CN116525690A - Solar cell and preparation method thereof - Google Patents
Solar cell and preparation method thereof Download PDFInfo
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- CN116525690A CN116525690A CN202310294495.2A CN202310294495A CN116525690A CN 116525690 A CN116525690 A CN 116525690A CN 202310294495 A CN202310294495 A CN 202310294495A CN 116525690 A CN116525690 A CN 116525690A
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- 239000010949 copper Substances 0.000 claims description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 37
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 238000000137 annealing Methods 0.000 claims description 32
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- 229910052782 aluminium Inorganic materials 0.000 description 4
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—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
-
- 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
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 heterojunction type
- H01L31/0745—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 heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—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 heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; 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
- H01L31/18—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
- H01L31/1864—Annealing
Abstract
The application provides a solar cell and a preparation method thereof, belonging to the technical field of solar cells; the solar cell comprises a cell substrate, wherein at least one surface of the cell substrate is provided with a transparent conductive oxide layer, a bonding layer is attached to the transparent conductive oxide layer, the bonding layer is provided with holes, a metal electrode is arranged on the bonding layer, and one side, close to the bonding layer, of the metal electrode passes through the holes and is connected with the transparent conductive oxide layer; the metal electrode has the advantages that the bulge is arranged on one side close to the bonding layer and penetrates through the hole, the circumference of the bulge is in close contact with the wall of the hole, and meanwhile, the bulge penetrating through the hole is connected with the transparent conductive oxide layer, so that the bonding force between the transparent conductive oxide layer and the metal electrode is increased, the adhesion effect of the metal electrode and the transparent conductive oxide layer is improved, the adhesion between the metal electrode and the transparent conductive oxide layer is improved, and the current extraction of the metal electrode is not influenced.
Description
Technical Field
The application relates to the technical field of solar cells, in particular to a solar cell and a preparation method thereof.
Background
The adoption of the copper interconnection technology to replace the traditional silk screen silver paste printing is a metallization cost reduction means of the solar cell, and is one of the technologies at the front edge of the photovoltaic industry at present. The copper interconnection technology is to form a metal seed layer on a transparent conductive oxide layer (TCO) by utilizing a magnetron sputtering mode, and then deposit a thin metal layer on the surface of the metal seed layer by an electrochemical method to form a metal electrode. To ensure a low light shielding area and a low contact resistance, it is required to prepare a narrow and thick metal electrode. Narrowing of the metal electrode may result in poor adhesion between the metal electrode and the transparent conductive oxide layer (TCO), increasing the risk of detachment of the metal electrode and the transparent conductive oxide layer, affecting the electrical performance of the solar cell.
Disclosure of Invention
The present application is directed to a solar cell and a method for manufacturing the same to improve adhesion between a metal electrode and a transparent conductive oxide layer.
In a first aspect, an embodiment of the present application provides a solar cell, where the solar cell includes a cell substrate, at least one surface of the cell substrate has a transparent conductive oxide layer, a bonding layer having a hole is attached to the transparent conductive oxide layer, a metal electrode is disposed on the bonding layer, and a side of the metal electrode, which is close to the bonding layer, passes through the hole and is connected with the transparent conductive oxide layer.
In the implementation process, the bonding layer is arranged between the metal electrode and the transparent conductive oxide layer, the bonding layer is provided with the hole, one side, close to the bonding layer, of the metal electrode passes through the hole and is connected with the transparent conductive oxide layer, the side, close to the bonding layer, of the metal electrode is provided with the bulge, the bulge passes through the hole, the circumference of the bulge is tightly contacted with the hole wall of the hole, and meanwhile, the bulge passing through the hole is connected with the transparent conductive oxide layer, so that the bonding force between the transparent conductive oxide layer and the metal electrode is increased, the adhesion effect between the metal electrode and the transparent conductive oxide layer is improved, and the adhesion between the metal electrode and the transparent conductive oxide layer is improved without influencing the extraction of the metal electrode to current.
With reference to the first aspect, in an optional embodiment of the present application, a material of the bonding layer is a transparent material; the bonding layer covers the entire surface of the transparent conductive oxide layer.
In the implementation process, after the subsequent solar cell packaging is completed, the bonding layer outside the metal electrode attachment area can play a role in blocking water vapor and sodium ions, so that the power attenuation of the assembly in a damp-heat environment is reduced, the reliability is improved, and meanwhile, as the material of the bonding layer is a transparent material, the influence on the transmittance of the solar cell can be reduced, and the performance of the solar cell is maintained.
With reference to the first aspect, in an alternative embodiment of the present application, the transmittance of the bonding layer is not less than 93%.
