CN112992402B - Silver and two-dimensional MXene mixed system conductor slurry for chip resistor and preparation method thereof - Google Patents
Silver and two-dimensional MXene mixed system conductor slurry for chip resistor and preparation method thereof Download PDFInfo
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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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
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- H—ELECTRICITY
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Abstract
The invention relates to a conductor paste for a chip resistor and a preparation method thereof, wherein the conductor paste comprises a conductive material, an inorganic bonding material and an organic carrier, the conductive material comprises silver and two-dimensional MXene, and the two-dimensional MXene is selected from one or more of carbide sheet layer material of an early transition metal, nitride sheet layer material of the early transition metal and carbonitride sheet layer material of the early transition metal. The conductor paste of the invention has good solder leaching resistance, sulfidization resistance and silver migration inhibition when used as an electrode material of a chip resistor, and has lower cost compared with the traditional silver palladium conductor paste.
Description
Technical Field
The invention belongs to the field of conductor paste for a chip resistor, and particularly relates to silver and two-dimensional MXene mixed system conductor paste for the chip resistor and a preparation method thereof.
Background
The chip resistor, commonly called as a chip resistor, is one of the most developed and mature components in the thick film hybrid integrated circuit, has the advantages of small volume, high energy density, light weight, high installation density, strong shock resistance, strong anti-interference capability, good high-frequency characteristic and the like, and is widely applied to various integrated circuits of electronic products, such as computers, mobile phones, medical treatment, aerospace, aviation, vehicle-mounted and other electronic products. At present, chip components have replaced most of traditional plug-in components and become the leading corners of electronic products, and include chip resistors, chip capacitors, chip inductors, chip semiconductor devices, and other chip products, wherein the chip resistors have the largest demand, account for more than 45% of the whole chip components, and the annual demand has exceeded 1 trillion.
Electronic paste is an extremely important place in the electronic field as a base material for manufacturing electronic components. The electronic paste used in the chip resistor includes a conductive paste and a resistance paste, wherein the conductive paste becomes an electrode by being printed on a substrate, and becomes an important raw material of the chip resistor. Due to the influence of the processing technology and the use environment, the chip resistor electrode needs to have certain characteristics of acid resistance, solder leaching resistance, silver migration resistance, silver sulfuration resistance and the like, so that the components of the conductor paste are required to meet the characteristics through special design, for example, the acid resistance and the solder leaching resistance can be improved by adding some metal oxides, the silver migration resistance and the silver sulfuration resistance can be improved by replacing the conductor material with silver palladium alloy, but the palladium cost is high, the cost of the whole device is improved, and the production is not facilitated.
Therefore, there is still a need in the art for a conductor paste for a chip resistor having excellent resistance to sulfidation and solder corrosion, which is simple in manufacturing process and low in cost.
Disclosure of Invention
Aiming at the problems, the invention provides novel conductor paste applied to a chip resistor and a preparation method thereof, which can improve the silver sulfuration resistance, silver migration resistance and solder leaching resistance of an electrode and overcome the defects of complex preparation process and high cost in the prior art.
Specifically, the invention provides a conductor paste for a chip resistor electrode, which comprises a conductive material, an inorganic bonding material and an organic vehicle, wherein the conductive material comprises silver powder and two-dimensional MXene, and the two-dimensional MXene is selected from one or more of carbide sheet layer material of an early transition metal, nitride sheet layer material of the early transition metal and carbonitride sheet layer material of the early transition metal.
In one or more embodiments, the silver powder is present in the conductive paste in an amount of 40 to 60wt.%, the two-dimensional MXene is present in an amount of 5 to 25wt.%, the inorganic binder is present in an amount of 5 to 15wt.%, and the organic vehicle is present in an amount of 5 to 50wt.%, based on the total weight of the conductive paste.
In one or more embodiments, the silver powder has a particle size of 0.5 to 12 μm.
In one or more embodiments, the two-dimensional MXene has a size of 0.5 to 15 μm.
In one or more embodiments, the two-dimensional MXene has a thickness of 2 to 10 nm.
In one or more embodiments, the inorganic bonding material is a lead-free glass frit.
In one or more embodiments, the organic vehicle includes a thickener and an organic solvent.
In one or more embodiments, the transition metal in the two-dimensional MXene is selected from one or more of Ti, V, Cr, Sc, Zr, Nb, Mo, Hf, and Ta.
