CN116344683A - Solar cell and preparation method thereof - Google Patents

Solar cell and preparation method thereof Download PDF

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CN116344683A
CN116344683A CN202310141036.0A CN202310141036A CN116344683A CN 116344683 A CN116344683 A CN 116344683A CN 202310141036 A CN202310141036 A CN 202310141036A CN 116344683 A CN116344683 A CN 116344683A
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membrane
seed layer
layer
treatment
solar cell
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陈旭辉
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Tongwei Solar Chengdu Co Ltd
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Tongwei Solar Chengdu Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
    • H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
    • 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
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    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
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    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—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
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0745—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
    • H01L31/0747—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
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Abstract

The present disclosure relates to a solar cell and a method of manufacturing the same. The preparation method comprises the following steps: depositing a seed layer on a solar cell substrate to obtain a membrane; performing oxide layer cleaning treatment on the membrane; performing antioxidation passivation treatment on the membrane; the film is subjected to a coating process, a printing process, a developing process, and an electroplating process to form a gate line on the surface of the film. Before the membrane is coated, the membrane is subjected to oxidation layer cleaning treatment to remove an oxidation layer on the surface of the membrane, and is subjected to antioxidation passivation treatment, namely, the membrane is subjected to hydrophobic and antioxidation treatment, so that the effects of protection and antioxidation can be achieved, and the seed layer is prevented from being heated and oxidized in the coating and drying process, so that the binding force between the seed layer substrate on the surface of the membrane and a mask material is enhanced, the problems of mask material drifting, pattern distortion, even photoresist collapse, diffusion plating after electroplating and the like caused by subsequent exposure and development of coating are improved, and the integrality of the seed layer is protected while the diffusion plating defects are reduced.

Description

Solar cell and preparation method thereof
Technical Field
The disclosure relates to the technical field of solar energy, in particular to a solar cell and a preparation method thereof.
Background
The energy source is mainly supplied by coal, petroleum and natural gas, and the energy source structure which excessively depends on fossil and non-renewable fuel has great negative environmental and economic effects. The large amounts of coal, natural gas, oil exploitation, transportation and combustion have caused significant environmental damage. The great development of solar renewable energy utilization technology is a necessary choice for ensuring the safety and sustainable development of future energy supply.
The current silver paste screen printing technology is the first choice for realizing the top grid electrode of the silicon heterojunction solar cell, namely, the reduction of the silver paste screen printing resistance and the thinning of metal wires still have difficulty, so that the aims of high efficiency and low cost of the solar cell are also difficult to realize. The advantages of better plasticity, smaller metal wire resistance, less shading loss, lower cost and the like of the copper metallized electrode are considered to break through the bottleneck of the silk screen technology, and effective attempt of improving carrier collection is a research hot spot of solar cell metallization. The direct electroplating of the metal electrode on the transparent conductive film is non-selective, and the adhesiveness between the directly electroplated metal and the transparent conductive film is poor, so that the manufacturing requirement of the solar cell module is difficult to meet, and therefore, a copper seed layer needs to be deposited on the transparent conductive film, and a patterned mask is used for realizing selective deposition and enhancing the adhesion of the electroplated grid line.
However, the adhesion force between the mask material and the copper seed layer is not negligible, the copper seed layer after sputtering is exposed in the air and oxidized by oxygen in the air to generate copper oxide, and impurities such as organic matters and dust are possibly attached to the surface of the copper seed layer after exposure in the air, so that the adhesion between the copper seed layer and the photoresist is poor. The subsequent printing and developing results in photoresist being easy to collapse and even fall off due to the fact that photoresist is punched by developing solution or deionized water in the developing process, so that developed patterns are distorted, coating quality is further affected in the electroplating process, uneven thickness of the seepage plating is caused, printing and developing after coating are seriously affected, yield of a production line is seriously affected, and testing efficiency of a battery piece is greatly affected.
Disclosure of Invention
The present disclosure provides a solar cell and a method for manufacturing the same, which solve at least some of the problems in the related art.
In a first aspect, an embodiment of the present disclosure provides a method for manufacturing a solar cell, the method including:
depositing a seed layer on a solar cell substrate to obtain a membrane;
performing oxide layer cleaning treatment on the membrane;
performing antioxidation passivation treatment on the membrane;
and coating, printing, developing and electroplating the membrane to form grid lines on the surface of the membrane.
