CN114517094B - Slurry for screen printing electrochemical etching and preparation method and application thereof - Google Patents

Slurry for screen printing electrochemical etching and preparation method and application thereof Download PDF

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Publication number
CN114517094B
CN114517094B CN202011310283.1A CN202011310283A CN114517094B CN 114517094 B CN114517094 B CN 114517094B CN 202011310283 A CN202011310283 A CN 202011310283A CN 114517094 B CN114517094 B CN 114517094B
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silicon wafer
screen printing
wafer substrate
etching
electrochemical etching
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CN114517094A (en
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崔巍
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CSI Cells Co Ltd
Canadian Solar Inc
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CSI Cells Co Ltd
Atlas Sunshine Power Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/12—Etching of semiconducting materials
    • 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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/0352—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035272—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
    • H01L31/035281—Shape of the body
    • 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
    • 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 provides a sizing agent for screen printing electrochemical etching, a preparation method and application thereof. The paste for screen printing electrochemical etching comprises the following components in percentage by mass: 0.35-15% of ammonium fluoride, 0.05-5% of hydrogen fluoride, 0.1-10% of thickener and the balance of solvent. The slurry may be used in screen printing electrochemical etching techniques to accomplish selective etching in one step.

Description

Slurry for screen printing electrochemical etching and preparation method and application thereof
Technical Field
The invention belongs to the field of battery manufacturing, and particularly relates to a sizing agent for screen printing electrochemical etching, and a preparation method and application thereof.
Background
The solar cell is a clean and environment-friendly energy technology, and the crystalline silicon solar cell technology has been rapidly developed for decades. Passivation emission junction and back battery (PERC) technology is a novel battery technology with low cost and high efficiency, and the excellent back surface passivation effect of the novel battery technology can greatly reduce the back surface recombination of the battery, so that the photoelectric conversion efficiency of the battery is improved, and the current p-type PERC technology has been industrialized.
The electrochemical screen printing technology is one development direction of screen printing in the industries of microelectronics, photovoltaics and the like, and effectively combines the electrochemistry of the screen printing machine, and selectively carries out electrochemical reaction on a device substrate. As an application direction of the technology, the screen printing electrochemical etching technology can effectively realize patterned selective etching on the surface of a conductor/semiconductor, and has higher research and application values. In the photovoltaic cell aspect, a silicon substrate is often required to be selectively etched to meet the preparation requirement of the cell, for example, the silicon substrate with a p-n junction silicon wafer after diffusion is etched to remove partial areas, so as to realize selective doping and the like. The existing etching method generally adopts a solution method to etch the silicon wafer, and the solution method is only used for etching the whole surface of the silicon wafer, so that the selectivity is difficult to realize.
CN106328765a discloses a process and method for preparing a high-efficiency PERC crystalline silicon solar cell. Sequentially comprises the steps of texturing, diffusion and etching, and is plated with Al 2 O 3 Back side SiN plating x Plating of front SiN x And (3) screen printing and sintering to obtain the PERC crystalline silicon solar cell.
CN107123702a discloses a method for preparing a back-side polished PERC battery, comprising the following steps: (1) depositing a single-sided protection film on the back surface of a silicon wafer; (2) Texturing the silicon wafer plated with the single-sided protection film, and removing the single-sided protection film on the silicon wafer in the pickling process after texturing; (3) diffusing the silicon wafer with the single-sided texturing; (4) performing conventional secondary cleaning; (5) And depositing an alumina/silicon nitride laminated passivation film on the back surface, then grooving by laser, and performing screen printing and sintering to obtain the back surface polished PERC battery.
However, although the screen printing technique is used in the above-described scheme, selective etching cannot be achieved.
Therefore, development of a paste for screen printing electrochemical etching which can perform selective etching in one step and is suitable for screen printing is an important point of current research in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a sizing agent for screen printing electrochemical etching, a preparation method and application thereof, wherein the sizing agent can be used for screen printing electrochemical etching technology, so that selective etching is completed in one step.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a paste for screen printing electrochemical etching, which comprises, in mass percent: 0.35-15% of ammonium fluoride, 0.05-5% of hydrogen fluoride, 0.1-10% of thickener and the balance of solvent.
In the invention, ammonium fluoride, hydrogen fluoride, a thickening agent and a solvent in the slurry are matched with each other, so that the slurry can be used for a screen printing electrochemical etching technology, and selective etching is completed in one step; wherein, the ammonium fluoride and the hydrogen fluoride provide necessary electrochemical oxidation-reduction reaction ions, and the electrode is used as a cathode to perform reduction reaction during etching so as to reduce the hydrogen ions into hydrogen; the silicon substrate is used as an anode, oxidation reaction is carried out, silicon is oxidized into silicon ions, the silicon ions are combined with the fluorine ions to generate fluorosilicate, and the fluorosilicate is dissolved in the slurry, so that the silicon substrate is partially etched, and the thickener can well adjust the state of the slurry, so that the silicon substrate is more suitable for screen printing electrochemical etching.
The ammonium fluoride content is 0.35 to 15%, for example, 0.35%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., based on 100% of the slurry content.
The hydrogen fluoride content is 0.05 to 5%, for example, 0.05%, 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc., based on 100% of the slurry content.
The thickener content is 0.1 to 10%, for example, 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 2%, 4%, 6%, 8%, 10%, etc., based on 100% of the slurry content.