In the above implementation process, since the bonding layer covers the transparent conductive oxide layer, the transmittance of the solar cell is affected, and the higher the transmittance is, the better the performance of the solar cell is, so the larger the transmittance of the bonding layer is, the better the inventor considers that it is a preferable and realizable range to control the transmittance of the bonding layer not less than 93%.
In combination with the first aspect, in an alternative embodiment of the present application, the material of the bonding layer includes at least one of SiOx and TiW, where x has a value of 1-2.
In the implementation process, the film formed by SiOx and TiW has high transmittance in the visible light wavelength range, can meet the requirement of the transmittance, basically does not cause other influences on the solar cell, is a preferred choice for the material of the bonding layer, and in actual operation, the material of the bonding layer can be chosen by a person skilled in the art according to actual conditions.
With reference to the first aspect, in an alternative embodiment of the present application, the thickness of the bonding layer is not greater than 80nm;
alternatively, the thickness of the bonding layer is 5-80nm.
In the implementation process, the thickness of the bonding layer is controlled to be not more than 80nm, in the annealing process after the metal seed layer is formed on the bonding layer, dense micro-hole holes penetrating through the thickness of the bonding layer can be formed on the bonding layer, meanwhile, the metal seed layer easily moves to pass through the dense micro-hole holes to form protrusions (the heat stability of the transparent conductive oxide layer is good, migration is not easy to occur, and therefore the metal seed layer passes through the dense micro-hole holes), the protrusions and the transparent conductive oxide layer form similar cambered surface contact, so that the contact area of the metal electrode and the transparent conductive oxide layer is increased, the metal electrode has good flow guiding effect, and current extraction is facilitated.
The thickness of the bonding layer is controlled to be not less than 5nm, so that the bonding layer can be guaranteed to have better capability of blocking water vapor and sodium ions, the possibility of power attenuation of the assembly in a damp and hot environment is reduced, and meanwhile, the damage of the transparent conductive oxide layer can be reduced when the metal seed layer is removed through corrosion. The skilled person can choose the appropriate thickness of the bonding layer according to the actual needs, for example 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm and 80nm.
In combination with the first aspect, in an alternative embodiment of the present application, the metal electrode includes a metal seed layer and a metal gate line layer that are stacked, and the metal seed layer is connected to the transparent conductive oxide layer through a hole of the bonding layer.
And the metal seed layer is firstly formed and then annealed, so that the metal seed layer penetrates through the holes of the bonding layer and forms bulges to be connected with the transparent conductive oxide layer while the dense holes are formed on the bonding layer.
With reference to the first aspect, in an optional embodiment of the present application, the metal seed layer is a copper seed layer, and the metal gate line layer is a copper gate line layer.
Compared with the traditional method for preparing the grid line by using silver paste, the method has the advantages that the cost for preparing the grid line by using copper as the material of the grid line is lower, and the preparation cost of the solar cell can be effectively reduced.
In a second aspect, an embodiment of the present application further provides a method for preparing a solar cell, where the method includes:
providing a battery matrix, wherein at least one surface of the battery matrix is provided with a transparent conductive oxide layer;
depositing a bonding layer on the surface of the transparent conductive oxide layer;
depositing a metal seed layer on the bonding layer;
annealing the battery matrix with the metal seed layer to form holes on the bonding layer, wherein the metal seed layer passes through the holes to be connected with the transparent conductive oxide layer;
and electroplating the metal seed layer to form a metal grid line layer to obtain the solar cell.
In the implementation process, the bonding layer is arranged between the transparent conductive oxide layer and the metal seed layer, the bonding layer is enabled to form a hole by annealing, meanwhile, the metal seed layer can penetrate through the hole to form a bulge by annealing, connection is achieved through the bulge and the transparent conductive oxide layer, the contact surface forms of the grid line, the transparent conductive oxide layer and the bonding layer are changed, the contact area of the metal seed layer and the transparent conductive oxide layer is increased, the adhesion force between the transparent conductive oxide layer and the metal seed layer is increased, the adhesion effect of the grid line and the transparent conductive oxide layer is improved, and the adhesion between the grid line and the transparent conductive oxide layer is improved.
With reference to the second aspect, in an optional embodiment of the present application, a material of the bonding layer includes at least one of SiOx and TiW, where x has a value of 1-2.
With reference to the second aspect, in an alternative embodiment of the present application, the metal seed layer is a copper seed layer, and the metal gate line layer is a copper gate line layer.
With reference to the second aspect, in an alternative embodiment of the present application, the thickness of the bonding layer is 5-80nm; the annealing treatment temperature is 180-200 ℃; the annealing treatment time is 5-30min.
