WO2023124614A1 - Metal electrode of solar cell, preparation method therefor, and solar cell - Google Patents

Metal electrode of solar cell, preparation method therefor, and solar cell Download PDF

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Publication number
WO2023124614A1
WO2023124614A1 PCT/CN2022/132622 CN2022132622W WO2023124614A1 WO 2023124614 A1 WO2023124614 A1 WO 2023124614A1 CN 2022132622 W CN2022132622 W CN 2022132622W WO 2023124614 A1 WO2023124614 A1 WO 2023124614A1
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solar cell
metal electrode
preparation
electrode
layer
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PCT/CN2022/132622
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French (fr)
Chinese (zh)
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何秉轩
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隆基绿能科技股份有限公司
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Publication of WO2023124614A1 publication Critical patent/WO2023124614A1/en

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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
    • H01L31/022433—Particular geometry of the grid contacts
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • 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

Definitions

  • the invention relates to the technical field of solar cells, in particular to a solar cell metal electrode, a preparation method thereof, and a solar cell.
  • Solar cells can convert solar energy into electricity and are an important source of clean energy.
  • the electrode is a key component of a solar cell, which mainly includes a fine grid electrode and a main grid electrode, and its function is to export and collect the current generated inside the solar cell.
  • the preparation of solar cell electrodes generally adopts the screen printing silver paste process, and the obtained electrode line width is more than 30 ⁇ m. Due to the high cost of silver paste, and the conductivity is much lower than that of metallic silver, in order to achieve certain conductivity requirements, it is necessary to make silver paste into relatively thick electrode grid lines, which requires more raw materials and further increases the cost; Moreover, when the electrode grid lines are thicker, more sunlight will be blocked and the power generation efficiency of the solar cell will be reduced.
  • An object of the present invention is to provide a novel method for preparing electrodes.
  • Another object of the present invention is to provide a prepared metal electrode.
  • Another object of the present invention is to provide a solar cell comprising the metal electrode.
  • the present invention provides a kind of preparation method of metal electrode of solar cell, and this preparation method comprises: the mask plate of patterned polymer material is fixed on the surface of substrate, then to this surface of substrate (that is, fixed on the substrate) metal is deposited on the surface of the patterned polymer material mask) to grow a metal electrode of a desired shape on the surface of the substrate to obtain the metal electrode of the solar cell.
  • the metal is deposited on the surface of the mask plate with the patterned polymer material fixed on the substrate, that is, the metal is deposited on the interface between the substrate and the mask plate made of the patterned polymer material, and finally the metal is deposited on the substrate close to the pattern.
  • a metal electrode is formed on one side of the mask plate made of a polymer material.
  • the above preparation method usually includes the operation of removing the patterned polymer mask.
  • the existing methods for preparing electrode patterns usually use photoresist or ink to form electrode patterns. After the electrode preparation is completed, the photoresist and ink need to be removed by chemical treatment, resulting in a large amount of waste water; and the patterning used in the present invention
  • the mask plate made of polymer material can be removed by mechanical peeling off, without chemical treatment, avoiding the problem of generating a large amount of waste water, and also significantly reducing costs.
  • the patterned polymer mask has slits corresponding to the metal electrodes.
  • the slits are generally formed by laser etching a mask made of polymer material.
  • the width of each slit can be 1 ⁇ m-100 ⁇ m, such as 1 ⁇ m-30 ⁇ m, 5 ⁇ m-30 ⁇ m, etc.
  • the width of each slit can be 1 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 17 ⁇ m, 18 ⁇ m, 20 ⁇ m, 22 ⁇ m, 25 ⁇ m, 28 ⁇ m, 30 ⁇ m, etc.; when the metal electrode is a bus electrode of a solar cell, the width of each slit can be 100 ⁇ m -500 ⁇ m, eg 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 250 ⁇ m, 300 ⁇ m, 350 ⁇ m, 400 ⁇ m, 450 ⁇ m, 500 ⁇ m, etc.
  • the specific width of the slit can also be determined according to the required electrode shape.
  • the length of the slit and the spacing between the slits are determined according to the design of the battery electrodes.
  • the mask plate is prepared by using a laser to etch a mask plate made of a polymer material according to a desired electrode shape.
  • the thickness of the polymer mask is generally 1 ⁇ m-100 ⁇ m, for example, 5 ⁇ m-30 ⁇ m, specifically 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, 50 ⁇ m.
  • the visible light transmittance of the mask plate made of polymer material is generally less than or equal to 90%.
  • the process of preparing a mask comprises using an ultrafast laser (laser with a pulse width of ps or even fs level) on a mask made of a polymer material A slit of the required electrode shape is prepared on the top.
  • an ultrafast laser laser with a pulse width of ps or even fs level
  • the polymer material includes but not limited to polyethylene terephthalate (PET), polyolefin (PO), polyvinyl chloride (PVC), polyimide, biaxially oriented polypropylene or other polymer materials whose thickness meets the requirements.
  • PET polyethylene terephthalate
  • PO polyolefin
  • PVC polyvinyl chloride
  • polyimide polyimide
  • the polyolefin may specifically be a polyolefin film; in some embodiments, the polyolefin may be polyvinyl chloride (PVC), biaxially oriented polypropylene, and the like.
  • the polymer material of the present invention can be in the form of a film without adhesive properties, or in the form of films with adhesive properties, which is commonly referred to as adhesive tape.
  • one side of the polymer mask may have an adhesive layer, and the adhesive layer is used to fix the patterned polymer mask to the substrate.
  • the material of the adhesive layer may include one or a combination of two or more of silica gel, acrylic glue, polyurethane, rubber, polyisobutylene, and the like.
  • the polymer mask used in the present invention has a better absorption effect on light in a certain wavelength range.
  • a laser with a specific wavelength can be used for etching, thereby reducing the demand for laser power and saving costs.
  • the absorption coefficient of the mask plate made of polymer material under the irradiation condition of ultraviolet light source is generally ⁇ 20%, and further can be ⁇ 20%. 50%, ⁇ 80%, wherein, the wavelength of the ultraviolet light source is 355 ⁇ 15nm.
  • the absorption coefficient of the mask plate made of polymer material under the irradiation condition of a green light source is generally ⁇ 20%, further Can be ⁇ 50%, ⁇ 80%, wherein the wavelength of the green light source is 530 ⁇ 15nm.
  • the absorption coefficient of the mask plate made of polymer material under the irradiation condition of infrared light source is generally ⁇ 20%, further Can be ⁇ 50%, ⁇ 80%, wherein, the wavelength of the infrared light source is 1045 ⁇ 20nm.
  • the viscosity of the polymer mask is generally adjusted according to the processing requirements, so as to ensure that the patterned polymer mask will not fall off the substrate when depositing electrodes, and will not It will cause damage to the substrate when removing the mask, avoid being too loose or too sticky.
  • the peel strength of the adhesive layer in the polymer mask is generally 1-50gf/cm, such as 5-40gf/cm, 15-30gf/cm, etc. ; Wherein, the preset temperature range is generally 15-30°C, such as 20-30°C, 20-25°C, etc.
  • the substrate in the method for preparing a solar cell metal electrode of the present invention, is a solar cell sheet without a metal electrode, and the surface of the substrate may be provided with a conductive layer having a conductive function.
  • the conductive layer may include one or a stacked combination of two or more of a TCO layer (transparent conductive layer), a seed layer, a doped layer, etc., preferably, the conductive layer is a TCO layer and/or a seed layer.
  • the conductive layer when the conductive layer is one of a TCO layer (transparent conductive layer), a seed layer, and a doped layer, the conductive layer is directly connected to the mask plate of the patterned polymer material.
  • the conductive layer when the conductive layer includes a seed layer and layers of other conductive structures, the seed layer is generally the surface layer of the conductive layer and is in direct contact with the mask plate of the patterned polymer material; when the conductive layer When including a TCO layer and other non-seed layer conductive structure layers (for example, the conductive layer is a TCO layer+doped layer), the TCO layer is generally a mask for the surface layer of the conductive layer and the patterned polymer material. Stencil direct contact.
  • the material of the seed layer may include: CuNi (nickel-copper alloy), Cu (copper), Ni (nickel), NiCr (nickel-chromium alloy), Cr (chromium), Ti (titanium), One or a combination of two or more of Ag (silver) and the like.
  • the metal used in the seed layer includes a single metal, or an alloy, or a stack of multiple metals, or a metal and an alloy stack, or an alloy and an alloy. superposition of alloys.
  • the seed layer can be formed by metal deposition methods such as magnetron sputtering and vacuum evaporation.
  • the thickness of the seed layer is generally 50nm-1000nm.