In one or more embodiments, the transition metal in the two-dimensional MXene is Ti.
In one or more embodiments, the two-dimensional MXene is a carbide sheet material of an early transition metal.
In one or more embodiments, the lead-free glass frit is a molten mixture of one or more of silicon oxide, boron oxide, aluminum oxide, tin oxide, bismuth oxide, antimony oxide, copper oxide, and titanium oxide.
In one or more embodiments, the lead-free glass frit is a molten mixture of silica, boria, alumina and tin oxide.
In one or more embodiments, the thickener is selected from one or more of ethylcellulose, poly alpha-methylstyrene, and polymethylmethacrylate.
In one or more embodiments, the thickening agent is ethyl cellulose.
In one or more embodiments, the organic solvent is selected from one or more of terpineol, butyl carbitol acetate, and tributyl citrate.
In one or more embodiments, the organic solvent is terpineol.
In one or more embodiments, the thickener is present in the organic vehicle in an amount of 20 to 40wt.%, based on the total weight of the organic vehicle.
In one or more embodiments, the two-dimensional MXene is Ti3C2A sheet material.
In one or more embodiments, the inorganic bonding material is a lead-free glass frit, which is prepared from 40 to 50wt.% SiO2、25-35wt% B2O3、5-15wt.% Al2O3And 5-15wt.% SnO2And (4) forming.
In one or more embodiments, the organic carrier is a butyl carbitol solution of ethyl cellulose.
In one or more embodiments, the concentration of the butyl carbitol solution of ethyl cellulose is from 25 to 35 wt.%.
In one or more embodiments, the two-dimensional MXene is produced by converting M into Mn+1AXnThe compound is obtained by selectively etching A metal, wherein M is an early transition metal, A is a third or fourth main group element, X is C and/or N, and N is 1, 2 or 3.
In one or more embodiments, M is selected from one or more of Ti, V, Cr, Sc, Zr, Nb, Mo, Hf, and Ta.
In one or more embodiments, M is Ti.
In one or more embodiments, a is Al and/or Si.
In one or more embodiments, a is Al.
In one or more embodiments, X is C.
In one or more embodiments, n is 2.
In one or more embodiments, the two-dimensional MXenen is prepared by the following method: etching M with a mixed aqueous solution of HF, HCl and LiFn+1AXnAnd (3) obtaining the two-dimensional MXene by a metal layer A in the middle of the compound and then performing freeze-thaw cycling.
In one or more embodiments, the M isn+1AXnThe compound being Ti3AlC2。
In one or more embodiments, the silver powder has a particle size of 0.5 to 12 μm and the two-dimensional MXene is Ti3C2Lamellar material of said Ti3C2The size of the sheet material is 0.5-15 μm, and the Ti is3C2The thickness of the sheet material is 2-10nm, the inorganic bonding material is lead-free glass powder, and the raw material of the lead-free glass powder is 40-50wt.% SiO2、25-35wt% B2O3、5-15wt.% Al2O3And 5-15wt.% SnO2The organic carrier is a butyl carbitol solution of ethyl cellulose with the concentration of 25-35 wt.%; the content of the silver powder is 40-60wt.%, the content of the two-dimensional MXene is 5-25wt.%, the content of the inorganic binding material is 10-15wt.%, and the content of the organic carrier is 5-30wt.% of the total weight of the conductor paste.
The present invention also provides a method for preparing the conductor paste according to any of the embodiments herein, the method comprising mixing and homogenizing the components of the conductor paste, and then rolling with a three-high mill to obtain the conductor paste.
The invention also provides a chip resistor, and an electrode of the chip resistor is prepared by adopting the conductor paste in any embodiment of the invention.
The invention also provides the use of two-dimensional MXene in the preparation of a conductor paste for a chip resistor electrode or in improving the resistance to sulfidisation, silver migration and/or solder leaching of a chip resistor electrode, wherein the two-dimensional MXene is selected from one or more of a carbide sheet material of an early transition metal, a nitride sheet material of an early transition metal and a carbonitride sheet material of an early transition metal.
In one or more embodiments, the two-dimensional MXene is as described in any embodiment herein.
Drawings
FIG. 1 is a schematic diagram of a printed pattern of a substrate for a sheet resistance test according to an embodiment.
