CN108986952B - Heating curing type conductive paste, application thereof and solar cell - Google Patents

Heating curing type conductive paste, application thereof and solar cell Download PDF

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CN108986952B
CN108986952B CN201810765213.1A CN201810765213A CN108986952B CN 108986952 B CN108986952 B CN 108986952B CN 201810765213 A CN201810765213 A CN 201810765213A CN 108986952 B CN108986952 B CN 108986952B
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powder
electroconductive
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particle size
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CN108986952A (en
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冈本珍范
万莉
刘海东
敖毅伟
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Changzhou Fusion New Material Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L31/02—Details
    • H01L31/02002—Arrangements for conducting electric current to or from the device in operations
    • H01L31/02005—Arrangements for conducting electric current to or from the device in operations for device characterised by at least one potential jump barrier or surface barrier
    • H01L31/02008—Arrangements for conducting electric current to or from the device in operations for device characterised by at least one potential jump barrier or surface barrier for solar cells or solar cell modules
    • 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

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  • Electromagnetism (AREA)
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Abstract

The invention discloses a heating-curable conductive paste, which contains conductive powder, a thermosetting component, a curing agent and a solvent, wherein the conductive powder is conductive powder with a bimodal particle size distribution, the first peak value of the particle size distribution of the conductive powder is between 0.1 and 2 microns, the second peak value of the particle size distribution of the conductive powder is between 5 and 20 microns, and the intensity ratio of the first peak value to the second peak value is within the range of 1:2 to 2: 1. The conductive paste is prepared from a spherical powder having a single peak particle size distribution as a raw material. The heating-curable conductive paste of the present invention can evaporate and remove the solvent within 10 minutes at 160 ℃ or less, and complete the curing process within 5 minutes at 180 ℃, thereby making it possible to produce an electrode having high conductivity from the heating-curable conductive paste composition.

Description

Heating curing type conductive paste, application thereof and solar cell
Technical Field
The present invention relates generally to a heat-curable conductive paste composition, and more particularly to: a heat-curable conductive paste composition having a highly conductive electrode, wiring, and the like can be formed by heat-curing a coating film formed by printing on a substrate, and use thereof and a solar cell comprising the same.
Background
In the past, a technique of forming an electrode, wiring, or the like on a base material of a film, a substrate, an electronic component, or the like has been widely used.
When a conductor pattern is formed at a relatively low temperature by using such a technique, a heat-curable material containing a thermosetting resin and conductive metal powder (conductive particles) is also used. Further, the above-mentioned heat-curable conductive paste composition is applied or printed on a substrate to form a selected conductor pattern (patterning step), and the conductor pattern on the substrate is baked and cured by heating (heat curing step), whereby electrodes, wirings, and the like of a desired conductor pattern can be formed on the substrate. In the following description, the above methods are collectively referred to simply as "slurry method".
In recent years, as electronic devices and electronic parts have been increasingly improved in performance, the requirements for the electrodes, the wirings, and the like mentioned in the above-mentioned processes have been increasing, that is, the resistance value has been required to be further reduced. However, it is very difficult to reduce the resistance values of electrodes, wirings, and the like while ensuring high performance of electronic devices.
For example, if an electrode of an electronic component whose quality is deteriorated by a high-temperature treatment is formed by a paste method, the electrode tends to be heated at a high temperature by heat curing in order to obtain an electrode having a lower resistance value, but there is a risk that the quality of the electronic component is also affected if the heating temperature is too high.
Specifically, for example, in a solar cell having an amorphous silicon layer, high-temperature heating accelerates deterioration of the amorphous silicon layer and warpage of the element substrate. In order to prevent such deterioration of the performance, a low heating temperature is generally used for forming the electrode.
However, the solar cell described above has a collector electrode, and when the collector electrode is formed by a paste method, the heating temperature in the heat curing step is generally set to 200 ℃ or higher. This is because the heating temperature is high, the volume shrinkage of the heat-curing component contained in the conductive paste composition is also large, and the conductive particles such as silver are closely connected, thereby realizing a collector electrode having a lower resistance value.