In the implementation process, the thickness of the bonding layer is controlled to be 5-80nm, meanwhile, the annealing treatment temperature is controlled to be 180-200 ℃ and the annealing treatment time is controlled to be 5-30min, so that enough penetrating holes are formed on the surface of the bonding layer made of SiOx, tiW and other materials, further, more protrusions are formed on the holes of the copper seed layer penetrating through the bonding layer to be connected with the transparent conductive oxide layer, the bonding area of the copper seed layer and the transparent conductive oxide layer is effectively increased, the flow guiding effect of the copper grid line is improved, and meanwhile, the passivation capability of the amorphous silicon layer of the silicon substrate is not affected.
With reference to the second aspect, in an alternative embodiment of the present application, the environment of the annealing treatment is a vacuum environment or an inert gas atmosphere environment.
In the implementation process, the control environment is a vacuum environment or an inert gas atmosphere environment, so that the reaction of the atmosphere of the environment and the solar cell can be avoided, and impurities are generated.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a solar cell provided in the prior art;
fig. 2 is a schematic structural diagram of a solar cell according to an embodiment of the present disclosure;
fig. 3 is a flowchart of a method provided in an embodiment of the present application.
Reference numerals: 1-crystalline silicon layer, 2-intrinsic amorphous silicon layer, 3-N type amorphous silicon layer, 4-P type amorphous silicon layer, 5-transparent conductive oxide layer, 6-bonding layer, 61-adhesion enhancing layer, 62-barrier layer, 7-metal electrode, 71-copper seed layer, 72-copper gate line layer, 73-tin layer.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In order to reduce the manufacturing cost of the solar cell, a heterojunction solar cell copper grid line metallization technology is proposed, and in the heterojunction solar cell copper grid line metallization technology, narrow and thick metal electrodes are required to be manufactured in order to ensure a low shading area and low contact resistance. For this reason, a double-layer electrode technology is proposed, referring to fig. 1, a narrow and thin copper seed layer 71 is first prepared, and then the copper seed layer 71 is thickened by electroplating, photoinduced plating, etc. to prepare a copper gate line layer 72, specifically, the preparation process of the whole heterojunction solar cell copper gate line metallization technology is as follows: after depositing a transparent conductive film, the heterojunction battery needs to sputter and deposit a copper seed layer 71 on the surface of the transparent conductive film as an electroplated adhesive layer and a conductive layer, then electroplating a mask on the copper seed layer 71 for pattern transfer, and covering the area which does not need to be electroplated with the mask to realize selective electroplating; after the metal plating is completed, the mask is stripped by using a chemical solution; finally, the masked copper seed layer 71 is etched and removed, and the etched and dried copper seed layer is cleaned and dried to obtain the copper electrode heterojunction solar cell with excellent shaping and good selectivity. However, the adhesion between the transparent conductive oxide layer 5 (TCO) and the copper seed layer 71 is poor, and the separation between the transparent conductive oxide layer 5 and the copper seed layer 71 easily occurs to cause the separation of the copper grid line, which affects the electrical performance of the solar cell and the appearance of the solar cell. In addition, in the subsequent step of removing the redundant copper seed layer 71, the copper seed layer 71 is etched by using an acidic solution, and the acidic solution damages the surface of the transparent conductive oxide layer 5, affects the surface microstructure of the transparent conductive oxide layer 5, causes nano-scale micro-holes, affects the optical and electrical properties of the transparent conductive oxide layer 5, and finally causes the reduction of the conversion efficiency of the solar cell.
According to the scheme, the bonding layer 6 is added between the copper seed layer 71 and the transparent conductive oxide layer 5, holes are formed in the bonding layer 6 through annealing, meanwhile, the copper seed layer 71 can penetrate through the holes to form protrusions, connection is achieved through the protrusions and the transparent conductive oxide layer 5, the contact surface forms of the metal electrode 7, the transparent conductive oxide layer 5 and the bonding layer 6 are changed, the contact area of the metal electrode 7 and the transparent conductive oxide layer 5 is increased, the bonding force between the transparent conductive oxide layer 5 and the metal electrode 7 is increased, the attachment effect and the flow guiding effect of the metal electrode 7 and the transparent conductive oxide layer 5 are improved, and the adhesiveness between the metal electrode 7 and the transparent conductive oxide layer 5 is improved. Meanwhile, the bonding layer 6 can play a role in blocking water vapor and sodium ions after the solar cell is packaged, so that the power attenuation of the solar cell in a damp-heat environment is reduced, and the reliability of the solar cell is improved.
Referring to fig. 2, the embodiment of the present application provides a solar cell, which includes a cell substrate, at least one surface of the cell substrate has a transparent conductive oxide layer 5, a bonding layer 6 is attached to the transparent conductive oxide layer 5, the bonding layer 6 has holes, a metal electrode 7 is disposed on the bonding layer 6, and one side of the metal electrode 7, which is close to the bonding layer 6, passes through the holes and is connected with the transparent conductive oxide layer 5.