FIG. 2 is a Transmission Electron Microscope (TEM) morphology image of two-dimensional MXene obtained in preparation example.
FIG. 3 is a Scanning Electron Microscope (SEM) morphology image of the stacking of lamellar particles formed by silver powder and two-dimensional MXene in the slurry.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Unless otherwise specified herein, "comprising," including, "" containing, "" having, "or the like, means" consisting of … … "and" consisting essentially of … …, "e.g.," a comprises a "means" a comprises a and the other, "and" a comprises a only.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The conductor paste comprises or consists of a conductive material, an inorganic bonding material and an organic carrier, wherein the conductive material comprises or consists of silver powder and two-dimensional MXene.
Typically, silver powder comprises 40-60wt.% of the conductor paste of the present invention, two-dimensional MXene comprises 5-25wt.% of the conductor paste of the present invention, the inorganic binder material comprises 5-15wt.% of the conductor paste of the present invention, and the organic vehicle comprises 5-50wt.% of the conductor paste of the present invention.
The silver powder suitable for use in the present invention may be spherical silver powder, rod-like silver powder, flake silver powder, or a combination thereof. The silver powder has a particle size of 0.5-12 μm. The silver powder may have a specific surface area of 0.1 to 2.0m2In the range of/g. In some embodiments, the mass fraction of silver powder to the conductor paste of the present invention is 40wt.%, 45wt.%, 50wt.%, 55wt.%, or 60 wt.%.
MXene is a class of two-dimensional inorganic compounds. Such materials consist of a transition metal carbide, nitride or carbonitride of several atomic layer thicknesses. Two-dimensional MXene suitable for use in the present invention is selected from the group consisting of early transition metal carbide, nitride and carbonitride lamellar materials. In the text, the early transition metal means a transition metal element in the 3 rd to 7 th sub-groups of the periodic table. In some embodiments, the two-dimensional MXene comprises an early transition metal selected from one or more of Ti, V, Cr, Sc, Zr, Nb, Mo, Hf and Ta. In some embodiments, the pre-transition metal contained by the two-dimensional MXene is Ti. In some embodiments, the two-dimensional MXene is Ti3C2A sheet material. In some embodiments, the two-dimensional MXene comprises 5wt.%, 10wt.%, 15wt.%, 20wt.%, or 25wt.% of the conductor paste of the present invention.Two-dimensional MXene suitable for use in the present invention preferably has a size of 0.5-15 μm and a thickness of 2-10 nm. The invention finds that the two-dimensional MXene is beneficial to improving the sulfuration resistance, silver migration resistance and solder leaching resistance of the conductor paste for the chip resistor electrode.
Two-dimensional MXene suitable for use in the present invention may be obtained by selective etching of a metal from a MAX phase, where M is an early transition metal, a is a third or fourth main group element, X is C and/or N, and N is 1, 2 or 3. MAX phase is a machinable ceramic material with a unique nano-layered crystal structure and has a chemical general formula of Mn+1AXnWherein M is an early transition metal, e.g., one or more selected from Ti, V, Cr, Sc, Zr, Nb, Mo, Hf, and Ta, e.g., Ti; a is a third or fourth main group element, for example one or two selected from Al and Si, for example Al; x is selected from one or two of C and N, such as C; n is 1, 2 or 3, for example 2. In some embodiments, the MAX phase is Ti3AlC2。
The reagent used for etching the a metal in the MAX phase may be a mixed aqueous solution of HF, HCl and LiF, i.e. a solution of HF, HCl and LiF dissolved in water. HF. In the mixed aqueous solution of HCl and LiF, the total concentration of HCl and HF may be 9 + -1 mol/L, and the molar ratio of HCl to HF may be (37 + -2): 3, the concentration of LiF can be 40-50 g/L. In some embodiments, the etching operation comprises: adding MAX phase powder into mixed aqueous solution of HF, HCl and LiF, stirring at 35 + -5 deg.C for 12-24h to form multilayer structure, and washing with water to obtain multilayer MXene precipitate. Suitable water for use in the present invention may be deionized water.
And after the metal layer A in the MAX phase is etched, the obtained multiple layers of MXene precipitates can be subjected to freeze-thaw cycling to obtain the two-dimensional MXene.