Therefore, in order to reduce the resistance value of the collector electrode while maintaining the quality of the amorphous silicon layer or the like, conditions opposite to the heating temperature in the heat curing stage have been required. Generally, a method of heating and curing a conductive paste composition at a relatively low temperature for a short time is used, with an emphasis on ensuring the quality of an amorphous silicon layer or the like. However, the collector electrode formed by this method cannot be heated at a high temperature to obtain a low resistance. Therefore, in order to improve the conversion efficiency of the solar cell, there is a demand for a physical property of the electroconductive paste composition that can realize a low resistance value after heating and curing at a low temperature for a short time.
The manufacturing process of the solar cell having the amorphous silicon layer is also changed day by day, and although the requirements of the manufacturing process of each company are different, all the solar cells have the same point that the process conditions used in the actual production are as follows: the solvent on the substrate was evaporated by radiant heat in an electric furnace (heating by infrared ray) at 160 ℃ for 10 minutes, and heated at 180 ℃ for 5 minutes to complete the heat curing.
In the results of the present study, it was shown that,
japanese patent document No. 5819712 discloses a composition which is cured by heating at a temperature in the range of 100 to 300 ℃, but the curing time must be 60 minutes, which is not satisfactory.
Japanese patent document No. 5859823 also mentions a composition for forming electrodes and wirings on a substrate by heat-curing a conductor pattern on the substrate at a temperature in the range of 150 to 250 ℃, but it requires hot air drying for 60 minutes, which is not in accordance with the above requirements.
Japanese patent document No. 5916633 mentions that a conductive paste capable of heat treatment at a low temperature of 200 ℃ or lower while obtaining a conductive film having a sufficiently low resistivity is also required for a curing time of 30 minutes, failing to satisfy the above requirements.
Japanese patent publication No. 8-92506 mentions that a composition for forming an electrode for a solar cell, which can be cured by heating at a temperature in the range of 150 ℃ to 200 ℃, does not satisfy the above-mentioned process requirements because a curing time of 20 to 90 minutes is required.
In addition, in the studies of the above four prior patent documents, silver powder is conductive particles (conductive metal powder) in the conductive paste composition, and it is all claimed that at least one of the thinned silver powder and the spherical silver powder is used, if both can be used at the same time, it is preferable.
Disclosure of Invention
The present invention has been made to satisfy the above-mentioned requirements, and provides a heat-curable conductive paste composition, which is capable of evaporating and removing a solvent at 160 ℃ or less for 10 minutes and completing a curing process at 180 ℃ for 5 minutes, thereby producing an electrode having high conductivity, and uses thereof, and a solar cell.
The technical scheme of the invention is as follows:
a heat-curable conductive paste comprising:
(A) a conductive powder;
(B) a thermosetting component;
(C) a curing agent; and
(D) a solvent, wherein,
the particle size distribution of the conductive powder is a bimodal distribution having two peaks, the first peak of the particle size distribution of the conductive powder is between 0.1 and 2 microns, the second peak is between 5 and 20 microns, and the ratio of the intensity of the first peak to the intensity of the second peak is in the range of 1:2 to 2: 1.
Preferably, the conductive powder has a particle size distribution with a first peak around 1 micron and a second peak around 10 microns.
Preferably, the conductive paste is prepared using spherical powder having a single peak particle size distribution as a raw material.
In a preferred embodiment, the conductive powder is prepared by the following method: a spherical powder having one particle size distribution is used as a base conductive powder, which is then divided into two parts in an arbitrary ratio, one of the parts is ground to be thin, and the ground part is mixed with the remaining part, thereby obtaining a conductive powder having a bimodal distribution in which the particle size distribution has two peaks. The thinning method can specifically adopt three-roll technology and the like.
The inventors of the present invention have studied and found that an electrode formed by curing a conductive paste prepared using a single silver powder having two kinds of peak values of particle size distribution in mechanical contact prepared by the above method at a low temperature for a short time can exhibit a desired conductive performance.
In a preferred embodiment, the selected conductive powder is comprised of at least one of silver powder, copper powder, silver-plated nickel powder, silver-plated aluminum powder, and silver-plated glass powder. Typically, the conductive powder is silver powder.