By adopting the design, the bonding layer 6 is arranged between the metal electrode 7 and the transparent conductive oxide layer 5, the bonding layer 6 is provided with the hole, one side, close to the bonding layer 6, of the metal electrode 7 passes through the hole and is connected with the transparent conductive oxide layer 5, one side, close to the bonding layer 6, of the metal electrode 7 is provided with the bulge, the bulge passes through the hole, the circumference of the bulge is tightly contacted with the wall of the hole, and meanwhile, the bulge passing through the hole is connected with the transparent conductive oxide layer 5, so that the bonding force between the transparent conductive oxide layer 5 and the metal electrode 7 is increased, the adhesion effect between the metal electrode 7 and the transparent conductive oxide layer 5 is improved, and the current extraction of the metal electrode 7 is not influenced.
In some embodiments, the structure of the battery substrate includes a crystalline silicon layer 1 (C-Si), an intrinsic amorphous silicon layer 2 (i-alpha-Si: H) provided on opposite surfaces of the crystalline silicon layer 1, an N-type amorphous silicon layer 3 (N-alpha-Si: H) provided on a surface of one intrinsic amorphous silicon layer 2 remote from the crystalline silicon layer 1, and a P-type amorphous silicon layer 4 (P-alpha-Si: H) provided on a surface of the other intrinsic amorphous silicon layer 2 remote from the crystalline silicon layer 1, and transparent conductive oxide layers 5 (TCO) are provided on both outer surfaces of the N-type amorphous silicon layer 3 and the P-type amorphous silicon layer 4 of the silicon substrate.
In some embodiments, the material of the bonding layer is a transparent material; the bonding layer 6 covers the entire surface of the transparent conductive oxide layer 5. After the subsequent solar cell packaging is completed, the bonding layer 6 outside the attachment area of the metal electrode 7 can play a role in blocking water vapor and sodium ions, so that the power attenuation of the assembly in a damp-heat environment is reduced, and the reliability is improved. Meanwhile, as the material of the bonding layer 6 is transparent, the influence on the transmittance of the solar cell can be reduced, and the performance of the solar cell can be maintained. For convenience of description, the region of the bonding layer 6 corresponding to the covered region of the metal electrode 7 will be hereinafter referred to as an adhesion enhancing layer 61, and the portion outside the corresponding covered region of the metal electrode 7 will be hereinafter referred to as a barrier layer 62.
To ensure the performance of the solar cell, in some embodiments, the transmittance of the bonding layer 6 is not less than 93%; the transmittance of the bonding layer 6 includes, but is not limited to, 93%, 94%, 95%, 96%, 97%, 98% and 99%. Since the bonding layer 6 is covered on the transparent conductive oxide layer 5, the transmittance of the solar cell is affected, and the higher the transmittance is, the better the performance of the solar cell is, so the larger the transmittance of the bonding layer 6 is, the better the inventors consider that it is a preferable and realizable range to control the transmittance of the bonding layer 6 to be not less than 93%. Specifically, the material of the bonding layer 6 may be at least one selected from SiOx and TiW, where x has a value of 1-2. The film formed by SiOx and TiW has high transmittance in the visible wavelength range, no optical loss, can meet the requirement of the transmittance, can not cause other influences on the solar cell, is a preferred choice for the material of the bonding layer 6, and in actual operation, the material of the bonding layer 6 can be chosen by a person skilled in the art according to actual conditions.
Meanwhile, in order to ensure the blocking effect of the bonding layer 6, in some embodiments, the thickness of the bonding layer 6 is not less than 5nm, and the thicker the bonding layer 6, the stronger the blocking capability thereof, the inventor considers that controlling the thickness of the bonding layer 6 to be not less than 5nm can ensure that the bonding layer 6 has better capability of blocking water vapor and sodium ions, reduce the possibility of power attenuation of the component in a wet and hot environment, and simultaneously reduce the damage of the transparent conductive oxide layer 5 when the metal seed layer is removed by corrosion. However, the transparent materials such as SiOx and TiW are mostly not conductive, and when the adhesion enhancing layer 61 of the bonding layer 6 is disposed between the transparent conductive oxide layer 5 and the metal electrode 7, the material affects the electrical performance of the whole solar cell, so in some embodiments, the thickness of the bonding layer 6 is not greater than 80nm, the thickness of the bonding layer 6 is controlled to be not greater than 80nm, dense micro holes penetrating the thickness of the bonding layer can be formed on the bonding layer 6 in the annealing process after the metal seed layer is formed on the bonding layer 6, meanwhile, the metal seed layer easily moves to form protrusions (the thermal stability of the transparent conductive oxide layer 5 is better, migration is not easy to occur, and therefore the metal seed layer passes through the dense micro holes), and the protrusions form similar arc surface contact with the transparent conductive oxide layer 5, so that the contact area between the metal electrode 7 and the transparent conductive oxide layer 5 is increased, the metal electrode 7 has good diversion effect, and current extraction is facilitated. It will be appreciated by those skilled in the art that the bonding layer 6 may not be limited by this thickness if the conductivity of the bonding layer 6 may be improved by other means or if there is a material that is capable of meeting both conductivity and transmittance requirements, i.e. in other embodiments the bonding layer 6 may have a thickness of greater than 80nm, such as 90nm, 100nm, etc.