  • the metal electrode of the required shape that is, a thin line that is basically consistent with the shape of the mask plate slit
  • the The patterned polymer mask is etched to remove the seed layer.
  • the thickness of the seed layer is 50nm-1000nm, and the thickness of the metal electrode is more than 5 ⁇ m. Since the thickness of the electrode is much larger than the thickness of the seed layer, the seed layer can be removed completely by using the etching process while the thickness of the electrode part is basically maintained. No change; the etched seed layer refers to the part of the seed layer covered by the original mask.
  • the etching process used includes wet etching, dry etching and the like.
  • dry etching generally exposes the seed layer to a plasma atmosphere, and etches and removes the seed layer through physical or chemical reactions.
  • wet etching generally uses chemical reagents to chemically react with the seed layer to etch and remove the seed layer.
  • the above preparation method may include: fixing a patterned polymer mask on the surface of the seed layer on a solar cell sheet without metal electrodes, Metal is deposited on the surface of the seed layer to grow a metal electrode of the desired shape on the solar cell, and after the metal electrode is formed, the patterned polymer mask is removed and the seed layer is etched to obtain a solar cell metal electrode .
  • the above preparation method may include: fixing a patterned polymer mask on the surface of the TCO layer of a solar cell without a metal electrode, Metal is deposited on the surface of the TCO to grow a metal electrode of a desired shape on the solar cell sheet, and after the metal electrode is formed, the patterned polymer mask is removed to obtain a solar cell metal electrode.
  • the above preparation method may include: fixing a patterned polymer mask on the doped layer of a solar cell sheet without metal electrodes On the surface of the doped layer, metal is deposited on the surface of the doped layer to grow a metal electrode of a desired shape on the solar cell sheet. After the metal electrode is formed, the patterned polymer mask is removed to obtain a solar cell metal electrode.
  • the above-mentioned substrate can also be other membrane plates, and after metal electrodes are plated on the substrate, it is transferred to a solar cell as an electrode of a solar cell sheet.
  • electrodes can be grown on a plastic film (it only needs to have a complete plane, such as a transparent PET film), and then the film with electrodes can be directly turned over and buckled on the solar cell sheet without metal electrodes, and the same can be achieved.
  • a plastic film it only needs to have a complete plane, such as a transparent PET film
  • the film with electrodes can be directly turned over and buckled on the solar cell sheet without metal electrodes, and the same can be achieved.
  • the purpose of the metal electrodes of solar cells can be grown on a plastic film (it only needs to have a complete plane, such as a transparent PET film), and then the film with electrodes can be directly turned over and buckled on the solar cell sheet without metal electrodes, and the same can be achieved.
  • the purpose of the metal electrodes of solar cells can be grown on a plastic film (it only needs to have a complete plane, such as a transparent PET film), and then the film with electrodes can be directly turned over and buckled on the solar cell sheet without metal electrodes, and the same
  • the method for fixing the mask plate of the polymer material on the substrate includes the combination of one or both of double-sided adhesive tape and glue . If the mask plate uses adhesive tape with adhesive properties, the fixing method can be direct pasting.
  • the solar cells include devices that have one or more PN junctions prepared and can generate photovoltaic effects.
  • the preparation method of the above-mentioned solar cell metal electrode may specifically include:
  • the mask plate of polymer material is processed by ultrafast laser and other lasers to obtain a mask plate of patterned polymer material.
  • the mask plate of patterned polymer material has a metal electrode corresponding slit.
  • fix the mask plate of the patterned polymer material on the surface of the substrate if the substrate has a conductive layer, fix the mask plate of the patterned polymer material on the surface of the conductive layer
  • fix The method can be double-sided tape, glue, direct paste (when the polymer mask has a tape with adhesive properties), etc.
  • the deposition method may be electroplating, etc., so as to grow metal electrodes of desired shape on the substrate.
  • the present invention also provides the metal electrode prepared according to the above method.
  • the electrode prepared by the present invention can be used directly.
  • the present invention also provides a method for preparing a solar cell, which includes the process of preparing a metal electrode according to the method for preparing a metal electrode for a solar cell in the present invention.
  • the present invention also provides a solar cell, which includes the above-mentioned metal electrode.
  • the solar cell may be a crystalline silicon solar cell, an amorphous silicon solar cell, or the like.
  • amorphous silicon solar cells may include thin film cells, stacked cells, perovskite cells, fuel cells, sensitized cells, cadmium telluride cells, and the like.
  • the preparation method of the solar cell metal electrode provided by the present invention has the following characteristics:
  • the electrode prepared by the present invention has low resistance and high conductivity.
  • the shading area of the metal electrode prepared by the present invention is smaller: the metal electrode produced by using a mask plate can be as thin as 1-30 ⁇ m, or even 1-20 ⁇ m, which is better than that produced by the existing screen printing process (30 ⁇ m-80 ⁇ m).
  • the metal electrodes are thinner, less shading, and precise and controllable, which can effectively improve the power generation efficiency.
  • the metal electrode prepared by the present invention is thinner than the metal electrode produced by the screen printing process, so the solar cell is less affected by the stress of the metal electrode.
  • FIG. 1 is a schematic flow diagram of making a metal electrode on a substrate with a conductive layer in the present invention.
  • FIG. 2 is a schematic flow chart of fabricating metal electrodes on a substrate with a TCO layer in the present invention.
  • FIG. 3 is a schematic flow diagram of fabricating a metal electrode on a substrate having a TCO layer and a seed layer in the present invention.
  • FIG. 4 is a schematic flow chart of fabricating a metal electrode on a substrate with a doped layer in the present invention.
  • FIG. 5 is a schematic flow diagram of directly fabricating metal electrodes on silicon wafers in the present invention.
  • Solar cell 01 conductive layer 02, patterned polymer mask 03, metal electrode 04, TCO layer 21, seed layer 22, doped layer 05, silicon wafer 11.
  • This embodiment provides a metal electrode applied to a crystalline silicon solar cell.
  • the preparation method of the electrode is shown in Figure 1, specifically including:
  • the mask plate is laser scribed to obtain a main slit corresponding to a bus electrode (bus bar) with a width of 400 ⁇ m and a thin slit corresponding to a collector electrode (fine grid line) with a width of 30 ⁇ m to form a pattern
  • the mask plate 03 of the polymer material is laser scribed to obtain a main slit corresponding to a bus electrode (bus bar) with a width of 400 ⁇ m and a thin slit corresponding to a collector electrode (fine grid line) with a width of 30 ⁇ m to form a pattern
  • the mask plate 03 of the polymer material is laser scribed to obtain a main slit corresponding to a bus electrode (bus bar) with a width of 400 ⁇ m and a thin slit corresponding to a collector electrode (fine grid line) with a width of 30 ⁇ m to form a pattern
  • the mask plate 03 of the polymer material is laser scribed to obtain a main slit corresponding to a bus electrode (bus bar)
  • the fixed mask plate is electroplated, and an electroplating layer (that is, an electrode layer) with a thickness of 25 ⁇ m is formed on one side of the mask plate to form a metal electrode 04 of a desired shape on the surface of the solar cell.
  • an electroplating layer that is, an electrode layer
  • step 1 and step 2 are carried out independently, and the sequence of the two is not particularly limited, or can also be carried out at the same time. The same is true for Step 1 and Step 2 in Embodiment 2 and Embodiment 3.
  • This embodiment provides a metal electrode applied to a crystalline silicon solar cell, and the preparation method of the electrode includes:
  • the mask plate is laser scribed to obtain a main slit corresponding to a bus electrode (bus bar) with a width of 200 ⁇ m and a thin slit corresponding to a collector electrode (fine grid line) with a width of 20 ⁇ m to form a pattern
  • the mask plate of the polymer material is laser scribed to obtain a main slit corresponding to a bus electrode (bus bar) with a width of 200 ⁇ m and a thin slit corresponding to a collector electrode (fine grid line) with a width of 20 ⁇ m to form a pattern
  • bus bar bus electrode
  • a thin slit corresponding to a collector electrode fine grid line
  • This embodiment provides a metal electrode applied to a crystalline silicon solar cell, and the preparation method of the electrode includes:
  • the mask plate is laser scribed to obtain the main slit corresponding to the bus electrode (bus bar) with a width of 200 ⁇ m and the corresponding collector electrode (fine grid line) with a width of 10 ⁇ m to form a pattern.
  • the mask plate of the polymer material.
  • Examples 1 to 3 provide the preparation of solar cells with metal electrodes in the case of using the solar cell as the substrate and the seed layer as the conductive layer.