In a preferred embodiment, the content of the conductive powder is 90% or more in the entire conductive paste.
In a preferred embodiment, the thermosetting component includes an epoxy resin, and a reaction inhibitor polyisocyanate compound.
In a preferred embodiment, the thermosetting component accounts for 2 to 8 wt% of the entire conductive paste.
The invention also provides a preparation method of the heating-curable conductive paste, which comprises a preparation method of conductive powder, wherein the preparation method of the conductive powder comprises the following steps: the method comprises the steps of taking spherical powder with single peak particle size distribution as a raw material, dividing the spherical powder into two parts in any proportion, grinding one part, mixing and dispersing the two parts, and then carrying out surface treatment.
The invention also provides application of the heating-curable conductive paste in solar cells.
The invention also provides a solar cell, which comprises an electrode and a wiring, wherein the electrode and/or the wiring are/is prepared by adopting the heating-curable conductive paste.
Compared with the prior art, the invention has the following beneficial effects:
the heating-curable conductive paste of the present invention can evaporate the solvent within 10 minutes at 160 ℃ or less and complete the curing process within 5 minutes at 180 ℃, thereby making it possible to produce an electrode having high conductivity.
Detailed Description
The present invention provides a heat-curable conductive paste which can evaporate and remove a solvent within 10 minutes at 160 ℃ or less and complete a curing process within 5 minutes at 180 ℃, thereby making it possible to produce an electrode having high conductivity.
The heat-curable conductive paste of the present invention comprises a conductive powder A, a heat-curable component B, a curing agent C and a solvent D, wherein the particle size distribution of the conductive powder is a bimodal distribution having 2 peaks.
(A) Conductive powder
Specifically, in the above-mentioned heat-curable electroconductive paste composition, the first peak of the particle size distribution of the selected electroconductive powder is around 1 μm, the second peak is around 10 μm, and the intensity ratio of the first peak to the second peak is in the range of 1:2 to 2: 1.
The inventors of the present invention have discussed the mixing of the spherical powder and the milled powder mentioned in ① prior art and the use of the two powders mentioned in ② prior art alone and the conductive resistance after a short time of low temperature curing, but have found that in either case, the two powders coagulate themselves and thus sufficient ohmic contact cannot be ensured.
In order to prevent coagulation of each powder, surface treatment is generally performed, but since the surface treatment agent has an outer film, ohmic contact is further deteriorated if it is left under a condition of curing at a low temperature for a short time.
Therefore, the inventors of the present invention have conducted studies on the conductive resistance after short-time low-temperature curing after dividing a spherical powder having one particle size distribution as a base conductive powder in an arbitrary ratio, grinding one of the parts thin by a three-roll process or the like, mixing it with the remaining divided matter, and then, have found that a single silver powder having two particle size distribution peaks which are mechanically contacted can exhibit desirable properties under short-time low-temperature curing conditions.
(B) Heat curable component
The thermosetting component (B) used in the electroconductive paste composition of the present invention may be any known thermosetting component, but is preferably an epoxy resin (B-a), and more preferably an epoxy resin (B-a) and a polyisocyanate compound (B-B) as a reaction inhibitor are used together.
The epoxy resin (B-a) in the thermosetting component (B) used in the present invention is not particularly limited, and any polyvalent epoxy resin having 2 or more epoxy rings or epoxy groups in one molecule can be used. Specifically, for example, glycerin type epoxy resins, alicyclic epoxy resins such as dicyclopentadiene epoxy resins, and aliphatic epoxy resins such as Butadienedimer epoxides are exemplified. More specifically, the glycerin-type epoxy resin includes: phenolic compounds such as 3-chloroepoxypropane, 3-chloro-2-epoxypropane, phenol formaldehyde and cresol phenol formaldehyde; polyvalent phenol compounds such as bis (phenol), watered bis (phenol) a, bis (phenol) F, bis (phenol) AD, and resorcin; polyvalent alcohol compounds such as ethylene glycol, pentalene glycol, glycerin, trimethylolpropane and erythritol; and polyamide compounds such as ethylenediamine, triethylenetetramine, and aniline. In addition, multivalent carboxylic acid compounds such as adipic acid, phthalic acid, and isophthalic acid are also included. These epoxy resins may be used alone or in combination of 2 or more thereof. The use of epoxy resins of the glycerol type is particularly preferred in the present invention.
