CN112397610A - Solar cell electrode printing method - Google Patents
Solar cell electrode printing method Download PDFInfo
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- CN112397610A CN112397610A CN202011129546.9A CN202011129546A CN112397610A CN 112397610 A CN112397610 A CN 112397610A CN 202011129546 A CN202011129546 A CN 202011129546A CN 112397610 A CN112397610 A CN 112397610A
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- 238000000034 method Methods 0.000 title claims abstract description 72
- 238000007639 printing Methods 0.000 title claims abstract description 62
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 172
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 171
- 239000010703 silicon Substances 0.000 claims abstract description 171
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 65
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000003513 alkali Substances 0.000 claims abstract description 46
- 238000005498 polishing Methods 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 125000004437 phosphorous atom Chemical group 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 5
- 230000005684 electric field Effects 0.000 abstract description 6
- 239000002002 slurry Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 27
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- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000001816 cooling Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000007888 film coating Substances 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
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- 239000011241 protective layer Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a solar cell electrode printing method, which comprises the following steps: cleaning, texturing, diffusing, laser doping, oxidizing, removing a back oxide layer, alkali polishing, coating, laser grooving and printing, wherein a silicon nitride film is coated on the surface of a silicon wafer during coating, and the thickness of the back silicon nitride film is 70-80 nm; the method comprises the steps of carrying out laser grooving on the back of a silicon wafer to obtain positioning points, enabling the vertical distance from the highest point of a melting protrusion of each positioning point to the back of the silicon wafer to be not more than 10 microns, and enabling a printer for printing electric field slurry on the back of the silicon wafer to adopt a red light lamp.
Description
Technical Field
The invention relates to the technical field of solar cell production, in particular to a solar cell electrode printing method.
Background
With the rapid development of the crystalline silicon battery technology, the alkali polishing technology has been popularized comprehensively, and the advantages of the alkali polishing technology include: 1. the reflectivity of the back surface is improved, long wave absorption is increased, meanwhile, the passivation effect of the back surface alumina and the silicon nitride is better, and the current and the open voltage of the battery are improved; 2. the sodium hydroxide is used for replacing HF and nitric acid, the treatment cost of fluorine and nitrogen in sewage is saved, the alkali polishing cost is only 25% of that of acid polishing, and the environment is protected.
The alkali polishing principle is as follows: and silicon oxide is used as a protective layer on the front surface of the silicon wafer, and high-concentration alkali (25% -40%) is used for polishing the back surface of the silicon wafer to form a smooth back surface. Because the reflectivity of the back of the silicon wafer after alkali polishing is improved to 53% from 26% (wet etching method), if the original power is still adopted for laser grooving, the abnormal phenomenon that the film opening is incomplete and the aluminum grid line and the silicon substrate cannot form good ohmic contact can occur to light spots with the same power in the grooving process, so that the contact of the battery needs to be ensured by increasing the laser power so as to improve the back contact.
However, after the power is increased, the positioning points are deeper, local unevenness is generated by ablation of the positioning points, so that a screen of a back printing machine for printing electric field slurry on the back is damaged, the service life of the screen is seriously influenced, and meanwhile, the hidden crack probability of a finished battery is increased due to the excessively deep positioning points, so that the fragment rate of the battery and the satisfaction degree of a customer are influenced.
Therefore, a method for printing the electrode of the solar cell, which is suitable for the alkali polishing process and can effectively protect equipment and improve the quality of the cell, is required to be found.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a solar cell electrode printing method, and the solar cell printed by the method has the advantages that the fragment rate of the cell is low, and the service life of a printing screen plate can be effectively prolonged.
In order to solve the technical problems, the invention provides the following technical scheme:
a solar cell electrode printing method comprises the following steps:
cleaning and texturing the surface of the silicon wafer by using an alkali solution;
introducing a phosphorus source to diffuse on the surface of the silicon wafer after texturing to prepare a PN junction;
doping phosphorus on the surface of the diffused silicon wafer into the silicon wafer by using laser to form a local heavily doped region;
oxidizing the doped silicon wafer by using oxygen to form a front-side oxide layer on the front side of the silicon wafer;
cleaning the back of the silicon wafer by using an HF solution to remove a back oxide layer;
carrying out alkali polishing treatment on the back of the silicon wafer after the back oxide layer is removed by using an alkali solution;
plating a silicon nitride film on the surface of the silicon wafer after the alkali polishing treatment, wherein the thickness of the silicon nitride film on the back of the silicon wafer is 70-80 nm;
carrying out laser grooving on the back of the silicon wafer to obtain a positioning point, wherein the vertical distance from the highest point of a melting bulge of the positioning point to the back of the silicon wafer is not more than 10 micrometers;
and printing the back of the grooved silicon wafer, wherein the corresponding printing machine adopts a red light lamp.
