CN114005889A - A kind of preparation method of solar cell metal grid line - Google Patents

A kind of preparation method of solar cell metal grid line Download PDF

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Publication number
CN114005889A
CN114005889A CN202010730286.4A CN202010730286A CN114005889A CN 114005889 A CN114005889 A CN 114005889A CN 202010730286 A CN202010730286 A CN 202010730286A CN 114005889 A CN114005889 A CN 114005889A
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layer
grid line
metal
amorphous silicon
seed
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宋广华
尤宇文
罗骞
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Gs Solar Fu Jian Co ltd
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Gs Solar Fu Jian Co ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/164—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells
    • H10F10/165—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells the heterojunctions being Group IV-IV heterojunctions, e.g. Si/Ge, SiGe/Si or Si/SiC photovoltaic cells
    • H10F10/166—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells the heterojunctions being Group IV-IV heterojunctions, e.g. Si/Ge, SiGe/Si or Si/SiC photovoltaic cells the Group IV-IV heterojunctions being heterojunctions of crystalline and amorphous materials, e.g. silicon heterojunction [SHJ] photovoltaic 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

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Abstract

The invention discloses a method for preparing a metal grid line of a solar cell, which comprises the following steps: depositing an intrinsic amorphous silicon layer and an n-type amorphous silicon layer on one surface of an n-type silicon substrate, depositing an intrinsic amorphous silicon layer and a p-type amorphous silicon layer on the other surface of the n-type silicon substrate, depositing a transparent conductive oxide film on the n-type amorphous silicon layer and the p-type amorphous silicon layer, and depositing a barrier layer on the transparent conductive oxide layer; depositing a seed layer on the barrier layer; forming a metal grid line pattern on the seed layer in an ink-jet printing mode; performing copper electroplating and tin electroplating on the surface of the seed copper in the pattern area by adopting a horizontal electroplating mode to form a metal grid line; and after the electroplating of the grid line lamination layer is finished, the mask layer, the seed layer and the barrier layer are etched to be clean, the transparent conductive oxide layer is exposed, and the preparation of the copper grid electrode is realized.

Description

Method for preparing metal grid line of solar cell
Technical Field
The invention relates to the field of solar cells, in particular to a method for preparing a metal grid line of a solar cell.
Background
The heterojunction solar cell is a solar cell with an amorphous silicon thin layer grown on a silicon substrate, has the characteristics of simple structure, low process temperature, high conversion efficiency and good temperature characteristic, is one of high-efficiency cells suitable for large-scale popularization and application, and has good development prospect.
Taking an n-type silicon substrate as an example, the main structure of the heterojunction solar cell shown in fig. 1 is as follows: depositing a thin film intrinsic amorphous silicon layer and a P-type amorphous silicon emitter layer on the illuminated surface of the n-type silicon substrate in sequence to form a heterogeneous PN junction with a thin film intrinsic amorphous silicon interlayer; and depositing a transparent conductive oxide layer on the two doped amorphous silicon thin layers by a sputtering method, and finally forming a grid-shaped metal electrode on the transparent conductive oxide layer.
Forming a grid-shaped metal electrode as a key step for manufacturing the heterojunction solar cell, wherein the conventional method comprises the following steps: and manufacturing a first electroplated copper lamination of the metal grid line by electroplating, wherein the first electroplated copper lamination is used as a main conducting layer of the metal grid line, and manufacturing a second electroplated tin lamination as a welding assistant layer of the metal grid line. And removing the photoresist film outside the grid line to expose the metal lamination covered by the photoresist film, removing the part of the metal lamination through corrosion, and finally exposing the surface of the solar cell.