In the present invention, it is preferable that the epoxy equivalent of the (B-a) epoxy resin is controlled within a range of 100 to 1000, and it is preferable that the epoxy equivalent is controlled within a range of 100 to 400. If the epoxy equivalent is less than 100, the heat resistance and durability of the cured film formed from the obtained electroconductive paste composition are likely to be insufficient. On the other hand, if the epoxy equivalent exceeds 1000, the thixotropy of the electroconductive paste composition is lowered.
In the present invention, the (B-B) anti-reactant polyisocyanate compound used together with the (B-a) epoxy resin may be any known anti-reactant agent for the isocyanate group of a polyisocyanate compound. Specific examples of the polyisocyanate compound to be used include aromatic isocyanate compounds such as phenyl diisocyanate (tolylendiisocyanate); aliphatic polyisocyanate compounds such as hexamethylene diisocyanate. These reaction inhibitor polyisocyanate compounds using a polyisocyanate compound may be used alone or in combination of 2 or more.
Among these polyisocyanate compounds, polymethylene polyethyl polyisocyanate containing 3 or more cores in the component is more likely to be used. Further, an isocyanate group-terminated compound synthesized by reacting polyisocyanate with a polyol by a known method can be used as the polyisocyanate compound in the present invention. The above-mentioned polyol is not particularly limited, and general polyether polyols, polyester polyols, polycarbonate polyols, and the like, which are well known, can be used.
Among these polyols, polyether polyols include polyvalent alcohols such as ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-decanediol, bisphenol A, hydrous bisphenol A and glycerin, or phenolic compounds plus ethylenedioxide, or 1-oxypropylene and butyleneoxide. The polyesters include, for example, condensates of polyvalent alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1-propanediol, 1, 4-butanediol, and 1, 6-hexanediol with polybasic acid such as 1-malonic acid, succinic acid, adipic acid, phthalic acid, and 1-terephthalic acid. Examples of the polycarbonate polyol include polyvalent alcohols such as ethylene Glycol, propylene Glycol, 1, 4-butanediol, 1, 6-hexanediol, and Neopentyl Glycol (Neopentyl Glycol), and reaction products of phenol compounds, 1-dimethyl carbonate, 1-diphenyl carbonate, and chlorine.
The reaction inhibitor for the polyisocyanate compound is not particularly limited, and any known compound such as imidazoles, phenols, oximes, etc. may be used.
(B) When the epoxy resin (B-a) and the reaction-preventing polyisocyanate compound (B-B) are used together as the heat-curable component, if the total weight of the two is 100 parts by weight, the weight mixing ratio of the two is preferably controlled to be: epoxy resin 30, which prevents the reaction of polyisocyanate compound 70-epoxy resin 90, and prevents the reaction of polyisocyanate compound 10.
Further, the epoxy resin (component) and the reaction-preventing polyisocyanate compound (component) described herein are not limited to 1 type of the epoxy resin or the reaction-preventing polyisocyanate compound, but include the case where a plurality of types are used together. For example, when 2 or more epoxy resins are used, the term "30 weight parts of the (B-a) epoxy resin component" means that the total amount of the 2 epoxy resins is 30 weight parts. The expression "component" described below is also applied to the other components (A), (C) to (E).
When the amount of the epoxy resin component (B-a) is less than 30 parts by weight, that is, when the amount of the polyisocyanate compound component (B-B) is more than 70 parts by weight, the strength and adhesiveness of the cured film (conductor pattern after curing) formed from the resulting electroconductive paste composition tend to be lowered. On the other hand, if the amount of the (B-a) epoxy resin component exceeds 90% by weight, that is, if the amount of the (B-B) reaction-preventing polyisocyanate compound component is less than 10% by weight, the effect of preventing the contact between the conductive powders by curing shrinkage of the (B-B) reaction-preventing polyisocyanate compound component is reduced, and the conductivity of the formed electrode, wiring, or the like tends to be reduced.