In some embodiments, the freeze-thaw cycle operation comprises: and dispersing the multi-layer MXene precipitate in water, cooling (for example, placing in an environment of-20 +/-5 ℃) to freeze the dispersion, then heating (for example, returning to room temperature) to thaw the dispersion, and circulating for several times to enable the MXene to delaminate, so that the two-dimensional MXene with the size of 500nm-15 mu m and the thickness of 2nm-10nm is formed. The lamella size can be reduced during etching and freeze-thaw cycles with the aid of ultrasonic dispersion.
In some embodiments, the two-dimensional MXene is prepared by the process of:
(1) 18.5g of LF are dissolved in 400mL of a 9M HCl/HF mixed acid solution, where V(HCl):V(HF)=37:3, stir 5-10min, slowly add 18.5g MAX phase powder (M)n+1AXnWhere M is an early transition metal, e.g. Ti, V, Cr, Sc, Zr, Nb, Mo, Hf, Ta, A is predominantly a third or fourth main group element, e.g. Al, Si, X is C or N or a C/N mixture, N =1, 2 or 3), e.g. Ti3AlC2Stirring in mixed acid liquor at 35 ℃ for 24h to etch the Al layer to form a multilayer structure, and then washing with deionized water to remove excessive acid liquor to obtain multilayer MXene precipitate;
(2) adding a proper amount of deionized water into the precipitate, uniformly stirring, placing in a freezing layer (-20 ℃) of a refrigerator for several hours to completely freeze the solution, then removing and placing at room temperature for natural thawing, and performing freeze-thaw cycling for several times, wherein the expanded ice layer promotes the MXene to be further stripped, and finally the ultrathin two-dimensional lamellar MXene dispersion liquid or the dried powder with the size of 500nm-15 mu m and the thickness of 2nm-10nm can be obtained.
The inorganic binder material suitable for use in the present invention is preferably a lead-free glass frit. The lead-free glass frit may be a molten mixture of one or more of silicon oxide, boron oxide, aluminum oxide, tin oxide, bismuth oxide, antimony oxide, copper oxide, and titanium oxide. Herein, the molten mixture means that the lead-free glass frit may be prepared by mixing and melting a plurality of raw materials selected from the group consisting of silicon oxide, boron oxide, aluminum oxide, tin oxide, bismuth oxide, antimony oxide, copper oxide and titanium oxide. In some embodiments, the lead-free glass frit is a molten mixture of silica, boria, alumina and tin oxide. In some embodiments, the lead-free glass frit is composed of 40-50wt.% SiO as a raw material2、25-35wt% B2O3、5-15wt.% Al2O3And 5-15wt.% SnO2The raw material, e.g. lead-free glass frit, may consist of 46.7 ± 2 wt.% SiO2、30±2 wt% B2O3、13.3±2 wt.% Al2O3And 10. + -. 2 wt.% SnO2And (4) forming. In some embodiments, the inorganic binder material comprises 10-15wt.% of the conductor paste of the present invention.
Organic carriers suitable for use in the present invention include thickeners and organic solvents. The thickener may be selected from one or more of ethyl cellulose, poly alpha-methyl styrene and polymethyl methacrylate. In some embodiments, the thickening agent is ethyl cellulose. The organic solvent may be selected from one or more of terpineol, butyl carbitol acetate and tributyl citrate. In some embodiments, the organic solvent is butyl carbitol. The thickener is typically present in the organic vehicle in an amount of 20 to 40wt.%, based on the total weight of the organic vehicle. In some embodiments, the organic carrier is a butyl carbitol solution of ethyl cellulose, preferably at a concentration (ethyl cellulose content) of 30 ± 5 wt.%. The uniform and transparent organic carrier can be obtained by adding the thickening agent into the organic solvent and stirring at 50-60 ℃ until the thickening agent is completely dissolved. In some embodiments, the mass fraction of organic vehicle in the conductor paste of the present invention is 5-30wt.%, e.g., 20 ± 10wt.%, 20 ± 5 wt.%.
The conductor paste can be obtained by mixing and uniformly stirring the components of the conductor paste and then rolling the mixture by a three-roll mill. The rolled slurry may be filtered to remove large size agglomerates and impurities, for example, a 200-400 mesh screen may be used.
