CN116332519A - Glass powder composition, glass powder, conductive silver paste and solar cell - Google Patents

Glass powder composition, glass powder, conductive silver paste and solar cell Download PDF

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Publication number
CN116332519A
CN116332519A CN202111590767.0A CN202111590767A CN116332519A CN 116332519 A CN116332519 A CN 116332519A CN 202111590767 A CN202111590767 A CN 202111590767A CN 116332519 A CN116332519 A CN 116332519A
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China
Prior art keywords
glass frit
silver paste
conductive silver
frit composition
solar cell
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CN202111590767.0A
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Inventor
汪山
周欣山
周彬
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Suzhou Jingyin New Material Technology Co ltd
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Suzhou Jingyin New Material Technology Co ltd
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Priority to CN202111590767.0A priority Critical patent/CN116332519A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • 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

Abstract

The invention provides a glass powder composition, glass powder, conductive silver paste and a solar cell. The glass frit composition contains 1-7wt% of WO 3 5-15wt% MoO 3 1-10wt% GeO 2 40-60wt% of TeO 2 . The invention also provides glass powder, conductive silver paste and a solar cell which are prepared from the glass powder composition. The conductive silver paste containing the glass powder or the conductive silver paste provided by the invention can replace a SE doping process, so that the manufacturing cost of the battery is reduced, and the manufactured solar battery can have high conversion efficiency and reliability.

Description

Glass powder composition, glass powder, conductive silver paste and solar cell
Technical Field
The invention relates to a glass powder composition, glass powder, conductive silver paste and a solar cell, and belongs to the technical field of solar cells.
Background
Solar cells generate electricity using the photovoltaic effect, with the most central structure being the PN junction. Generally, the P-type silicon wafer of the current mainstream is doped with N-type phosphorus, and the SE technology (selective emitter) used in the diffusion process of the current battery mainstream is to carry out heavy doping under metallization and shallow doping in non-metallization places. The existing SE technology is generally realized by firstly diffusing and then carrying out laser doping at the place needing metallization, the technology needs to increase the investment of laser equipment, meanwhile, the SE technology needs to be matched by screen printing technology, the printed fine grid lines are required to be aligned to the laser doped area, the printing requirement is high, and the productivity and the yield of screen printing are affected. If the sheet resistance is low, the doping concentration is high, serious Auger recombination is caused, the minority carrier lifetime is low, the open-circuit voltage and the short-circuit current are reduced, if the sheet resistance is close to the sheet resistance (high sheet resistance) of the shallow doping region of the SE process, the doping concentration is low, the interface state of the silicon surface and the Fermi-pinning effect are caused, the series resistance is large, and the conversion efficiency of the solar cell is low.
Chinese application 201910507352.9.7 discloses a glass composition for crystalline silicon solar PERC cell front side silver paste and a method for preparing the same, which can be used to match the diffusion SE process. Chinese patent application 201880000355.7 discloses a crystalline silicon solar cell front-side conductive paste, a preparation method thereof and a solar cell, wherein the glass composition can be matched with high sheet resistance, but from practical examples, the difference between the effect and the open-circuit voltage and conversion efficiency of the current SE technology is larger, and the difference between the practical sheet resistance and the sheet resistance of the current SE shallow doped region is larger.
The main current doping process of the solar cell uses an SE process, most of current conductive paste is used for matching with a diffusion SE process, less paste is matched with non-SE high sheet resistance, the front conductive paste of China application patent 201880000355.7 is not SE high sheet resistance conductive paste, the actually matched sheet resistance is lower than the sheet resistance of a shallow doping area of the current SE process, the doping concentration is higher than the concentration of the shallow doping area of SE, auger recombination is serious, the open circuit voltage and conversion efficiency of the cell are lower, and the application value is low, so that the current SE process is difficult to replace.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a novel glass system and a conductive paste based on the glass system, wherein the conductive paste can form good ohmic contact with a battery under the conditions of high sheet resistance and low doping concentration, can be used for replacing a mass production SE doping process, and reduces the production cost of a solar battery.
To achieve the above object, the present invention provides a glass frit composition comprising, in weight percent, 1 to 7% by weight of WO 3 5-15wt% MoO 3 1-10wt% GeO 2 40-60wt% of TeO 2 。
According to a specific embodiment of the present invention, preferably, the glass frit composition contains 1 to 7wt% of WO 3 5-15wt% MoO 3 1-10wt% GeO 2 40-60wt% of TeO 2 。
According to a particular embodiment of the invention, preferably the TeO 2 The content of (C) is 42-51wt%.