Optionally, the seed layer includes a copper seed layer, and the performing an oxide layer cleaning treatment on the membrane includes:
immersing the membrane in a low concentration acidic solution;
and performing first processing treatment to remove the oxide layer on the surface of the membrane.
Optionally, the low-concentration acidic solution comprises a hydrochloric acid solution, and the hydrochloric acid solution is initially proportioned by hydrochloric acid with the concentration of 45% -50% and pure water according to the volume concentration ratio of 1:20-1:25.
Optionally, the first processing is performed according to a first processing parameter, where the first processing parameter includes: the soaking temperature is 30-35 ℃ and the soaking time is 90-115 s.
Optionally, the seed layer includes a copper seed layer, and the performing oxidation-resistant passivation treatment on the membrane includes:
immersing the membrane in a passivation solution;
and performing a second processing treatment to form a hydrophobic passivation film on the surface of the membrane.
Optionally, the second processing is performed according to a second processing parameter, the second processing parameter including: the soaking temperature is 40-60 ℃ and the soaking time is 15-30 s; and/or
The thickness of the hydrophobic passivation film is 40-50 angstroms.
Optionally, the seed layer includes a copper seed layer, and before the oxide layer cleaning treatment is performed on the membrane, the method further includes:
and carrying out oil removal treatment on the membrane.
Optionally, the degreasing treatment is performed on the membrane, including:
soaking the membrane in an oil removing solution;
and executing a third processing treatment to remove greasy dirt on the surface of the membrane.
Optionally, the degreasing solution is prepared by using a degreasing agent and pure water according to a volume concentration ratio of 4:96-7:93.
Optionally, the third processing is performed according to a third processing parameter, the third processing parameter including: the soaking temperature is 25-35 ℃ and the soaking time is 90-120 s.
In a second aspect, embodiments of the present disclosure provide a solar cell obtained according to the method of manufacturing of the first aspect.
The technical scheme provided by the embodiment of the disclosure can comprise the following beneficial effects:
according to the preparation method of the solar cell, before the membrane is subjected to coating treatment, the oxidation layer is cleaned on the membrane to remove the oxidation layer on the surface of the membrane, and the membrane is subjected to antioxidation passivation treatment, namely, the substrate is subjected to hydrophobicity and antioxidation treatment, so that the protection and antioxidation effects can be achieved, the seed layer is prevented from being heated and oxidized in the coating and drying process, the binding force between the seed layer substrate on the surface of the membrane and a mask material is enhanced, the problems of mask material drift, pattern distortion, even photoresist collapse, diffusion plating after electroplating and the like caused by subsequent exposure and development of the coating are improved, and the integrity of the seed layer is protected while the diffusion plating defect is reduced.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure.
Fig. 1 is a schematic structural view of a solar cell according to an exemplary embodiment of the present disclosure.
Fig. 2 is a flow chart of a method of manufacturing a solar cell according to an exemplary embodiment of the present disclosure.
Fig. 3 is a flow chart detailing a method of fabricating a solar cell according to an exemplary embodiment of the present disclosure.
Fig. 4 is a flow chart detailing a method of fabricating a solar cell according to an exemplary embodiment of the present disclosure.
Fig. 5 is a flow chart detailing a method of fabricating a solar cell according to an exemplary embodiment of the present disclosure.
Fig. 6 is a graph of poor permeation improvement of a solar cell employing a method of manufacturing a solar cell according to an exemplary embodiment of the present disclosure.
Fig. 7 is a graph of efficiency improvement of a solar cell employing a method of manufacturing a solar cell according to an exemplary embodiment of the present disclosure.
Fig. 8 is a detailed flowchart of a method of manufacturing a solar cell according to an exemplary embodiment of the present disclosure.
Wherein, 90-N type silicon chip; 91-a first intrinsic amorphous silicon layer; 92-N type amorphous silicon film layer; 93-a first transparent conductive film layer; 94-a second intrinsic amorphous silicon layer; a 95-P type amorphous silicon film layer; 96-a second transparent conductive film layer; 97-seed layer; 98-grid line; 99-protective layer.
Detailed Description
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. Rather, they are merely examples of apparatus and methods consistent with some aspects of the present disclosure as detailed in the accompanying claims.
In order to better understand the technical scheme of the present disclosure, the following describes the solar cell of the present disclosure and the preparation method thereof in detail with reference to the accompanying drawings. The features of the following examples and embodiments may be combined with each other without conflict.
