CN116189958A - Low-temperature conductive paste composition, low-temperature conductive paste, conductive coating, electrode and heterojunction solar cell - Google Patents

Low-temperature conductive paste composition, low-temperature conductive paste, conductive coating, electrode and heterojunction solar cell Download PDF

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CN116189958A
CN116189958A CN202310094298.6A CN202310094298A CN116189958A CN 116189958 A CN116189958 A CN 116189958A CN 202310094298 A CN202310094298 A CN 202310094298A CN 116189958 A CN116189958 A CN 116189958A
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silver
low
conductive paste
particles
salt
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CN116189958B (en
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周冰
胡恒广
闫冬成
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Tunghsu Technology Group Co Ltd
Hebei Guangxing Semiconductor Technology Co Ltd
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Tunghsu Technology Group Co Ltd
Hebei Guangxing Semiconductor Technology Co Ltd
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    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
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    • H01—ELECTRIC ELEMENTS
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0745—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
    • H01L31/0747—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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Abstract

The invention relates to the field of heterojunction solar cells, and discloses a low-temperature conductive paste composition, a low-temperature conductive paste, a conductive coating, an electrode and a heterojunction solar cell. The composition contains the following components which are stored independently or stored in a mixed manner of more than two of the following components: conductive particles, polymeric resins, silver salts, and metal salts; the metal element in the metal salt is selected from at least one of group IA metal element and group IIA metal element; the content of the conductive particles is 65-97wt% based on the total mass of the composition; the content of the polymer resin is 2.5-25wt%; the silver salt content is 0.3-5wt% on a dry basis; the content of metal salt is 0.05-5wt% based on dry basis. The composition can reduce the contact resistance between the conductive coating and the TCO film in the electrode, and reduce the resistivity of the heterojunction solar cell electrode, thereby increasing the conductivity and improving the adhesive strength between the conductive coating and the TCO film.

Description

Low-temperature conductive paste composition, low-temperature conductive paste, conductive coating, electrode and heterojunction solar cell
Technical Field
The invention relates to the technical field of heterojunction solar cells, in particular to a low-temperature conductive paste composition, a low-temperature conductive paste, a conductive coating, an electrode and a heterojunction solar cell.
Background
A solar cell is a device that converts solar energy into electric energy. It generates electrons and holes by absorbing the visible light irradiated from the sun on the substrate, and guides the electrons and holes to form a current through positive and negative electrodes on both sides of the substrate.
Heterojunction (HJT) solar cells have a transparent conductive oxide film (TCO) on the substrate surface, and then conduction and transport of current is accomplished through the charge collecting electrode (metal). An important factor for improving the photoelectric conversion efficiency of the HJT solar cell is to reduce the electrode resistance. How to further reduce the resistance of the electrode itself, improve the conductivity thereof, and reduce the contact resistance between the conductive coating and the TCO film in the electrode is an important subject of current research.
The current heterojunction main grid conductive silver paste mainly has the following problems: 1. the welding tension is lower after the used conductive silver paste is solidified, and the weldability is poor; 2. the main gate electrode with partial high tensile force only improves the welding tensile force by improving the resin content or the proportion of the flake silver powder, so that the volume resistivity is relatively high or the printability is poor; 3. the aging tension of the conductive silver paste used under certain conditions after solidification is poor.
Disclosure of Invention
The invention aims to solve the problems of poor conductivity of electrodes of heterojunction solar cells and poor adhesion strength between a charge collecting electrode and a TCO transparent electrode in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a low-temperature conductive paste composition containing the following components stored independently or in a mixture of two or more:
conductive particles, polymeric resins, silver salts, and metal salts; the metal element in the metal salt is selected from at least one of group IA metal element and group IIA metal element;
wherein the content of the conductive particles is 65-97wt% based on the total mass of the low-temperature conductive paste composition; the content of the polymer resin is 2.5-25wt%; the silver salt content is 0.3-5wt% on a dry basis; the content of the metal salt is 0.05-5wt% based on dry basis.
In a second aspect, the present invention provides a low-temperature conductive paste, which is obtained by mixing the components in the low-temperature conductive paste composition according to the first aspect.
According to a third aspect of the present invention, there is provided a conductive coating obtained by curing the low-temperature conductive paste according to the second aspect.