According to a specific embodiment of the present invention, preferably, the glass frit composition contains 1.5 to 6.5wt% of WO in weight percent 3 6.5 to 9.5wt% MoO 2 1-10wt% GeO 2 40-53wt% of TeO 2 。
According to a specific embodiment of the present invention, preferably, the glass frit composition further comprises ZnO, B 2 O 3 、SiO 2 、PbO、Al 2 O 3 、P 2 O 5 、CuO、MgO、CaO、Li 2 O、Na 2 O、K 2 One or more than two of O.
According to a specific embodiment of the present invention, preferably, the glass frit composition further comprises 1 to 3wt% of ZnO,1 to 3wt% of B 2 O 3 1-3wt% of SiO 2 12-20wt% of PbO, 0-2wt% (preferably below 2 wt%) of Al 2 O 3 1-3wt% of P 2 O 5 1-3wt% of CuO, 4-8wt% of MgO, 0-2wt% (preferably less than 2 wt%) of CaO, 5-12wt% of Li 2 O, 0-2wt% Na 2 O、0-2wt% of K 2 One or more than two of O.
According to a specific embodiment of the present invention, preferably, the glass frit composition contains 1.5 to 6.5wt% of WO 3 6.5 to 9.5wt% MoO 2 1-10wt% GeO 2 40-53wt% of TeO 2 1-3wt% ZnO,1-3wt% B 2 O 3 1-2.5wt% SiO 2 12-18wt% of PbO,3-7wt% of MgO,1-3wt% of P 2 O 5 4-9.5wt% of Li 2 O。
According to a specific embodiment of the present invention, preferably, the glass frit composition does not contain Bi element, preferably does not contain Bi 2 O 3 。
According to a particular embodiment of the invention, preferably in the glass frit composition, WO 3 、MoO 3 、GeO 2 、TeO 2 、ZnO、B 2 O 3 、SiO 2 、PbO、Al 2 O 3 、P 2 O 5 、GuO、MgO、CaO、Li 2 O、Na 2 O、K 2 One or a combination of two or more of O is replaced by a carbonate salt of a corresponding metallic or metalloid element capable of providing a molar amount, for example: according to WO 3 The mass of (2) is calculated to give the number of moles of W, assuming Xmol, from which Xmol of W (CO 3 ) 3 The mass of (2) is taken as W (CO) 3 ) 3 The amount to be added to the glass frit composition. Wherein "carbonate" includes not only various elements and Carbonate (CO) 3 2- ) Salts formed, also including bicarbonate (acid carbonate), basic carbonate.
The invention also provides glass powder which is prepared from the glass powder composition provided by the invention.
According to a specific embodiment of the present invention, the glass frit may be prepared by the steps of: mixing the glass powder composition, and heating and melting at 750-1000 ℃ for 30-120 min; cooling to obtain fragments; the fragments are further crushed and then ball-milled to obtain the glass powder with the required particle size distribution.
According to a specific embodiment of the present invention, it is preferable that the fineness of the particle diameter of the glass frit composition satisfies D50. Ltoreq.10. Mu.m.
According to a specific embodiment of the present invention, preferably, the glass frit is one or a combination of two or more of amorphous glass frit, crystalline glass frit, partially amorphous glass frit.
The invention also provides conductive silver paste, wherein the conductive silver paste contains 1-4% of glass powder by weight percent, and the glass powder is the glass powder provided by the invention.
According to a specific embodiment of the present invention, preferably, the conductive silver paste further contains silver powder (conductive phase) and an organic carrier; more preferably, the silver powder is contained in an amount of 85 to 92% by weight and the organic vehicle is contained in an amount of 5 to 12% by weight.
According to a specific embodiment of the present invention, preferably, the silver powder has a particle diameter of 1 to 5 μm and a tap density of 5 to 9g/cm 3 。
According to a specific embodiment of the present invention, in the conductive silver paste: the glass powder is mainly used for wetting silver powder, corroding a passivation layer and bonding silver silicon in the sintering process, and has a main influence on the contact resistance of the conductive silver paste and the battery; silver powder is used as a conductive phase and mainly plays a role in conduction, and is used for collecting photo-generated carriers after sintering; the organic carrier is mainly used for dispersing silver powder, so that the slurry has good rheological property and can be well subjected to screen printing.