  • the conductive layer can be a TCO layer, and the flow process of preparing a metal electrode under this condition is as shown in Figure 2; the conductive layer can also be a TCO layer and a seed layer deposited sequentially from bottom to top, under this condition
  • the process for preparing metal electrodes is shown in Figure 3; when the conductive layer is specifically a doped layer, the process for preparing metal electrodes under this condition is shown in Figure 4; silicon wafers can also be used instead of solar cells as substrates, under this condition
  • the process of preparing metal electrodes is shown in Fig. 5.
  • the process of preparing the metal electrode shown in FIG. 2 to FIG. 5 is similar to the process of preparing the metal electrode in Example 1 to Example 3.
  • the current method of screen printing uses silver paste as the electrode, and the general resistivity of the silver paste is 6 ⁇ 10 -8 ⁇ m.
  • the metal electrode produced by the present invention has low resistance and higher conductivity.
  • the electrode thickness formed by electroplating copper is much thinner than that formed by screen-printed silver paste, because under the condition of satisfying the conductivity, the smaller the resistivity, the smaller the thickness requirement. The thinner the electrode, the thinner the thickness of the electrode, the smaller the change in thermal expansion and contraction of the electrode, which can effectively reduce the stress effect of the electrode on the battery sheet.
  • the current collector electrode width of screen printing is generally above 30 ⁇ m.
  • the invention utilizes a patterned mask to electroplate a collector electrode with a width of less than 30 ⁇ m, which can be between 1 and 30 ⁇ m, and the width of the collector electrode becomes smaller, increasing the light-absorbing area of the battery and improving power generation efficiency.

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Abstract

Provided in the present invention are a metal electrode of a solar cell, a preparation method therefor, and a solar cell. The preparation method for a metal electrode of a solar cell in the present invention comprises: fixing a patterned mask of a polymer material on a surface of a substrate; and then depositing a metal onto the surface of the substrate, so as to grow a metal electrode of a required shape on the surface of the substrate, and obtain the metal electrode of a solar cell. Also provided in the present invention is a metal electrode prepared by the method. Further provided in the present invention is a solar cell including the metal electrode. The method in the present invention is low in manufacturing cost; and the prepared electrode has a high conductivity, a small light-shielding area, and a high photoelectric conversion rate.

Description

一种太阳能电池金属电极及其制备方法与太阳能电池A kind of solar battery metal electrode and its preparation method and solar battery
相关申请的交叉引用Cross References to Related Applications
本公开要求在2021年12月31日提交中国专利局、申请号为202111682953.7、名称为“一种太阳能电池金属电极及其制备方法与太阳能电池”的专利申请的优先权，其全部内容通过引用结合在本公开中。This disclosure claims the priority of a patent application filed with the China Patent Office on December 31, 2021, with application number 202111682953.7 and titled "A Metal Electrode for Solar Cells and Its Preparation Method and Solar Cell", the entire contents of which are incorporated by reference in this disclosure.
技术领域technical field
本发明涉及太阳能电池技术领域，尤其是关于一种太阳能电池金属电极及其制备方法与太阳能电池。The invention relates to the technical field of solar cells, in particular to a solar cell metal electrode, a preparation method thereof, and a solar cell.
背景技术Background technique
太阳能电池能够将太阳能转化为电能，是清洁能源的重要来源。电极是太阳能电池的关键组成部件，其主要包括细栅电极和主栅电极，作用是将太阳能电池内部发出的电流导出并汇集。Solar cells can convert solar energy into electricity and are an important source of clean energy. The electrode is a key component of a solar cell, which mainly includes a fine grid electrode and a main grid electrode, and its function is to export and collect the current generated inside the solar cell.
目前太阳能电池电极的制备普遍采用丝网印刷银浆工艺，得到的电极线宽在30μm以上。由于银浆成本较高，且导电率比金属银低很多，为了实现一定的导电性能需求，需要将银浆制成相对比较粗的电极栅线，从而需要较多的原材料，进一步增加了成本；而且电极栅线较粗时，会导致更多的太阳光被遮挡，降低太阳能电池的发电效率。At present, the preparation of solar cell electrodes generally adopts the screen printing silver paste process, and the obtained electrode line width is more than 30 μm. Due to the high cost of silver paste, and the conductivity is much lower than that of metallic silver, in order to achieve certain conductivity requirements, it is necessary to make silver paste into relatively thick electrode grid lines, which requires more raw materials and further increases the cost; Moreover, when the electrode grid lines are thicker, more sunlight will be blocked and the power generation efficiency of the solar cell will be reduced.
另，目前有少量工艺使用光刻胶或者油墨制备电极图案，然后使用电镀工艺在图案空白处生长电极，该工艺需要化学腐蚀光刻胶或油墨，导致大量废水的产生，另外，光刻工艺本身的成本也很高。In addition, there are currently a small number of processes that use photoresist or ink to prepare electrode patterns, and then use electroplating to grow electrodes in the blank areas of the pattern. This process requires chemical corrosion of photoresist or ink, resulting in a large amount of waste water. In addition, the photolithography process itself The cost is also high.
发明内容Contents of the invention
本发明的一个目的在于提供一种新颖的制备电极的方法。An object of the present invention is to provide a novel method for preparing electrodes.
本发明的另一目的在于提供一种所制备得到的金属电极。Another object of the present invention is to provide a prepared metal electrode.
本发明的另一目的在于提供包含所述金属电极的太阳能电池。Another object of the present invention is to provide a solar cell comprising the metal electrode.
一方面，本发明提供了一种太阳能电池金属电极的制备方法，该制备方法包括：将图案化的高分子材质的掩膜版固定在基板的表面，然后向基板的该表面(即基板上固定有图案化的高分子材质的掩模版的表面)沉积金属，以在基板的表面生长出所需形状的金属电极，得到所述太阳能电池金属电极。On the one hand, the present invention provides a kind of preparation method of metal electrode of solar cell, and this preparation method comprises: the mask plate of patterned polymer material is fixed on the surface of substrate, then to this surface of substrate (that is, fixed on the substrate) metal is deposited on the surface of the patterned polymer material mask) to grow a metal electrode of a desired shape on the surface of the substrate to obtain the metal electrode of the solar cell.
在上述制备方法中，向基板固定有图案化的高分子材质的掩模版的表面沉积金属，即为向基板与图案化的高分子材质的掩模版之间的界面沉积金属，最终在基板靠近图案化的高分子材质的掩模版的一侧表面形成金属电极。In the above preparation method, the metal is deposited on the surface of the mask plate with the patterned polymer material fixed on the substrate, that is, the metal is deposited on the interface between the substrate and the mask plate made of the patterned polymer material, and finally the metal is deposited on the substrate close to the pattern. A metal electrode is formed on one side of the mask plate made of a polymer material.
根据本发明的具体实施方案，在基板表面已生长出所需形状的金属电极之后，上述制备方法中通常会包括去除图案化的高分子材质的掩膜版的操作。现有的制备电极图案方法通常会采用光刻胶或者油墨来形成电极图案，在完成电极制备后，需要通过化学处理的方式去除光刻胶、油墨，产生大量废水；而本发明采用的图案化的高分子材质的掩膜版的通过机械揭离的方式即可实现去除，无需化学处理，避免产生大量废水的问题，同时也明显降低成本。According to a specific embodiment of the present invention, after the desired shape of the metal electrode is grown on the surface of the substrate, the above preparation method usually includes the operation of removing the patterned polymer mask. The existing methods for preparing electrode patterns usually use photoresist or ink to form electrode patterns. After the electrode preparation is completed, the photoresist and ink need to be removed by chemical treatment, resulting in a large amount of waste water; and the patterning used in the present invention The mask plate made of polymer material can be removed by mechanical peeling off, without chemical treatment, avoiding the problem of generating a large amount of waste water, and also significantly reducing costs.
根据本发明的具体实施方案，本发明的太阳能电池金属电极的制备方法中，所述图案化的高分子材质的掩模版上具有与所述金属电极对应的狭缝。所述狭缝一般为两条以上。所述狭缝一般通过激光刻蚀高分子材质的掩膜版形成。具体地，在所述金属电极为太阳能电池的集电电极时，每条狭缝的宽度可以为1μm-100μm，例如为1μm-30μm、5μm-30μm等，具体地，每条狭缝的宽度可以为1μm、5μm、8μm、10μm、12μm、15μm、17μm、18μm、20μm、22μm、25μm、28μm、30μm等；在所述金属电极为太阳能电池的汇流电极时，每条狭缝的宽度可以为100μm-500μm，例如100μm、150μm、200μm、250μm、300μm、350μm、400μm、450μm、500μm等。狭缝具体宽度也可具体根据需要的电极形状而定。狭缝长度、狭缝之间的间距根据电池电极设计决定。According to a specific embodiment of the present invention, in the method for preparing a solar cell metal electrode of the present invention, the patterned polymer mask has slits corresponding to the metal electrodes. Generally, there are more than two slits. The slits are generally formed by laser etching a mask made of polymer material. Specifically, when the metal electrode is a collector electrode of a solar cell, the width of each slit can be 1 μm-100 μm, such as 1 μm-30 μm, 5 μm-30 μm, etc. Specifically, the width of each slit can be 1 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 17 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, etc.; when the metal electrode is a bus electrode of a solar cell, the width of each slit can be 100 μm -500 μm, eg 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, etc. The specific width of the slit can also be determined according to the required electrode shape. The length of the slit and the spacing between the slits are determined according to the design of the battery electrodes.