In a fourth aspect, the present invention provides an electrode comprising a TCO film and the conductive coating of the third aspect.
A fifth aspect of the invention provides a heterojunction solar cell comprising an electrode according to the fourth aspect.
Through the technical scheme, the low-temperature conductive paste composition provided by the invention can reduce the contact resistance between the conductive coating and the TCO film in the electrode, and reduce the resistivity of the heterojunction solar cell electrode, so that the conductivity is increased. In addition, the adhesion strength between the conductive coating and the TCO film can be improved. The electrode prepared by the low-temperature conductive paste composition can improve the photoelectric conversion efficiency of a heterojunction solar cell.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a low-temperature conductive paste composition containing the following components, each independently stored or stored in a mixed manner of two or more:
conductive particles, polymeric resins, silver salts, and metal salts; the metal element in the metal salt is selected from at least one of group IA metal element and group IIA metal element;
wherein the content of the conductive particles is 65-97wt% based on the total mass of the low-temperature conductive paste composition; the content of the polymer resin is 2.5-25wt%; the silver salt content is 0.3-5wt% on a dry basis; the content of the metal salt is 0.05-5wt% based on dry basis.
The inventors of the present invention found in the course of the study that a low-temperature conductive paste composition prepared by combining a specific content of a silver salt with a metal salt (at least one of a group IA metal element and a group IIA metal element in the metal salt) and then compounding a specific content of conductive particles and a linear polymer resin, the combination of the silver salt and the metal salt, and other components in the composition create more conditions for adhesive connection between the metal conductive particles while also contributing to reduction of porosity after the curing reaction, thereby reducing resistivity and improving shear strength, and the resulting low-temperature conductive paste can significantly improve the conductive properties of an electrode prepared therefrom and the adhesive strength between the conductive coating and the TCO film in the electrode.
According to some embodiments of the present invention, preferably, the content of the conductive particles is 85 to 95wt% based on the total mass of the low temperature conductive paste composition; the content of the polymer resin is 5-10wt%; the silver salt content is 0.5-4wt% on a dry basis; the metal salt is present in an amount of 0.1 to 2wt% on a dry basis.
According to some embodiments of the invention, preferably, the mass ratio of the total mass of the silver salt and the metal salt to the polymeric resin is 0.3 to 1:1, wherein the silver salt is on a dry basis and the metal salt is on a dry basis.
With the above preferred embodiments, it is advantageous to further improve the conductivity of the electrode prepared therefrom and the adhesion strength between the conductive coating and the TCO film in the electrode.
According to some embodiments of the invention, preferably, the silver salt is an organic silver salt and/or an inorganic silver salt; more preferablyThe organic silver salt is selected from silver acetate (CH) 3 COOAg), silver propionate (C 2 H 5 COOAg), silver butyrate (C) 3 H 7 COOAg), silver oxalate (Ag 2 C 2 O 4 ) Silver benzoate (C) 6 H 5 COOAg), silver 2-ethylhexanoate (CH 3 (CH 2 ) 3 CH(C 2 H 5 )CO 2 Ag), silver picrate (C) 6 H 2 AgN 3 O 7 ) And silver alginate (C) 6 H 7 O 6 Ag), more preferably at least one of silver acetate, silver oxalate and silver 2-ethylhexanoate. The preferred embodiment described above can generate a large amount of active radicals in the thermally induced reaction, which is advantageous in obtaining a bonded body having sufficient strength. The organic silver salt may use a commercially available organic silver salt reagent such as Sigma-Aldrich_204374 silver acetate.
According to some embodiments of the invention, preferably, the inorganic silver salt is selected from the group consisting of silver diammine hydroxide (Ag (NH) 3 ) 2 OH), silver nitrate (AgNO 3 ) Silver carbonate (Ag) 2 CO 3 ) Silver chloride (AgCl), silver sulfide (Ag) 2 S), silver sulfate (Ag 2 SO 4 ) And at least one of silver bromide (AgBr), preferably at least one of silver diammine hydroxide, silver carbonate and silver nitrate. The inorganic silver salt may be a commercially available inorganic silver salt reagent such as silver carbonate, bang Chemicals-534-16-7.
