of the second SiNx/Hy layer is 10nm, and the refractive index is 2.15; the thickness of the third SiNx: Hy layer is 13nm, and the refractive index is 2.10.
The SiOxNy layer consists of 2 SiOxNy layers with different refractive indexes and thicknesses, and sequentially comprises a first SiOxNy layer and a second SiOxNy layer from bottom to top, wherein the first SiOxNy layer is connected with the SiNx Hy layer; the thickness of the first SiOxNy layer is 12nm, and the refractive index is 1.98; the thickness of the second SiOxNy layer is 10nm, and the refractive index is 1.91.
The SiOx layer consists of 1 SiOx layer with different refractive indexes and thicknesses, and sequentially comprises a first SiOx layer from bottom to top, and the first SiOx layer is connected with an SiOxNy layer; the first SiOx layer has a thickness of 10nm and a refractive index of 1.50.
The back composite film is prepared by adopting tubular PECVD equipment and consists of AlOx/SiOxNy/SiNx: Hy multilayer films, the total thickness of the back composite film is 150 mu m, and the refractive index is 2.05.
The back aluminum film is prepared by adopting screen printing back silver paste sintering, and the thickness of the aluminum film is 25 micrometers;
the back silver electrode is prepared by adopting screen printing back silver paste sintering, and the height of the back electrode is 6 mu m;
the front silver electrode is prepared by adopting screen printing front silver paste after sintering, and the height of the front silver electrode is 11 microns.
The solar cell obtained in example 1-2 was subjected to technical testing and compared with the cell prepared by the prior art, and the results are as follows:
item Uoc(V) Isc(A) Rser(Ω) Rshunt(Ω) FF(％) Eta(％) IRev2
Prior Art 0.6777 9.794 0.00174 1024.8 81.40 22.114 0.052
Example 1 0.6792 9.841 0.00179 937.9 81.35 22.254 0.050
Example 2 0.6791 9.846 0.00179 988.5 81.40 22.280 0.050
As can be seen from the above table, the open-circuit voltage Uoc, the short-circuit current Isc, the series resistance Rser, the parallel resistance Rshunt, the fill factor FF, and the reverse current IRev2 when the reverse voltage is 12 v of the tubular PERC solar cell prepared in the embodiments 1 and 2 of the present invention are all similar to the cell prepared in the prior art, and the conversion efficiency Eta is slightly improved compared with the cell prepared in the prior art, so that the present invention not only can satisfy the requirements of the all-black photovoltaic module, but also can be applied to the conventional white back panel photovoltaic module. Moreover, the tubular PERC solar cells prepared in examples 1 and 2 can remarkably eliminate the appearance color difference of the black module, and the blue phenomenon does not occur on the edges of the cell sheets of the module.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims (10)

1. A solar cell for a black crystalline silicon photovoltaic module is characterized by sequentially comprising a back silver electrode, a back aluminum film, a back composite film, a p-type silicon wafer, an n-type doped layer, a front composite film and a front silver electrode from bottom to top, wherein the front composite film comprises a SiNx Hy layer, a SiOxNy layer and a SiOx layer, the SiNx Hy layer is connected with the n-type doped layer, and the SiOx layer is connected with the front silver electrode;
the SiNx Hy layer consists of 3-4 SiNx Hy layers with different refractive indexes and thicknesses;
the SiOxNy layer consists of 2-3 SiOxNy layers with different refractive indexes and thicknesses;
the SiOx layer is composed of 1-2 SiOx layers with different refractive indexes and thicknesses.
2. The solar cell for the all-black-crystal-silicon photovoltaic module as claimed in claim 1, wherein the SiNx Hy layer sequentially comprises a first SiNx Hy layer, a second SiNx Hy layer, a third SiNx Hy layer and a fourth SiNx Hy layer from bottom to top, and the first SiNx Hy layer is connected with the n-type doped layer;
the thickness of the first SiNx and Hy layer is 9-15 nm, and the refractive index is 2.2-2.3;
the thickness of the second SiNx-Hy layer is 9-15 nm, and the refractive index is 2.15-2.2;
the thickness of the Hy layer of the third SiNx is 10-17 nm, and the refractive index is 2.10-2.15;
the thickness of the fourth SiNx Hy layer is 8-14 nm, and the refractive index is 2.05-2.10.