Preferably, the paste for screen printing electrochemical etching comprises the following components in percentage by mass: 2-4% of ammonium fluoride, 1-2% of hydrogen fluoride, 2-4% of thickener and the balance of solvent.
Preferably, the thickener is selected from any one or a combination of at least two of xanthan gum, guar gum, cationic guar gum, hydroxypropyl guar gum, quaternary ammonium salts, polyurethanes, celluloses or polyacrylic acids, preferably a combination of xanthan gum and polyurethane thickener.
In the invention, xanthan gum and polyurethane thickener are compounded to serve as a thickener, and the xanthan gum and polyurethane thickener are matched with each other to effectively adjust the thixotropy and stability of the sizing agent, so that the phenomena of sizing agent deposition, flocculation and the like are prevented on the premise of meeting the screen printing requirement.
Preferably, the solid content of the polyurethane thickener is 30-60wt%, for example, 30wt%, 32wt%, 34wt%, 36wt%, 38wt%, 40wt%, 45wt%, 48wt%, 50wt%, 55wt%, 60wt%, etc., and the viscosity of the polyurethane thickener is 1500-3500cp, for example, 1500cp, 1800cp, 2000cp, 2500cp, 3000cp, 3200cp, 3300cp, 3500cp, etc.
In the present invention, the polyurethane thickener is commercially available, including but not limited to, nantong, altai chemical Co., ltd., HT-820, le Shun RM-2020NPR, hengyu chemical RM-8W, etc.
Preferably, the thickener comprises, in mass percent: 50-70% of xanthan gum and 30-50% of polyurethane thickener.
The content of the xanthan gum is 50-70% based on 100% by mass of the thickener, and may be, for example, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, etc.
The content of the polyurethane thickener is 30 to 50% by mass of the thickener of 100%, and may be, for example, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, etc.
Preferably, the solvent comprises water, preferably deionized water.
Preferably, the solvent further comprises any one or a combination of at least two of methanol, ethanol, isopropanol, formic acid, acetic acid or diethyl ether.
Preferably, the solvent comprises the following components in percentage by mass: 70-100% of water and 0-30% of isopropanol.
The water content is 70-100% by mass of the solvent, and may be, for example, 70%, 75%, 80%, 85%, 90%, 95%, 100%, etc.
The isopropyl alcohol content is 0 to 30% by mass of the solvent of 100%, and may be, for example, 0%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 25%, 30%, etc.
In the invention, water is used as a main solvent, and auxiliary solvents such as alcohols and the like are added, thereby being beneficial to improving the stability of the slurry.
Preferably, the viscosity of the paste for screen printing electrochemical etching is 20000 to 70000mpa·s, for example 20000mpa·s, 25000mpa·s, 30000mpa·s, 35000mpa·s, 40000mpa·s, 45000mpa·s, 50000mpa·s, 55000mpa·s, 60000mpa·s, 70000mpa·s, or the like.
In a second aspect, the present invention provides a method for preparing a paste for screen printing electrochemical etching according to the first aspect, the method comprising the steps of:
(1) Mixing and stirring a thickening agent and a solvent to obtain first prefabricated slurry;
(2) Performing ultrasonic crushing and grinding treatment on the first prefabricated slurry obtained in the step (1) to obtain a second prefabricated slurry;
(3) Mixing the second prefabricated slurry obtained in the step (2), ammonium fluoride and hydrogen fluoride, and stirring and dispersing to obtain a third prefabricated slurry;
(4) And (3) standing and filtering the third prefabricated slurry obtained in the step (3) to obtain the slurry for screen printing electrochemical etching.
In the invention, the solvent is preheated and then mixed with the thickener, so that the compatibility of each component in the electroplating slurry can be further improved, the outer layer of the thickener is prevented from swelling into a micelle after absorbing water, and the water is prevented from entering the inner layer, thereby affecting the exertion of the effect; and then ultrasonic crushing, grinding and standing are carried out, so that the particle size of the hydrogen fluoride in the slurry is reduced, and the screen transmittance of the slurry is improved.
Preferably, the temperature of the mixing and stirring in the step (1) is 60-70 ℃, for example, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, etc., the rotation speed of the mixing and stirring is 200-8000rpm, for example, 200rpm, 1000rpm, 2000rpm, 4000rpm, 6000rpm, 8000rpm, etc., and the time of the mixing and stirring is 20-60min, for example, 20min, 30min, 40min, 50min, 60min, etc.
Preferably, the power of the ultrasonic pulverization in the step (2) is 1000-2000W, for example, 1000W, 1200W, 1400W, 1600W, 1800W, 2000W, etc., and the time of the ultrasonic pulverization is 10-30min, for example, 10min, 15min, 20min, 25min, 30min, etc.
Preferably, the particle size of the second pre-slurry in step (2) is 5-50 μm, for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, etc. may be used.
Preferably, the temperature of the standing in the step (4) is 20 to 30 ℃, for example, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃ and the like, and the time of the standing is 20 to 40min, for example, 20min, 25min, 30min, 35min, 40min and the like.
Preferably, the filtration in step (4) is carried out using a polyester mesh having a pore size < 20 μm, which may be, for example, 2 μm, 4 μm, 8 μm, 12 μm, 16 μm, 20 μm, etc.