In a preferred embodiment, the vertical distance from the highest point of the melting bulge of the positioning point to the back surface of the silicon wafer is 2-8 μm.
In a preferred embodiment, when plate PECVD is used for coating, the alkali-polished silicon wafer surface is coated with a silicon nitride film, which includes:
and plating a silicon nitride film on the surface of the silicon wafer subjected to alkali polishing in a plate PECVD (plasma enhanced chemical vapor deposition), wherein the strip speed is set to be 250 +/-15 cm/min, and the thickness of the silicon nitride film on the back of the silicon wafer is 70-80 nm.
In a preferred embodiment, when the tubular PECVD is used for coating, the alkali-polished silicon wafer surface is coated with a silicon nitride film, which comprises:
setting the special gas flow in the tubular PECVD as follows: when the bottom layer film is plated, the ammonia gas flow rate is 5300-6000sccm, and the silane flow rate is 580-780 sccm; when the middle layer film is plated, the flow rate of ammonia gas is 5500-6200sccm, and the flow rate of silane is 1200-1400 sccm; when the upper layer film is plated, the flow rate of ammonia gas is 5800-6500sccm, the flow rate of silane is 800-1000sccm, and the thickness of the silicon nitride on the back surface of the silicon wafer is 70-80 nm.
In a preferred embodiment, the laser grooving on the back surface of the silicon wafer to obtain the positioning point, wherein a vertical distance from a highest point of the melting protrusion of the positioning point to the back surface of the silicon wafer is not more than 10 μm, and the method comprises the following steps:
the speed of the back positioning point pattern is set to 1100-1150mm/s, the power of the back positioning point is 4-5W, and the frequency is 10-15 KHz.
In a preferred embodiment, the laser grooving on the back surface of the silicon wafer to obtain the positioning point, wherein a vertical distance from a highest point of the melting protrusion of the positioning point to the back surface of the silicon wafer is not more than 10 μm, and the method comprises the following steps:
setting the pattern speed of the back positioning point to be 800-850mm/s, the power of the back positioning point to be 3-4W and the frequency to be 10-15 KHz; and/or the presence of a gas in the gas,
setting the pattern speed of the back positioning point to be 800-850mm/s, the power of the back positioning point to be 4-5W and the frequency to be 9-10 KHz.
In a preferred embodiment, the cleaning and texturing of the silicon wafer surface with the alkaline solution includes:
and cleaning the silicon wafer by using a 3-5% NaOH solution at the temperature of 80-90 ℃, and making the surface of the silicon wafer into a pyramid suede.
In a preferred embodiment, the introducing the phosphorus source to diffuse and prepare the PN junction on the surface of the textured silicon wafer comprises:
preparing a layer of PN junction on the surface of the silicon wafer after texturing in the presence of phosphorus atoms at the temperature of 700-900 ℃.
In a preferred embodiment, the doping phosphorus on the surface of the diffused silicon wafer into the silicon wafer by using a laser to form a local heavily doped region includes:
setting the laser power to 35-40W, and doping phosphorus atoms in phosphorosilicate glass on the surface of the diffused silicon wafer into the silicon wafer by using laser to form a local heavily doped region so as to improve ohmic contact of the front grid line.
In a preferred embodiment, the oxidizing the doped silicon wafer with oxygen to form a front-side oxide layer on the front side of the silicon wafer comprises:
inserting a silicon wafer in a back-to-back mode;
introducing oxygen to oxidize the silicon wafer for 10-30min at the temperature of 600-700 ℃ and the oxygen flow of 2000-5000sccm to obtain the thickness of the front surface oxide layer of the silicon wafer of 1-2 nm.
In a preferred embodiment, the alkali polishing treatment of the back surface of the silicon wafer after the back surface oxide layer is removed by using an alkali solution includes:
polishing the back of the silicon wafer by using 3-5% NaOH solution at the temperature of 50-70 ℃;
and cleaning and dehydrating the polished silicon wafer by using 5% -9% of HF solution.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the invention provides a solar cell electrode printing method, which comprises the following steps: the method comprises the following steps: cleaning, texturing, diffusing, laser doping, oxidizing, removing a PSG layer, alkali polishing, coating, laser grooving and printing, wherein a silicon nitride film is coated on the surface of a silicon wafer during coating, and the thickness of the silicon nitride film on the back is 70-80 nm; carrying out laser grooving on the back of a silicon wafer to obtain positioning points, wherein the vertical distance from the highest point of a melting bulge of each positioning point to the back of the silicon wafer is not more than 10 mu m, and a back printer for printing back electric field slurry adopts a red light lamp;
further, when the silicon nitride film on the back of the silicon wafer is plated to a specified thickness during film plating in the process, the silicon nitride film is blue, the positioning points are white, and under the cooperation of the blue film, the white positioning points and a red light of a printer, the chromatic aberration of the white positioning points on the surface of the blue film under the irradiation of red light is more obvious compared with the original white light, so that the accuracy of a printing camera for capturing the positioning points can be improved, and the passing rate of the battery plate at the printer on the back can be improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "vertical," "parallel," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like, indicate orientations or positional relationships that are merely used to facilitate description of the invention and to simplify description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the invention. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In view of the problem that the back positioning points are likely to cause the phenomena of hidden cracking of the solar cell and damage to the screen of the back printing machine in the printing process of the solar cell electrode, the present embodiment provides a method capable of effectively overcoming the above problems.