The embodiments of the present disclosure provide a solar cell, which may be obtained according to the method of manufacturing a solar cell of the embodiments of the present disclosure, and the solar cell may include a solar cell substrate, and a seed layer, a gate line, and a protective layer deposited on the solar cell substrate. The solar cell may be a copper interconnect (THL) crystalline silicon Heterojunction (HJT) solar cell.
Referring to fig. 1, the solar cell, for example, an N-type crystalline silicon heterojunction solar cell, may include: an N-type silicon wafer 90, a first intrinsic amorphous silicon layer 91 sequentially deposited on the front surface of the N-type silicon wafer 90, N
The amorphous silicon thin film layer 92 (i.e., an N-type doped layer) and the first transparent conductive thin film layer 93, the second intrinsic amorphous silicon layer 94, the P-type amorphous silicon thin film layer 95 (i.e., a P-type doped layer) and the second transparent conductive thin film layer 96 sequentially deposited on the back surface of the N-type silicon wafer 90, and the seed layer 97, the gate line 98 and the protective layer 99 formed on the first transparent conductive thin film layer 93 and the second transparent conductive thin film layer 96. The first transparent conductive film layer 93 and the second transparent conductive film layer 96 may be TCO transparent conductive oxide film layers (hereinafter referred to as ITO conductive films) using ITO (indium tin oxide) materials. The seed layer 97 may be a copper seed layer and the gate line 98 may be a copper gate line forming a copper interconnect crystalline silicon heterojunction solar cell. Seed layer 97 may be deposited by PVD physical vapor deposition. Of course, the seed layer 97 may be a seed layer made of another material, and the gate line 98 may be a gate line made of another material. The protective layer 99 may be a tin protective layer or a protective layer made of other materials. It should be noted that, the solar cell may be a P-type crystalline silicon heterojunction solar cell, and may include: the semiconductor device comprises a P-type silicon wafer, a first intrinsic amorphous silicon layer, a P-type amorphous silicon film layer (i.e. a P-type doped layer) and a first transparent conductive film layer which are sequentially deposited on the front surface of the P-type silicon wafer, a second intrinsic amorphous silicon layer, an N-type amorphous silicon film layer (i.e. an N-type doped layer) and a second transparent conductive film layer which are sequentially deposited on the back surface of the P-type silicon wafer, and a seed layer, a grid line and a protective layer which are formed on the first transparent conductive film layer and the second transparent conductive film layer.
The solar cell takes a copper interconnection N-type crystalline silicon heterojunction solar cell as an example, and the preparation process comprises the following steps: firstly, performing texturing and cleaning treatment on an N-type monocrystalline silicon wafer to obtain an N-type silicon wafer 90, then depositing a first intrinsic amorphous silicon layer 91 and an N-type amorphous silicon film layer 92 on the front surface of the N-type silicon wafer 90, depositing a second intrinsic amorphous silicon layer 94 and a P-type amorphous silicon film layer 95 on the back surface of the N-type silicon wafer 90, and then depositing a first intrinsic amorphous silicon layer 91 and an N-type amorphous silicon film layer 95 on the back surface of the N-type silicon wafer 90
A first transparent conductive film layer 93 is plated on the amorphous silicon film layer 92, and a second transparent conductive film layer 96 is plated on the second intrinsic amorphous silicon layer 94 and the P-type amorphous silicon film layer 95. Then, copper seed layers 97 are plated on the first transparent conductive film layer 93 and the second transparent conductive film layer 96, respectively, to obtain Huang Mopian (note that a semi-finished product obtained by depositing a copper seed layer is called a yellow film, and a semi-finished product obtained by depositing a seed layer of another material may be called a film of another name). And then, a grid line pattern is formed on the copper seed layer 97 by using technologies such as coating, laser printing, exposure and development, electroplating and the like, and finally, the copper seed layer 97 is electroplated with a copper grid line 98 and a tin protective layer 99 in copper electroplating solution and tin electroplating solution respectively through electrolytic cell effect.
In general, copper seed layer after sputtering is exposed to air and oxidized by oxygen in air to generate copper oxide, and impurities such as organic matters and dust (among these impurities, copper oxide is also the most dominant impurity) may be attached to the surface of copper seed layer, since copper oxide is a hydrophilic polar molecule, the larger the surface roughness is, the smaller the contact area is when contacting with photoresist, further the solvent and resin components are mainly nonpolar molecules in photoresist, and water molecules in air are adsorbed on the surface of substrate to form-OH on the surface of substrate, and finally polar molecules are formed, so the adhesiveness with photoresist is poor. The subsequent printing and developing results in photoresist being easy to collapse or even fall off due to the fact that photoresist is punched by developing solution or deionized water in the developing process, so that pattern distortion is caused, coating quality is further influenced in the electroplating process, uneven thickness of the coating is caused, printing and developing after coating are seriously influenced, yield of a production line is seriously influenced, shading area of a grid line is increased due to uneven thickness of the coating, and Isc (short circuit current) is reduced, so that testing efficiency of a battery piece is greatly influenced.