In a third aspect, the present invention provides the use of a paste for screen-printed electrochemical etching according to the first aspect for the preparation of a photovoltaic cell.
Preferably, the photovoltaic cell is a p-type selective emitter PERC cell.
In a fourth aspect, the present invention provides a method for preparing a p-type selective emitter PERC cell, where the method for preparing the p-type selective emitter PERC cell includes: and (3) carrying out screen printing electrochemical etching, namely carrying out etching on the surface of the silicon wafer substrate by matching with the slurry for screen printing electrochemical etching according to the first aspect, so as to obtain the p-type selective emitter PERC cell.
Preferably, the etching on the surface of the silicon wafer substrate specifically comprises: adding the slurry for screen printing electrochemical etching in the first aspect into an etching screen plate of an electrochemical screen printing device, enabling the slurry to contact with the silicon wafer substrate through an opening part of the etching screen plate, and performing screen printing electrochemical etching;
preferably, the printing speed of the electrochemical screen printing device is 0.02-0.50m/s, for example, 0.02m/s, 0.05m/s, 0.1m/s, 0.2m/s, 0.3m/s, 0.4m/s, 0.5m/s, etc., and the power output voltage of the electrochemical screen printing device is 5-15V, for example, 5V, 6V, 7V, 8V, 9V, 10V, 11V, 12V, 13V, 14V, 15V, etc.
Preferably, the etching depth of the surface of the silicon wafer substrate is 5-50nm, for example, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm and the like.
Preferably, the silicon wafer substrate is subjected to pretreatment before etching the surface of the silicon wafer substrate, and the pretreatment specifically comprises the following steps:
(a) And (3) wool making: etching the silicon wafer substrate by using corrosive liquid;
(b) Diffusion: forming PN junction on the front surface of the silicon wafer substrate after the texturing treatment by using high-temperature diffusion phosphorus;
preferably, the texturing in the step (a) is specifically: soaking the silicon wafer substrate in potassium hydroxide solution, performing texturing treatment for 3-30min (for example, 3min, 5min, 10min, 15min, 20min, 25min, 30min and the like) at 50-70 ℃ (for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃ and the like), etching pit texture on the silicon wafer, wherein the thinning amount of the silicon wafer substrate after texturing is 0.2-0.6g (for example, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g and the like), and the reflectivity of the silicon wafer substrate is 8-20% (for example, 8%, 10%, 12%, 14%, 16%, 18%, 20% and the like).
Preferably, the diffusing in step (b) is specifically: placing the textured silicon wafer substrate in a tubular diffusion furnace for phosphorus diffusion treatment, controlling the temperature of the tubular diffusion furnace to 600-900 ℃ (such as 600 ℃, 700 ℃, 800 ℃, 900 ℃ and the like), controlling the square resistance of the tubular diffusion furnace to 80-160 omega (such as 80 omega, 90 omega, 100 omega, 110 omega, 120 omega, 140 omega, 160 omega and the like), controlling the time of the phosphorus diffusion treatment to 60-200min (such as 60min, 80min, 90min, 100min, 120min, 150min, 200min and the like), forming PN junctions on the surface of the silicon wafer through a phosphorus diffusion process, and controlling the PN junction depth to 0.2-0.5 mu m (such as 0.2 mu m, 0.25 mu m, 0.3 mu m, 0.4 mu m, 0.5 mu m and the like).
Preferably, after etching the surface of the silicon wafer substrate, cleaning and drying treatment are required to be performed on the silicon wafer substrate, wherein the cleaning and drying treatment specifically comprises the following steps: the silicon wafer is rinsed with water and dried with nitrogen, and then dried for 0.2-10min, e.g., 0.2min, 0.5min, 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, etc., under the atmosphere or inert gas atmosphere of 100-200deg.C (e.g., 100deg.C, 120deg.C, 140deg.C, 160deg.C, 180deg.C, 200deg.C, etc.).
Preferably, after the cleaning and drying treatment, the silicon wafer substrate is further treated, and the treatment specifically comprises the following steps:
(A) Polishing: polishing the back surface of the silicon wafer substrate after diffusion treatment by using a strong acid solution, and removing the phosphosilicate glass layers on the front surface and the back surface of the silicon wafer substrate by using the strong acid solution;
(B) Coating: depositing an aluminum oxide film and a silicon nitride film on the back surface of the polished silicon wafer substrate, and depositing a silicon nitride film on the front surface of the polished silicon wafer substrate;
(C) Laser grooving: slotting a silicon wafer substrate after coating by using laser;
(D) Printing paste: respectively printing a silver electrode and an aluminum electrode on the back surface of the silicon wafer substrate subjected to laser grooving, printing the silver electrode on the front surface of the substrate, and drying;
(E) Sintering: and sintering the silicon wafer substrate after the printing paste.
Preferably, the polishing in step (a) is specifically: using HF and HNO 3 Polishing the back surface of the silicon wafer substrate, and removing the phosphosilicate glass layer on the front and back surfaces by using an HF solution.