The method for printing the electrode of the solar cell protected by the invention will be described in detail below.
The embodiment provides a method for printing an electrode of a solar cell, which comprises the following steps:
s1, cleaning and texturing: cleaning and texturing the surface of the silicon wafer by using an alkali solution; the method specifically comprises the following steps:
and (3) cleaning and texturing the surface of the silicon wafer by using a 3-5% NaOH solution at the temperature of 80-90 ℃ to prepare a pyramid suede.
S2, diffusion: introducing a phosphorus source to diffuse on the surface of the silicon wafer after texturing to prepare a PN junction;
and (3) performing diffusion treatment on the textured silicon wafer by utilizing the principle of gas phase diffusion at the temperature of 700-900 ℃ and in the presence of phosphorus atoms, and preparing a PN junction on the surface of the silicon wafer.
S3, laser doping: doping phosphorus on the surface of the diffused silicon wafer into the silicon wafer by using laser to form a local heavily doped region; the method specifically comprises the following steps:
setting the laser power to 35-40W, and doping phosphorus atoms in phosphorosilicate glass on the surface of the diffused silicon wafer into the silicon wafer by using laser to form a local heavily doped region so as to reduce the position of a front grid line and improve ohmic contact of the front grid line.
S4, oxidation: oxidizing the doped silicon wafer by using oxygen to form a front-side oxide layer on the front side of the silicon wafer; the method specifically comprises the following steps:
s41, inserting the silicon wafer in a back-to-back mode, and oxidizing only the front side of the silicon wafer in the back-to-back mode to avoid oxidizing the back side of the silicon wafer;
s412, introducing oxygen to oxidize the front surface of the silicon wafer for 10-30min at the temperature of 600-.
S5, removing a back oxide layer: and cleaning the back surface of the silicon wafer by using 10% -30% HF solution to remove a back surface oxidation layer (a phosphorosilicate glass layer, namely a PSG layer). In step S4, although the oxidation is performed in a back-to-back manner, phosphorus atoms will still diffuse from the front surface to the back surface and form a PSG layer, which is not beneficial for subsequent polishing, because a short-circuit channel is formed at the edge of the silicon wafer by diffusion junction formation, photo-generated electrons collected by the front surface of the PN junction will flow to the back surface of the PN junction along the region with phosphorus diffused at the edge to cause a short circuit, and the PN junction at the edge is removed by etching through the PSG to avoid the short circuit at the edge.
S6, alkali polishing: carrying out alkali polishing treatment on the back of the silicon wafer with the PSG layer removed by using an alkali solution;
s61, polishing the back of the silicon wafer by using a 3-5% NaOH solution at the temperature of 50-70 ℃;
and S62, cleaning and dehydrating the polished back of the silicon wafer by using 5-9% HF solution.
The embodiment adopts the alkali polishing technology, so that the reflectivity of the back of the battery can be improved, the process can be optimized, and the environmental friendliness is improved.
S7, coating: and plating a silicon nitride film on the surface of the silicon wafer after the alkali polishing treatment, wherein the thickness of the silicon nitride film on the back surface of the silicon wafer is 70-80 nm.
In this embodiment, silicon nitride is plated on both the front and back surfaces of the silicon wafer during plating, so that double-sided passivation is performed in the subsequent steps to prepare a double-sided PERC cell.
In one embodiment, when plate PECVD is used for plating, the method for plating a silicon nitride film on the surface of a silicon wafer after alkali polishing treatment specifically comprises:
and plating a silicon nitride film on the surface of the silicon wafer subjected to alkali polishing in a plate PECVD (plasma enhanced chemical vapor deposition), wherein the strip speed is set to be 250 +/-15 cm/min, and the thickness of the silicon nitride film on the back of the silicon wafer is 70-80nm so as to enable the silicon nitride film on the back to be blue. The front side film process was unchanged.
In the prior art, the belt speed is 230 +/-15 cm/min, the thickness of the obtained back silicon nitride film is 95-100nm, and the back silicon nitride film is yellow.