根据本发明的具体实施方案，本发明的太阳能电池金属电极的制备方法中，所述掩模版是采用激光依据所需电极形状刻蚀高分子材质的掩膜版制备的。在一些具体实施方案中，所述高分子材质的掩膜版的厚度一般为1μm-100μm，例如可以是5μm-30μm，具体可以是5μm、10μm、15μm、20μm、25μm、30μm、35μm、40μm、45μm、50μm。所述高分子材质的掩模版的可见光透过率一般小于等于90％。According to a specific embodiment of the present invention, in the method for preparing a solar cell metal electrode of the present invention, the mask plate is prepared by using a laser to etch a mask plate made of a polymer material according to a desired electrode shape. In some specific embodiments, the thickness of the polymer mask is generally 1 μm-100 μm, for example, 5 μm-30 μm, specifically 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45μm, 50μm. The visible light transmittance of the mask plate made of polymer material is generally less than or equal to 90%.
根据本发明的具体实施方案，本发明的太阳能电池金属电极的制备方法中，制备掩模版的过程包括采用超快激光(脉冲宽度在ps甚至fs量级的激光)在高分子材质的掩膜版上制备出需要的电极形状的狭缝。采用本发明的方法能够制作加工精细的高分子材质的掩模版。根据本发明的具体实施方案，本发明的太阳能电池金属电极的制备方法中，所述高分子材质包括但不限于聚 对苯二甲酸乙二酯(PET)、聚烯烃(PO)、聚氯乙烯(PVC)、聚酰亚胺、双向拉伸聚丙烯或者其他厚度满足要求的其他高分子材质。其中，所述聚烯烃可以具体为聚烯烃薄膜；在一些实施方案中，所述聚烯烃可以是聚氯乙烯(PVC)、双向拉伸聚丙烯等。本发明所述的高分子材质可以是不带粘贴性能的薄膜形式，也可是带粘贴性能的薄膜形式，也即通常所说的胶带。According to a specific embodiment of the present invention, in the method for preparing a solar cell metal electrode of the present invention, the process of preparing a mask comprises using an ultrafast laser (laser with a pulse width of ps or even fs level) on a mask made of a polymer material A slit of the required electrode shape is prepared on the top. By adopting the method of the invention, it is possible to manufacture a finely processed mask made of polymer material. According to a specific embodiment of the present invention, in the preparation method of the solar cell metal electrode of the present invention, the polymer material includes but not limited to polyethylene terephthalate (PET), polyolefin (PO), polyvinyl chloride (PVC), polyimide, biaxially oriented polypropylene or other polymer materials whose thickness meets the requirements. Wherein, the polyolefin may specifically be a polyolefin film; in some embodiments, the polyolefin may be polyvinyl chloride (PVC), biaxially oriented polypropylene, and the like. The polymer material of the present invention can be in the form of a film without adhesive properties, or in the form of films with adhesive properties, which is commonly referred to as adhesive tape.
根据本发明的具体实施方案，所述高分子材质的掩模版的一面可以具有粘性层，该粘性层用于实现图案化高分子材质的掩膜版与所述基板之间的固定。所述粘性层的材料可以包括硅胶、亚克力胶、聚氨酯、橡胶、聚异丁烯等中的一种或两种以上的组合。According to a specific embodiment of the present invention, one side of the polymer mask may have an adhesive layer, and the adhesive layer is used to fix the patterned polymer mask to the substrate. The material of the adhesive layer may include one or a combination of two or more of silica gel, acrylic glue, polyurethane, rubber, polyisobutylene, and the like.
根据本发明的具体实施方案，本发明所用的高分子材质的掩膜版对一定波长范围的光有较好的吸收效果。在形成图案化高分子材质的掩膜版时，可以利用特定波长的激光进行刻蚀，从而降低激光功率的需求，节约成本。According to a specific embodiment of the present invention, the polymer mask used in the present invention has a better absorption effect on light in a certain wavelength range. When forming a mask made of a patterned polymer material, a laser with a specific wavelength can be used for etching, thereby reducing the demand for laser power and saving costs.
根据本发明的具体实施方案，当所述高分子材质的掩膜版的厚度在200μm以下时，该高分子材质的掩模版在紫外光光源照射条件下的吸收系数一般≥20％、进一步可以≥50％、≥80％，其中，所述紫外光光源的波长为355±15nm。According to a specific embodiment of the present invention, when the thickness of the mask plate made of polymer material is below 200 μm, the absorption coefficient of the mask plate made of polymer material under the irradiation condition of ultraviolet light source is generally ≥ 20%, and further can be ≥ 20%. 50%, ≥80%, wherein, the wavelength of the ultraviolet light source is 355±15nm.
根据本发明的具体实施方案，当所述高分子材质的掩膜版的厚度在200μm以下时，所述高分子材质的掩膜版在绿光光源照射条件下的吸收系数一般≥20％、进一步可以≥50％、≥80％，其中，所述绿光光源的波长为530±15nm。According to a specific embodiment of the present invention, when the thickness of the mask plate made of polymer material is below 200 μm, the absorption coefficient of the mask plate made of polymer material under the irradiation condition of a green light source is generally ≥ 20%, further Can be ≥50%, ≥80%, wherein the wavelength of the green light source is 530±15nm.
根据本发明的具体实施方案，当所述高分子材质的掩膜版的厚度在200μm以下时，所述高分子材质的掩膜版在红外光光源照射条件下的吸收系数一般≥20％、进一步可以≥50％、≥80％，其中，所述红外光光源的波长为1045±20nm。According to a specific embodiment of the present invention, when the thickness of the mask plate made of polymer material is below 200 μm, the absorption coefficient of the mask plate made of polymer material under the irradiation condition of infrared light source is generally ≥20%, further Can be ≥50%, ≥80%, wherein, the wavelength of the infrared light source is 1045±20nm.
在本发明的具体实施方案中，所述高分子材质的掩膜版的粘性一般根据加工要求进行调整，既保证图案化高分子材质的掩膜版在沉积电极时不会从基板脱落，也不会在去除掩膜版时对基板造成破坏，避免过松或过粘。在一些具体实施方案中，所述高分子材质的掩模版中的粘性层在预设温度区间的剥离强度一般为1-50gf/cm，例如可以是5-40gf/cm、15-30gf/cm等；其中，所述预设温度区间一般为15-30℃，例如20-30℃、20-25℃等。In a specific embodiment of the present invention, the viscosity of the polymer mask is generally adjusted according to the processing requirements, so as to ensure that the patterned polymer mask will not fall off the substrate when depositing electrodes, and will not It will cause damage to the substrate when removing the mask, avoid being too loose or too sticky. In some specific embodiments, the peel strength of the adhesive layer in the polymer mask is generally 1-50gf/cm, such as 5-40gf/cm, 15-30gf/cm, etc. ; Wherein, the preset temperature range is generally 15-30°C, such as 20-30°C, 20-25°C, etc.
根据本发明的具体实施方案，本发明的太阳能电池金属电极的制备方法 中，所述基板是未有金属电极的太阳能电池片，所述基板的表面可以设有具有导电功能的导电层。例如：导电层可以包括TCO层(透明导电层)、种子层、掺杂层等中的一种或两种以上的叠层组合，优选地，导电层为TCO层和/或种子层。According to a specific embodiment of the present invention, in the method for preparing a solar cell metal electrode of the present invention, the substrate is a solar cell sheet without a metal electrode, and the surface of the substrate may be provided with a conductive layer having a conductive function. For example: the conductive layer may include one or a stacked combination of two or more of a TCO layer (transparent conductive layer), a seed layer, a doped layer, etc., preferably, the conductive layer is a TCO layer and/or a seed layer.