In some embodiments, the conductive paste is prepared by a method comprising:
(1) preparing materials: weighing silver powder, two-dimensional MXene, lead-free glass powder and an organic carrier according to the amount designed by a formula and placing the silver powder, the two-dimensional MXene, the lead-free glass powder and the organic carrier in a container;
(2) mixing: stirring the materials in the container by using a dispersion stirrer to uniformly mix the materials, and standing for several hours after stirring to fully infiltrate the inorganic powder into the organic carrier;
(3) rolling: further mixing the stirred mixture by a three-high mill to ensure that all components are uniformly dispersed and ground to a certain fineness;
(4) and (3) filtering: filtering the rolled slurry by a filter screen with 200-400 meshes to remove large-size agglomerates and impurities.
The invention also includes conductor pastes prepared using the methods described herein.
The invention also comprises a chip resistor, which consists of a substrate, electrodes, a resistor, a primary package and a secondary package, wherein the electrodes of the chip resistor are prepared by adopting the conductor paste in any embodiment of the invention. Methods of preparing the conductor paste of the present invention into electrodes of chip resistors and preparing the electrodes and other parts of chip resistors into chip resistors are conventional in the art.
The invention also includes the use of two-dimensional MXene for the preparation of a conductor paste for chip resistor electrodes or for improving the resistance of chip resistor electrodes to sulfidation, silver migration and/or solder leaching.
The invention has the following beneficial effects: according to the novel conductor paste for the chip resistor, the ultrathin layer two-dimensional MXene and the metal silver particles form a layer-by-layer stacking structure, so that the silver particles can be protected from being vulcanized and leached by solder, the electrode has certain sulfuration resistance, silver migration resistance and solder leaching resistance, the two-dimensional MXene has excellent conductivity close to metal, the content of noble metal can be reduced when the two-dimensional MXene is added into a system, and the cost of the system is far lower than that of the silver-palladium alloy conductor paste.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
The sheet resistance test method adopted in the embodiment is as follows:
uniformly stirring a sample by using a paste mixing cutter, taking a small amount of the sample, and printing a pattern shown in figure 1 on an alumina substrate by screen printing; after printing, naturally leveling for 10-15 min, drying at 125 ℃ for 10min, sintering at 800 ℃ for 30min, and testing the resistance value R of the substrate with the sintered sample by using a digital multimeter; calculating the approximate square resistance value by the formula (1)R □：
R □ 
（1）
Wherein R is a resistance value with the unit of omega;R □is the sheet resistance value with the unit of omega/□; n is the number of squares.
Preparation example
The preparation example prepares two-dimensional MXene by the following steps:
(1) 18.5g of LiF are dissolved in 400mL of a mixed acid solution of HCl and HF in a total concentration of 9mol/L of HCl and HF, where V(HCl):V(HF)=37:3, stir 8min, slowly add 18.5g Ti3AlC2Stirring the mixed acid solution for 24 hours at 35 ℃ to etch the Al layer to form a multilayer structure, and then washing the multilayer structure with deionized water to remove excessive acid solution to obtain multilayer MXene precipitate;
(2) adding a proper amount of deionized water into the precipitate, uniformly stirring, placing the precipitate in a freezing layer (-20 ℃) of a refrigerator for a plurality of hours to completely freeze the solution, taking out the precipitate, naturally thawing the solution at room temperature, performing freeze-thaw cycle for a plurality of times, promoting the MXene to be further peeled by the expanded ice layer, finally obtaining the dispersion liquid of the ultrathin two-dimensional lamellar MXene with the size of 500nm-15 mu m and the thickness of 2nm-10nm, and drying to obtain the two-dimensional MXene powder.
FIG. 2 is a transmission electron microscope morphology image of two-dimensional MXene obtained in preparation example. From fig. 2 it can be seen that the prepared two-dimensional MXene is an ultra-thin sheet material with dimensions approximately in the range of 0.5-15 μm.
Example 1
In this embodiment, a silver and two-dimensional MXene mixed system conductor paste is prepared through the following steps:
(1) 40wt.% of spherical silver powder (with the particle diameter of 0.5-12 μm), 25wt.% of two-dimensional MXene powder obtained in the preparation example and 15wt.% of lead-free glass powder (the raw material composition of the powder is 46.7 wt.% of SiO)2、30 wt% B2O3、13.3 wt.% Al2O3And 10wt.% SnO2) And 20wt.% of an organic carrier (butyl carbitol solution of ethyl cellulose, 30% by mass);
(2) stirring the weighed materials by using a dispersion stirrer to uniformly mix the materials, and standing for several hours after stirring to fully infiltrate the organic carrier into the inorganic powder;
(3) further mixing the stirred mixture by a three-high mill to ensure that all components are uniformly dispersed and ground to a certain fineness;
(4) and filtering the rolled slurry through a 300-mesh filter screen to remove large-size agglomerates and impurities, thereby obtaining the required conductive slurry.