Preferably, the thickness of the aluminum oxide film on the back surface of the silicon wafer substrate obtained by coating in the step (B) is 5-15nm (for example, 5nm, 8nm, 10nm, 12nm, 15nm, etc.), the thickness of the silicon nitride film on the back surface of the silicon wafer substrate is 50-200nm (for example, 50nm, 100nm, 150nm, 200nm, etc.), and the refractive index is 1.7-2.5 (for example, 1.7, 1.9, 2.0, 2.1, 2.2, 2.5, etc.); the silicon nitride film on the front side of the silicon wafer substrate has a thickness of 50-150nm (e.g., 50nm, 60nm, 80nm, 100nm, 125nm, 150nm, etc.) and a refractive index of 1.9-2.4 (e.g., 1.9, 2.0, 2.1, 2.2, 2.4, etc.).
Preferably, the laser grooving in the step (C) is specifically: the back side film is grooved and perforated on the back side of the substrate by a laser with a wavelength of 400-1200nm (for example, 400nm, 600nm, 800nm, 1000nm, 1200nm, etc.) and an output power of 3-30W (for example, 3W, 5W, 7W, 10W, 15W, 20W, 25W, 30W, etc.).
Preferably, the sintering temperature in step (E) is 700-800 ℃, and may be 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃, etc., for example.
In the screen printing electrochemical etching of the surface of the silicon wafer substrate by adopting the slurry, the etching depth is 8-45nm, for example, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, 28nm, 30nm, 32nm, 34nm, 36nm, 38nm, 40nm, 45nm and the like.
Compared with the prior art, the invention has the following beneficial effects:
the paste for screen printing electrochemical etching is matched with the screen printing electrochemical etching equipment and the screen printing electrochemical etching method, and selective etching of the appointed area can be realized through only one printing step.
Drawings
FIG. 1 is a schematic diagram of the steps of a method for preparing a slurry according to the present invention;
FIG. 2 is a schematic diagram showing steps of a method for etching a silicon substrate by using the slurry in combination with a screen printing electrochemical etching technology according to the present invention;
FIG. 3 is a schematic diagram showing the steps of a method for preparing a p-type selective emitter PERC cell according to the present invention;
FIG. 4 is a schematic view of a screen printing plating apparatus according to the invention;
the device comprises a printer sliding part 11, a printer sliding track 12, an ink return knife lifting part 13, an ink return knife 14, a doctor blade lifting part 15, a doctor blade 16, a metal electrode 17, a printer slide platform 18, a screen frame 21, an insulated organic film 22, a screen 23, a screen 24, a screen opening part (with or without an organic film), an electrochemical slurry 31, a silicon wafer substrate 41, a wire 51 and a power supply 52, and a power supply control device;
FIG. 5 is a schematic diagram of an etched screen layout;
wherein 101 is a screen non-opening, 102 is a screen opening, and 103 is a screen frame.
FIG. 6 is a schematic diagram of steps for further processing a silicon wafer substrate to form a cell after etching.
FIG. 7 is a schematic illustration of a positive silver screen stencil pattern of a front side printed silver electrode of a substrate;
where 201 is the cell metal grid, 202 is the cell substrate, and 203 is the cell edge.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Fig. 1 is a schematic diagram of steps of a preparation method of the slurry according to the present invention, wherein the preparation method comprises the following steps: (1) Mixing and stirring a thickening agent and a solvent to obtain first prefabricated slurry; (2) Performing ultrasonic crushing and grinding treatment on the first prefabricated slurry obtained in the step (1) to obtain a second prefabricated slurry; (3) Mixing the second prefabricated slurry obtained in the step (2), ammonium fluoride and hydrogen fluoride, and stirring and dispersing to obtain a third prefabricated slurry; (4) And (3) standing and filtering the third prefabricated slurry obtained in the step (3) to obtain the slurry for screen printing electrochemical etching.
Fig. 2 is a schematic diagram of steps of a method for etching a silicon substrate by using the paste in combination with a screen printing electrochemical etching technology according to the present invention, and as shown in fig. 2, the method for etching a silicon substrate by using the paste in combination with a screen printing electrochemical etching technology sequentially includes: and (3) preprocessing the silicon wafer substrate, screen printing, cleaning and drying to obtain the product.
Fig. 3 is a schematic diagram of steps of a method for preparing a p-type selective emitter PERC battery according to the present invention, and as shown in fig. 3, the etched substrate is cleaned, dried and then treated according to a further treatment method according to the present invention, thereby obtaining a battery.
Fig. 4 is a schematic diagram of a screen printing electroplating device according to the invention, and 31 in fig. 4 is an electrochemical paste according to the invention, 41 is a silicon wafer substrate, and by means of the device, the paste according to the invention is matched with a screen printing electrochemical etching technology to etch the silicon substrate.
FIG. 5 is a schematic diagram of an etched screen layout; wherein 101 is a screen non-opening, 102 is a screen opening, and 103 is a screen frame.
FIG. 6 is a schematic diagram of the steps of further processing the etched silicon wafer substrate to form a battery, as shown in FIG. 6, and then sequentially polishing the back surface, coating the front surface, grooving the back surface by laser, printing the front surface pattern, and sintering to finally form the battery.
Fig. 7 is a schematic diagram of a positive silver screen pattern of silver electrodes printed on the front side of a substrate, where 201 is the cell metal grid, 202 is the cell substrate, and 203 is the cell edge.
The following embodiments partially segment the source: polyurethane thickeners are purchased from: (Hengyu chemical industry, hydrophobic modified polyurethane thickener RM-12W), hydrofluoric acid are purchased from: (manufacturer: national drug, concentration: 40% or more, CAS number: 7664-39-3).