According to a specific embodiment of the present invention, preferably, the silver powder is a surface-treated silver powder, and the dispersion stability of the silver powder in the conductive silver paste can be improved by modification; more preferably, the modifier used for the surface treatment of the silver powder comprises one or more of oleic acid, linoleic acid, linolenic acid, a silane coupling agent, hard fatty acid, fatty acid amine, polyvinylpyrrolidone, fatty alcohol polyoxyethylene ether, a block macromolecular surfactant and the like. The surface treatment for the silver powder may be performed in a conventional manner in the art.
According to a specific embodiment of the present invention, preferably, the organic carrier includes a resin, an organic solvent and an auxiliary agent, and the addition amounts of the three are 1% -20%, 75% -95% and 0.1% -4%, respectively.
According to a specific embodiment of the present invention, preferably, the resin is one or a combination of two or more of a cellulose resin, an epoxy resin, and an acrylic resin.
According to a specific embodiment of the present invention, preferably, the organic solvent is one or a combination of two or more of terpineol, butyl carbitol acetate, and dodecanol ester.
According to a specific embodiment of the present invention, preferably, the auxiliary agent includes one or a combination of two or more of a dispersant, a thixotropic agent, a lubricant, a humectant and a plasticizer. Wherein the dispersant is preferably a macromolecular dispersant such as polyether, polyester, polyamide or polysilicone; the lubricant is preferably surfactant and/or silicone oil; the thixotropic agent is preferably one or more than two of hydrogenated castor oil, polyamide, fumed silica and the like; the humectant is preferably one or more of diethylene glycol, triethylene glycol, PEG400, glycerol, ethylene glycol, sorbitol, 1, 2-propylene glycol, diethylene glycol butyl ether, ethylene glycol, polyethylene glycol, N-methyl-2-pyrrolidone, condensate of polyalcohol and ethylene oxide, xylitol, etc.; the plasticizer is preferably one or more of aliphatic dibasic acid ester, phthalic acid ester, terephthalic acid ester, benzene polyacid ester, benzoate, polyol ester epoxy, citric acid ester, polyester and the like.
According to a specific embodiment of the present invention, it is preferable that the average blade fineness of the conductive silver paste is 10 μm or less, more preferably 5 μm or less.
The conductive silver paste can be prepared by the following steps:
1) Preparation of organic vehicle body: mixing resin and organic solvent in proportion, and stirring at room temperature or under heating;
2) And (3) preparing slurry: mixing silver powder, glass powder composition and organic carrier, stirring, and grinding and dispersing with a three-roller machine to obtain conductive silver paste with average scraper fineness below 10 μm, preferably below 5 μm.
In the preparation process of the conductive silver paste, the auxiliary agent can be added in the step 1) of preparing the organic carrier, can also be added in the step 2) of preparing the paste, or can be added in part in the step 1) and in part in the step 2).
The invention also provides a solar cell, wherein the front electrode of the solar cell is made of the conductive silver paste containing the glass powder composition and/or the conductive silver paste provided by the invention. More preferably, the solar cell is a solar cell manufactured by a high sheet resistance process.
The glass powder composition and silver paste formed by the glass powder composition can be used in solar cells with high sheet resistance. The glass system of W-Mo-Ge-Te can corrode the passivation layer and does not further corrode the silicon wafer, so that the doping concentration on the surface of the silicon wafer is not affected by glass, and the silver paste can have good contact resistance with the battery piece and simultaneously maintain good binding force. The solar cell manufactured by the silver paste has high conversion efficiency and reliability, can replace the SE doping process, and reduces the manufacturing cost of the cell.
The invention also provides a preparation method of the solar cell, which is a high sheet resistance process and comprises the following steps:
firstly, preparing an anti-reflection suede on one side surface of a silicon substrate, for example, corroding by using alkali solution or acid solution to form a pyramid-shaped (single crystal) or rugged (polycrystal) anti-reflection suede;
forming an N-type diffusion layer on the other side of the P-type silicon substrate to form a PN junction, forming the N-type diffusion layer (preferably using phosphorus oxychloride as a diffusion source) by adopting a gas phase thermal diffusion method, wherein the diffused sheet resistance is 120-170 omega/sq, and then removing phosphorus at the edge, such as wet etching or dry etching;
thirdly, performing thermal diffusion on the N surface to form SiO 2 Then plating SiNx antireflection layer (or similar other coating with good antireflection and passivation effects) on the P surface 2 O 3 And SiNx dullnessForming a layer, and then carrying out laser grooving at the printing position of the P-surface aluminum back surface field;
fourthly, forming a vertical and horizontal main grid and a fine grid on the N-face anti-reflection film through a screen printing mode by using the conductive silver paste, printing a back electrode and an aluminum back field on one side of the P type, and co-firing at the sintering temperature of 700-900 ℃ to form an electrode body.