在本发明的具体实施方案中，当所述导电层为TCO层(透明导电层)、种子层、掺杂层中的一种时，该导电层与图案化的高分子材质的掩膜版直接接触；当所述导电层同时包括种子层和其他导电结构的层时，所述种子层一般为所述导电层的表层、与图案化的高分子材质的掩模版直接接触；当所述导电层同时包括TCO层和其他非种子层的导电结构的层(例如导电层为TCO层+掺杂层)时，所述TCO层一般为所述导电层的表层、与图案化的高分子材质的掩模版直接接触。In a specific embodiment of the present invention, when the conductive layer is one of a TCO layer (transparent conductive layer), a seed layer, and a doped layer, the conductive layer is directly connected to the mask plate of the patterned polymer material. Contact; when the conductive layer includes a seed layer and layers of other conductive structures, the seed layer is generally the surface layer of the conductive layer and is in direct contact with the mask plate of the patterned polymer material; when the conductive layer When including a TCO layer and other non-seed layer conductive structure layers (for example, the conductive layer is a TCO layer+doped layer), the TCO layer is generally a mask for the surface layer of the conductive layer and the patterned polymer material. Stencil direct contact.
在一些具体实施方案中，所述种子层的材料可以包括：CuNi(镍铜合金)、Cu(铜)、Ni(镍)、NiCr(镍铬合金)、Cr(铬)、Ti(钛)、Ag(银)等中的一种或两种以上的组合。根据本发明的具体实施方案，本发明的太阳能电池金属电极的制备方法中，所述种子层采用的金属包括单一金属、或者合金、或者多种金属的叠加、或金属与合金叠加、或者合金与合金的叠加。In some specific embodiments, the material of the seed layer may include: CuNi (nickel-copper alloy), Cu (copper), Ni (nickel), NiCr (nickel-chromium alloy), Cr (chromium), Ti (titanium), One or a combination of two or more of Ag (silver) and the like. According to a specific embodiment of the present invention, in the preparation method of the solar cell metal electrode of the present invention, the metal used in the seed layer includes a single metal, or an alloy, or a stack of multiple metals, or a metal and an alloy stack, or an alloy and an alloy. superposition of alloys.
根据本发明的具体实施方案，所述种子层可以通过磁控溅射、真空蒸发等金属沉积方法形成。According to a specific embodiment of the present invention, the seed layer can be formed by metal deposition methods such as magnetron sputtering and vacuum evaporation.
根据本发明的具体实施方案，所述种子层的厚度一般为50nm-1000nm。According to a specific embodiment of the present invention, the thickness of the seed layer is generally 50nm-1000nm.
根据本发明的具体实施方案，本发明的太阳能电池金属电极的制备方法中，可在太阳能电池片上生长出所需形状(即与掩模版狭缝形状基本一致的细线)的金属电极后，去除图案化的高分子材质的掩模版，刻蚀去除种子层。本发明中，种子层的厚度为50nm-1000nm，金属电极的厚度为5μm以上，由于电极的厚度远大于种子层的厚度，因此，采用刻蚀工艺能够将种子层去除干净而电极部分厚度基本保持不变；被刻蚀掉的种子层是指原来掩模板覆盖的种子层部分。According to a specific embodiment of the present invention, in the preparation method of the solar cell metal electrode of the present invention, after the metal electrode of the required shape (that is, a thin line that is basically consistent with the shape of the mask plate slit) can be grown on the solar cell sheet, the The patterned polymer mask is etched to remove the seed layer. In the present invention, the thickness of the seed layer is 50nm-1000nm, and the thickness of the metal electrode is more than 5 μm. Since the thickness of the electrode is much larger than the thickness of the seed layer, the seed layer can be removed completely by using the etching process while the thickness of the electrode part is basically maintained. No change; the etched seed layer refers to the part of the seed layer covered by the original mask.
根据本发明的具体实施方案，本发明的太阳能电池金属电极的制备方法中，采用的刻蚀工艺包括湿法刻蚀、干法刻蚀等。其中，干法刻蚀一般是将种子层暴露在等离子体气氛中，通过物理或化学反应将所述种子层刻蚀去除。湿法刻蚀一般是利用化学试剂与种子层发生化学反应，以将种子层刻蚀去除。According to a specific embodiment of the present invention, in the method for preparing the solar cell metal electrode of the present invention, the etching process used includes wet etching, dry etching and the like. Wherein, dry etching generally exposes the seed layer to a plasma atmosphere, and etches and removes the seed layer through physical or chemical reactions. Wet etching generally uses chemical reagents to chemically react with the seed layer to etch and remove the seed layer.
根据本发明的具体实施方案，当基板具有的导电层包括种子层时，上述制备方法可以包括：将图案化的高分子材质的掩模版固定在未有金属电极的太阳能电池片上的种子层表面，在所述种子层表面沉积金属，以在太阳能电池片上生长出所需形状的金属电极，形成金属电极后将图案化的高分子材质的掩模版去除并刻蚀掉种子层，得到太阳能电池金属电极。According to a specific embodiment of the present invention, when the conductive layer of the substrate includes a seed layer, the above preparation method may include: fixing a patterned polymer mask on the surface of the seed layer on a solar cell sheet without metal electrodes, Metal is deposited on the surface of the seed layer to grow a metal electrode of the desired shape on the solar cell, and after the metal electrode is formed, the patterned polymer mask is removed and the seed layer is etched to obtain a solar cell metal electrode .
根据本发明的具体实施方案，当基板具有的导电层包括TCO层时，上述制备方法可以包括：将图案化的高分子材质的掩模版固定在未有金属电极的太阳能电池片的TCO层表面，在所述TCO表面沉积金属，以在太阳能电池片上生长出所需形状的金属电极，形成金属电极后将图案化的高分子材质的掩模版去除，得到太阳能电池金属电极。According to a specific embodiment of the present invention, when the conductive layer of the substrate includes a TCO layer, the above preparation method may include: fixing a patterned polymer mask on the surface of the TCO layer of a solar cell without a metal electrode, Metal is deposited on the surface of the TCO to grow a metal electrode of a desired shape on the solar cell sheet, and after the metal electrode is formed, the patterned polymer mask is removed to obtain a solar cell metal electrode.
根据本发明的具体实施方案，当基板具有的导电层包括掺杂层时，上述制备方法可以包括：将图案化的高分子材质的掩模版固定在未有金属电极的太阳能电池片的掺杂层表面，在所述掺杂层表面沉积金属，以在太阳能电池片上生长出所需形状的金属电极，形成金属电极后将图案化的高分子材质的掩模版去除，得到太阳能电池金属电极。在本发明的具体实施方案中，上述基板也可以是其他膜板，在基板上镀金属电极后，将其转移到太阳能电池中作为太阳能电池片的电极。例如，可以是在一个塑料薄膜(具有完整平面即可，例如透明的PET薄膜)上生长出来电极，然后将带有电极的薄膜直接翻过来扣在未有金属电极的太阳电池片上，同样实现制作出太阳能电池片的金属电极的目的。According to a specific embodiment of the present invention, when the conductive layer of the substrate includes a doped layer, the above preparation method may include: fixing a patterned polymer mask on the doped layer of a solar cell sheet without metal electrodes On the surface of the doped layer, metal is deposited on the surface of the doped layer to grow a metal electrode of a desired shape on the solar cell sheet. After the metal electrode is formed, the patterned polymer mask is removed to obtain a solar cell metal electrode. In a specific embodiment of the present invention, the above-mentioned substrate can also be other membrane plates, and after metal electrodes are plated on the substrate, it is transferred to a solar cell as an electrode of a solar cell sheet. For example, electrodes can be grown on a plastic film (it only needs to have a complete plane, such as a transparent PET film), and then the film with electrodes can be directly turned over and buckled on the solar cell sheet without metal electrodes, and the same can be achieved. The purpose of the metal electrodes of solar cells.
根据本发明的具体实施方案，本发明的太阳能电池金属电极的制备方法中，将高分子材质的掩模版固定在基板上的方法包括采用双面胶、胶水中的一种或两种的组合方式。如果掩模版采用的是带粘贴性能的胶带时，则固定方法可为直接粘贴。According to a specific embodiment of the present invention, in the preparation method of the metal electrode of the solar cell of the present invention, the method for fixing the mask plate of the polymer material on the substrate includes the combination of one or both of double-sided adhesive tape and glue . If the mask plate uses adhesive tape with adhesive properties, the fixing method can be direct pasting.
本发明中，所述太阳能电池片包括已经制备完一个或多个PN结并能产生光生伏特效应的器件统称。In the present invention, the solar cells include devices that have one or more PN junctions prepared and can generate photovoltaic effects.
根据本发明的具体实施方案，上述太阳能电池金属电极的制备方法具体可以包括：According to a specific embodiment of the present invention, the preparation method of the above-mentioned solar cell metal electrode may specifically include:
1、依据所需电极形状，通过超快激光等激光加工高分子材质的掩模版，得到图案化的高分子材质的掩膜版，该图案化的高分子材质的掩膜版具有金 属电极对应的狭缝。1. According to the required electrode shape, the mask plate of polymer material is processed by ultrafast laser and other lasers to obtain a mask plate of patterned polymer material. The mask plate of patterned polymer material has a metal electrode corresponding slit.