In another embodiment, when the tubular PECVD is used for coating, the step of coating the silicon nitride film on the surface of the silicon wafer after the alkali polishing treatment specifically comprises:
adjusting the special gas flow in the tubular PECVD, and setting as follows: when the bottom layer film is plated, the ammonia gas flow rate is 5300-6000sccm, and the silane flow rate is 580-780 sccm; when the middle layer film is plated, the flow rate of ammonia gas is 5500-6200sccm, and the flow rate of silane is 1200-1400 sccm; when the upper layer film is plated, the ammonia gas flow is 5800-6500sccm, the silane flow is 800-1000sccm, and the silicon nitride thickness of the back surface of the silicon wafer is 70-80nm, so that the silicon nitride film on the back surface is blue.
Correspondingly, in the prior art, the special gas flow rate is as follows: when the bottom layer film is plated, the ammonia gas flow rate is 6300-7000sccm, and the silane flow rate is 680-880 sccm; when the middle layer film is plated, the flow rate of ammonia is 6500-7200sccm, and the flow rate of silane is 1400-1600 sccm; when the upper film is plated, the ammonia gas flow is 6800-7500sccm, the silane flow is 950-1200sccm, and the silicon nitride thickness of the back surface of the silicon wafer is 95-100nm, which is compared with the thickness of the plated film in the embodiment, and the color of the back surface film is yellow.
S8, laser grooving: and carrying out laser grooving on the back of the silicon wafer to obtain a positioning point, wherein the vertical distance from the highest point of the melting bulge of the positioning point to the back of the silicon wafer is not more than 10 micrometers. And preferably, the vertical distance from the highest point of the melting bulge of the positioning point to the back surface of the silicon wafer is 2-8 mu m.
The method specifically comprises the following steps: and setting the graph speed and/or power and/or frequency of the back positioning point as corresponding preset values so that the local concave-convex amplitude of the back positioning point generated by ablation is smaller, and the whole positioning point is white when the concave-convex amplitude is smaller.
Illustratively, in one embodiment, when the power or frequency of the anchor points of the device cannot be adjusted individually, the velocity of the position pattern of the back anchor points is set to 1100-1150mm/s, the power of the back anchor points is set to 4-5W, and the frequency is set to 10-15KHz, so that the back anchor points are white. It should be noted that the speed of the positioning point pattern before adjustment is 800-. Compared with the scheme before adjustment, the speed of the position patterns of the positioning points is reduced, the overlapping rate of the positioning patterns is reduced, and the local ablation and protrusion degree is reduced, so that the positioning points are white, the film layer is thin when the film is coated based on S7, and the film layer can be opened through to form good ohmic contact after grooving even if the local ablation and protrusion degree is small.
In another embodiment, when the positioning point and line power or frequency of the equipment can be adjusted independently, the speed of the back positioning point pattern is set to 800-Z(ii) a Or, the speed of the back positioning point pattern is 800-Z(ii) a Or, the speed of the back positioning point pattern is 800-ZThe back anchor point can also be made white. It should be noted that the speed of the front back positioning point pattern is adjusted to 800-. This embodiment compares to the scheme before adjustment by reducing the power or frequency of the anchor pointOr in the case that both are reduced in adaptability, because the film layer is thinner during the coating of the S7 film, even if the overlapping rate between the positioning patterns is reduced, the local ablation and the protrusion degree are reduced to make the positioning points white, and the film layer can be opened to form a good ohmic contact during the grooving process.
Therefore, in the laser grooving step, the local ablation and the protrusion degree caused by the positioning point are reduced by setting the relevant process parameters of the positioning point on the back surface of the silicon chip, so that the subfissure probability of the battery piece and the damage of the positioning point to the screen of the back surface printing machine are reduced.
S9, printing: the printing back printing machine for printing the back electric field paste adopts a red light lamp.
Through the process adjustment of the steps S7 and S8, the back of the silicon wafer is blue film-white point, the chromatic aberration is obvious, on the basis, the white light lamp of the back printer is replaced by the red light lamp, the chromatic aberration of the blue film-white point can be further improved, the identification accuracy of the camera of the printing back printer on the positioning point can be improved, and the passing rate of the back printer is improved.
Of course, the light sources of other printing machines may not be adjusted, and this embodiment is not limited thereto.
And S10, sintering the printed silicon wafer, cooling to obtain a finished product of the solar cell, and packaging.
The method is further illustrated in the following specific examples.
Example 1
The embodiment provides a printing method of a back electrode of a solar cell, which comprises the following steps:
s1, cleaning and texturing: and (2) putting the silicon substrate into a 3-5% NaOH solution at the temperature of 80-90 ℃ for 2min, cleaning the surface of the silicon substrate to remove the surface damage of the silicon wafer, continuously putting the silicon substrate into the NaOH solution for 10min, and carrying out surface texturing treatment to prepare a pyramid suede, so that the specific surface area is increased to receive more photons, and meanwhile, the reflection of incident light is reduced. The temperature and the concentration of the NaOH solution are set conventionally, for convenience of implementation, the temperature is set to be 90 ℃ during cleaning, the concentration of the NaOH solution is 5%, the temperature is set to be 80 ℃ during wool making, and the concentration of the NaOH solution is 3%.