(C) Curing agent
The curing agent in the electroconductive paste composition of the present invention may be suitably selected depending on the kind of the heat-curable component (B) to be used, but as described above, in the practice of the present invention, at least (B-a) an epoxy resin is used, but it is preferable to use both (B-a) an epoxy resin and (B-B) a reaction-preventing polyisocyanate compound, and therefore, a curing agent (C) suitable for this purpose can be used: imidazoles, lewis acids containing boron fluoride, and their ligands, or salts, amines, 3-grade amines, dicyandiamide, phenol resins, acid anhydrides, and the like.
Specific examples of the imidazoles include imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-undecanimidazole.
Boron fluoride-containing lewis acids and their ligands and salts, specifically including: boron trifluoride diethyl etherate, boron trifluoride phenol, boron trifluoride piperidine, and the like.
Specifically, the amine may be an AJICURE series produced by Kakkiso K.K., Japan, or a FUJICURE series produced by Fuji chemical Industrial Co., Ltd.
Stage 3 amines can be used in particular: dimethyl octylamine, dimethyl decylamine, dimethyl dodecylamine, and the like.
The phenol resin may specifically be used: JER170 and JER171N manufactured by Mitsubishi chemical corporation, MEH-8000H, MEH-8005 manufactured by Minghe Kaisha, and the like.
Anhydrides specifically can be used: anhydrous phthalic acid, anhydrous maleic acid, anhydrous cis-1, 2,3, 6-tetrahydrophthalic acid, and the like, or RIKACIDMH-700, RIKACIDHNA-100, and the like, which are available from New Japan chemical and chemical Co.
These (C) curing agents may be used alone or in combination with other curing agents. The amount of the (C) curing agent to be added is not particularly limited, but is preferably within a range from 3 to 30 parts by weight, more preferably from 3 to 15 parts by weight, most preferably from 3 to 10 parts by weight, based on the (B-a) epoxy resin, that is, based on 100 parts by weight of the (B-a) epoxy resin component. If the amount of the curing agent (C) is less than 3 parts by weight based on 100 parts by weight of the epoxy resin, the curing of the heat-curable component (B) will be insufficient, and good electrical conductivity will not be obtained in the formed electrodes and wiring. On the other hand, if the amount exceeds 30% by weight, the paste viscosity in the conductive paste composition becomes high, and the cost reduction is not facilitated.
(D) Solvent(s)
As the solvent (D) used in the electroconductive paste composition of the present invention, a well-known solvent can be used. Specifically, there may be used: glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol dibutyl ether; acetates of these glycol ethers; esters such as DBE (dihydrochloride) and 2,2, 4-trimethyl-1, 3-pentanediol isobutyrate; ketones such as cyclohexanone; monoterpene alcohols and the like; and acetates of these monoterpene alcohols; gbl (gamma abuthyrolactone); limonene; n-methyl-2-pyrrolidone, and the like. These solvents may be used alone or in combination of two or more.
The conductive paste composition is mainly used for forming a conductor pattern by screen printing. Therefore, in order to prevent the screen-printed substrate from drying out, a high boiling point solvent having a boiling point of 200 ℃ or higher is used for half or more of the (D) solvent components in the conductive paste composition.
Specific examples of the high boiling point solvent include diethylene glycol ethyl acetate, GBL (Gamma butyrolactone), and n-methyl-2-pyrrolidone. These high boiling point solvents may be used either singly or in combination.
In this context, a range of values from one value to another is a general expression avoiding any recitation of all values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the invention will be understood to cover all modifications and variations of this invention provided they come within the scope of the appended claims.
Examples
1. Preparation of samples of examples and comparative examples
A thermosetting conductive paste was prepared according to the formulation of example 1 in table 1 below, in the following manner:
(1) mixing epoxy resin, a polyisocyanate compound and a DBE solvent according to the ratio of 2.5:2:2.68, stirring and heating to 80 ℃, preserving heat for 2 hours, filtering after the solution is clear, cooling to room temperature to obtain a dissolved resin solution, and placing the dissolved resin solution in a closed container for later use;
(2) preparing conductive powder:
a. the conductive powder in example 1 was prepared by selecting spherical silver powder having a particle size of 1.5 μm as a base powder, taking out 41% of the spherical powder, grinding it using a three-roll mill until the particle size increased to 10 μm, and mixing with the remaining 59% of the spherical powder.
b. Comparative example: according to the proportion in the table 1, a plurality of proportions of spherical silver powder with the grain diameter of 1.5 mu m and flake silver powder with the grain diameter of 10 mu m are respectively mixed.