According to some embodiments of the present invention, preferably, the organic silver salt is contained in an amount of 1 to 3wt% on a dry basis based on the total mass of the low temperature conductive paste composition; the content of the inorganic silver salt is 0.5-1wt% based on dry basis.
According to some embodiments of the invention, preferably, the metal element in the metal salt is selected from at least one of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium, preferably at least one of potassium, cesium and barium.
According to some embodiments of the invention, preferably, the metal salt is an organometallic salt and/or an inorganic metal salt. Wherein the organic metal salt comprises a saturated aliphatic metal salt and/or an unsaturated aliphatic metal salt, preferably the organic metal salt is selected from at least one of cesium 2-ethylhexanoate, barium cyclohexylbutyrate, calcium 2-ethylhexanoate, potassium stearate, cesium stearate, potassium cyclohexylbutyrate, cesium cyclohexylbutyrate, potassium 2-ethylhexanoate, potassium alginate, cesium alginate and cesium oleate. The organometallic salts are not only water soluble but also alcohol soluble. The organometallic salts may be used as commercially available agents such as cesium stearate of michaeli technology_m02240.
According to some embodiments of the invention, preferably, the inorganic metal salt is selected from at least one of a hydroxide, a halide, and a carbonate containing the metal element.
According to some embodiments of the present invention, it is preferable that the content of the organic metal salt is 0.2 to 1wt% on a dry basis based on the total mass of the low temperature conductive paste composition.
According to some embodiments of the present invention, it is preferable that the inorganic metal salt is contained in an amount of 0.1 to 1wt% on a dry basis based on the total mass of the low temperature conductive paste composition.
According to some embodiments of the invention, the metal element in the metal salt is present in the conductive paste in the form of a metal ion.
According to some embodiments of the invention, the metal salt is provided in the form of an aqueous and/or alcoholic solution. Preferably, in the aqueous and/or alcoholic solution of the metal salt, the mass fraction of the metal salt may be 0.5 to 40wt%.
According to some embodiments of the present invention, the conductive particles may be any conductive particles known in the art to be suitable for preparing heterojunction solar cells, and are not particularly limited in this regard, and all of them can achieve the object of the present invention to some extent. Preferably, the conductive particles are selected from at least one of silver particles, copper particles, platinum particles, palladium particles, gold particles, tin particles, lead particles, indium particles, aluminum particles, bismuth particles, nickel particles, and zinc particles, preferably silver particles; more preferably, the silver particles have an average particle diameter of 0.1 to 10 μm.
According to some embodiments of the present invention, the shape of the conductive particles is not particularly limited, and may be selected according to actual needs, which can achieve the object of the present invention to some extent. For example, the conductive particles may be in the form of a sheet, a sphere, a column, a block, or the like.
The conductive particles according to the preferred embodiments described above are advantageous for further improving the conductive properties of the electrode prepared therefrom and the adhesion strength between the conductive coating and the TCO film in the electrode.
In some embodiments of the present invention, the polymeric resin may remain in the cured conductive coating after the conductive paste is cured, and may be used as an adhesive for bonding between conductive particles and/or between conductive particles and an underlying substrate.
In order to further improve the conductive properties of the electrode prepared therefrom and the adhesive strength between the conductive coating and the TCO film in the electrode, the polymeric resin is preferably a linear polymeric resin, preferably a novolac epoxy resin and/or a novolac resin. The linear polymeric resin has an adjustable viscosity and flowability; the linear polymeric resin has designable crosslinking density and active groups through a special molecular design and synthesis method, and can be used as a prepolymer to further form a crosslinking network structure; the linear polymer resin synthesized by a certain molecular design has better moisture resistance and crack resistance.
Wherein the novolac epoxy resin can be prepared by reacting an oligomeric epoxy molecule composition with dihydric phenol according to the method disclosed in document 1 (Auad M, et al, "Synthesis and properties of epoxy-phenolic clay nanocomposites @" Express Polymer Letters,1 (2007): 629-639). The phenolic novolac epoxy resin contains 50 to 90% of equivalent of aliphatic diepoxide and 10 to 50% of equivalent of aromatic diepoxide, and has a number average molecular weight of 500 to 10000 (linear). Preferably, the novolac epoxy resin has a number average molecular weight of 3000 to 7000, contains 60 to 70% of aliphatic diepoxide equivalent weight and 30 to 40% of aromatic diepoxide equivalent weight.