The obtained conductive paste is printed on an alumina substrate by screen printing, sintered at 800 ℃, placed in the air at normal temperature and normal humidity for 10 days, tested for the square resistance change, and examined for the effect of vulcanization resistance. And (3) placing the substrate printed with the paste in a tin soldering tank at 260 ℃, testing the sheet resistance, and inspecting the effect of the soldering resistance. The results are shown in Table 1.
From fig. 3, it can be seen that the two-dimensional MXene and the silver particles in the slurry form a layer-by-layer stacking structure, and the two-dimensional MXene plays a role in protecting the silver particles.
It can be seen from table 1 that the prepared conductive paste has excellent resistance to sulfidation and solder corrosion.
Example 2
In this embodiment, a silver and two-dimensional MXene mixed system conductor paste is prepared through the following steps:
(1) weighing 45wt% of spherical silver powder (particle diameter of 0.5-12 μm), 20wt.% of two-dimensional MXene powder obtained in preparation example, and 15wt.% of lead-free glass powder (raw material composition of the powder is 46.7 wt.% SiO)2、30 wt.% B2O3、13.3 wt.% Al2O3And 10wt.% SnO2) And 20wt.% of an organic carrier (butyl carbitol solution of ethyl cellulose, 30% by mass);
(2) stirring the weighed materials by a dispersion stirrer to uniformly mix the materials, and standing for several hours after stirring to fully soak inorganic powder in the record body;
(3) further mixing the stirred mixture by a three-high mill to ensure that all components are uniformly dispersed and ground to a certain fineness;
(4) and filtering the rolled slurry through a 300-mesh filter screen to remove large-size agglomerates and impurities, thereby obtaining the required conductive slurry.
The obtained conductive paste is printed on an alumina substrate by screen printing, sintered at 800 ℃, placed in the air at normal temperature and normal humidity for 10 days, tested for the square resistance change, and examined for the effect of vulcanization resistance. And (3) placing the substrate printed with the paste in a tin soldering tank at 260 ℃, testing the sheet resistance, and inspecting the effect of the soldering resistance. The results are shown in Table 1.
Example 3
In this embodiment, a silver and two-dimensional MXene mixed system conductor paste is prepared through the following steps:
(1) 50wt.% of spherical silver powder (with the particle diameter of 0.5-12 μm), 15wt.% of two-dimensional MXene powder obtained in the preparation example and 15wt.% of lead-free glass powder (the raw material composition of the powder is 46.7 wt.% of SiO)2、30 wt.% B2O3、13.3 wt.% Al2O3And 10wt.% SnO2) And 20wt.% of an organic carrier (butyl carbitol solution of ethyl cellulose, 30% by mass);
(2) stirring the weighed materials by a dispersion stirrer to uniformly mix the materials, and standing for several hours after stirring to fully soak inorganic powder in the record body;
(3) further mixing the stirred mixture by a three-high mill to ensure that all components are uniformly dispersed and ground to a certain fineness;
(4) and filtering the rolled slurry through a 300-mesh filter screen to remove large-size agglomerates and impurities, thereby obtaining the required conductive slurry.
The obtained conductive paste is printed on an alumina substrate by screen printing, sintered at 800 ℃, placed in the air at normal temperature and normal humidity for 10 days, tested for the square resistance change, and examined for the effect of vulcanization resistance. And (3) placing the substrate printed with the paste in a tin soldering tank at 260 ℃, testing the sheet resistance, and inspecting the effect of the soldering resistance. The results are shown in Table 1.