In order to achieve both conductivity and barrier properties, the inventors consider it to be a suitable range to control the thickness of the bonding layer 6 to be 5-80nm, optionally the thickness of the bonding layer 6 to be 10-50nm, and optionally the thickness of the bonding layer 6 to be 10-30nm; the person skilled in the art can choose the appropriate thickness according to the actual needs, for example 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, etc.
Optionally, the metal electrode 7 includes a metal seed layer and a metal gate line layer stacked, and the metal seed layer is connected to the transparent conductive oxide layer 5 through a hole of the bonding layer 6. And the metal seed layer is firstly formed and then annealed, so that the metal seed layer penetrates through the holes of the bonding layer and forms bulges to be connected with the transparent conductive oxide layer while the dense holes are formed on the bonding layer.
To reduce the manufacturing cost of the solar cell, in some embodiments, the metal seed layer is a copper seed layer 71, the metal gate line layer is a copper gate line layer 72, and a side of the copper seed layer 71 near the bonding layer 6 is connected to the transparent conductive oxide layer 5 through the hole. Compared with the traditional method for preparing the grid line by using silver paste, the method has the advantages that the cost for preparing the grid line by using copper as the material of the grid line is lower, and the preparation cost of the solar cell can be effectively reduced.
In other embodiments, the metal seed layer may also be an aluminum seed layer, and the metal gate line layer is an aluminum gate line layer, which is not limited in this application.
Referring to fig. 3, an embodiment of the present application provides a method for manufacturing a solar cell, including:
s0. to obtain a battery matrix;
in this embodiment, a battery substrate is obtained by a preparation method, which includes: and texturing the silicon wafer to form pyramid textured surfaces on the surface of the silicon wafer, and then preparing the intrinsic amorphous silicon layer 2 and the doped amorphous silicon layer to obtain a battery matrix.
In this embodiment, the structure of the battery substrate includes a crystalline silicon layer 1 (C-Si), an intrinsic amorphous silicon layer 2 (i- α -Si: H) provided on opposite surfaces of the crystalline silicon layer 1, an N-type amorphous silicon layer 3 (N- α -Si: H) provided on a surface of one intrinsic amorphous silicon layer 2 remote from the crystalline silicon layer 1, and a P-type amorphous silicon layer 4 (P- α -Si: H) belonging to a surface of the other intrinsic amorphous silicon layer 2 remote from the crystalline silicon layer 1.
S1, preparing a transparent conductive oxide layer 5 on a battery matrix to obtain a blue membrane;
the blue membrane has a structure comprising the battery matrix and a transparent conductive oxide layer 5 attached to the outer surfaces of the N-type amorphous silicon layer 3 and the P-type amorphous silicon layer 4 of the battery matrix.
S2, preparing a bonding layer 6 on the blue membrane; the preparation method can adopt deposition.
Alternatively, the material of the bonding layer 6 may be at least one selected from SiOx and TiW. The thickness of the bonding layer is 5-80nm, the film formed by SiOx and TiW has high transmittance in the visible light wavelength range, no optical loss is caused, the requirement of the transmittance can be met, and other influences on the solar cell can be avoided.
The following description will be made with SiOx as the material of the bonding layer 6, specifically as follows: and depositing a film layer on the transparent conductive oxide layer 5 by using PEVCD equipment, wherein the deposition time is 1-10 minutes, the silane flow is 100-1000sccm, the carbon dioxide flow is 30-200sccm, the process temperature is 100-200 ℃, the RF power is 200-1000W, and the cavity pressure is 10-50pa. Alternatively, the deposition time is 2-9 minutes, the silane flow rate is 300-900sccm, the carbon dioxide flow rate is 40-100sccm, the process temperature is 130-170 ℃, the RF power is 400-800W, the cavity pressure is 20-40pa, alternatively, the deposition time is 2 minutes, the silane flow rate is 800sccm, the carbon dioxide flow rate is 80sccm, the process temperature is 150 ℃, the RF power is 600W, and the cavity pressure is 30pa.
The deposition time is mainly controlled to control the thickness of the film layer to be 5-80nm, and the time comprises purge time, gas inlet time, evacuation time and the like.