The embodiment of the disclosure provides a preparation method of a solar cell, which can be used for preparing the solar cell. Referring to fig. 2, the preparation method includes steps S1 to S4:
step S1: and depositing a seed layer on the solar cell substrate to obtain the membrane.
Step S2: and performing oxide layer cleaning treatment on the membrane.
Step S3: and performing antioxidation passivation treatment on the membrane.
Step S4: and coating, printing, developing and electroplating the membrane to form grid lines on the surface of the membrane. Alternatively, the seed layer may be a copper seed layer, and the gate line may be a copper gate line, so as to form a copper-interconnection crystalline silicon heterojunction solar cell, which will be described below by taking the copper-interconnection crystalline silicon heterojunction solar cell as an example. The seed layer may be deposited by PVD physical vapor deposition. Of course, the seed layer may be a seed layer made of other materials, and the gate line may be a gate line made of other materials. It should be noted that, the semi-finished product obtained by depositing the copper seed layer may be referred to as a yellow film, and the semi-finished product obtained by depositing the seed layer of other materials may be referred to as a film of other names. Furthermore, a protective layer can be further prepared on the surface of the grid line to protect the grid line. The protective layer can be a tin protective layer or a protective layer made of other materials.
According to the technical scheme, before the membrane is coated, the oxidation layer on the surface of the membrane is removed by the oxidation layer cleaning treatment, the oxidation-resisting passivation treatment is carried out on the membrane, namely the hydrophobic and oxidation-resisting treatment is carried out on the substrate, so that the effects of protection and oxidation prevention can be achieved, the copper seed layer is prevented from being heated and oxidized in the coating and drying process, the binding force between the copper seed layer substrate on the surface of the membrane and a mask material is enhanced, the problems of mask material drifting, pattern distortion, even photoresist collapse, diffusion plating after electroplating and the like caused by subsequent exposure and development of the coating are solved, and the integrity of the copper seed layer is protected while the diffusion plating defect is reduced.
In some alternative embodiments, the solar cell may be an N-type crystalline silicon heterojunction solar cell with copper interconnect, and the solar cell substrate may include: the semiconductor device comprises an N-type silicon wafer, a first intrinsic amorphous silicon layer, an N-type amorphous silicon film layer (namely an N-type doped layer) and a first transparent conductive film layer which are sequentially deposited on the front surface of the N-type silicon wafer, and a second intrinsic amorphous silicon layer, a P-type amorphous silicon film layer (namely a P-type doped layer) and a second transparent conductive film layer which are sequentially deposited on the back surface of the N-type silicon wafer. And S1, depositing a seed layer on a solar cell substrate to obtain a membrane. The N-type monocrystalline silicon wafer may be subjected to a texturing and cleaning treatment to obtain an N-type silicon wafer 90, then a first intrinsic amorphous silicon layer 91 and an N-type amorphous silicon thin film layer 92 are deposited on the front surface of the N-type silicon wafer 90, a second intrinsic amorphous silicon layer 94 and a P-type amorphous silicon thin film layer 95 are deposited on the back surface of the N-type silicon wafer 90, then a first transparent conductive thin film layer 93 is plated on the first intrinsic amorphous silicon layer 91, and a second transparent conductive thin film layer 96 is plated on the second intrinsic amorphous silicon layer 94. Then, seed layers 97 are respectively plated on the first transparent conductive film layer 93 and the second transparent conductive film layer 96 to obtain a membrane. It should be noted that, the solar cell may also be a P-type crystalline silicon heterojunction solar cell, and the solar cell substrate may include: the semiconductor device comprises a P-type silicon wafer, a first intrinsic amorphous silicon layer, a P-type amorphous silicon film layer (namely a P-type doped layer) and a first transparent conductive film layer which are sequentially deposited on the front surface of the P-type silicon wafer, and a second intrinsic amorphous silicon layer, an N-type amorphous silicon film layer (namely an N-type doped layer) and a second transparent conductive film layer which are sequentially deposited on the back surface of the P-type silicon wafer.