S2, diffusion: and (3) placing the textured silicon wafer into a diffusion furnace, performing diffusion treatment on the textured silicon wafer by utilizing the principle of gas phase diffusion at the temperature of 700-900 ℃ and in the presence of phosphorus atoms, and preparing a layer of PN junction on the surface of the silicon wafer. The phosphorus atom can be obtained by reacting phosphorus oxychloride with a silicon wafer. And (3) making phosphorus atoms enter the surface layer of the silicon wafer by utilizing gas phase diffusion, and performing permeation diffusion to the inside of the silicon wafer through gaps among silicon atoms to form a PN junction. Likewise, the temperature may be 800 ℃.
S3, laser doping: setting the laser power to be 35-40W, doping the laser in the phosphorosilicate glass on the surface of the diffused silicon wafer into the silicon wafer by utilizing the laser to form a local heavily doped region so as to reduce the position of a front grid line and improve the ohmic contact of the front grid line, wherein the average square resistance is 80-95 omega after the heavily doping is finished. Wherein the laser power is set to 40W and the frequency is 140 KHz.
S4, oxidation: oxidizing the doped silicon wafer by using oxygen to form a front-side oxide layer on the front side of the silicon wafer, wherein the method comprises the following steps:
s41, inserting the silicon wafer into an oxidation furnace in a back-to-back mode to protect the back surface of the silicon wafer from being oxidized;
s412, introducing oxygen to oxidize the front surface of the silicon wafer for 10-30min at the temperature of 600-700 ℃, wherein the oxygen flow is 2000-. In the embodiment, the temperature is 650 ℃, the time of introducing oxygen is 25min, the oxygen flow is 4000sccm, and the thickness of the front oxide layer of the silicon wafer is 2 nm.
S5, back oxide removal (PSG removal): and cleaning the back of the silicon wafer by using 10-30% HF solution in a chain type water floating mode to remove the PSG layer on the back. The concentration of the HF solution in this example was 20%.
S6, alkali polishing: carrying out alkali polishing treatment on the back surface of the silicon wafer with the PSG layer removed by using an alkali solution;
s61, polishing the back of the silicon wafer by using a 3-5% NaOH solution at the temperature of 50-70 ℃; the temperature used in this example was 60 ℃.
And S62, cleaning and dehydrating the polished back of the silicon wafer by using 5-9% HF solution. The HF solution in this example was 9%.
S7, the method adopts plate PECVD for film coating, and the silicon nitride film is coated on the surface of the silicon wafer after alkali polishing treatment, and the method specifically comprises the following steps:
and plating a silicon nitride film on the surface of the silicon wafer subjected to alkali polishing in a plate PECVD (plasma enhanced chemical vapor deposition), setting the band speed to be 250 +/-15 cm/min, and obtaining the silicon nitride film on the back of the silicon wafer, wherein the thickness of the silicon nitride film on the back of the silicon wafer is 70nm so as to make the silicon nitride film on the back appear blue. The front side film process was unchanged.
S8, laser grooving: the power or frequency of the locating point of the laser grooving equipment adopted in the embodiment cannot be independently adjusted (such as DR laser grooving equipment), the speed of the position graph of the back locating point is set to be 1100mm/s, the power of the back locating point is set to be 4W, and the frequency is set to be 15KHz, so that the back locating point is white.
And S9, printing the back of the grooved silicon wafer, wherein the back printer adopts a red light lamp.
And S10, sintering the printed silicon wafer, cooling to obtain a finished product of the solar cell, and packaging.
Statistics is carried out on the production conditions of the solar cell prepared by the printing method in the embodiment, and the following results are found: 60000 solar cells were prepared, in which the chipping rate was 0.25%, the one-pass rate of the back-side printing machine was 99%, and the screen life was 40 hours on average.
Example 2
This example provides a method for printing a back electrode of a solar cell, which has steps similar to those of example 1, except that:
s7, coating: the embodiment adopts plate-type PECVD for coating, and the silicon nitride film is coated on the surface of the silicon wafer after alkali polishing treatment, which specifically comprises the following steps:
and plating a silicon nitride film on the surface of the silicon wafer subjected to alkali polishing in a plate PECVD (plasma enhanced chemical vapor deposition), setting the band speed to be 250 +/-15 cm/min, and obtaining the silicon nitride film on the back of the silicon wafer, wherein the thickness of the silicon nitride film on the back of the silicon wafer is 80nm, so that the silicon nitride film on the back is blue. The front side film process was unchanged.