In the prior art, a dry film is pasted on the surface of a battery, and then a pattern is manufactured through exposure and development; placing the battery piece in a hanger, clamping the battery piece through the hanger, and feeding the battery piece into vertical continuous electroplating equipment for electroplating to obtain a first electroplated copper lamination and a second electroplated tin lamination; and taking the solar cell out of the hanger, removing the mask layer, the barrier layer and the seed layer through film removing etching equipment, and finally exposing the surface of the solar cell. The problem that a certain degree of bad proportion exists in the process of manufacturing the pattern and the pattern is difficult to improve is solved, and the hanger is adopted to clamp the battery piece for electroplating, so that the equipment investment cost of putting the battery piece into the hanger, the equipment investment cost of taking the battery piece out of the hanger, the hanger investment cost, the hanger use cost, the stripping cost and the fragment proportion of a certain degree exist, and the production cost is difficult to effectively reduce.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing a metal grid line of a solar cell, which solves the problems that the fragment proportion is difficult to reduce and the production cost of the grid line is high in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method of making a solar cell metal grid line comprising: depositing an intrinsic amorphous silicon layer and an n-type amorphous silicon layer on one surface of an n-type silicon substrate, depositing an intrinsic amorphous silicon layer and a p-type amorphous silicon layer on the other surface of the n-type silicon substrate, depositing a transparent conductive oxide layer on the n-type amorphous silicon layer and the p-type amorphous silicon layer, and depositing a barrier layer on the transparent conductive oxide layer; depositing a seed layer on the barrier layer; covering a hot-melt material on the seed layer in a non-grid line position area in an ink-jet printing mode to form a mask layer and expose the seed layer at the grid line position; manufacturing a conductive grid line lamination and an auxiliary welding layer on the surface of the exposed seed layer in a horizontal electroplating mode; and removing the mask layer, the seed layer and the barrier layer at the covering position of the mask layer by using chemical corrosive liquid in a horizontal corrosion mode to expose the surface of the battery and the welding assistant layer.
Further, the conductive grid line lamination is an electroplated copper lamination with the thickness of 5-40 microns.
Further, the solder-boosting layer is a tin-plating lamination layer with the thickness of 1-20 microns.
Furthermore, after the mask layer, the seed layer and the barrier layer are removed and arranged in horizontal copper plating and horizontal tin plating, the grid line is continuously manufactured.
Further, the transparent conductive oxide layer adopts an ITO layer or a doped indium oxide layer.
Further, the barrier layer is a Ti metal layer or a Ta metal layer, the Ti metal layer is a TiNx metal layer or a TiW metal layer, and the Ta metal layer is a TaNx metal layer, and the thickness of the Ta metal layer is 1-50 nanometers.
Further, the seed layer includes: a copper seed layer, a nickel seed layer, a silver seed layer, and an aluminum seed layer.
From the above description of the structure of the present invention, compared with the prior art, the present invention has the following advantages:
according to the method for preparing the metal grid line of the solar cell, the hot-melt material is covered on the region of the non-grid line position, the mask layer is manufactured, only one process is needed for completion, and the method has the advantages of high yield, simplicity in operation and the like. And manufacturing a conductive grid line lamination layer and an auxiliary welding layer on the surface of the exposed seed layer in a horizontal electroplating mode, then entering horizontal corrosion equipment, continuously removing the mask layer, the barrier layer and the seed layer, and finally exposing the surface of the battery and the auxiliary welding layer. Because the battery is manufactured in the horizontal electroplating and horizontal corrosion modes, a hanger is not needed, equipment for placing the battery pieces into the hanger, equipment investment cost for taking the battery pieces out of the hanger, hanger investment cost, hanger use cost and hanging stripping cost are saved, the breakage rate of the battery can be obviously improved, and the production and manufacturing cost is further reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural diagram of an n-type silicon substrate heterojunction solar cell;
FIG. 2 is a schematic view of a metal grid line on the surface of a battery plate according to the present invention;