Referring to fig. 3, in some alternative embodiments, the seed layer includes a copper seed layer, and step S2, performing an oxide layer cleaning treatment on the membrane may further include steps S21 to S22:
step S21: the membrane is immersed in a low concentration acidic solution.
Step S22: and performing first processing treatment to remove the oxide layer on the surface of the membrane. It will be appreciated that removal of the oxide layer (typically copper oxide) from the copper seed layer surface of the diaphragm is more advantageous for subsequent operations. Optionally, the low-concentration acidic solution comprises a hydrochloric acid solution, and the hydrochloric acid solution is initially proportioned by hydrochloric acid with the concentration of 45% -50% and pure water according to the volume concentration ratio of 1:20-1:25. Further, the first processing may be performed according to a first processing parameter, which may include: the soaking temperature is 30-35 ℃ and the soaking time is 90-115 s.
In general, the deoxidized copper process directly uses high-concentration sulfuric acid for reaction cleaning, and besides copper oxide, partial stripping reaction of a copper seed layer (90-100 nm) can be caused, so that the quality of copper seeds is seriously affected, and meanwhile, oxidizing acids such as sulfuric acid, nitric acid and the like can perform oxidation reaction on an ITO transparent conductive film at the bottom of the copper seed layer, so that oxygen vacancies of the ITO transparent conductive film are reduced, the conductivity of the ITO film layer is deteriorated, and poor ohmic contact between a copper grid line and a blue film silicon substrate is produced in the later stage. Therefore, the copper oxide layer on the surface of the membrane is pickled by adopting the low-concentration hydrochloric acid solution, and the problems can be effectively avoided.
Referring to fig. 4, in some alternative embodiments, the seed layer includes a copper seed layer, and step S3, performing an oxidation passivation treatment on the membrane may further include steps S31 to S32:
step S31: the membrane is immersed in a passivating solution.
Step S32: and performing a second processing treatment to form a hydrophobic passivation film on the surface of the membrane. It can be appreciated that the hydrophobic passivation film is more beneficial to subsequent operations, namely, the hydrophobic passivation film is formed on the surface of the seed layer of the membrane. Optionally, the second processing may be performed according to a second processing parameter, which may include: the soaking temperature is 40-60 ℃ and the soaking time is 15-30 s. The hydrophobic passivation film may have a thickness of 40 to 50 angstroms.
Typically, the film is coated on both sides and dried, and the coating process is performed in the following sequence: the film P surface coating, P surface drying, N surface coating and N surface drying are carried out, and when the P surface is dried, the N surface copper seed layer is not protected by photoresist, and is made of pure copper with the purity of 99.99 percent, so that the purity is higher, and oxygen, ozone and CO in the air are easy to be carried out in a heating environment 2 And H 2 O forms an oxide layer and a patina-like compound, so that the sputtered copper seed layer is exposed to airCan be oxidized and combined to generate copper oxide and compound, and simultaneously, organic matters, dust and other impurities can be attached to the surface of the copper seed crystal layer when the copper seed crystal layer is exposed in the air, and the subsequent process production can be influenced. Among these impurities, copper oxide is again the predominant impurity. And the bottom copper exposed out of the groove is easy to oxidize in the wet developing process, and the binding force of a plating layer is influenced in the subsequent electroplating process, so that broken grids and grid lines are separated. The chemical reaction formula of copper and substances in the air is as follows:
2Cu+O 2 ＝2CuO；
3Cu+O 3 ＝3CuO；
2Cu+CO 2 +H 2 O+O 2 ＝Cu 2 (OH)2CO 3 (basic copper carbonate, commonly known as patina);
therefore, the method can prevent the copper seed layer from being oxidized and prevent the copper seed layer from being heated and oxidized in the coating and drying process by performing the antioxidation passivation treatment on the membrane before electroplating. Specifically, after the membrane is pickled by low-concentration acidic solution, the oxidation-resistant passivation treatment process comprises the steps of passivating copper by using a copper passivating agent and an additional formula thereof, and protecting and anti-oxidizing a compact hydrophobic passivation film formed on the surface of copper by using a liquid medicine, wherein the liquid medicine comprises MSD-899 environment-friendly copper passivating agent, and the main components comprise benzotriazole, sodium benzoate, absolute ethyl alcohol, sodium tripolyphosphate and a surfactant. The main mechanism is BTA (benzene propane triazole, C6H5N 3) and BTA induced fatty acid amide compound, and the alkyl amide corrosion inhibitor forms a stable protective film with stronger protective effect on the surfaces of copper and copper alloy.