The glass powder composition is a glass system of W-Mo-Ge-Te, wherein Ge and Te can form a stable glass network structure, W, mo can enable glass to have a higher softening point temperature, cannot corrode a silicon wafer, and therefore cannot influence the doping concentration of the silicon surface (the conventional glass system can further corrode the silicon wafer surface after corroding a passivation layer, so that the actual doping concentration of a contact part between the silicon wafer surface and slurry becomes low), meanwhile, the formed glass is more uniformly distributed on the silicon wafer, electrons can be better transferred through tunneling effect, and the contact resistance of the slurry and the silicon wafer is reduced, so that under the condition of high sheet resistance, the conductive slurry still has good contact resistance with the silicon, and meanwhile, good bonding force is kept.
The conductive silver paste containing the glass powder or the conductive silver paste provided by the invention can replace a SE doping process, so that the manufacturing cost of the battery is reduced, and the manufactured solar battery can have high conversion efficiency and reliability.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
This example provides 11 sets of glass frit compositions, in weight percent oxide as shown in table 1, wherein number 11 is the control:
TABLE 1
Figure BDA0003429016880000061
The preparation method of the glass powder comprises the following steps: mixing the above components in proportion, then placing in a muffle furnace, heating at 900-1100 ℃ for 45-90 min, quenching with water, cooling with a steel plate to obtain glass fragments, further crushing the fragments, and ball milling with a planetary ball mill to obtain glass powder of W-Mo-Ge-Te system with required particle size distribution (D50: 0.1-5 μm) and Pb-Te glass of a control group.
Example 2
The embodiment provides a conductive silver paste, wherein the conductive paste comprises 88.5 parts of silver powder, 2.5 parts of glass powder and 9 parts of an organic carrier based on 100 parts of the total weight of the conductive silver paste. Silver powder requires particle size: 1-5 μm (D50), tap density: 5-9g/cm 3 。
The organic carrier consists of a solvent, resin and an auxiliary agent, wherein the solvent is a mixture of terpineol, butyl carbitol acetate and dodecyl ester with the mass ratio of 1:4:1, the solvent accounts for 78 percent, the resin is a mixture of ethyl cellulose and acrylic acid with the mass ratio of 1:4, the resin accounts for 20 percent, the auxiliary agent is a mixture of hydrogenated castor oil and silicone oil with the mass ratio of 1:5, and the auxiliary agent accounts for 2 percent.
The conductive silver paste is prepared by the following steps:
adding resin into the solvent, fully stirring under the heating condition of 70-100 ℃, and adding an auxiliary agent after the resin is completely dissolved to obtain a required organic carrier;
the glass powder composition, silver powder and organic carrier in table 1 are mixed and stirred uniformly in proportion, and are ground and dispersed by a three-roller machine to obtain the required conductive paste, and the conductive paste with the average scraper fineness of less than 5 mu m is selected for standby.
Example 3
The embodiment provides a solar cell, which is prepared by the following steps:
the semiconductor substrate is a P-type silicon substrate doped with boron or gallium, wherein the P-type silicon substrate is a silicon wafer with the thickness of 150-200 mu m and the side length of 156-210 mm;
etching one side of a silicon substrate by using alkali solution or acid solution to prepare pyramid (single crystal) or rugged (polycrystal) anti-reflection suede;
forming an N-type diffusion layer on the other side of the P-type silicon substrate to form a PN junction, wherein the N-type diffusion layer can be a gas-phase thermal diffusion method with phosphorus oxychloride as a diffusion source, the diffused sheet resistance is 120-170 omega/sq, and removing phosphorus at the edge through wet etching or dry etching;
thirdly, performing thermal diffusion on the N surface to form a layer of SiO 2 Then plating a SiNx antireflection layer, or similar other coating with good antireflection and passivation effects, plating Al on the P surface 2 O 3 And a passivation layer of SiNx, and then carrying out laser grooving at the printing position of the P-surface aluminum back surface field;
fourthly, forming a vertical and horizontal main grid and a fine grid on the N-face anti-reflection film through a screen printing mode by using the conductive silver paste, printing a back electrode and an aluminum back field on one side of the P type, and co-firing at the sintering temperature of 700-900 ℃ to form an electrode body.