(3) Uniformly mixing the dissolved resin solution, boron trifluoride ether and imidazole curing agent according to the proportion of 7.18:0.1:0.1, adding conductive powder according to the proportion shown in the table 1, dispersing, grinding by three rollers to prepare a conductive slurry sample, filtering, and packaging to perform related performance tests.
The proportions of the conductive fillers are shown in Table 1.
2. And (3) performance testing:
1) and (3) testing the adhesive force:
a. printing the prepared conductive paste on a silicon substrate with the thickness of 180 mu m and the printing pattern of 2 x 60mm, wherein the thickness of the silicon substrate is 75 x 75 mm;
b. putting the printed sample into a constant-temperature oven at 150 ℃, heating for 30s, and taking out;
c. soldering to the cured sample using a 1mm wide 63/37 lead-tin solder tape at 330 ℃;
d. and (5) reversing 180 degrees, testing the adhesive force between the solder strip and the cured conductive paste, and recording the average value.
2) Line resistivity test:
a. printing the prepared conductive paste on a silicon substrate with the thickness of 180 mu m and the printing pattern of 3 x 3mm, wherein the thickness of the silicon substrate is 200 mu m;
b. putting the printed sample into a constant-temperature oven at 150 ℃, heating for 30s, and taking out;
c. the resistance of the cured sample was measured using a microohm meter 5 times and averaged.
TABLE 1
Figure BDA0001728874500000101
As can be seen from Table 1, the line resistivity of the silver powder of the embodiment 1 of the invention is obviously lower than that of the comparative example, and the adhesion force is obviously higher than that of the comparative example, which shows that the silver powder with the double distribution peaks of the silver powder of the embodiment and the invention has the advantages of solving the problem of dispersion and agglomeration of the silver powder with two different morphologies, and improving the conductivity and mechanical properties of the prepared electrode.
In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.

Claims (8)

1. A heat-curable electroconductive paste comprising an electroconductive powder, a heat-curable component, a curing agent and a solvent, wherein the electroconductive powder is an electroconductive powder having a particle size distribution in a bimodal distribution, the electroconductive powder has a first peak in the particle size distribution of 0.1 to 2 μm and a second peak in the particle size distribution of 5 to 20 μm, and the intensity ratio of the first peak to the second peak is in the range of 1:2 to 2: 1; the conductive powder is single powder prepared by taking spherical powder with single peak particle size distribution as a raw material, dividing the spherical powder into two parts in any proportion, grinding one part of the spherical powder, mixing and dispersing the two parts of the spherical powder and performing surface treatment on the mixture.
2. The thermosetting electroconductive paste according to claim 1, wherein the first peak of the particle size distribution of the electroconductive powder is around 1 μm, and the second peak is around 10 μm.
3. The conductive paste according to claim 1, wherein the conductive powder is at least one of silver powder, copper powder, silver-plated nickel powder, silver-plated aluminum powder, and silver-plated glass powder.
4. The thermosetting electroconductive paste according to claim 1, wherein the content of the electroconductive powder in the entire electroconductive paste is 90% or more.
5. The thermosetting electroconductive paste according to claim 1, wherein the thermosetting component comprises an epoxy resin and a reaction inhibitor polyisocyanate compound.
6. The heat-curable electroconductive paste according to claim 1 or 5, wherein the thermosetting component is contained in a ratio of 2 to 8% by weight in the entire electroconductive paste.
7. Use of the heat-curable conductive paste according to any one of claims 1 to 6 for a solar cell.
8. A solar cell comprising electrodes and wiring, characterized in that the electrodes and/or wiring are made using the heat-curable conductive paste according to any one of claims 1 to 6.
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