The phenolic novolac resin can be prepared by subjecting 2, 6-dibromo-4- (bromomethyl) phenol to an aromatic electrophilic substitution reaction according to the method disclosed in document 2 (Uyigue L, et al, "Estimation of Product Yield and Kinetic Parameters of Phenolic Resin Pre-Polymer Synthesis using Acid and Base as catalyst." IOSR Journal of Engineering,9, (2018): 14-25.). The hydroxyl and the bromo contained in the phenolic novolac polymer have thermal initiation reactivity, and can further form a crosslinked network structure. The number average molecular weight of the novolac epoxy resin is 500 to 12000, and preferably, the number average molecular weight of the novolac epoxy resin is 5000 to 9000.
According to some embodiments of the invention, preferably, the novolac epoxy resin and the novolac resin are used in combination. More preferably, the mass ratio of the novolac epoxy resin to the novolac resin is 1-5:1, preferably 1-2.5:1.
the use of the polymeric resins of the preferred embodiments described above is advantageous for further improving the conductive properties of the electrodes made therefrom and the adhesion strength between the conductive coating and the TCO film in the electrodes.
According to some embodiments of the present invention, preferably, the low-temperature conductive paste composition further contains a solvent; the solvent is advantageous in further promoting the dissolution of the polymeric resin, silver salt and metal salt, allowing the conductive paste to be uniformly mixed and have viscosity. Preferably, the solvent is selected from at least one of alcohols, ethers, esters and ether alcohols, preferably at least one of isopropanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, butyl acetate alcohol, alpha-terpineol, texanol, butyl acetate, diethylene glycol diethyl ether and 2-butoxyethanol.
According to some embodiments of the present invention, it is preferable that the solvent is contained in an amount of 0.5 to 10wt% based on the total mass of the low temperature conductive paste composition.
Here, when the silver salt and the metal salt are provided in the form of an aqueous solution, the solvent contained in the low-temperature conductive paste composition does not include water in the aqueous solution.
According to some embodiments of the present invention, the low temperature conductive paste composition may further contain any additive known in the art to be suitable for preparing heterojunction solar cells to improve the properties of the conductive paste. The additives include, but are not limited to, sensitizers, coupling agents, dispersants, leveling agents, viscosity modifiers, defoamers, thixotropic agents, stabilizers, surfactants, hardeners, rheology additives, resin diluents, or combinations thereof. Preferably, the additive is at least one of oleic acid, diethylenetriamine and isobutyltriethoxysilicon. Preferably, the content of the additive is not more than 5wt%, for example, may be 0.1wt% to 5wt%, based on the total mass of the conductive paste composition.
In the present invention, the term "on a dry basis" refers to a pure compound, for example, when the metal salt is provided in the form of an aqueous and/or alcoholic solution, the metal salt on a dry basis refers to a metal salt on a solute basis. Silver salts on a dry basis refer to silver salts on a pure compound basis.
In a second aspect, the present invention provides a low-temperature conductive paste, which is obtained by mixing the components in the low-temperature conductive paste composition according to the first aspect.
According to some embodiments of the present invention, the mixing order of the components in the low-temperature conductive paste composition is not particularly limited as long as a uniform conductive paste can be obtained.
According to a third aspect of the present invention, there is provided a conductive coating obtained by curing the low-temperature conductive paste according to the second aspect.
According to some embodiments of the present invention, the curing may be performed with reference to the prior art, and the manner and condition of the curing, the apparatus, and the like are not particularly limited. For example, the curing temperature may be 100-350 ℃ and the curing time may be 1 minute to 2 hours.
In a fourth aspect, the present invention provides an electrode comprising a TCO film and the conductive coating of the third aspect.
A fifth aspect of the invention provides a heterojunction solar cell comprising an electrode according to the fourth aspect.
In addition, the electrode can be applied to other fields, such as the field of touch screens.
The present invention will be described in detail by examples.
In the following examples, all the raw materials used were commercially available unless otherwise specified.