In some alternative embodiments, the seed layer includes a copper seed layer, and before the oxide layer cleaning treatment is performed on the membrane, the method may further include the steps of: and (3) carrying out oil removal treatment on the membrane to remove greasy dirt on the surface of the membrane.
Referring to fig. 5, the degreasing treatment of the membrane may include steps S01-02:
step S01: the membrane is immersed in an oil removal solution.
Step S02: and executing a third processing treatment to remove greasy dirt on the surface of the membrane. It will be appreciated that degreasing, i.e. degreasing, of the copper seed layer surface of the membrane is more advantageous for subsequent operations. Optionally, the degreasing solution is prepared by using a degreasing agent and pure water according to a volume concentration ratio of 4:96-7:93. Further, the third processing may be performed according to a third processing parameter, the third processing parameter including: the soaking temperature is 25-35 ℃ and the soaking time is 90-120 s.
According to the preparation method of the solar cell, after the film is formed by depositing the copper seed layer and before the coating process, the film is subjected to oxide layer cleaning treatment so as to achieve the effect of removing copper oxide, the copper seed layer is subjected to antioxidation passivation treatment, and then the baking process of the photoresist is optimized, so that the adhesion between the photoresist and the copper seed layer is better.
Compared with the prior art, the bonding force and the adhesive force of the photoresist and the copper seed layer can be obviously improved, the degree of pattern distortion after coating, printing and developing until electroplating, film removing and back etching is small, the grid line is good in appearance, the shading area is reduced, and the battery efficiency is improved by 0.12%. The film oxide layer and the compound are greatly reduced, the cleanliness is higher, the shading area is reduced, the Isc (short circuit current) and the FF (filling factor) are improved, and meanwhile, the abnormal phenomenon that the copper seed layer is subjected to secondary oxidation in the coating and developing process and the integrity of the grid line is influenced in the subsequent electroplating process is avoided. As shown in fig. 6 and 7, the poor appearance of the diffusion coating can be reduced, the efficiency can be improved, wherein the poor diffusion coating proportion can be reduced from 36.66% to 10.26%, and the reduction is 72.01%. The proportion of broken gate is reduced from 15% to 3.5%.
Referring to fig. 8, the process flow of the solar cell of the present disclosure may mainly include: the preparation method comprises the steps of preparing a membrane, removing oil, cleaning an oxide layer, performing antioxidation treatment, coating, printing, developing, wrapping, electroplating, removing a film, back etching, injecting light, and testing and sorting. The degreasing, oxide layer cleaning and antioxidation treatment can be regarded as a pretreatment process before the coating process, and the pretreatment can specifically include: deoiling, water washing, oxide layer cleaning, water washing, drying, antioxidation treatment, pure water washing, drying, and the dried membrane battery piece can enter the next process (namely the coating process) for production.
In the following, a method for manufacturing a solar cell of the present disclosure will be described in detail, taking a copper-interconnection N-type crystalline silicon heterojunction solar cell as an example.
First, as shown in fig. 1, an N-type monocrystalline silicon wafer is subjected to a texturing cleaning treatment to obtain an N-type silicon wafer 90, then a first intrinsic amorphous silicon layer 91 and an N-type amorphous silicon thin film layer 92 are deposited on the front surface of the N-type silicon wafer 90, a second intrinsic amorphous silicon layer 94 and a P-type amorphous silicon thin film layer 95 are deposited on the back surface of the N-type silicon wafer 90, then a first transparent conductive thin film layer 93 is plated on the first intrinsic amorphous silicon layer 91, and a second transparent conductive thin film layer 96 is plated on the second intrinsic amorphous silicon layer 94. Then, a seed layer 97 is copper-plated on the first transparent conductive film layer 93 and the second transparent conductive film layer 96, respectively, to obtain a film sheet.
Then, a total of 200pcs (pieces) of solar cells of 2 baskets were produced at a time using a first tank having a volume of 150 to 180L. Firstly, an oil removing agent (which can be a clean oil removing agent SF-99001) and pure water (which can be deionized pure water and H2O) are used for carrying out initial proportioning according to the volume concentration ratio of 4-7:96-93 to obtain an oil removing solution, and then the membrane is soaked in the oil removing solution for oil removing treatment, wherein the soaking temperature can be set to be 25-35 ℃, and the soaking time can be set to be 90-120 s.