S8, laser grooving: the power or frequency of the locating point of the laser grooving equipment adopted in the embodiment cannot be independently adjusted, the speed of the position graph of the back locating point is set to 1150mm/s, the power of the back locating point is 5W, and the frequency is 12KHz, so that the back locating point is white.
Statistics is carried out on the production conditions of the solar cell prepared by the printing method in the embodiment, and the following results are found: 60000 solar cells were prepared, in which the chipping rate was 0.20%, the one-pass rate of the back-side printing machine was 99.5%, and the screen life was 45 hours on average.
Example 3
This example provides a method for printing a back electrode of a solar cell, which has steps similar to those of example 1, except that:
s7, coating: the embodiment adopts plate-type PECVD for coating, and the silicon nitride film is coated on the surface of the silicon wafer after alkali polishing treatment, which specifically comprises the following steps:
and plating a silicon nitride film on the surface of the silicon wafer subjected to alkali polishing in a plate PECVD (plasma enhanced chemical vapor deposition), setting the band speed to be 250 +/-15 cm/min, and obtaining the silicon nitride film on the back of the silicon wafer, wherein the thickness of the silicon nitride film on the back of the silicon wafer is 75nm, so that the silicon nitride film on the back is blue. The front side film process was unchanged.
S8, laser grooving: the power or frequency of the locating point of the laser grooving equipment adopted in the embodiment cannot be independently adjusted, the speed of the position graph of the back locating point is set to be 1125mm/s, the power of the back locating point is 4W, and the frequency is 15KHz, so that the back locating point is white.
Statistics is carried out on the production conditions of the solar cell prepared by the printing method in the embodiment, and the following results are found: 60000 solar cells were prepared, in which the chipping rate was 0.22%, the one-pass rate of the back-side printing machine was 99.3%, and the screen life was 42 hours on average.
Example 4
This example provides a method for printing a back electrode of a solar cell, which has steps similar to those of example 1, except that:
s7, coating: when the tubular PECVD is adopted for coating, the silicon nitride film is coated on the surface of the silicon wafer after the alkali polishing treatment, and the method specifically comprises the following steps:
adjusting the special gas flow in the PECVD, and setting as follows: when the bottom layer film is plated, the flow rate of ammonia gas is 5300sccm, and the flow rate of silane is 580 sccm; when the middle layer film is plated, the flow rate of ammonia gas is 5500sccm, and the flow rate of silane is 1200 sccm; when the film is plated, the flow rate of ammonia gas is 5800-sccm, the flow rate of silane is 800sccm, and the thickness of the silicon nitride on the back surface of the silicon wafer is 72nm so that the silicon nitride film on the back surface is blue.
S8, laser grooving: the positioning point and line power or frequency of the laser grooving equipment adopted by the embodiment can be independently adjusted, the speed of the back positioning point graph is set to be 800mm/s, the power of the back positioning point is 3W, and the frequency is 10KHZSo that the back positioning point is white.
Statistics is carried out on the production conditions of the solar cell prepared by the printing method in the embodiment, and the following results are found: 60000 solar cells were prepared, in which the chipping rate was 0.20%, the one-pass rate of the back-side printing machine was 99.5%, and the screen life was 45 hours on average.
Example 5
This example provides a method for printing a back electrode of a solar cell, which has steps similar to those of example 1, except that:
s7, coating: when the tubular PECVD is adopted for coating, the silicon nitride film is coated on the surface of the silicon wafer after the alkali polishing treatment, and the method specifically comprises the following steps:
adjusting the special gas flow in the PECVD, and setting as follows: when the bottom layer film is plated, the flow rate of ammonia gas is 6000sccm, and the flow rate of silane is 780 sccm; when the middle layer film is plated, the flow rate of ammonia gas is 6200sccm, and the flow rate of silane is 1400 sccm; and when the film is plated, the flow rate of ammonia gas is 6500sccm, the flow rate of silane is 1000sccm, and the thickness of the silicon nitride on the back surface of the silicon wafer is 78nm so that the silicon nitride film on the back surface is blue.
S8, laser grooving: the positioning point and line power or frequency of the laser grooving equipment adopted by the embodiment can be independently adjusted, the back positioning point graph speed is 850mm/s, and the power of the back positioning point is set to be 4W or the frequency is set to be 9KHZSo that the back positioning point is white.
Statistics is carried out on the production conditions of the solar cell prepared by the printing method in the embodiment, and the following results are found: 60000 solar cells were prepared, in which the chipping rate was 0.24%, the one-pass rate of the back-side printing press was 99.1%, and the screen life was 42 hours on average.