3. The solar cell of claim 2, wherein the SiOxNy layer comprises a first SiOxNy layer, a second SiOxNy layer and a third SiOxNy layer from bottom to top in sequence, and the first SiOxNy layer is connected with the SiNx Hy layer;
the thickness of the first SiOxNy layer is 7 nm-14 nm, and the refractive index is 1.95-2.0;
the thickness of the second SiOxNy layer is 6 nm-12 nm, and the refractive index is 1.90-1.95;
the third SiOxNy layer has a thickness of 5 to 10nm and a refractive index of 1.80 to 1.90.
4. The solar cell of claim 3, wherein the SiOx layer comprises a first SiOx layer and a second SiOx layer in this order from bottom to top, the first SiOx layer being bonded to the SiOxNy layer;
the thickness of the first SiOx layer is 5 nm-10 nm, and the refractive index is 1.50-1.80;
the second SiOx layer has a thickness of 3 to 7nm and a refractive index of 1.40 to 1.55.
5. The solar cell for the all-black-crystal-silicon photovoltaic module as claimed in claim 1, wherein the SiNx: Hy layer sequentially comprises a first SiNx: Hy layer, a second SiNx: Hy layer and a third SiNx: Hy layer from bottom to top, and the first SiNx: Hy layer is connected with the n-type doped layer;
the thickness of the first SiNx and Hy layer is 9-15 nm, and the refractive index is 2.2-2.3;
the thickness of the second SiNx-Hy layer is 9-15 nm, and the refractive index is 2.15-2.2;
the thickness of the third SiNx/Hy layer is 10-17 nm, and the refractive index is 2.10-2.15.
6. The solar cell of claim 5, wherein the SiOxNy layer comprises a first SiOxNy layer and a second SiOxNy layer in sequence from bottom to top, wherein the first SiOxNy layer is connected with a SiNx Hy layer;
the thickness of the first SiOxNy layer is 7 nm-14 nm, and the refractive index is 1.95-2.0;
the thickness of the second SiOxNy layer is 6 nm-12 nm, and the refractive index is 1.90-1.95.
7. The solar cell of claim 6, wherein the SiOx layer comprises, in order from bottom to top, a first SiOx layer that is bonded to an SiOxNy layer;
the first SiOx layer has a thickness of 5nm to 10nm and a refractive index of 1.50 to 1.80.
8. The solar cell for the all-black crystalline silicon photovoltaic module as claimed in claim 1, wherein the back composite film is prepared by adopting a tubular PECVD device and is composed of AlOx/SiOxNy/SiNx: Hy multilayer films, the total thickness of the back composite film is 120-150 μm, and the refractive index is 2.03-2.08.
9. The solar cell for the all-black crystalline silicon photovoltaic module as claimed in claim 1, wherein the p-type silicon wafer is a monocrystalline silicon wafer or a polycrystalline silicon wafer, the resistivity is 0.5 Ω -cm to 1.5 Ω -cm, and the thickness is 170 μm to 190 μm;
the height of the front silver electrode is 9-14 mu m;
the thickness of the back aluminum film is 15-30 μm;
the height of the back silver electrode is 3-8 μm.
10. A method of manufacturing a solar cell for an all-black-crystalline silicon photovoltaic module according to claim 1, comprising:
(1) selecting a p-type silicon wafer, and cleaning and texturing the silicon wafer;
(2) carrying out n-type layer diffusion on the silicon wafer after cleaning and texturing;
(3) carrying out an SE laser process on the front surface of the silicon wafer to form front surface selective doping;
(4) removing the n-type layer on the back and the edge of the silicon wafer and the redundant phosphorosilicate glass on the front by an etching process;
(5) preparing a back composite film by adopting tubular PERC equipment;
(6) preparing a front composite film by adopting tubular PERC equipment, wherein the front composite film comprises a SiNx Hy layer, a SiOxNy layer and a SiOx layer, and the SiNx Hy layer consists of 3-4 SiNx Hy layers with different refractive indexes and thicknesses; the SiOxNy layer consists of 2-3 SiOxNy layers with different refractive indexes and thicknesses; the SiOx layer is composed of 1-2 SiOx layers with different refractive indexes and thicknesses.
(7) Performing laser tapping treatment on the back surface of the silicon wafer so as to facilitate the silicon wafer to be in contact with a back aluminum film and a back electrode;
(8) preparing a back silver electrode, a back aluminum film and a front silver electrode by screen printing, and sintering;
(9) and (3) activating hydrogen in the battery by adopting light injection equipment through carrier injection, and passivating defects in the silicon wafer body.
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