Example 1
The embodiment provides a paste for screen printing electrochemical etching, and the preparation method of the paste for screen printing electrochemical etching comprises the following steps:
(1) After 93g of deionized water is preheated to 65 ℃, 1.5g of xanthan gum and 1g of polyurethane thickener are added, and then stirring is carried out for 20min at the speed of 500rpm at 65 ℃ to obtain first pre-slurry;
(2) Ultrasonically crushing the first prefabricated slurry obtained in the step (1) for 10min under the power of 1000W, and then grinding the crushed first prefabricated slurry by a three-roller grinder to obtain second prefabricated slurry with the particle size of 1-20 mu m;
(3) Mixing the second pre-slurry obtained in the step (2), 3g of ammonium fluoride and 1.5g of hydrofluoric acid, and stirring at a speed of 200rpm for 30min at 25 ℃ to obtain a third pre-slurry;
(4) And (3) standing the third prefabricated slurry obtained in the step (3) for 30min at 25 ℃, and filtering by adopting a polyester net with the aperture of 5 mu m to obtain the slurry for screen printing electrochemical etching.
Example 2
The embodiment provides a paste for screen printing electrochemical etching, and the preparation method of the paste for screen printing electrochemical etching comprises the following steps:
(1) After 94g of deionized water is preheated to 65 ℃, 1g of xanthan gum and 1g of polyurethane thickener are added, and stirring is carried out for 20min at the speed of 500rpm at 65 ℃ to obtain first pre-slurry;
(2) Ultrasonically crushing the first prefabricated slurry obtained in the step (1) for 10min under the power of 1000W, and then grinding the crushed first prefabricated slurry by a three-roller grinder to obtain second prefabricated slurry with the particle size of 1-20 mu m;
(3) Mixing the second pre-slurry obtained in the step (2), 2g of ammonium fluoride and 2g of hydrofluoric acid, and stirring at a speed of 200rpm for 30min at 25 ℃ to obtain a third pre-slurry;
(4) And (3) standing the third prefabricated slurry obtained in the step (3) for 30min at 25 ℃, and filtering by adopting a polyester net with the aperture of 5 mu m to obtain the slurry for screen printing electrochemical etching.
Example 3
The embodiment provides a paste for screen printing electrochemical etching, and the preparation method of the paste for screen printing electrochemical etching comprises the following steps:
(1) 91g of deionized water is preheated to 65 ℃, 2.8g of xanthan gum and 1.2g of polyurethane thickener are added, and then the mixture is stirred for 10 minutes at the temperature of 65 ℃ at the rotating speed of 700rpm, so as to obtain first pre-slurry;
(2) Ultrasonically crushing the first prefabricated slurry obtained in the step (1) for 10min under the power of 1000W, and then grinding the crushed first prefabricated slurry by a three-roller grinder to obtain second prefabricated slurry with the particle size of 1-10 mu m;
(3) Mixing the second pre-slurry obtained in the step (2), 4g of ammonium fluoride and 1g of hydrofluoric acid, and stirring at 25 ℃ for 30min at a rotating speed of 500rpm to obtain a third pre-slurry;
(4) And (3) standing the third prefabricated slurry obtained in the step (3) for 30min at 25 ℃, and filtering by adopting a polyester net with the aperture of 5 mu m to obtain the slurry for screen printing electrochemical etching.
Example 4
This example provides a paste for screen printing electrochemical etching, which differs from example 1 only in that 93g of deionized water is replaced with a mixture of 73g of deionized water and 20g of isopropyl alcohol, and the other steps are the same as in example 1.
Example 5
This example provides a screen printing electrochemical etching slurry differing from example 1 only in that 93g of deionized water was replaced with 93g of isopropyl alcohol, and the other steps were the same as in example 1.
Example 6
The present example provides a paste for screen printing electrochemical etching, which is different from example 1 only in that the addition amount of xanthan gum in step (2) is 1g, the addition amount of polyurethane thickener is 1.5g, and the content of other components and the preparation method are the same as example 1.
Example 7
The present example provides a paste for screen printing electrochemical etching, which is different from example 1 only in that the addition amount of xanthan gum in step (2) is 2g, the addition amount of polyurethane thickener is 0.5g, and the content of other components and the preparation method are the same as example 1.
Example 8
The present example provides a screen printing electrochemical etching slurry differing from example 1 only in that xanthan gum is not added in step (2), only 2.5g of polyurethane thickener is added, and other component contents and preparation methods are the same as example 1.
Example 9
The present example provides a paste for screen printing electrochemical etching, which differs from example 1 only in that the polyurethane thickener is not added in step (2), only 2.5g of xanthan gum is added, and other component contents and preparation methods are the same as example 1.
Example 10
The embodiment provides a paste for screen printing electrochemical etching, and the preparation method of the paste for screen printing electrochemical etching comprises the following steps:
(1) 91g of deionized water is preheated to 65 ℃, 2.8g of xanthan gum, 1.2g of polyurethane thickener, 4g of ammonium fluoride and 1g of hydrofluoric acid are added, and then stirring is carried out for 30min at the temperature of 65 ℃ at the speed of 500rpm, so as to obtain first pre-slurry;
(2) Ultrasonically crushing the first prefabricated slurry obtained in the step (1) for 10min under the power of 1000W, and then grinding the crushed first prefabricated slurry by a three-roller grinder to obtain second prefabricated slurry with the particle size of 1-20 mu m;
(3) And (3) standing the second prefabricated slurry obtained in the step (2) for 30min at 25 ℃, and filtering by adopting a polyester net with the aperture of 5 mu m to obtain the slurry for screen printing electrochemical etching.