And S3, depositing a metal seed layer on the blue membrane provided with the bonding layer 6. Optionally, the metal seed layer is formed by means of magnetron sputtering. The metal seed layer may be a copper seed layer 71, alternatively, the copper seed layer 71 may have a thickness of 50-200nm and a sputtering power of 2-8KW. In other embodiments, the metal seed layer may also be an aluminum seed layer.
S4, annealing the battery matrix with the metal seed layer to enable the bonding layer to form holes, and enabling the metal seed layer to penetrate through the holes and be connected with the transparent conductive oxide layer.
Optionally, the metal seed layer is copper seed layer 71 (Huang Mopian), and Huang Mopian is annealed in an annealing furnace at 180-200deg.C including but not limited to 180deg.C, 185 deg.C, 190 deg.C, 195 deg.C and 200deg.C for 5-30min including but not limited to 5min, 10min, 15min, 20min, 25min and 30min, under vacuum or under inert gas protection, wherein the inert gas is nitrogen.
The inventors found that when the annealing treatment is performed at 180-200 ℃ for 5-30min, and the film thickness of the SiOx bonding layer 6 is 5-80nm, particularly when the film thickness of the bonding layer 6 is 10-20nm, dense micro holes can be formed on the bonding layer 6, the micro holes penetrate through the bonding layer 6, the copper seed layer 71 is easy to move through the dense micro holes to form protrusions (the heat stability of the transparent conductive oxide layer 5 is better, only a trace of migration or movement exists, and therefore the copper seed layer 71 penetrates through the dense micro holes), and the protrusions are in contact with the transparent conductive oxide layer 5 in a similar cambered surface, so that the contact area between the copper seed layer 71 and the transparent conductive oxide layer is increased, the grid line has a good flow guiding effect, current is led out, and the bonding fastness between the copper seed layer 71 and the transparent conductive oxide layer 5 is higher.
S5, electroplating the metal seed layer to form a metal grid line layer, and obtaining the solar cell. Optionally, the metal gate line layer is a copper gate line layer, and in other embodiments, the metal gate line layer may also be an aluminum gate line layer or the like.
In this embodiment, the preparation of the copper gate line layer 72 includes taping, coating, printing, developing, electroplating, and stripping back etching. Wherein, bordure specifically includes: wrapping the periphery of the annealed yellow membrane by using edge-wrapping glue, wherein the width of the edge-wrapping glue is 0.8-1.2mm. The coating specifically comprises the following steps: coating photosensitive ink on the front and back surfaces of the yellow membrane with the edges, and completely covering the front and back surfaces of the yellow membrane with the thickness of 80-200 mu m; the printing specifically comprises the following steps: the exposure is performed by printing on photosensitive ink by laser (wavelength 400-450 nm) according to a pre-designed raster pattern, and the exposed part is dissolved in a developing process. The developing specifically comprises dissolving the exposed part of the ink by using an alkaline solution to expose the underlying copper seeds, and the unexposed part does not participate in the reaction. The electroplating specifically comprises the following steps: the thickness of the copper grid line layer 72 is 5-20 mu m, and the thickness of the tin layer 73 is 3-10 mu m. The film removing and back etching specifically comprises the following steps: the photosensitive ink and the side bags Bian Jiao on the whole surface of the cell are removed by adopting an alkali solution, and the copper seed layer 71 on the surface is removed by adopting an acidic solution for soaking.
In the process of preparing the copper gate line layer 72, particularly when removing the excessive copper seed layer 71, the inventor also found that, since all surfaces of the transparent conductive oxide layer 5 are covered with the bonding layer 6, the bonding layer 6 can play a role in blocking corrosion loss of the transparent conductive oxide layer 5 by acidic liquid, playing a role in protecting the transparent conductive oxide layer 5, and further ensuring optical and electrical properties of the solar cell.
S6, performing light injection treatment on the solar cell to finish cell preparation, wherein in the embodiment, the light injection intensity is 60 solar light intensities, the temperature is controlled at 200 ℃ and the time is 60S, and the manufacture of the solar cell is finished.
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
A method of fabricating a solar cell, the method comprising:
s1, preparing a silicon-based heterojunction solar cell blue membrane; the battery blue membrane film layer structure comprises the following components in sequence: a first Transparent Conductive Oxide (TCO) layer, an N-type amorphous silicon layer (N-alpha-Si: H), an intrinsic amorphous silicon layer (i-alpha-Si: H), crystalline silicon (C-Si), an intrinsic amorphous silicon layer (i-alpha-Si: H), a P-type amorphous silicon layer (P-alpha-Si: H), a second Transparent Conductive Oxide (TCO) layer;
s2, depositing a first SiOx layer and a second SiOx layer on the transparent conductive oxide layer by using PEVCD equipment, wherein the thickness of the first SiOx layer and the second SiOx layer is 5nm, the deposition time is 1 minute, the silane flow is 500sccm, the carbon dioxide flow is 100sccm, the process temperature is 150 ℃, the RF power is 600W, and the cavity pressure is 30pa.