FIG. 3 is a schematic structural diagram of the intrinsic amorphous silicon layer, the amorphous silicon thin film layer, the conductive oxide layer and the barrier layer deposited according to the present invention;
fig. 4 is a schematic structural diagram of the present invention after a hot-melt material is coated on a region other than a gate line to form a metal gate line;
fig. 5 is a schematic structural view of the metal gate line region after two gate line stacks are formed;
FIG. 6 is a schematic structural view of the hot melt material mask layer removed according to the present invention;
fig. 7 is a schematic view of the metal gate line structure after the metal seed layer and the barrier layer are removed.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 2 to 7, a method for preparing a metal grid line of a solar cell according to the present invention comprises: depositing an intrinsic amorphous silicon layer 2 and an n-type amorphous silicon layer 3 on one surface of an n-type silicon substrate 1, depositing an intrinsic amorphous silicon layer 2 and a p-type amorphous silicon layer 4 on the other surface of the n-type silicon substrate, depositing a transparent conductive oxide layer 5 on the n-type amorphous silicon layer 3 and the p-type amorphous silicon layer 4, and depositing a barrier layer 6 on the transparent conductive oxide layer 5; depositing a seed layer 7 on the barrier layer 6; the manufacturing method of the metal grid line further comprises the following steps: forming a metal grid line pattern 9 on the seed layer 7 by ink-jet printing the hot-melt material layer 8 and exposing the seed layer 7; and manufacturing a conductive grid line lamination layer 10 and an auxiliary welding layer 11 on the surface of the exposed seed layer 7, finally removing the hot-melt material layer 8, and removing the seed layer 6 and the barrier layer 7 at the covering positions by using chemical corrosive liquid to expose the surface of the battery and the auxiliary welding layer 11.
The transparent conductive oxide layer 5 adopts an ITO layer or a doped indium oxide layer, the barrier layer is a Ti metal layer or a Ta metal layer, the Ti metal layer is a TiNx metal layer or a TiW metal layer, and the Ta metal layer is a TaNx metal layer with the thickness of 1-50 nanometers; the seed layer 7 includes: the thickness of the copper seed layer, the nickel seed layer, the silver seed layer and the aluminum seed layer is between 1 and 1000 nanometers.
The conductive grid line lamination layer 10 is an electroplated copper lamination layer serving as a main conductive layer of the metal grid line, and the thickness of the conductive grid line lamination layer is 5-40 micrometers; the soldering assistant layer 11 is an electrolytic tinning lamination layer and has a soldering assistant effect on the main conducting layer of the metal grid line, and the thickness of the soldering assistant layer is 1-20 micrometers;
according to the structure, the method for preparing the metal grid line of the solar cell is prepared by adopting the following steps:
the method comprises the steps of firstly, depositing an intrinsic amorphous silicon layer 2 on the surface of an n-type silicon substrate 1 on the surface of the n-type silicon substrate 1 corroded by alkaline or acidic solution, and manufacturing an n-type amorphous silicon layer 3 and a p-type amorphous silicon layer 4 by adopting a CVD method, wherein the surface reflectivity of the n-type silicon substrate 1 is less than 5% in the wavelength range of 300-1100 nm; then, respectively depositing a transparent conductive oxide layer 5 on the p-type amorphous silicon layer 4 and the n-type amorphous silicon layer 3 by adopting a PVD sputtering method, wherein the transparent conductive oxide layer 5 adopts an ITO layer (indium tin oxide) or an indium oxide layer doped with other elements, and has the characteristics that light passes through a material with the thickness of 100 nanometers, the transmittance is at least more than 90 percent, the resistivity of the transparent conductive oxide layer 5 is usually less than 3.5 multiplied by 10 < -4 > ohm-cm, and the thickness is between 50 and 120 nanometers; simultaneously depositing a barrier layer 6 on the transparent conductive oxide layer 5 by a PVD sputtering method, wherein the barrier layer 6 is a Ti metal layer with the thickness of 10-50 nanometers; and simultaneously depositing a seed layer 7 on the barrier layer 6 by a chemical plating or PVD sputtering method, wherein the seed layer 7 is a copper seed layer and has the thickness of 50-10000 nanometers. As shown in fig. 3.
And secondly, printing a layer of hot-melt material 8 on the seed layer 7 by ink jet, forming a metal grid line pattern 9, and exposing the seed layer 7 in the metal grid line pattern 9, wherein the hot-melt material is paraffin or paraffin modifier. As shown in fig. 4.