Example 4
In this embodiment, a silver and two-dimensional MXene mixed system conductor paste is prepared through the following steps:
(1) 55wt.% of spherical silver powder (with the particle diameter of 0.5-12 μm), 10wt.% of two-dimensional MXene powder obtained in the preparation example and 15wt.% of lead-free glass powder (the raw material composition of the powder is 46.7 wt.% of SiO)2、30 wt% B2O3、13.3 wt.% Al2O3And 10wt.% SnO2) And 20wt.% of an organic carrier (butyl carbitol solution of ethyl cellulose, 30% by mass);
(2) stirring the weighed materials by a dispersion stirrer to uniformly mix the materials, and standing for several hours after stirring to fully soak inorganic powder in the record body;
(3) further mixing the stirred mixture by a three-high mill to ensure that all components are uniformly dispersed and ground to a certain fineness;
(4) and filtering the rolled slurry through a filter screen with a certain mesh number to remove large-size aggregates and impurities, thereby obtaining the required conductive slurry.
The obtained conductive paste is printed on an alumina substrate by screen printing, sintered at 800 ℃, placed in the air at normal temperature and normal humidity for 10 days, tested for the square resistance change, and examined for the effect of vulcanization resistance. And (3) placing the substrate printed with the paste in a tin soldering tank at 260 ℃, testing the sheet resistance, and inspecting the effect of the soldering resistance. The results are shown in Table 1.
Example 5
In this embodiment, a silver and two-dimensional MXene mixed system conductor paste is prepared through the following steps:
(1) 60wt.% of spherical silver powder (with the particle diameter of 0.5-12 μm), 5wt.% of two-dimensional MXene powder obtained in the preparation example and 15wt.% of lead-free glass powder (the raw material composition of the powder is 46.7 wt.% of SiO)2、30 wt% B2O3、13.3 wt.% Al2O3And 10wt.% SnO2) And 20wt.% of an organic carrier (butyl carbitol solution of ethyl cellulose, 30% by mass);
(2) stirring the weighed materials by a dispersion stirrer to uniformly mix the materials, and standing for several hours after stirring to fully soak inorganic powder in the record body;
(3) further mixing the stirred mixture by a three-high mill to ensure that all components are uniformly dispersed and ground to a certain fineness;
(4) and filtering the rolled slurry through a 300-mesh filter screen to remove large-size agglomerates and impurities, thereby obtaining the required conductive slurry.
The obtained conductive paste is printed on an alumina substrate by screen printing, sintered at 800 ℃, placed in the air at normal temperature and normal humidity for 10 days, tested for the square resistance change, and examined for the effect of vulcanization resistance. And (3) placing the substrate printed with the paste in a tin soldering tank at 260 ℃, testing the sheet resistance, and inspecting the effect of the soldering resistance. The results are shown in Table 1.
Comparative example 1
The comparative example prepared silver conductor paste by the following steps:
(1) weighing 65 wt.% of spherical silver powder (with the particle diameter of 0.5-12 μm) and 15wt.% of lead-free glass powder (the raw material composition of which is 46.7 wt.% of SiO)2、30 wt% B2O3、13.3 wt.% Al2O3And 10wt.% SnO2) And 20wt.% of an organic carrier (butyl carbitol solution of ethyl cellulose, 30% by mass);
(2) stirring the weighed materials by a dispersion stirrer to uniformly mix the materials, and standing for several hours after stirring to fully soak inorganic powder in the record body;
(3) further mixing the stirred mixture by a three-high mill to ensure that all components are uniformly dispersed and ground to a certain fineness;
(4) and filtering the rolled slurry through a 300-mesh filter screen to remove large-size agglomerates and impurities, thereby obtaining the required conductive slurry.
The obtained conductive paste is printed on an alumina substrate by screen printing, sintered at 800 ℃, placed in the air at normal temperature and normal humidity for 10 days, tested for the square resistance change, and examined for the effect of vulcanization resistance. And (3) placing the substrate printed with the paste in a tin soldering tank at 260 ℃, testing the sheet resistance, and inspecting the effect of the soldering resistance. The results are shown in Table 1. And (3) placing the substrate printed with the paste in a tin soldering tank at 260 ℃, testing the sheet resistance, and inspecting the effect of the soldering resistance. The results are shown in Table 1.
Table 1: sheet resistance test results of electrodes obtained by printing paste on substrate
As can be seen from table 1, the electrode made of the conductive paste of the present invention has small resistance change before and after 10 days of standing and before and after tin immersion, and is excellent in solder leaching resistance, sulfidization resistance, and silver migration inhibition.