S3, sputtering and preparing copper seed layers on the first SiOx layer and the second SiOx layer which are prepared into the blue film by adopting PVD equipment to obtain the yellow film, wherein the thickness of the copper seed layer is 100nm, and the sputtering power is 5KW.
S4, annealing the battery piece in an annealing furnace at 190 ℃ for 18 minutes under the vacuum environment or nitrogen protection.
S5, wrapping the periphery of the yellow membrane by using edge-wrapping glue, wherein the width of the edge-wrapping glue is 1mm.
S6, coating photosensitive ink on the front side and the back side of the Huang Mopian, completely covering the front surface and the back surface of the yellow membrane, and controlling the thickness to be 150 mu m.
S7, exposing the photosensitive ink by laser printing according to a pre-designed grating line pattern, wherein the exposed part is dissolved in a developing process, and the laser wavelength of the laser printing is 430nm.
S8, dissolving the exposed part of the ink by using an alkaline solution, exposing the copper seeds at the bottom layer, and enabling the unexposed part not to participate in the reaction.
S9, electrochemically plating copper grid line layers and tin layers, wherein the thickness of the copper grid line layers is 12 mu m, and the thickness of the tin layers is 6 mu m.
S10, removing all photosensitive ink and side bags Bian Jiao on the surface of the battery piece by using an alkali solution;
s11, soaking in an acidic solution, and removing the copper seed layer on the surface.
S12, performing light injection treatment on the solar cell to finish cell preparation, wherein the light injection intensity is 60 solar light intensities, the temperature is controlled at 200 ℃, and the time is 60S, so that the solar cell is manufactured.
Example 2
This example is identical to example 1 except for steps S2 and S4.
The step S2 in this embodiment specifically includes: s2, depositing a first SiOx layer and a second SiOx layer on the transparent conductive oxide layer by using PEVCD equipment, wherein the thickness of the first SiOx layer and the second SiOx layer is 20nm, the deposition time is 3 minutes, the silane flow is 500sccm, the carbon dioxide flow is 100sccm, the process temperature is 150 ℃, the RF power is 600W, and the cavity pressure is 30pa.
The step S4 in this embodiment specifically includes: s4, annealing the battery piece in an annealing furnace at 180 ℃ for 5 minutes under the vacuum environment or nitrogen protection.
Example 3
This example is identical to example 1 except for steps S2 and S4.
The step S2 in this embodiment specifically includes: s2, depositing a first SiOx layer and a second SiOx layer on the transparent conductive oxide layer by using PEVCD equipment, wherein the thickness of the first SiOx layer and the second SiOx layer is 80nm, the deposition time is 8 minutes, the silane flow is 500sccm, the carbon dioxide flow is 100sccm, the process temperature is 150 ℃, the RF power is 600W, and the cavity pressure is 30pa.
The step S4 in this embodiment specifically includes: s4, annealing the battery piece in an annealing furnace at 200 ℃ for 30 minutes under the vacuum environment or nitrogen protection.
Example 4
This example is identical to example 1 except for the step S2.
The step S2 in this embodiment specifically includes: s2, depositing a first SiOx layer and a second SiOx layer on the transparent conductive oxide layer by using PEVCD equipment, wherein the thickness of the first SiOx layer and the second SiOx layer is 100nm, the deposition time is 10 minutes, the silane flow is 500sccm, the carbon dioxide flow is 100sccm, the process temperature is 150 ℃, the RF power is 600W, and the cavity pressure is 30pa.
Example 5
This example is identical to example 1 except for the step S2.
The step S2 in this embodiment specifically includes: s2, depositing a first SiOx layer and a second SiOx layer on the transparent conductive oxide layer by using PEVCD equipment, wherein the thickness of the first SiOx layer and the second SiOx layer is 10nm, the deposition time is 1.5 minutes, the silane flow rate is 500sccm, the carbon dioxide flow rate is 100sccm, the process temperature is 150 ℃, the RF power is 600W, and the cavity pressure is 30pa.
Example 6
This example is identical to example 1 except for the step S4.
The step S4 in this embodiment specifically includes: s4, annealing the battery piece in an annealing furnace at 200 ℃ for 50 minutes under the vacuum environment or nitrogen protection.
Example 7
This example is identical to example 1 except for the step S4.
The step S4 in this embodiment specifically includes: s4, annealing the battery piece in an annealing furnace at 150 ℃ for 18 minutes under the vacuum environment or nitrogen protection.
Comparative example 1
This comparative example was not conducted in the steps S2 and S4 of example 1, and the remaining steps were the same as example 1.
Comparative example 2
This comparative example was not conducted in the step S4 of example 1, and the remaining steps were the same as in example 1.