2、将所述图案化的高分子材质的掩膜版固定在所述基板的表面(如果基板具有导电层，则将图案化高分子材质的掩膜版固定在所述导电层表面)，固定的方式可以双面胶、胶水、直接粘贴(当高分子掩膜版具有粘贴性能的胶带时)等。2. Fix the mask plate of the patterned polymer material on the surface of the substrate (if the substrate has a conductive layer, fix the mask plate of the patterned polymer material on the surface of the conductive layer), fix The method can be double-sided tape, glue, direct paste (when the polymer mask has a tape with adhesive properties), etc.
3、在所述基板固定有图案化的高分子材质的掩模版的一面沉积金属(沉积方式可以是电镀等)，以在所述基板上生长出所需形状的金属电极。3. Deposit metal on the side of the substrate on which the patterned polymer mask is fixed (the deposition method may be electroplating, etc.), so as to grow metal electrodes of desired shape on the substrate.
4、除去所述图案化的高分子材质的掩模版，得到太阳能电池金属电极(当基板具有种子层作为导电层时，则还需通过干法刻蚀、湿法刻蚀等方法刻蚀去除所述种子层)。4. Remove the mask plate of the patterned polymer material to obtain the metal electrode of the solar cell (when the substrate has a seed layer as a conductive layer, it is necessary to etch and remove all the metal electrodes by dry etching, wet etching, etc. above the seed layer).
另一方面，本发明还提供了按照上述方法所制备得到的金属电极。本发明所制备的电极，可直接使用。On the other hand, the present invention also provides the metal electrode prepared according to the above method. The electrode prepared by the present invention can be used directly.
另一方面，本发明还提供了一种太阳能电池的制备方法，其包括按照本发明所述太阳能电池金属电极的制备方法制备金属电极的过程。On the other hand, the present invention also provides a method for preparing a solar cell, which includes the process of preparing a metal electrode according to the method for preparing a metal electrode for a solar cell in the present invention.
本发明还提供了一种太阳能电池，其包括上述金属电极。在具体实施方案中，所述太阳能电池可以是晶硅太阳能电池、非晶硅太阳能电池等。其中，非晶硅太阳能电池可以包括薄膜电池、叠层电池、钙钛矿电池、燃料电池、敏化电池、碲化镉电池等。The present invention also provides a solar cell, which includes the above-mentioned metal electrode. In a specific embodiment, the solar cell may be a crystalline silicon solar cell, an amorphous silicon solar cell, or the like. Among them, amorphous silicon solar cells may include thin film cells, stacked cells, perovskite cells, fuel cells, sensitized cells, cadmium telluride cells, and the like.
综上所述，本发明提供的太阳能电池金属电极的制备方法具有以下特点：In summary, the preparation method of the solar cell metal electrode provided by the present invention has the following characteristics:
1、制作成本低：本发明所用的掩模版、激光制备工艺以及电镀工艺成本均较低。1. Low production cost: the cost of the mask plate, laser preparation process and electroplating process used in the present invention is relatively low.
2、相比于现有技术利用丝网印刷银浆制备的电极，本发明制备得到的电极电阻低、导电率高。2. Compared with the electrode prepared by screen printing silver paste in the prior art, the electrode prepared by the present invention has low resistance and high conductivity.
3、本发明制备的金属电极遮光面积更小：利用掩膜板制作出的金属电极可以细至1-30μm、甚至达到1-20μm，比现有丝网印刷工艺(30μm-80μm)制作出的金属电极更细，遮光更小，且精确可控，能够有效提高发电效率。3. The shading area of the metal electrode prepared by the present invention is smaller: the metal electrode produced by using a mask plate can be as thin as 1-30 μm, or even 1-20 μm, which is better than that produced by the existing screen printing process (30 μm-80 μm). The metal electrodes are thinner, less shading, and precise and controllable, which can effectively improve the power generation efficiency.
4、在满足导电性能及发电效率的前提下，本发明制备的金属电极与丝网印刷工艺制作出的金属电极相比，厚度更薄，因此太阳能电池受金属电极的应力影响更小。4. Under the premise of satisfying the conductivity and power generation efficiency, the metal electrode prepared by the present invention is thinner than the metal electrode produced by the screen printing process, so the solar cell is less affected by the stress of the metal electrode.
附图说明Description of drawings
为了更清楚地说明本发明实施例的技术方案，下面将对本发明实施例的描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the accompanying drawings that need to be used in the description of the embodiments of the present invention. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention , for those skilled in the art, other drawings can also be obtained according to these drawings without paying creative labor.
图1为本发明中在具有导电层的基板上制作金属电极的流程示意图。FIG. 1 is a schematic flow diagram of making a metal electrode on a substrate with a conductive layer in the present invention.
图2为本发明中在具有TCO层的基板上制作金属电极的流程示意图。FIG. 2 is a schematic flow chart of fabricating metal electrodes on a substrate with a TCO layer in the present invention.
图3为本发明中在具有TCO层和种子层的基板上制作金属电极的流程示意图。FIG. 3 is a schematic flow diagram of fabricating a metal electrode on a substrate having a TCO layer and a seed layer in the present invention.
图4为本发明中在具有掺杂层的基板上制作金属电极的流程示意图。FIG. 4 is a schematic flow chart of fabricating a metal electrode on a substrate with a doped layer in the present invention.
图5为本发明中在硅片上直接制作金属电极的流程示意图。FIG. 5 is a schematic flow diagram of directly fabricating metal electrodes on silicon wafers in the present invention.
附图标记说明：Explanation of reference signs:
太阳能电池片01、导电层02、图案化的高分子材质的掩膜版03、金属电极04、TCO层21、种子层22、掺杂层05、硅片11。 Solar cell 01, conductive layer 02, patterned polymer mask 03, metal electrode 04, TCO layer 21, seed layer 22, doped layer 05, silicon wafer 11.
具体实施例specific embodiment
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.
实施例1Example 1
本实施例提供了一种应用在晶硅太阳能电池上的金属电极，该电极的制备方法如图1所示，具体包括：This embodiment provides a metal electrode applied to a crystalline silicon solar cell. The preparation method of the electrode is shown in Figure 1, specifically including:
1、选择厚度为20μm、在25℃温度的剥离强度为15gf/cm、可见光透光率为60％的PET材质的掩模版，依据所需电极形状，通过超快激光(激光光源波长为355nm紫外光)对该掩膜版进行激光刻划，得到对应汇流电极(主栅线)的宽度为400μm的主狭缝和对应集电电极(细栅线)的宽度为30μm的细狭缝，形成图案化的高分子材质的掩膜版03。1. Select a PET reticle with a thickness of 20 μm, a peel strength of 15 gf/cm at a temperature of 25°C, and a visible light transmittance of 60%. Light) The mask plate is laser scribed to obtain a main slit corresponding to a bus electrode (bus bar) with a width of 400 μm and a thin slit corresponding to a collector electrode (fine grid line) with a width of 30 μm to form a pattern The mask plate 03 of the polymer material.
2、利用磁控溅射的方式在未有金属电极的太阳能电池片01(以下简称：太阳能电池片)表面沉积100nm厚的铜种子层(作为导电层02)，将经过激光刻划的图案化的高分子材质的掩膜版03粘贴在太阳能电池片01的铜种子层表面。2. Deposit a 100nm-thick copper seed layer (as the conductive layer 02) on the surface of the solar cell 01 (hereinafter referred to as: solar cell) without metal electrodes by means of magnetron sputtering, and pattern the laser-scribed The mask plate 03 made of polymer material is pasted on the surface of the copper seed layer of the solar cell 01.
3、对固定后的掩膜版进行电镀，在该掩膜版的一面形成25μm厚度的电 镀层(即为电极层)，以在太阳能电池表面形成所需形状的金属电极04。3. The fixed mask plate is electroplated, and an electroplating layer (that is, an electrode layer) with a thickness of 25 μm is formed on one side of the mask plate to form a metal electrode 04 of a desired shape on the surface of the solar cell.
4、除去所述图案化的高分子材质的掩模版04，将暴露出种子层和电镀层的电池片置于刻蚀液(例如酸性液体)中1分钟，将种子层和极小部分的电极刻蚀，得到具有金属电极的太阳能电池片。4. Remove the mask plate 04 of the patterned polymer material, place the battery sheet with the seed layer and electroplating layer exposed in an etching solution (such as an acidic liquid) for 1 minute, and remove the seed layer and a very small part of the electrode Etching to obtain solar cells with metal electrodes.