The electrical performance test is carried out on the solar cell, specifically: test under standard conditions (atmospheric quality AM 1.5, illumination intensity 1000W/m using a solar simulated electrical efficiency tester 2 Test temperature 25 ℃). The series resistance and conversion efficiency results are shown in table 2, wherein the serial numbers correspond to the corresponding serial numbers in table 1.
TABLE 2
Sequence number Rs(mΩ) Conversion efficiency
1 1.31 23.06％
2 1.42 23.02％
3 1.62 22.98％
4 1.33 23.08％
5 1.38 23.04％
6 1.42 23.07％
7 1.45 23.02％
8 1.34 23.10％
9 1.49 22.95％
10 1.43 23.11％
Example 4
The embodiment provides a solar cell, which is prepared by the following steps:
the semiconductor substrate is a P-type silicon substrate doped with boron or gallium, the P-type silicon substrate is a silicon wafer with the thickness of 150-200 mu m and the side length of 156-210 mm;
firstly, etching one side of a silicon substrate by using alkali solution or acid solution to form pyramid-shaped (single crystal) or rugged (polycrystal) anti-reflection suede;
forming an N-type diffusion layer on the other side of the P-type silicon substrate to form a PN junction, wherein the N-type diffusion layer can be a gas-phase thermal diffusion method by taking phosphorus oxychloride as a diffusion source, the diffused sheet resistance is 120-170 omega/sq, then the sheet resistance of a re-doped region after SE is 70-120 omega/sq through laser SE, and then removing the phosphorus at the edge through wet etching or dry etching;
thirdly, performing thermal diffusion on the N surface to form a layer of SiO 2 Then plating a SiNx antireflection layer, or similar other coating with good antireflection and passivation effects, plating Al on the P surface 2 O 3 And a passivation layer of SiNx, and then carrying out laser grooving at the printing position of the P-surface aluminum back surface field;
fourthly, forming a vertical and horizontal main grid and a fine grid on the anti-reflection film of the N surface through a screen printing mode by conducting silver paste manufactured by 11 # glass in the table 1, printing a back electrode and an aluminum back field on the P type side, and co-firing at the sintering temperature of 700-900 ℃ to form the electrode body.
The electrical performance test is carried out on the solar cell, specifically: test under standard conditions (atmospheric quality AM 1.5, illumination intensity 1000W/m using a solar simulated electrical efficiency tester 2 Test temperature 25 ℃). The series resistance and conversion efficiency results are shown in table 3.
TABLE 3 Table 3
Sequence number Rs(mΩ) Conversion efficiency
11 1.38 23.09％
From the data, the glass powder system has smaller series resistance on the high-sheet-resistance battery piece than the conventional system slurry, and the conversion efficiency reaches 23% of that of the main flow SE PERC process. The non-SE high sheet resistance process matched with the conductive paste can replace the conventional SE process, reduce the equipment investment of a battery factory, improve the yield and reduce the production cost of the solar battery.

Claims (13)

1. A glass frit composition, wherein the glass frit composition comprises 1-7wt% of WO 3 5-15wt% MoO 3 1-10wt% GeO 2 40-60wt% of TeO 2 。
2. The glass frit composition of claim 1, wherein the TeO 2 The content of (C) is 42-51wt%.
3. The glass frit composition according to claim 1 or 2, wherein the glass frit composition further comprises 1-3wt% ZnO,1-3wt% B 2 O 3 1-3wt% of SiO 2 12-20wt% of PbO, 0-2wt% (preferably below 2 wt%) of Al 2 O 3 1-3wt% of P 2 O 5 1-3wt% of CuO, 4-8wt% of MgO, 0-2wt% (preferably less than 2 wt%) of CaO, 5-12wt% of Li 2 O, 0-2wt% Na 2 O, 0-2wt% K 2 One or more than two of O.
4. A glass frit composition according to any of claims 1-3, wherein the glass frit composition does not comprise Bi element, preferably does not comprise Bi 2 O 3 。
5. The glass frit composition according to any of claims 1-4, wherein the WO 3 、MoO 3 、GeO 2 、TeO 2 、ZnO、B 2 O 3 、SiO 2 、PbO、Al 2 O 3 、P 2 O 5 、CuO、MgO、CaO、Li 2 O、Na 2 O、K 2 One or a combination of two or more of O is replaced by a carbonate salt capable of providing a molar amount of the corresponding metallic element or metalloid element.