(1) Conductive particles
Conductive particles 1: flake silver powder with flake diameter of 1-3 μm is purchased from Beijing De island gold technology Co., ltd;
conductive particles 2: spherical silver powder with an average particle diameter of 2 μm, such as Advanced Materials _47MR-01C nano silver powder;
conductive particles 3: spherical silver powder with average particle diameter of 0.2-1 μm, which is purchased from Allatin, model S110970;
(2) Polymeric resins
Polymeric resin 1: novolac epoxy resin (prepared by the method disclosed in document 1) having a number average molecular weight of 3000 to 7000;
polymeric resin 2: phenolic novolac resin (prepared by the method disclosed in document 2) has a number average molecular weight of 5000 to 9000.
(3) Organic silver salts
Silver acetate: purchased from microphone company;
silver oxalate: purchased from maka;
silver 2-ethylhexanoate: purchased from Sigma-Aldrich company;
(4) Inorganic silver salt
Diammine silver hydroxide: purchased from pre-derivative chemical company;
silver carbonate: purchased from bang Cheng chemical company;
silver nitrate: purchased from alfa elsa company;
(5) Organic metal salt
Potassium cyclohexylbutyrate (OAM-1): purchased from western reagent company;
potassium stearate (OAM-2): purchased from euro gold practice company; cesium 2-ethylhexanoate (OAM-3): purchased from national pharmaceutical agents;
cesium stearate (OAM-4): purchased from Sigma-Aldrich company; barium cyclohexylbutyrate (OAM-5): purchased from brewster reagent company;
(6) Inorganic metal salt
AM-1:10wt% aqueous potassium chloride;
AM-2:10wt% barium hydroxide aqueous solution;
AM-3:22.5wt% cesium hydroxide aqueous solution;
AM-4:22.5wt% cesium chloride aqueous solution;
AM-5:0.5wt% cesium carbonate aqueous solution;
(7) Solvent(s)
Isopropyl alcohol (IPA): purchased from microphone company;
butyl acetate alcohol (BCA): purchased from Sigma-Aldrich company; alpha-Terpineol (TP): purchased from alfa elsa company;
(8) Additive agent
Oleic acid: purchased from cereal chemicals company;
diethylenetriamine: purchased from maka;
example 1
Mixing all components in the low-temperature conductive paste composition to obtain conductive paste;
the mixing step specifically comprises the following steps: premixing polymeric resin, silver salt, metal salt, solvent and additive by using a planetary centrifugal mixer, adding conductive particles into the obtained premix, stirring and mixing by using a planetary stirrer, and dispersing and grinding the obtained mixture by using a three-roller grinder;
the premixing conditions are as follows: the temperature is 25 ℃, the time is 30min, and the mixing speed is 300rpm;
the conditions of stirring and mixing are as follows: the temperature is 50 ℃, the time is 60min, and the mixing speed is 500rpm;
the kinds and amounts of the respective components are shown in Table 1.
The other examples were conducted in the same manner as in example 1 except that the kinds and amounts of the respective components were as shown in Table 1, and the other examples were the same as in example 1, to obtain low-temperature conductive paste.
Comparative examples 1 to 4
The procedure of example 1 was followed except that the kinds and amounts of the respective components were as shown in Table 1, and the rest was the same as in example 1, to obtain a conductive paste.
TABLE 1
Figure BDA0004071207850000101
Figure BDA0004071207850000111
Table 1 (subsequent)
Figure BDA0004071207850000112
Figure BDA0004071207850000121
Table 1 (subsequent)
Figure BDA0004071207850000122
Figure BDA0004071207850000131
Test example 1
The test example was used to test the resistivity of the electrode made of the low temperature conductive paste.
In the test example, a single crystal silicon wafer substrate was used. The single crystal silicon wafer substrate is an n-type Si wafer grown by Czochralski method, and has a thickness of 200 μm and a resistivity of 5. Omega. Cm. Firstly, carrying out surface texture on the Si wafer by using an alkaline aqueous solution; then, siN with the thickness of 80nm is formed on the textured silicon wafer x H dielectric layer.