以上方法中，步骤1与步骤2是独立进行的，二者的先后顺序没有特别限制、或者也可以同时进行。实施例2、实施例3中的步骤1和步骤2也是如此。In the above method, step 1 and step 2 are carried out independently, and the sequence of the two is not particularly limited, or can also be carried out at the same time. The same is true for Step 1 and Step 2 in Embodiment 2 and Embodiment 3.
实施例2Example 2
本实施例提供了一种应用在晶硅太阳能电池上的金属电极，该电极的制备方法包括：This embodiment provides a metal electrode applied to a crystalline silicon solar cell, and the preparation method of the electrode includes:
1、选择厚度为30μm、在20℃温度的剥离强度为30gf/cm、可见光透光率为50％的PO材质的掩模版，依据所需电极形状，通过超快激光(激光光源波长为535nm绿光)对该掩膜版进行激光刻划，得到对应汇流电极(主栅线)的宽度为200μm的主狭缝和对应集电电极(细栅线)的宽度为20μm的细狭缝，形成图案化的高分子材质的掩膜版。1. Select a reticle made of PO material with a thickness of 30 μm, a peel strength of 30 gf/cm at a temperature of 20°C, and a visible light transmittance of 50%. Light) The mask plate is laser scribed to obtain a main slit corresponding to a bus electrode (bus bar) with a width of 200 μm and a thin slit corresponding to a collector electrode (fine grid line) with a width of 20 μm to form a pattern The mask plate of the polymer material.
2、利用真空蒸发的方式在太阳能电池片表面沉积200nm厚的镍种子层。2. Deposit a nickel seed layer with a thickness of 200 nm on the surface of the solar cell by vacuum evaporation.
3、将经过激光刻划的图案化的高分子材质的掩膜版粘贴在太阳能电池片的镍种子层表面。3. Paste the laser-scribed patterned polymer mask on the surface of the nickel seed layer of the solar cell.
4、对固定后的掩膜版进行电镀，在该掩膜版的一面形成20μm厚度的电镀层(即为电极层)，以在太阳能电池片表面形成所需形状的金属电极。4. Perform electroplating on the fixed mask, and form an electroplating layer (that is, an electrode layer) with a thickness of 20 μm on one side of the mask to form a metal electrode of a desired shape on the surface of the solar cell.
5、除去所述图案化的高分子材质的掩模版，将暴露出种子层和电镀层的电池片置于刻蚀液中3分钟，将种子层和极小部分的电极刻蚀，得到具有金属电极的太阳能电池片。5. Remove the mask plate of the patterned polymer material, place the battery sheet with the seed layer and electroplating layer exposed in the etching solution for 3 minutes, etch the seed layer and a very small part of the electrode to obtain a Electrodes of solar cells.
实施例3Example 3
本实施例提供了一种应用在晶硅太阳能电池上的金属电极，该电极的制备方法包括：This embodiment provides a metal electrode applied to a crystalline silicon solar cell, and the preparation method of the electrode includes:
1、选择厚度为30μm、在30℃温度的剥离强度为20gf/cm、可见光透光率为60％的PET材质的掩模版，依据所需电极形状，通过超快激光(激光光源波长为355nm紫外光)对该掩膜版进行激光刻划，得到对应汇流电极(主栅线)的宽度为200μm的主狭缝和对应集电电极(细栅线)的宽度为10μm 的细狭缝，形成图案化的高分子材质的掩膜版。1. Select a PET reticle with a thickness of 30 μm, a peel strength of 20 gf/cm at a temperature of 30°C, and a visible light transmittance of 60%. Light) The mask plate is laser scribed to obtain the main slit corresponding to the bus electrode (bus bar) with a width of 200 μm and the corresponding collector electrode (fine grid line) with a width of 10 μm to form a pattern. The mask plate of the polymer material.
2、利用磁控溅射在太阳能电池片表面沉积50nm厚的铜种子层。2. Depositing a copper seed layer with a thickness of 50 nm on the surface of the solar cell by magnetron sputtering.
3、将经过激光刻划的图案化的高分子材质的掩膜版粘贴在太阳能电池片表面的铜种子层上。3. Paste the laser-scribed patterned polymer mask on the copper seed layer on the surface of the solar cell.
4、对固定后的掩膜版进行电镀，在该掩膜版的一面形成20μm厚度的电镀层(即为电极层)，以在太阳能电池片表面形成所需形状的金属电极。4. Perform electroplating on the fixed mask, and form an electroplating layer (that is, an electrode layer) with a thickness of 20 μm on one side of the mask to form a metal electrode of a desired shape on the surface of the solar cell.
5、除去所述图案化的高分子材质的掩模版，将暴露出种子层和电镀层的电池片置于氩气的等离子体气氛中，将种子层和极小部分的电极刻蚀，得到具有金属电极的太阳能电池片。5. Remove the mask plate of the patterned polymer material, place the battery sheet with the seed layer and electroplating layer exposed in an argon plasma atmosphere, etch the seed layer and a very small part of the electrode to obtain a Solar cells with metal electrodes.
实施例1至实施例3提供了以太阳能电池片为基板、以种子层为导电层的情况制备具有金属电极的太阳能电池片。在本发明的具体实施方案中，导电层可以是TCO层，则该条件下制备金属电极的流程如图2所示；导电层也可以是由下至上依次沉积的TCO层和种子层，该条件下制备金属电极的流程如图3所示；当导电层具体为掺杂层，该条件下制备金属电极的流程如图4所示；也可以用硅片替代太阳能电池片作为基板，该条件下制备金属电极的流程如图5所示。图2至图5所示的制备金属电极的过程与实施例1至实施例3的制备金属电极的过程相似。Examples 1 to 3 provide the preparation of solar cells with metal electrodes in the case of using the solar cell as the substrate and the seed layer as the conductive layer. In a specific embodiment of the present invention, the conductive layer can be a TCO layer, and the flow process of preparing a metal electrode under this condition is as shown in Figure 2; the conductive layer can also be a TCO layer and a seed layer deposited sequentially from bottom to top, under this condition The process for preparing metal electrodes is shown in Figure 3; when the conductive layer is specifically a doped layer, the process for preparing metal electrodes under this condition is shown in Figure 4; silicon wafers can also be used instead of solar cells as substrates, under this condition The process of preparing metal electrodes is shown in Fig. 5. The process of preparing the metal electrode shown in FIG. 2 to FIG. 5 is similar to the process of preparing the metal electrode in Example 1 to Example 3.
测试例1test case 1
本发明最终制备的电极为纯金属，以实施例1、实施例3的纯铜金属电极为例，铜的电阻率ρ＝1.75×10 -8Ω·m。物理意义：长1m横截面积为1mm 2的铜导线的电阻为1.75×10 -8Ω。 The electrodes finally prepared in the present invention are pure metals. Taking the pure copper metal electrodes of Examples 1 and 3 as examples, the resistivity of copper is ρ=1.75×10 −8 Ω·m. Physical meaning: the resistance of a copper wire with a length of 1 m and a cross-sectional area of 1 mm 2 is 1.75×10 -8 Ω.
而现有采用丝网印刷的方式以银浆作为电极，银浆的一般电阻率为6×10 -8Ω·m。 However, the current method of screen printing uses silver paste as the electrode, and the general resistivity of the silver paste is 6×10 -8 Ω·m.
从上述电阻率比较结果可知，本发明制作的金属电极电阻小、电导率更高。另外，在电极为相同宽度的条件下，电镀铜形成的电极厚度要比丝网印刷的银浆形成的电极厚度要薄很多，因为在满足导电性能条件下，电阻率越小，其厚度要求就越薄，另外，电极厚度变薄，电极的热胀冷缩的变化幅度小，可以有效降低电极对电池片的应力影响。From the above resistivity comparison results, it can be seen that the metal electrode produced by the present invention has low resistance and higher conductivity. In addition, under the condition that the electrodes have the same width, the electrode thickness formed by electroplating copper is much thinner than that formed by screen-printed silver paste, because under the condition of satisfying the conductivity, the smaller the resistivity, the smaller the thickness requirement. The thinner the electrode, the thinner the thickness of the electrode, the smaller the change in thermal expansion and contraction of the electrode, which can effectively reduce the stress effect of the electrode on the battery sheet.
另外，目前丝网印刷的集电电极宽度一般在30μm以上。本发明利用图案化的掩膜能电镀出小于30μm宽度的集电电极，可以做到1-30μm之间，集电 电极宽度变小，增加电池的吸光面积，可以提高发电效率。In addition, the current collector electrode width of screen printing is generally above 30 μm. The invention utilizes a patterned mask to electroplate a collector electrode with a width of less than 30 μm, which can be between 1 and 30 μm, and the width of the collector electrode becomes smaller, increasing the light-absorbing area of the battery and improving power generation efficiency.