6. A glass frit made from the glass frit composition of any of claims 1-5;
preferably, the fineness of the particle diameter of the glass frit composition satisfies D50. Ltoreq.10 μm;
more preferably, the glass frit is one or a combination of two or more of an amorphous glass frit composition, a crystalline glass frit composition, a partially crystalline glass frit composition, and a partially amorphous glass frit composition.
7. A conductive silver paste, wherein the conductive silver paste contains 1% -4% by weight of glass powder, and the glass powder is the glass powder of claim 6.
8. The conductive silver paste of claim 7, wherein the conductive silver paste further comprises silver powder and an organic carrier; preferably, the silver powder is 85-92% by weight, and the organic carrier is 5-12% by weight;
preferably, the grain diameter of the silver powder is 1-5 mu m, and the tap density is 5-9g/cm 3 。
9. The conductive silver paste of claim 8, wherein the silver powder is a surface-treated silver powder;
preferably, the modifier used for the surface treatment of the silver powder comprises one or more than two of oleic acid, linoleic acid, linolenic acid, silane coupling agent, hard fatty acid, fatty acid amine, polyvinylpyrrolidone, fatty alcohol polyoxyethylene ether and block macromolecular surfactant.
10. The conductive silver paste according to any one of claims 7 to 9, wherein the organic carrier comprises resin, an organic solvent and an auxiliary agent, and the addition amounts of the three are 1 to 20%, 75 to 95% and 0.1 to 4%, respectively;
preferably, the resin is one or a combination of more than two of cellulose resin, epoxy resin and acrylic resin;
preferably, the organic solvent is one or a combination of more than two of terpineol, butyl carbitol acetate and dodecanol ester;
preferably, the auxiliary agent comprises one or a combination of more than two of dispersing agent, thixotropic agent, lubricant, humectant and plasticizer;
more preferably, the dispersant is a macromolecular dispersant, such as a polyether, polyester, polyamide or polysilicone; the lubricant is surfactant and/or silicone oil; the thixotropic agent is one or the combination of more than two of hydrogenated castor oil, polyamide and fumed silica; the humectant is one or more than two of diethylene glycol, triethylene glycol, PEG400, glycerol, ethylene glycol, sorbitol, 1, 2-propylene glycol, diethylene glycol butyl ether, ethylene glycol, polyethylene glycol, N-methyl-2-pyrrolidone, condensate of polyalcohol and ethylene oxide and xylitol; the plasticizer is one or more than two of aliphatic dibasic acid ester, phthalic acid ester, terephthalic acid ester, benzene polyacid ester, benzoate, polyol ester epoxy, citric acid ester and polyester.
11. The conductive silver paste according to claim 10, wherein the conductive silver paste has an average blade fineness of 10 μm or less, preferably 5 μm or less.
12. A solar cell, wherein the front electrode of the solar cell is made of the conductive silver paste comprising the glass frit of claim 6 and/or the conductive silver paste of any one of claims 7 to 11; preferably, the solar cell is a solar cell manufactured by a high sheet resistance process.
13. The method for manufacturing a solar cell according to claim 12, comprising the steps of:
firstly, manufacturing an antireflection suede on one side surface of a silicon substrate;
forming an N-type diffusion layer on the other side of the P-type silicon substrate to form a PN junction, forming the N-type diffusion layer (preferably using phosphorus oxychloride as a diffusion source) by adopting a gas phase thermal diffusion method, wherein the diffused sheet resistance is 120-170 omega/sq, and then removing phosphorus at the edge;
thirdly, performing thermal diffusion on the N surface to form SiO 2 Then plating SiNx antireflection layer, plating Al on the P surface 2 O 3 And a passivation layer of SiNx, and then carrying out laser grooving at the printing position of the P-surface aluminum back surface field;
fourthly, forming a vertical and horizontal main grid and a fine grid on the N-face anti-reflection film through a screen printing mode by using the conductive silver paste, printing a back electrode and an aluminum back field on one side of the P type, and co-firing at the sintering temperature of 700-900 ℃ to form an electrode body.
CN202111590767.0A 2021-12-23 2021-12-23 Glass powder composition, glass powder, conductive silver paste and solar cell Pending CN116332519A (en)

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