The conductive pastes of examples and comparative examples were screen-printed and coated on a monocrystalline silicon wafer substrate, respectively, and vacuum-dried at room temperature for 3 hours. Then, curing was performed at 200 ℃ using circulated hot air for 50 minutes to obtain fine wire electrodes. The resistance of the filament electrode was then measured with an AEMC 6240 micro-resistance meter and the width and length of the filament was measured with a WI-5000 interferometric coaxial three-dimensional stereomicroscope. The pattern specification of the thin wire electrode formed above was 40 μm in width of the intermediate line segment, 9cm in length, and 2mm×2mm in contact pads at the head and tail. The resistance of the wire is measured by four-terminal sensing between the contact pads, normalized by the length of the grid line, and multiplied by the cross-sectional area (measured using an alpha step profiler) to obtain the resistivity (p) of the grid line. Each resistivity dataset was obtained by averaging the values measured for four different grid lines. The resistivity test results are shown in table 2.
Test example 2
The test example was used to test the contact resistivity between the electrode made of the conductive paste and the TCO film.
The single crystal silicon wafer substrate in the above test example 1 was subjected to deposition of an ITO (indium tin oxide transparent conductive layer) layer having a thickness of 90nm and a resistivity of 20 Ω/sq by radio frequency sputtering. The ITO coated wafer was used for contact resistance measurements on Ag grid lines generated from the above silver paste.
The conductive pastes of the above examples and comparative examples were screen-printed and coated on TCO and dried (vacuum drying at room temperature for 3 hours), and then cured by circulating hot air at a temperature of 200 ℃ for 50 minutes to obtain an electrode pattern. The electrode pattern consisted of 5 linear electrodes with a line width of 0.5mm and a length of 50mm, with a line spacing of 3mm. Then, the resistance between the line electrodes of different pitches was measured using an AEMC 6240 micro-resistance meter, and the resistance values between the line electrodes were matched. Calculating distance by Transmission Line Modeling (TLM) to obtain contact resistivity (ρ) with the substrate C ) The test results are shown in Table 2.
Test example 3
The test example was used to test the adhesion strength between the conductive coating and the TCO film in the electrode made of the conductive paste. The conductive pastes of examples and comparative examples were screen-printed and coated on TCO and dried (vacuum drying at room temperature for 3 hours), respectively, and then cured by circulating hot air at a temperature of 200 ℃ for 50 minutes to obtain electrode patterns. The test electrode was 5cm long by 2mm wide in pattern specification, and then a tin-plated copper tape 1mm wide was soldered to the test electrode. The substrate was fixed on a tensile tester platform to test peel strength. The tensiometer type is NLB-100 electronic push-pull pressure meter. The test conditions were that the solder tape was peeled off at an angle of 180 ° at a speed of 60mm/min, and a pull force value was obtained, recorded every 1 second. The obtained tension was an average value of 5cm long electrodes, and the results are shown in Table 2.
TABLE 2
Project Resistivity (ρ) Contact resistivity (. Rho.) C ) Peel strength of
Unit (B) Ω·cm Ω·cm N/mm
Example 1 5.9×10 -6 0.65 1.6
Example 2 9.6×10 -6 0.95 1.1
Example 3 9.2×10 -6 0.97 0.9
Example 4 1.5×10 -5 1.1 1.1
Example 5 9.9×10 -6 0.85 1.3
Example 6 2.2×10 -5 1.9 1.3
Example 7 8.8×10 -6 1.1 1.2
Example 8 2.9×10 -5 2.1 1.3
Comparative example 1 3.7×10 -5 4.1 1.3
Comparative example 2 3.3×10 -5 3.6 1.2
Comparative example 3 2.9×10 -5 3.3 1.1
Comparative example 4 3.5×10 -5 3.8 0.8
From the above results, it can be seen that the low-temperature conductive paste composition provided by the invention can reduce the contact resistance between the conductive coating and the TCO film in the electrode, and reduce the resistivity of the heterojunction solar cell electrode, thereby increasing the conductivity. In addition, the adhesion strength between the conductive coating and the TCO film can be improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (10)

1. A low-temperature conductive paste composition, characterized in that the low-temperature conductive paste composition contains the following components which are stored independently or in a mixed state of two or more:
conductive particles, polymeric resins, silver salts, and metal salts; the metal element in the metal salt is selected from at least one of group IA metal element and group IIA metal element;
wherein the content of the conductive particles is 65-97wt% based on the total mass of the low-temperature conductive paste composition; the content of the polymer resin is 2.5-25wt%; the silver salt content is 0.3-5wt% on a dry basis; the content of the metal salt is 0.05-5wt% based on dry basis.