Comparative example 1
This comparative example provides a paste for screen printing electrochemical etching, which differs from example 1 only in that 3g of ammonium fluoride is replaced by 3g of sodium fluoride in step (3), and the content of other components and the preparation method are the same as example 1.
Comparative example 2
This comparative example provides a paste for screen printing electrochemical etching, which differs from example 1 only in that 1.5g of hydrofluoric acid is replaced by 1.5g of hydrochloric acid in step (3), and the other component contents and the preparation method are the same as in example 1.
Comparative example 3
The comparative example provides a paste for screen printing electrochemical etching, which is different from example 1 only in that the ammonium fluoride content is 4.5g without adding hydrofluoric acid in the step (3), and other component contents and preparation methods are the same as those in example 1.
Comparative example 4
This comparative example provides a paste for screen printing electrochemical etching, which differs from example 1 only in that ammonium fluoride is not added in step (3), the content of hydrofluoric acid is 4.5g, and other component contents and preparation methods are the same as in example 1.
Performance testing
The p-type selective emitter PERC cell was prepared by electroplating using the paste for screen printing electrochemical etching provided in examples 1 to 10 and the paste for screen printing electrochemical etching provided in comparative examples 1 to 4, respectively, and the specific preparation method was:
s1, preprocessing, wherein the preprocessing specifically comprises the following steps:
(a) And (3) wool making: soaking a silicon wafer substrate in a potassium hydroxide solution with the mass concentration of 8wt%, performing texturing treatment at 60 ℃ for 15min, etching pit textured surfaces on the silicon wafer, wherein the average thinning amount of the silicon wafer substrate after texturing is 0.3g, and the average reflectivity of the silicon wafer substrate is 10%;
(b) Diffusion: placing the silicon wafer substrate subjected to texturing treatment in a tubular diffusion furnace for phosphorus diffusion treatment, wherein the temperature of the tubular diffusion furnace is controlled at 850 ℃, the square resistance of the tubular diffusion furnace is controlled at 100+/-5 omega, the time of phosphorus diffusion treatment is controlled at 100min, PN junctions are formed on the surface of the silicon wafer through a phosphorus diffusion process, and the PN junction depth is controlled at 0.2 mu m;
s2, screen printing electrochemical etching, wherein the etching specifically comprises the following steps:
respectively adding the slurry obtained in each embodiment and the slurry obtained in the comparative embodiment into an etching screen plate of an electrochemical screen printing device, enabling the slurry to contact with the silicon wafer substrate through an opening part of the etching screen plate, and performing screen printing electrochemical etching, wherein the average printing speed of the electrochemical screen printing device is 0.02mm/s, the average power supply output voltage of the electrochemical screen printing device is 8V, and the average etching depth of the surface of the silicon wafer substrate is 8-45nm;
s3, cleaning and drying treatment, wherein the cleaning and drying treatment specifically comprises the following steps:
washing a silicon wafer substrate by deionized water, drying by nitrogen, and drying for 5min in an atmospheric environment at 150 ℃;
the above-described time, temperature, etching depth and etching surface roughness of the screen printing electrochemical etching slurries provided in examples 1 to 10 and the screen printing electrochemical etching slurries provided in comparative examples 1 to 4 were recorded, and the specific results are shown in table 1 below:
TABLE 1
As can be seen from the test data in Table 1, in the screen printing electrochemical etching of the surface of the silicon wafer substrate by using the slurry provided by the invention, the etching depth is 8-45nm, and the sheet resistance of the etching area is 105-160Ω. By means of the screen printing electrochemical etching equipment and the screen printing electrochemical etching method, selective etching of the designated area can be achieved through only one printing step, and etching condition temperature, etching depth and etching surface roughness can be guaranteed correspondingly. The ammonium fluoride, hydrofluoric acid, a thickening agent and a solvent in the slurry are mutually matched, so that the slurry can be used for a screen printing electrochemical etching technology, and selective etching is completed in one step; wherein ammonium fluoride and hydrofluoric acid provide necessary electrochemical redox reaction ions, and the thickener can well adjust the state of the slurry, so that the slurry is more suitable for screen printing electrochemical etching.
And (3) continuing the cleaning and drying treatment of the S3, and continuing further treatment of the silicon wafer substrate, wherein the further treatment specifically comprises the following steps:
(A) Polishing: using HF and HNO 3 Polishing the back surface of the silicon wafer substrate, and removing the phosphosilicate glass layer on the front surface and the back surface by using an HF solution;
(B) Coating: depositing an 8nm aluminum oxide film and a 120nm silicon nitride film on the back surface of the polished silicon wafer substrate, and depositing an 80nm silicon nitride film on the front surface of the polished silicon wafer substrate;
(C) Laser grooving: grooving the back surface of the substrate by using a laser with the wavelength of 560nm and the output power of 15W, and punching through a back surface film;
(D) Printing paste: respectively printing a silver electrode and an aluminum electrode on the back surface of the silicon wafer substrate subjected to laser grooving, drying at the temperature of 300 ℃ to 30s, printing the silver electrode on the front surface of the substrate, and drying at the temperature of 350 ℃ to 30s after printing;
(E) Sintering at 760 deg.c for 3min.