The oil removing solution is an acid copper oil removing agent, and the formula comprises sodium hydroxide, sodium carbonate, triethanolamine, sodium tripolyphosphate, sodium pyrophosphate, lauric acid diethanolamide, fluoride, water and the like, wherein the fluoride is the most commonly used penetrating agent in the acid oil removing agent, and the oil removing effect can be obviously enhanced by adding the fluoride. The oil removing principle is that the surfactant and the builder are comprehensively reflected in wetting, penetrating, emulsifying and dispersing and dissolving effects, hydrophilic groups and lipophilic groups in the molecular structure of the surfactant are utilized to be adsorbed on the interface between the oil stain and the solution, the hydrophilic groups point to the solution, the lipophilic groups point to the oil stain, and the surfactant are directionally arranged, so that the interfacial tension of oil-liquid is greatly reduced.
And then placing the membrane into a second tank for deionized water bubbling cleaning for 30-50 s, and removing residual particulate matters and part of the liquid medicine.
Further, a total of 200pcs (pieces) of solar cells of 2 baskets can be produced at a time using a third tank having a volume of 150 to 180L. Hydrochloric acid (HCL) with concentration of 45-50% and deionized pure water (H) are firstly used 2 O) carrying out initial proportioning according to the volume concentration ratio of 1:20-25 to obtain a low-concentration hydrochloric acid solution, then soaking the membrane in the hydrochloric acid solution for oxide layer cleaning treatment, wherein the soaking temperature can be set to be 30-35 ℃, and the soaking time can be set to be 90-115 s. The reaction of dilute hydrochloric acid and copper oxide is utilized to remove some metal oxides, and the reaction mechanism is as follows:
Cu 2 (OH) 2 CO 3 +4HCl＝2CuCl 2 +3H 2 O+CO 2 ↑；
CuO+2HCL＝CuCl 2 +H 2 O；
and then placing the membrane into a fourth tank for deionized water bubbling cleaning for 4 times, wherein the cleaning time can be set to 30s each time, and residual particulate matters and part of liquid medicine are removed. After washing, the membrane is put into a fifth groove (namely a drying groove) for drying, and the drying temperature can be set to be 50-65 ℃. Drying with nitrogen and drainage.
Further, a total of 200pcs (chips) of solar cells of 2 baskets can be produced at a time by using a sixth tank having a volume of 150 to 180L. MSD-899 environment-friendly copper passivating agent is used, the proportion is 100% of stock solution to obtain passivating solution, the membrane is soaked in the passivating solution to perform antioxidation passivating treatment, the copper seed layer is subjected to antioxidation treatment, and a hydrophobic passivating film Cu (C) is formed on the surface of the copper seed layer of the membrane 6 H 4 N 3 ) 2 . The soaking temperature can be set to 40-60 ℃ and the soaking time can be set to 15-30 s.
The main reaction mechanism is as follows: cu+2HC 6 H 4 N 3 →Cu(C 6 H 4 N 3 ) 2 +H2↑；
Wherein Cu (C) 6 H 4 N 3 ) 2 Is a compact passivation film with the thickness of about 40-50 angstroms, and the chelating polymer is extremely stable and is difficult to be corroded and destroyed, thus having good anti-discoloration effect and being betterGood metallic luster is maintained and the conductivity of the copper seed layer is hardly affected.
And then placing the membrane into a seventh groove for deionized water bubbling cleaning for 4 times, wherein the cleaning time can be set to be 30 seconds each time, and removing residual liquid medicine. Finally, the membrane is put into an eighth groove (namely a drying groove), and the membrane is dried by drying nitrogen, wherein the drying temperature can be set to 75-85 ℃.
According to the technical scheme, the film of the solar cell is subjected to reaction and cleaning through the pretreatment process flow and the corresponding process formula, so that the surface oxide layer, metal particle impurities, dust impurities and organic matters are completely removed, and the copper seed layer is subjected to antioxidation treatment, so that the adhesion between the copper seed layer and photoresist is greatly improved, and the abnormal phenomenon of diffusion plating caused by the fact that the photoresist drifts, collapses and plating solution goes deep during electroplating due to the fact that the substrate is not firmly adhered with the photoresist after coating, printing and developing is solved. The surface cleanliness of the membrane is improved, the copper seed layer is prevented from being secondarily oxidized in the coating and developing process, the abnormal phenomenon affecting the integrity of the grid line in the subsequent electroplating process is avoided, and the efficiency and yield of the battery piece are greatly improved.