Example 6
This example provides a method for printing a back electrode of a solar cell, which has steps similar to those of example 1, except that:
s7, coating: when the tubular PECVD is adopted for coating, the silicon nitride film is coated on the surface of the silicon wafer after the alkali polishing treatment, and the method specifically comprises the following steps:
adjusting the special gas flow in the PECVD, and setting as follows: when the bottom layer film is plated, the flow rate of ammonia gas is 5650sccm, and the flow rate of silane is 730 sccm; when the middle layer film is plated, the flow rate of ammonia gas is 5850sccm, and the flow rate of silane is 1300 sccm; when the upper film is plated, the flow rate of ammonia gas is 6150sccm, the flow rate of silane is 900sccm, and the thickness of the silicon nitride on the back surface of the silicon wafer is 76nm so that the silicon nitride film on the back surface is blue.
S8, the locating point and line power or frequency of the laser grooving equipment adopted by the embodiment can be adjusted independently, the speed of the back locating point graph is set to be 830mm/S, the power of the back locating point is 3.5W, and the frequency is 9.5KHz, so that the back locating point is white.
Statistics is carried out on the production conditions of the solar cell prepared by the printing method in the embodiment, and the following results are found: 60000 solar cells were prepared, in which the chipping rate was 0.23%, the one-pass rate of the back-side printing machine was 99.3%, and the screen life was 43 hours on average.
Comparative example 1
This example provides a method for printing a back electrode of a solar cell, which has steps similar to those of example 1, except that:
s7, plating a silicon nitride film on the surface of the silicon wafer after the alkali polishing treatment in a plate PECVD (plasma enhanced chemical vapor deposition), wherein the strip speed is set to be 200 +/-15 cm/min, the thickness of the silicon nitride film on the back of the silicon wafer is 95nm, and the silicon nitride film on the back is yellow.
S8, laser grooving, wherein the pattern speed of the positioning point is 1000mm/S, the power of the back positioning point is 4-5W, the frequency is 10-15KHz, and the back positioning point is black.
S9, printing: a second printing machine for printing the back electric field slurry adopts a white light lamp.
Test results of this comparative example 1: the 60000 solar cell sheet was prepared, in which the chipping rate was 0.35%, the one-pass rate of the back-side printing machine was 98%, and the screen life was 24 hours on average.
Comparative example 2
This example provides a method for printing a back electrode of a solar cell, which has steps similar to those of example 1, except that:
s7, setting the special gas flow rate in the tubular PECVD as follows: when the bottom layer film is plated, the flow rate of ammonia gas is 6800sccm, and the flow rate of silane is 850 sccm; when the middle layer film is plated, the flow rate of ammonia gas is 7000sccm, and the flow rate of silane is 1520 sccm; when the film is plated, the flow rate of ammonia gas is 7200sccm, the flow rate of silane is 1130sccm, the thickness of the silicon nitride on the back surface of the silicon wafer is 90nm, and the silicon nitride film on the back surface is yellow;
s8, laser grooving, setting the pattern speed of the back positioning point to 800-ZThe positioning points on the back surface are black.
S9, printing: a second printing machine for printing the back electric field slurry adopts a white light lamp.
Test results of this comparative example 2: the 60000 solar cell sheets were prepared, in which the chipping rate was 0.34%, the one-pass rate of the back-side printing machine was 98%, and the screen life was 25 hours on average.
The specific process parameters and test results are shown in table 1 below:
TABLE 1 comparison table of technological parameters and test results
As can be seen from table 1, in the printing method for the back electrode of the solar cell provided in this embodiment, during film plating, the silicon nitride film on the back surface of the silicon wafer is plated to a specified thickness to make the silicon nitride film blue, and when laser grooving is performed, the local ablation and protrusion degree caused by the positioning point is reduced by setting the relevant process parameters of the positioning point at the positioning point on the back surface of the silicon wafer, so as to reduce the subfissure probability (less than 0.25%) of the cell and the damage of the positioning point on the screen of the back printing machine, and prolong the service life of the screen (more than 40 hours);
furthermore, under the cooperation of the blue film and the white positioning point on the back surface of the battery piece under the process and the red light of the back printer, the chromatic aberration of the white positioning point on the surface of the blue film under the irradiation of red light is more obvious compared with the original white light, the accuracy of the printing camera for capturing the positioning point can be improved, and the passing rate (more than 99%) of the battery piece at the back printer is improved.
All the above optional technical solutions may be combined arbitrarily to form optional embodiments of the present invention, that is, any multiple embodiments may be combined to meet the requirements of different application scenarios, which are within the protection scope of the present application and are not described herein again.