Each performance test was performed on the p-type selective emitter PERC cells prepared from the above-described slurries for screen printing electrochemical etching provided in examples 1 to 10 and the slurries for screen printing electrochemical etching provided in comparative examples 1 to 5, and comparative example 5 was added: the step S2 is not performed. The specific test results are shown in table 2 below:
TABLE 2
Project Voc(mV) Isc(A) Rs(mΩ) Rsh(Ω) FF(％) Eta(％)
Example 1 8.5 0.086 0.03 144.0 0.03 0.41
Example 2 8.3 0.075 0.01 155.3 0.06 0.38
Example 3 7.3 0.077 0.04 31.8 -0.08 0.35
Example 4 8.0 0.088 0.05 45.5 -0.20 0.33
Example 5 0.3 0.012 0.02 -11.2 -0.09 -0.03
Example 6 6.3 0.045 0.33 -48.3 -0.65 0.13
Example 7 4.2 -0.020 0.62 -88.3 -1.28 -0.27
Example 8 0.8 0.022 0.02 13.8 0.02 0.07
Example 9 3.6 -0.045 0.88 48.8 -1.66 -0.43
Example 10 1.6 0.011 0.02 -11.6 -0.11 0.05
Comparative example 1 4.4 0.046 0.12 88.7 -0.02 0.22
Comparative example 2 0.4 -0.020 0.04 13.3 -0.06 -0.03
Comparative example 3 0.7 -0.006 -0.01 -46.8 0.04 0.03
Comparative example 4 5.5 0.056 0.25 72.0 -0.47 0.19
Comparative example 5 0 0 0 0 0 0
The battery efficiency data in table 2 is the relative change between various batteries and comparative example 5. As can be seen from the test data in Table 2, the etching method of the invention does not affect the conversion efficiency of PERC cells. The paste for screen printing electrochemical etching is matched with the screen printing electrochemical etching equipment and the screen printing electrochemical etching method, and selective etching of the appointed area can be realized through only one printing step. Compared with comparative example 5, the finally prepared battery has the Voc value variation of 7.3-8.5mV, the Isc value variation of 0.075-0.088A, the Rs value variation of 0.01-0.05 mΩ, the Rsh value variation of 31-156 Ω, the FF value variation of-0.2-0.06%, and the Eta value variation of 0.33-0.41% (wherein the positive number is increased and the negative number is decreased).
The applicant states that the present invention is illustrated by the above examples as well as the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (29)

1. The slurry for screen printing electrochemical etching is characterized by comprising the following components in percentage by mass: 0.35-15% of ammonium fluoride, 0.05-5% of hydrogen fluoride, 0.1-10% of thickener and the balance of solvent;
the thickener is a combination of xanthan gum and polyurethane thickener.
2. The paste for screen printing electrochemical etching according to claim 1, comprising, in mass percent: 2-4% of ammonium fluoride, 1-2% of hydrogen fluoride, 2-4% of thickener and the balance of solvent.
3. The paste for screen printing electrochemical etching according to claim 1, wherein the solid content of the polyurethane thickener is 30 to 60wt%, and the viscosity of the polyurethane thickener is 1500 to 3500cp.
4. The paste for screen printing electrochemical etching according to claim 1, wherein the thickener comprises, in mass percent: 50-70% of xanthan gum and 30-50% of polyurethane thickener.
5. The screen printing electrochemical etching slurry of claim 1 wherein the solvent comprises water.
6. The paste for screen printing electrochemical etching according to claim 5, wherein the solvent further comprises any one or a combination of at least two of methanol, ethanol, isopropanol, formic acid, acetic acid, or diethyl ether.
7. The paste for screen printing electrochemical etching according to claim 6, wherein the solvent comprises, in mass percent: 70-100% of water and 0-30% of isopropanol.
8. The paste for screen printing electrochemical etching according to claim 1, wherein the viscosity of the paste for screen printing electrochemical etching is 20000 to 70000 mPa-s.
9. The method for producing a paste for screen printing electrochemical etching according to any one of claims 1 to 8, comprising the steps of:
(1) Mixing and stirring a thickening agent and a solvent to obtain first prefabricated slurry;
(2) Performing ultrasonic crushing and grinding treatment on the first prefabricated slurry obtained in the step (1) to obtain a second prefabricated slurry;
(3) Mixing the second prefabricated slurry obtained in the step (2), ammonium fluoride and hydrogen fluoride, and stirring and dispersing to obtain a third prefabricated slurry;
(4) And (3) standing and filtering the third prefabricated slurry obtained in the step (3) to obtain the slurry for screen printing electrochemical etching.
10. The method according to claim 9, wherein the temperature of the mixing and stirring in the step (1) is 60 to 70 ℃, the rotational speed of the mixing and stirring is 200 to 8000rpm, and the time of the mixing and stirring is 20 to 60 minutes.
11. The method according to claim 9, wherein the power of the ultrasonic pulverization in the step (2) is 1000 to 2000W, and the time of the ultrasonic pulverization is 10 to 30min.
12. The method according to claim 9, wherein the particle size of the second pre-slurry in step (2) is 5 to 50 μm.
13. The method according to claim 9, wherein the temperature of the standing in the step (4) is 20 to 30 ℃ and the time of the standing is 20 to 40min.