The main parameter controls for examples 1-7 and comparative examples 1-2 are shown in the following table:
| thickness nm of bonding layer | Annealing temperature (DEG C) | Annealing time min | |
| Example 1 | 5 | 190 | 18 |
| Example 2 | 20 | 180 | 5 |
| Example 3 | 80 | 200 | 30 |
| Example 4 | 100 | 190 | 18 |
| Example 5 | 10 | 190 | 18 |
| Example 6 | 5 | 200 | 50 |
| Example 7 | 5 | 150 | 18 |
| Comparative example 1 | / | / | / |
| Comparative example 2 | 5 | / | / |
In the table, "/" indicates that no progress is made.
The solar cells provided in examples 1 to 6 and comparative examples 1 to 2 were subjected to performance test, and the results are shown in the following table:
| cell efficiency (%) | Main grid tension of battery (N) | DH1000 attenuation value (%) | |
| Example 1 | 24.32 | 2.63 | 2.98 |
| Example 2 | 23.89 | 2.74 | 2.88 |
| Example 3 | 22.22 | 3.02 | 2.54 |
| Example 4 | 22.13 | 2.83 | 2.45 |
| Example 5 | 24.24 | 2.65 | 2.86 |
| Example 6 | 24.29 | 2.76 | 2.73 |
| Example 7 | 24.33 | 2.54 | 2.7 |
| Comparative example 1 | 24 | 1.48 | 3.67 |
| Comparative example 2 | 23.1 | 1.3 | 3.01 |
The solar cell IV tester is used for testing the cell efficiency, the solar cell tensile tester is used for testing the tensile test, and DH1000 attenuation values are as follows: after the cell laminate modules were assembled, a wet heat test was performed for 1000 hours to obtain a power attenuation value.
As can be seen from comparison of comparative example 1 and examples, the solar cell prepared by the method provided in the examples of the present application has significantly improved gate line adhesion, a cell main gate tension is improved by at least 1.06N, by about 71.62%, and is obtained by comparison of examples 1-5, along with an increase in the thickness of the bonding layer, a decrease in DH1000 attenuation value is caused, which indicates that the thicker the thickness is, the stronger the blocking capability is, but the cell efficiency is also reduced, and by comparison of example 7 and example 1, the annealing temperature affects the cell main gate tension, and the annealing temperature is increased, and the greater the cell main gate tension is, the better the gate line adhesion is.
The foregoing is merely a specific embodiment of the present application and is not intended to limit the present application, and various modifications and variations may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. The solar cell is characterized by comprising a cell substrate, wherein at least one surface of the cell substrate is provided with a transparent conductive oxide layer, a bonding layer with holes is attached to the transparent conductive oxide layer, a metal electrode is arranged on the bonding layer, and one side, close to the bonding layer, of the metal electrode penetrates through the holes and is connected with the transparent conductive oxide layer.
2. The solar cell according to claim 1, wherein the material of the bonding layer is a transparent material; the bonding layer covers the entire surface of the transparent conductive oxide layer.
3. The solar cell according to claim 2, wherein the transmittance of the bonding layer is not less than 93%;
optionally, the material of the bonding layer includes at least one of SiOx and TiW, where x has a value of 1-2.
4. The solar cell of claim 1, wherein the thickness of the bonding layer is no greater than 80nm;
optionally, the thickness of the bonding layer is 5-80nm.
5. The solar cell of claim 1, wherein the metal electrode comprises a metal seed layer and a metal gate line layer arranged in a stack, the metal seed layer being connected to the transparent conductive oxide layer through a hole of the bonding layer;
optionally, the metal seed layer is a copper seed layer, and the metal gate line layer is a copper gate line layer.
6. A method of manufacturing a solar cell, the method comprising:
providing a battery matrix, wherein at least one surface of the battery matrix is provided with a transparent conductive oxide layer;
depositing a bonding layer on the surface of the transparent conductive oxide layer;
depositing a metal seed layer on the bonding layer;
annealing the battery matrix with the metal seed layer to form holes on the bonding layer, wherein the metal seed layer penetrates through the holes to be connected with the transparent conductive oxide layer;
and electroplating the metal seed layer to form a metal grid line layer to obtain the solar cell.
7. The method of claim 6, wherein the bonding layer comprises at least one of SiOx and TiW, wherein x has a value of 1-2.
8. The method of claim 6, wherein the metal seed layer is a copper seed layer and the metal gate line layer is a copper gate line layer.
9. The method of manufacturing a solar cell according to claim 8, wherein the thickness of the bonding layer is 5-80nm; the temperature of the annealing treatment is 180-200 ℃; the annealing treatment time is 5-30min.
10. The method according to claim 6, wherein the annealing treatment is performed in a vacuum atmosphere or an inert gas atmosphere.
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