Claims (7)
1. The application of two-dimensional MXene in improving the sulfuration resistance, silver migration resistance and/or solder leaching resistance of the chip resistor electrode, characterized in that the application comprises preparing a chip resistor electrode by using conductor paste containing two-dimensional MXene, wherein the conductor paste comprises a conductive material, an inorganic binder material and an organic vehicle, the conductive material comprises silver powder and two-dimensional MXene, the two-dimensional MXene is selected from one or more of carbide sheet material of an early transition metal, nitride sheet material of the early transition metal and carbonitride sheet material of the early transition metal, the content of the silver powder is 40-60wt.%, the content of the two-dimensional MXene is 10-25wt.%, the content of the inorganic binding material is 5-15wt.%, and the content of the organic carrier is 5-30wt.% of the total weight of the conductor paste.
2. The application of claim 1, wherein the application has one or more of the following features:
the particle size of the silver powder is 0.5-12 μm;
the size of the two-dimensional MXene is 0.5-15 μm;
the thickness of the two-dimensional MXene is 2-10 nm;
the inorganic bonding material is lead-free glass powder;
the organic vehicle includes a thickener and an organic solvent.
3. The application of claim 2, wherein the application has one or more of the following features:
the transition metal in the two-dimensional MXene is selected from one or more of Ti, V, Cr, Sc, Zr, Nb, Mo, Hf and Ta;
the lead-free glass powder is a molten mixture of one or more of silicon oxide, boron oxide, aluminum oxide, tin oxide, bismuth oxide, antimony oxide, copper oxide and titanium oxide;
the thickening agent is selected from one or more of ethyl cellulose, poly alpha-methyl styrene and polymethyl methacrylate;
the organic solvent is selected from one or more of terpineol, butyl carbitol acetate and tributyl citrate;
the content of the thickening agent in the organic carrier is 20-40 wt% based on the total weight of the organic carrier.
4. The application of claim 1, wherein the application has one or more of the following features:
the two-dimensional MXene is Ti3C2A sheet material;
the inorganic bonding material is lead-free glass powder, and the lead-free glass powder is prepared from 40-50wt.% of SiO2、25-35wt% B2O3、5-15wt.% Al2O3And 5-15wt.% SnO2Composition is carried out;
the organic vehicle is a butyl carbitol solution of ethyl cellulose at a concentration of 25-35 wt.%.
5. The application of claim 1, wherein the two-dimensional MXene is obtained by converting from Mn+1AXnThe compound is obtained by selectively etching A metal, wherein M is an early transition metal, A is a third or fourth main group element, X is C and/or N, and N is 1, 2 or 3.
6. The application of claim 5, wherein the application has one or more of the following features:
m is one or more selected from Ti, V, Cr, Sc, Zr, Nb, Mo, Hf and Ta;
a is Al and/or Si;
the two-dimensional MXenen is prepared by the following method: etching M with a mixed aqueous solution of HF, HCl and LiFn+1AXnAnd (3) obtaining the two-dimensional MXene by a metal layer A in the middle of the compound and then performing freeze-thaw cycling.
7. The use according to claim 1, wherein the silver powder has a particle size of 0.5 to 12 μm and the two-dimensional MXene is Ti3C2Lamellar material of said Ti3C2The size of the sheet material is 0.5-15 μm, and the Ti is3C2The thickness of the lamellar material is 2-10nm, the inorganic bonding material is lead-free glass powder, and the raw material of the lead-free glass powder is 40-50wt.% SiO2、25-35wt% B2O3、5-15wt.% Al2O3And 5-15wt.% SnO2The organic carrier is a butyl carbitol solution of ethyl cellulose with the concentration of 25-35 wt.%; the content of the silver powder is 40-60wt.%, the content of the two-dimensional MXene is 10-25wt.%, the content of the inorganic binding material is 10-15wt.%, and the content of the organic carrier is 5-30wt.% of the total weight of the conductor paste.
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| WO2023026188A1 (en) * | 2021-08-24 | 2023-03-02 | King Abdullah University Of Science And Technology | MXene-SILVER CONDUCTIVE PASTE, ELECTRODE, AND METHOD |
| CN113851251B (en) * | 2021-11-30 | 2022-03-29 | 西安宏星电子浆料科技股份有限公司 | Transitional pore filling slurry for connecting upper and lower gold and silver layers of membrane tape in LTCC substrate |
| CN114822915A (en) * | 2022-05-23 | 2022-07-29 | 徐州纳烯新材料研究院有限公司 | MXene-based composite conductive paste and preparation method and application thereof |
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