14. The process according to claim 9, wherein the filtration in step (4) is carried out using a polyester mesh having a pore size of < 20 μm.
15. Use of a paste for screen-printed electrochemical etching according to any of claims 1 to 8 for the preparation of photovoltaic cells.
16. The use according to claim 15, wherein the photovoltaic cell is a p-type selective emitter PERC cell.
17. The preparation method of the p-type selective emitter PERC battery is characterized by comprising the following steps of: and (3) carrying out screen printing electrochemical etching, and carrying out etching on the surface of the silicon wafer substrate by matching with the slurry for screen printing electrochemical etching according to any one of claims 1-8 to obtain the p-type selective emitter PERC battery.
18. The method for preparing a p-type selective emitter PERC cell according to claim 17, wherein the etching on the surface of the silicon wafer substrate is specifically: adding the paste for screen printing electrochemical etching according to any one of claims 1 to 8 to an etching screen of an electrochemical screen printing device, and enabling the paste to contact with the silicon wafer substrate through an opening part of the etching screen to perform screen printing electrochemical etching.
19. The method of manufacturing a p-type selective emitter PERC battery according to claim 18, wherein the printing speed of the electrochemical screen printing device is 0.005-0.50m/s, and the power output voltage of the electrochemical screen printing device is 5-15V.
20. The method for preparing a p-type selective emitter PERC cell according to claim 17, wherein the etching depth of the surface of the silicon wafer substrate is 5-50nm.
21. The method for preparing a p-type selective emitter PERC battery according to claim 17, wherein the pretreatment of the silicon wafer substrate is required before etching the surface of the silicon wafer substrate, the pretreatment specifically comprising the steps of:
(a) And (3) wool making: etching the silicon wafer substrate by using corrosive liquid;
(b) Diffusion: and forming PN junction on the front surface of the silicon wafer substrate after the texturing treatment by using high-temperature diffusion phosphorus.
22. The method of manufacturing a p-type selective emitter PERC cell according to claim 21, wherein said texturing in step (a) is specifically: soaking a silicon wafer substrate in potassium hydroxide solution, performing texturing treatment at 50-70 ℃ for 3-30min, etching pit textured surfaces on the silicon wafer, wherein the thinning amount of the textured silicon wafer substrate is 0.2-0.6g, and the reflectivity of the silicon wafer substrate is 8-20%.
23. The method of preparing a p-type selective emitter PERC cell according to claim 21, wherein said diffusing in step (b) is specifically: placing the silicon wafer substrate subjected to the texturing treatment into a tubular diffusion furnace for phosphorus diffusion treatment, controlling the temperature of the tubular diffusion furnace to be 600-900 ℃, controlling the square resistance of the tubular diffusion furnace to be 80-160 omega, controlling the time of phosphorus diffusion treatment to be 60-200min, forming PN junctions on the surface of the silicon wafer through a phosphorus diffusion process, and controlling the PN junction depth to be 0.2-0.5 mu m.
24. The method for preparing a p-type selective emitter PERC battery according to claim 17, wherein after etching the surface of the silicon substrate, cleaning and drying the silicon substrate are required, and the cleaning and drying processes specifically include: and (3) flushing the silicon wafer by adopting water, drying by using nitrogen, and drying for 0.2-10min in the atmosphere or inert gas environment at the temperature of 100-200 ℃.
25. The method for preparing a p-type selective emitter PERC cell according to claim 24, wherein the cleaning and drying process is followed by further processing of the silicon wafer substrate, the process comprising the steps of:
(A) Polishing: polishing the back surface of the silicon wafer substrate after diffusion treatment by using a strong acid solution, and removing the phosphosilicate glass layers on the front surface and the back surface of the silicon wafer substrate by using the strong acid solution;
(B) Coating: depositing an aluminum oxide film and a silicon nitride film on the back surface of the polished silicon wafer substrate, and depositing a silicon nitride film on the front surface of the polished silicon wafer substrate;
(C) Laser grooving: slotting a silicon wafer substrate after coating by using laser;
(D) Printing paste: respectively printing a silver electrode and an aluminum electrode on the back surface of the silicon wafer substrate subjected to laser grooving, printing the silver electrode on the front surface of the substrate, and drying;
(E) Sintering: and sintering the silicon wafer substrate after the printing paste.
26. The method of claim 25, wherein the polishing in step (a) is specifically: using HF and HNO 3 Polishing the back surface of the silicon wafer substrate, and removing the phosphosilicate glass layer on the front and back surfaces by using an HF solution.
27. The method for manufacturing a p-type selective emitter PERC battery according to claim 25, wherein the thickness of the aluminum oxide film on the back surface of the silicon wafer substrate obtained by coating in the step (B) is 5-15nm, the thickness of the silicon nitride film on the back surface of the silicon wafer substrate is 50-200nm, and the refractive index is 1.7-2.5; the thickness of the silicon nitride film on the front surface of the silicon wafer substrate is 50-150nm, and the refractive index is 1.9-2.4.
28. The method of claim 25, wherein the laser grooving in step (C) is specifically: and grooving the back surface of the substrate by using a laser with the wavelength of 400-1200nm and the output power of 3-30W, and punching through the back surface film.
29. The method of preparing a p-type selective emitter PERC cell according to claim 25, wherein the sintering temperature in step (E) is 700-800 ℃.
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