2. The low-temperature conductive paste composition according to claim 1, wherein the content of the conductive particles is 85 to 95wt% based on the total mass of the low-temperature conductive paste composition; the content of the polymer resin is 5-10wt%; the silver salt content is 0.5-4wt% on a dry basis; the content of the metal salt is 0.1-2wt% based on dry basis;
and/or the mass ratio of the total mass of the silver salt and the metal salt to the polymeric resin is 0.3 to 1:1, wherein the silver salt is on a dry basis and the metal salt is on a dry basis.
3. The low-temperature conductive paste composition according to claim 1, wherein the silver salt is an organic silver salt and/or an inorganic silver salt; wherein the organic silver salt is selected from at least one of silver acetate, silver propionate, silver butyrate, silver oxalate, silver benzoate, silver 2-ethylhexanoate, silver picrate and silver alginate, preferably at least one of silver acetate, silver oxalate and silver 2-ethylhexanoate;
the inorganic silver salt is selected from at least one of diammine silver hydroxide, silver nitrate, silver carbonate, silver chloride, silver sulfide, silver sulfate and silver bromide, preferably at least one of diammine silver hydroxide, silver carbonate and silver nitrate;
preferably, the metal element in the metal salt is selected from at least one of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium, preferably at least one of potassium, cesium, and barium;
and/or the metal salt is organic metal salt and/or inorganic metal salt; wherein the organic metal salt is selected from at least one of cesium 2-ethylhexanoate, barium cyclohexylbutyrate, calcium 2-ethylhexanoate, potassium stearate, cesium stearate, potassium cyclohexylbutyrate, cesium cyclohexylbutyrate, potassium 2-ethylhexanoate, potassium alginate, cesium alginate and cesium oleate;
the inorganic metal salt is selected from at least one of a hydroxide, a halide and a carbonate containing the metal element.
4. A low-temperature conductive paste composition according to any one of claims 1 to 3, wherein the conductive particles are selected from at least one of silver particles, copper particles, platinum particles, palladium particles, gold particles, tin particles, lead particles, indium particles, aluminum particles, bismuth particles, nickel particles and zinc particles, preferably silver particles; more preferably, the silver particles have an average particle diameter of 0.1 to 10 μm.
5. A low temperature conductive paste composition according to any of claims 1-3, wherein said polymeric resin is a linear polymeric resin, preferably a novolac epoxy resin and/or a novolac resin; wherein the phenolic novolac epoxy resin contains 50-90%, preferably 60-70%, of aliphatic diepoxide equivalents and 10-50%, preferably 30-40%, of aromatic diepoxide equivalents;
and/or the number average molecular weight of the novolac epoxy resin is 500-10000, preferably 3000 to 7000; the number average molecular weight of the phenolic novolac resin is 500-12000, preferably 5000-9000;
preferably, the mass ratio of the novolac epoxy resin to the novolac resin is 1-5:1, preferably 1-2.5:1.
6. the low-temperature conductive paste composition according to any one of claims 1 to 3, further comprising a solvent; the solvent is selected from at least one of alcohol, ether, ester and ether alcohol, preferably at least one of isopropanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, butyl acetate alcohol, alpha-terpineol, texanol, butyl acetate, diethylene glycol diethyl ether and 2-butoxyethanol;
and/or the content of the solvent is 0.5-10wt% based on the total mass of the low-temperature conductive paste composition.
7. A low-temperature conductive paste, characterized in that the low-temperature conductive paste is obtained by mixing the components in the low-temperature conductive paste composition according to any one of claims 1 to 6.
8. A conductive coating obtained by curing the low-temperature conductive paste according to claim 7.
9. An electrode comprising a TCO film and the conductive coating of claim 8.
10. A heterojunction solar cell characterized in that it comprises the electrode of claim 9.
CN202310094298.6A 2023-02-10 2023-02-10 Low-temperature conductive paste composition, low-temperature conductive paste, conductive coating, electrode and heterojunction solar cell Active CN116189958B (en)

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