以上所述仅为本发明的较佳实施例而已，亦可用于其它类型太阳电池，并不用以限制本发明，凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above description is only a preferred embodiment of the present invention, and can also be used for other types of solar cells, and is not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, etc. , should be included within the protection scope of the present invention.

Claims (10)

  1. 一种太阳能电池金属电极的制备方法，该制备方法包括：A method for preparing a solar cell metal electrode, the preparation method comprising:
    将图案化的高分子材质的掩模版固定在基板的表面，然后向所述基板的该表面沉积金属以在所述基板的表面生长出所需形状的金属电极，得到所述太阳能电池金属电极。A patterned polymer mask is fixed on the surface of the substrate, and then metal is deposited on the surface of the substrate to grow a metal electrode of a desired shape on the surface of the substrate to obtain the metal electrode of the solar cell.
  2. 根据权利要求1所述的制备方法，其中，所述图案化的高分子材质的掩模版上具有与所述金属电极对应的狭缝；The preparation method according to claim 1, wherein the patterned polymer mask has slits corresponding to the metal electrodes;
    优选地，当所述金属电极为太阳能电池的集电电极时，每条狭缝的宽度为1μm-100μm，更优选为1μm-30μm，进一步优选为5μm-30μm；Preferably, when the metal electrode is a collector electrode of a solar cell, the width of each slit is 1 μm-100 μm, more preferably 1 μm-30 μm, further preferably 5 μm-30 μm;
    优选地，当所述金属电极为太阳能电池的汇流电极时，每条狭缝的宽度为100μm-500μm。Preferably, when the metal electrode is a bus electrode of a solar cell, the width of each slit is 100 μm-500 μm.
  3. 根据权利要求1或2所述的制备方法，其中，所述图案化的高分子材质的掩模版是依据所需电极形状通过激光加工高分子材质的掩模版后得到的；The preparation method according to claim 1 or 2, wherein the patterned polymer reticle is obtained by laser processing the polymer reticle according to the desired electrode shape;
    优选地，所述高分子材质的掩模版的厚度为1μm-100μm、更优选为5μm-30μm；Preferably, the thickness of the polymer mask is 1 μm-100 μm, more preferably 5 μm-30 μm;
    优选地，所述高分子材质的掩模版的可见光透过率≤90％；Preferably, the visible light transmittance of the mask plate made of polymer material is ≤90%;
    优选地，所述激光为超快激光。Preferably, the laser is an ultrafast laser.
  4. 根据权利要求3所述的制备方法，其中，所述高分子材质包括聚对苯二甲酸乙二酯、聚烯烃、聚酰亚胺中的一种或两种以上的组合；优选地，所述聚烯烃包括聚氯乙烯和/或双向拉伸聚丙烯；The preparation method according to claim 3, wherein the polymer material comprises one or a combination of two or more of polyethylene terephthalate, polyolefin, and polyimide; preferably, the Polyolefins including polyvinyl chloride and/or biaxially oriented polypropylene;
    优选地，所述高分子材质的掩模版的一面具有粘性层；Preferably, one side of the mask made of polymer material has an adhesive layer;
    更优选地，所述粘性层的材料包括硅胶、亚克力胶、聚氨酯、橡胶、聚异丁烯中的一种或两种以上的组合。More preferably, the material of the adhesive layer includes one or a combination of two or more of silica gel, acrylic glue, polyurethane, rubber, and polyisobutylene.
  5. 根据权利要求3或4所述的制备方法，其中，当所述高分子材质的掩膜版的厚度在200μm以下时，该高分子材质的掩模版在紫外光光源照射条件下的吸收系数≥20％、优选≥50％、更优选≥80％，其中，所述紫外光光源的波长为355±15nm；The preparation method according to claim 3 or 4, wherein, when the thickness of the polymer reticle is below 200 μm, the absorption coefficient of the polymer reticle under the irradiation condition of an ultraviolet light source is ≥20 %, preferably ≥ 50%, more preferably ≥ 80%, wherein the wavelength of the ultraviolet light source is 355±15nm;
    当所述高分子材质的掩模版的厚度在200μm以下时，所述高分子材质的掩模版在绿光光源照射条件下的吸收系数≥20％、优选≥50％、更优选≥80％，其中，所述绿光光源的波长为530±15nm；When the thickness of the reticle made of polymer material is below 200 μm, the absorption coefficient of the reticle made of polymer material under the irradiation condition of green light source is ≥20%, preferably ≥50%, more preferably ≥80%, wherein , the wavelength of the green light source is 530±15nm;
    当所述高分子材质的掩模版的厚度在200μm以下时，所述高分子材质的掩模版在红外光光源照射条件下的吸收系数≥20％、优选≥50％、更优选≥80％，其中，所述红外光光源的波长为1045±20nm。When the thickness of the polymer reticle is below 200 μm, the absorption coefficient of the polymer reticle under the irradiation conditions of an infrared light source is ≥20%, preferably ≥50%, more preferably ≥80%, wherein , the wavelength of the infrared light source is 1045±20nm.
  6. 根据权利要求4所述的制备方法，其中，所述粘性层在预设温度区间的剥离强度为1-50gf/cm，优选为5-40gf/cm，进一步优选为15-30gf/cm；其中，所述预设温度区间为15-30℃，优选为20-30℃，进一步优选为20-25℃。The preparation method according to claim 4, wherein, the peel strength of the adhesive layer in the preset temperature range is 1-50gf/cm, preferably 5-40gf/cm, more preferably 15-30gf/cm; wherein, The preset temperature range is 15-30°C, preferably 20-30°C, more preferably 20-25°C.
  7. 根据权利要求1-6任一项所述的制备方法，其中，所述基板表面具有导电层，所述图案化的高分子材质的掩模版固定于基板的导电层表面；The preparation method according to any one of claims 1-6, wherein the surface of the substrate has a conductive layer, and the patterned polymer mask is fixed on the surface of the conductive layer of the substrate;
    优选地，所述导电层包括TCO层、种子层、掺杂层中的一种或两种以上的叠层组合；Preferably, the conductive layer includes one of TCO layer, seed layer and doped layer or a combination of two or more stacked layers;
    更优选地，所述导电层包括TCO层和种子层的叠层组合，所述种子层为所述导电层的表层；其中，所述种子层的材料优选包括CuNi、Cu、Ni、NiCr、Cr、Ti、Ag中的一种或两种以上的组合；所述种子层的厚度优选为50nm-1000nm。More preferably, the conductive layer includes a stacked combination of a TCO layer and a seed layer, and the seed layer is the surface layer of the conductive layer; wherein, the material of the seed layer preferably includes CuNi, Cu, Ni, NiCr, Cr , Ti, Ag or a combination of two or more; the thickness of the seed layer is preferably 50nm-1000nm.
  8. 根据权利要求1-7任一项所述的制备方法，该制备方法还包括：The preparation method according to any one of claims 1-7, which further comprises:
    在生长出所需形状的金属电极后，除去所述图案化的高分子材质的掩模版；After growing the metal electrode of the desired shape, removing the mask plate of the patterned polymer material;
    优选地，当所述基板具有导电层且所述导电层包括种子层时，所述制备方法还包括在生长出所需形状的金属电极之后刻蚀去除所述种子层的操作；Preferably, when the substrate has a conductive layer and the conductive layer includes a seed layer, the preparation method further includes an operation of etching and removing the seed layer after growing a metal electrode of a desired shape;
    优选地，所述刻蚀的方法包括干法刻蚀和/或湿法刻蚀。Preferably, the etching method includes dry etching and/or wet etching.
  9. 一种太阳能电池金属电极，其是由权利要求1-8任一项所述的制备方法得到的。A solar cell metal electrode obtained by the preparation method described in any one of claims 1-8.
  10. 一种太阳能电池，其包括权利要求9所述的太阳能电池金属电极；A solar cell, comprising the solar cell metal electrode according to claim 9;
    所述太阳能电池包括晶硅太阳能电池。The solar cells include crystalline silicon solar cells.
PCT/CN2022/132622 2021-12-31 2022-11-17 Metal electrode of solar cell, preparation method therefor, and solar cell WO2023124614A1 (en)

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CN105390569A (en) * 2015-12-21 2016-03-09 浙江晶科能源有限公司 Manufacture method of positive electrode of solar cell
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CN102569506A (en) * 2011-12-29 2012-07-11 广东爱康太阳能科技有限公司 Method for preparing metal electrode of solar battery from silane mask
CN103137791A (en) * 2013-03-13 2013-06-05 中国科学院上海微系统与信息技术研究所 Preparing heterojunction solar cell method of combining wet process deposition with low temperature heat treatment
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