Then, the membrane after the pretreatment procedure is subjected to edge wrapping treatment, four edges and edge positions of the membrane are wrapped by edge wrapping glue, the width of the edge wrapping glue is less than or equal to 50um, and the thickness of the edge wrapping glue is 10-15 um. And then coating the film with photoresist, and covering the copper oxide leaked from the film completely, wherein the thickness of the photoresist is controlled to be 10-15 um. And then laser printing is carried out, and the established pattern is printed on the photosensitive film according to the designed grid line pattern, so that the photosensitive film is sensitive to the light and can be differentiated from the region which is not sensitive to the light. And then developing, and cleaning and removing the photosensitive photoresist area by using an alkaline solution to expose the copper oxide film layer at the bottom layer. And then electroplating, namely firstly carrying out degreasing pretreatment by using 5% sodium bicarbonate solution, further electroplating copper grid lines in a copper sulfate electroplating solution, wherein the height of the copper grid lines is controlled to be 8-10 um, and electroplating tin grid lines in a tin methylsulfonate electroplating solution, wherein the height of the tin grid lines is controlled to be 2-4 um. And then performing film removal and back etching treatment, firstly removing all photoresist and mask materials in alkaline (NaOH, KOH and the like) solution, secondly removing a copper seed layer and a copper oxide film layer in a non-grid line area in dilute sulfuric acid solution, and finally leaving only grid lines on the surface of the ITO conductive film. And then carrying out light injection treatment on the cell after film removal and back etching, wherein the light injection temperature can be set to be 200-220 ℃ and the time is 60-120 s. And finally, manufacturing the battery piece and testing the combination force of the battery grid line.
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosed technology. This disclosure is intended to cover any adaptations, uses, or adaptations of the disclosure following the general principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
It is to be understood that the present disclosure is not limited to the precise arrangements and instrumentalities shown in the drawings, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the present disclosure is limited only by the appended claims.

Claims (11)

1. A method of manufacturing a solar cell, comprising:
depositing a seed layer on a solar cell substrate to obtain a membrane;
performing oxide layer cleaning treatment on the membrane;
performing antioxidation passivation treatment on the membrane;
and coating, printing, developing and electroplating the membrane to form grid lines on the surface of the membrane.
2. The method of claim 1, wherein the seed layer comprises a copper seed layer, and wherein the performing an oxide layer cleaning process on the membrane comprises:
immersing the membrane in a low concentration acidic solution;
and performing first processing treatment to remove the oxide layer on the surface of the membrane.
3. The preparation method according to claim 2, wherein the low-concentration acidic solution comprises a hydrochloric acid solution, and the hydrochloric acid solution is initially proportioned by using 45% -50% hydrochloric acid and pure water according to a volume concentration ratio of 1:20-1:25.
4. The method of manufacturing according to claim 2, wherein the first processing is performed according to a first processing parameter comprising: the soaking temperature is 30-35 ℃ and the soaking time is 90-115 s.
5. The method of claim 1, wherein the seed layer comprises a copper seed layer, and wherein the oxidation-resistant passivation of the membrane comprises:
immersing the membrane in a passivation solution;
and performing a second processing treatment to form a hydrophobic passivation film on the surface of the membrane.
6. The method of manufacturing according to claim 5, wherein the second processing is performed according to a second processing parameter, the second processing parameter comprising: the soaking temperature is 40-60 ℃ and the soaking time is 15-30 s; and/or
The thickness of the hydrophobic passivation film is 40-50 angstroms.
7. The method of claim 1, wherein the seed layer comprises a copper seed layer, and wherein the step of performing an oxide layer cleaning treatment on the membrane further comprises:
and carrying out oil removal treatment on the membrane.
8. The method of manufacturing according to claim 7, wherein the degreasing treatment of the membrane sheet comprises:
soaking the membrane in an oil removing solution;
and executing a third processing treatment to remove greasy dirt on the surface of the membrane.
9. The preparation method of claim 8, wherein the degreasing solution is prepared by using a degreasing agent and pure water according to a volume concentration ratio of 4:96-7:93.
10. The method of manufacturing according to claim 8, wherein the third processing is performed according to a third processing parameter, the third processing parameter comprising: the soaking temperature is 25-35 ℃ and the soaking time is 90-120 s.
11. Solar cell, characterized in that it is obtained according to the preparation method of any one of claims 1 to 10.
CN202310141036.0A 2023-02-20 2023-02-20 Solar cell and preparation method thereof Pending CN116344683A (en)

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