And thirdly, manufacturing a grid line lamination layer on the surface of the seed layer 7 exposed in the metal grid line pattern 9 by adopting a horizontal electroplating process. The conductive grid line lamination 10 is an electroplated copper lamination and is used as a main conductive layer of the metal grid line, and the thickness of the conductive grid line lamination is 5-40 micrometers; the solder mask layer 11 is an electrolytic tin plating lamination or a chemical tin plating lamination, and is used as a solder mask layer of the metal grid line and a protective layer of the copper lamination, and the thickness of the solder mask layer is 1-20 microns. As shown in fig. 5.
And fourthly, removing the hot-melt material of the mask, and removing the seed layer 7 and the barrier layer 6 at the covering positions by using chemical corrosive liquid to expose the surface of the cell. The process adopts a horizontal corrosion process, copper plating and tin plating are performed horizontally, and grid line manufacturing is completed in the continuous horizontal conveying process of the battery. So far, the fabrication of the whole gate line is completed as shown in fig. 6 and 7.
According to the invention, the mask layer 8 is manufactured in an ink-jet printing mode, the two grid line laminated layers 10 are manufactured through horizontal copper electroplating, horizontal tin electroplating or chemical tin plating, then the mask layer and the seed layer 7 and the barrier layer 6 at the covering positions of the mask layer are removed through a horizontal corrosion process, and the horizontal manufacturing process is adopted in the whole grid line manufacturing process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1.一种制备太阳能电池金属栅线的方法，其特征在于，包括：在n型硅衬底一面沉积本征非晶硅层及n型非晶硅层，另一面沉积本征非晶硅层及p型非晶硅层，并在n型非晶硅层和p型非晶硅层上沉积透明导电氧化物层，在所述透明导电氧化物层上沉积阻挡层；在所述阻挡层上沉积种子层；在种子层上通过喷墨打印的方式，将热熔性材料覆盖于非栅线位置的区域，形成掩膜层，暴露出栅线位置的种子层；通过水平电镀的方式，在暴露出的种子层表面制作导电栅线叠层和助焊层；通过水平腐蚀方式，用化学腐蚀液去除掩膜层、及其覆盖位置的种子层、阻挡层，暴露出电池表面和助焊层。1. a method for preparing a solar cell metal grid line is characterized in that, comprising: depositing an intrinsic amorphous silicon layer and an n-type amorphous silicon layer on one side of an n-type silicon substrate, and depositing an intrinsic amorphous silicon layer on the other side and a p-type amorphous silicon layer, and a transparent conductive oxide layer is deposited on the n-type amorphous silicon layer and the p-type amorphous silicon layer, and a barrier layer is deposited on the transparent conductive oxide layer; on the barrier layer Depositing a seed layer; by inkjet printing on the seed layer, cover the area of the non-grid line position with a hot-melt material to form a mask layer, exposing the seed layer at the grid line position; by horizontal electroplating, in the The surface of the exposed seed layer is made into a conductive grid line stack and a solder flux layer; by horizontal etching, chemical etching solution is used to remove the mask layer, and the seed layer and barrier layer in the covering position to expose the battery surface and the solder flux layer. . 2.根据权利要求1所述一种制备太阳能电池金属栅线的方法，其特征在于：所述导电栅线叠层厚度在5-40微米之间。2 . The method for preparing a metal grid line for a solar cell according to claim 1 , wherein the thickness of the conductive grid line stack is between 5 and 40 μm. 3 . 3.根据权利要求1所述一种制备太阳能电池金属栅线的方法，其特征在于：所述助焊层厚度在1-20微米之间。