It should be understood that the above-mentioned embodiments are merely preferred embodiments of the present invention, and not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A solar cell electrode printing method is characterized by comprising the following steps:
cleaning and texturing the surface of the silicon wafer by using an alkali solution;
introducing a phosphorus source to diffuse on the surface of the silicon wafer after texturing to prepare a PN junction;
doping phosphorus on the surface of the diffused silicon wafer into the silicon wafer by using laser to form a local heavily doped region;
oxidizing the doped silicon wafer by using oxygen to form a front-side oxide layer on the front side of the silicon wafer;
cleaning the back of the silicon wafer by using an HF solution to remove a back oxide layer;
carrying out alkali polishing treatment on the back of the silicon wafer after the back oxide layer is removed by using an alkali solution;
plating a silicon nitride film on the surface of the silicon wafer after the alkali polishing treatment, wherein the thickness of the silicon nitride film on the back of the silicon wafer is 70-80 nm;
carrying out laser grooving on the back of the silicon wafer to obtain a positioning point, wherein the vertical distance from the highest point of a melting bulge of the positioning point to the back of the silicon wafer is not more than 10 micrometers;
and printing the back of the grooved silicon wafer, wherein a red light lamp is adopted by a corresponding back printer.
2. The method according to claim 1, wherein the vertical distance from the highest point of the melting projection of the positioning point to the back surface of the silicon wafer is 2-8 μm.
3. The method of claim 1, wherein when plate PECVD is used for coating, the silicon wafer surface after the alkali polishing treatment is coated with a silicon nitride film, and the method comprises the following steps:
and plating a silicon nitride film on the surface of the silicon wafer subjected to alkali polishing in a plate PECVD (plasma enhanced chemical vapor deposition), wherein the strip speed is set to be 250 +/-15 cm/min, and the thickness of the silicon nitride film on the back of the silicon wafer is 70-80 nm.
4. The method of claim 1, wherein when the tubular PECVD is used for coating, the silicon wafer surface after the alkali polishing treatment is coated with a silicon nitride film, and the method comprises the following steps:
setting the special gas flow in the tubular PECVD as follows: when the bottom layer film is plated, the ammonia gas flow rate is 5300-6000sccm, and the silane flow rate is 580-780 sccm; when the middle layer film is plated, the flow rate of ammonia gas is 5500-6200sccm, and the flow rate of silane is 1200-1400 sccm; when the upper layer film is plated, the flow rate of ammonia gas is 5800-6500sccm, the flow rate of silane is 800-1000sccm, and the thickness of the silicon nitride on the back surface of the silicon wafer is 70-80 nm.
5. The method of claim 1, wherein the laser grooving on the back surface of the silicon wafer to obtain the positioning point, wherein the vertical distance from the highest point of the melting protrusion of the positioning point to the back surface of the silicon wafer is not more than 10 μm, and the method comprises the following steps:
the speed of the back positioning point pattern is set to 1100-1150mm/s, the power of the back positioning point is 4-5W, and the frequency is 10-15 KHz.
6. The method of claim 1, wherein the laser grooving on the back surface of the silicon wafer to obtain the positioning point, wherein the vertical distance from the highest point of the melting protrusion of the positioning point to the back surface of the silicon wafer is not more than 10 μm, and the method comprises the following steps:
setting the pattern speed of the back positioning point to be 800-850mm/s, the power of the back positioning point to be 3-4W and the frequency to be 10-15 KHz; and/or the presence of a gas in the gas,
setting the pattern speed of the back positioning point to be 800-850mm/s, the power of the back positioning point to be 4-5W and the frequency to be 9-10 KHz.
7. The method according to any one of claims 2 to 6, wherein the cleaning and texturing of the surface of the silicon wafer with the alkali solution comprises:
and cleaning the silicon wafer by using a 3-5% NaOH solution at the temperature of 80-90 ℃, and making the surface of the silicon wafer into a pyramid suede.
8. The method as claimed in any one of claims 2 to 6, wherein the introducing the phosphorus source to diffuse on the surface of the textured silicon wafer to prepare the PN junction comprises the following steps:
preparing a layer of PN junction on the surface of the silicon wafer after texturing in the presence of phosphorus atoms at the temperature of 700-900 ℃.
9. The method according to any one of claims 2 to 6, wherein the doping phosphorus on the diffused surface of the silicon wafer into the silicon wafer by using the laser to form the local heavily doped region comprises:
setting the laser power to 35-40W, and doping phosphorus atoms in phosphorosilicate glass on the surface of the diffused silicon wafer into the silicon wafer by using laser to form a local heavily doped region so as to improve ohmic contact of the front grid line.
10. The method according to any one of claims 2 to 6, wherein the oxidizing the doped silicon wafer with oxygen to form a front-side oxide layer on the front side of the silicon wafer comprises:
inserting a silicon wafer in a back-to-back mode;
introducing oxygen to oxidize the silicon wafer for 10-30min at the temperature of 600-700 ℃ and the oxygen flow of 2000-5000sccm to obtain the thickness of the front surface oxide layer of the silicon wafer of 1-2 nm.
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