3 . The method for preparing a metal grid line of a solar cell according to claim 1 , wherein the thickness of the soldering flux layer is between 1 and 20 microns. 4 . 4.根据权利要求1所述一种制备太阳能电池金属栅线的方法，其特征在于：所述掩膜层厚度在1-50微米之间。4 . The method for preparing a metal grid line of a solar cell according to claim 1 , wherein the thickness of the mask layer is between 1-50 μm. 5 . 5.根据权利要求1所述一种制备太阳能电池金属栅线的方法，其特征在于：所述掩膜层采用热熔性材料，为石蜡材料或石蜡改性材料。5 . The method for preparing metal grid lines of a solar cell according to claim 1 , wherein the mask layer is made of a hot-melt material, which is a paraffin material or a paraffin modified material. 6 . 6.根据权利要求1所述一种制备太阳能电池金属栅线的方法，其特征在于：所述去除掩膜层、种子层、阻挡层采用水平腐蚀方式，布置于水平镀铜、水平镀锡后，栅线制作连续进行。6 . The method for preparing metal grid lines of solar cells according to claim 1 , wherein the removal of the mask layer, the seed layer and the barrier layer adopts a horizontal corrosion method, and is arranged after horizontal copper plating and horizontal tin plating. 7 . , the grid line production is carried out continuously. 7.根据权利要求1所述一种制备太阳能电池金属栅线的方法，其特征在于：所述导电氧化物层采用ITO层或掺杂的氧化铟层。7 . The method of claim 1 , wherein the conductive oxide layer is an ITO layer or a doped indium oxide layer. 8 . 8.根据权利要求1所述一种制备太阳能电池金属栅线的方法，其特征在于：所述阻挡层为Ti金属层或Ta金属层。8 . The method of claim 1 , wherein the barrier layer is a Ti metal layer or a Ta metal layer. 9 . 9.根据权利要求3所述一种制备太阳能电池金属栅线的方法，其特征在于：所述Ti金属层为TiNx金属层、TiW金属层，所述Ta金属层为TaNx金属层，其厚度在1-50纳米之间。9. The method for preparing a metal grid line of a solar cell according to claim 3, wherein the Ti metal layer is a TiNx metal layer, a TiW metal layer, the Ta metal layer is a TaNx metal layer, and its thickness is Between 1-50 nanometers. 10.根据权利要求1所述一种制备太阳能电池金属栅线的方法，其特征在于：所述种子层为铜种子层、镍种子层、银种子层、铝种子层中任意一种。10 . The method of claim 1 , wherein the seed layer is any one of a copper seed layer, a nickel seed layer, a silver seed layer, and an aluminum seed layer. 11 .
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114823978A (en) * 2022-04-24 2022-07-29 王涛 Solar cell and manufacturing method thereof
CN115084312A (en) * 2022-03-11 2022-09-20 浙江爱旭太阳能科技有限公司 Preparation method of solar cell, solar cell module and power generation system
CN115498050A (en) * 2022-09-23 2022-12-20 通威太阳能（成都）有限公司 A kind of solar cell and its preparation method
CN115663066A (en) * 2022-10-27 2023-01-31 通威太阳能（安徽）有限公司 Solar cell and preparation method thereof
CN118039737A (en) * 2024-02-04 2024-05-14 苏州皓申智能科技有限公司 Battery piece and electroplating method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115084312A (en) * 2022-03-11 2022-09-20 浙江爱旭太阳能科技有限公司 Preparation method of solar cell, solar cell module and power generation system
CN114823978A (en) * 2022-04-24 2022-07-29 王涛 Solar cell and manufacturing method thereof
CN115498050A (en) * 2022-09-23 2022-12-20 通威太阳能（成都）有限公司 A kind of solar cell and its preparation method
CN115498050B (en) * 2022-09-23 2024-03-29 通威太阳能（成都）有限公司 A solar cell and its preparation method
CN115663066A (en) * 2022-10-27 2023-01-31 通威太阳能（安徽）有限公司 Solar cell and preparation method thereof
CN115663066B (en) * 2022-10-27 2023-12-29 通威太阳能（安徽）有限公司 Solar cell manufacturing method and solar cell
WO2024087620A1 (en) * 2022-10-27 2024-05-02 通威太阳能（安徽）有限公司 Preparation method for solar cell, and solar cell
CN118039737A (en) * 2024-02-04 2024-05-14 苏州皓申智能科技有限公司 Battery piece and electroplating method thereof

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Application publication date: 20220201