CN116779213A - Low-temperature sintered conductive silver paste and preparation method and application thereof - Google Patents

Low-temperature sintered conductive silver paste and preparation method and application thereof Download PDF

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CN116779213A
CN116779213A CN202310763087.7A CN202310763087A CN116779213A CN 116779213 A CN116779213 A CN 116779213A CN 202310763087 A CN202310763087 A CN 202310763087A CN 116779213 A CN116779213 A CN 116779213A
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silver paste
silver
silver powder
low
temperature sintered
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罗艳玲
胡林政
温馨
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Suzhou Jinyi New Material Technology 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
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/302—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

The invention discloses low-temperature sintered silver paste and a preparation method and application thereof, wherein the raw materials of the low-temperature sintered silver paste comprise, by weight, 25-35% of spherical silver powder, 20-30% of flaky silver powder, 20-25% of nano silver powder and 6-10% of high polymer, wherein the high polymer is bisphenol A epoxy resin containing strong polar groups, the polar groups can attract silver ions to migrate to the surface of the silver powder, the reactivity of silver is improved, and covalent bonds formed with the silver powder reduce holes, the shear strength of the silver paste is improved, meanwhile, the sintering temperature is reduced, and the silver paste has excellent adhesive force and conductivity.

Description

Low-temperature sintered conductive silver paste and preparation method and application thereof
Technical Field
The invention relates to the technical field of semiconductor packaging materials, in particular to low-temperature sintered silver paste with high shear strength and adhesive force, and a preparation method and application thereof.
Background
Sintering techniques allow the interdiffusion of atoms at the surface of the material by high temperatures, thereby forming dense crystals, and low temperature sintering techniques typically reduce the sintering temperature by reducing the size of the sintered particles. The nanometer silver powder provides another brand new idea for packaging the semiconductor chip due to the unique nanometer characteristic. The melting point of silver is 961 ℃, and when the particle size reaches the nanometer level, the melting point can be obviously reduced to about 100 ℃, so that the interconnection of electronic products or chips can be realized through low-temperature sintering, the melting point of a sintered sintering layer is recovered to the conventional melting point of silver, the normal use of the electronic products at high temperature can be met, and the silver has excellent heat conduction and electrical conductivity and good chemical stability, and is the interconnection material with the most application prospect of third-generation semiconductor packaging.
However, the silver paste prepared by the prior disclosed silver paste and the preparation method still have certain defects in the aspects of adhesive force, conductivity, shearing strength and the like. In the invention patent with publication number CN116130143A and name of high-temperature resistant elastic conductive silver paste and preparation method thereof, a high-temperature resistant elastic conductive silver paste and preparation method thereof are disclosed, and the specification thereof discloses: the high-temperature-resistant elastic conductive silver paste comprises the following raw materials in parts by weight: 5-15 parts of modified epoxy resin, 0.5-9 parts of curing agent, 1-5 parts of epoxy resin mixture, 5-10 parts of diluent, 0.1-0.5 part of silane coupling agent, 0.01-0.2 part of curing accelerator, 0.01-0.5 part of dispersing agent, 0.2-2 parts of thixotropic agent and 70-90 parts of conductive filler. The silver paste prepared by the method has excellent high temperature resistance, and has the defect of low adhesive force, so that the shearing strength is low.
The specification discloses a silver soldering paste which is prepared from silver ammonia complex solution and aldehyde group organic solvent (R1-CHO, R1 is alkyl), wherein the molar ratio of the silver ammonia complex solution to the aldehyde group organic solvent is 1:1-1:5; the silver-ammonia complex is prepared from silver ketocarboxylate and an amino organic solvent; the molar ratio of the silver ketocarboxylate to the amino organic solvent is 1:1-1:5. The silver ammonia complex solution and the aldehyde group organic solvent are combined, so that the silver ammonia complex has higher shearing strength. The defect is that the silver content is high after sintering, and the cost cannot be controlled.
Patent publication number CN109979639a, entitled hybrid conductive silver paste for packaging a nano chip, discloses a hybrid conductive silver paste for packaging a nano chip, and its specification discloses: the mixed conductive silver paste for packaging the nano chip comprises, by weight, 65% -85% of silver powder, 5% -25% of an organic solvent, 1% -2% of a dispersing agent, 10% -20% of an organic carrier, 0.5% -5% of a surfactant and 0.1% -5% of a diluent, wherein the sintering temperature of the silver paste is relatively high.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, improve the adhesive force and the shearing strength of slurry by reducing holes, and provide low-temperature sintered conductive silver slurry with high shearing strength and good adhesive force, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention proposes the following technical solutions: the low-temperature sintered silver paste comprises the following raw materials in percentage by weight:
spherical silver powder: 25-35%;
flake silver powder: 20-30%;
nano silver powder: 20-25%;
high molecular polymer: 6-10%;
solvent: 3-20%;
other additives: 0.5 to 5 percent;
wherein the high molecular polymer is bisphenol A epoxy resin containing polar groups.
Preferably, the particle diameter of the spherical silver powder ranges from 1 to 20 μm, and the particle diameter of the plate-like silver powder ranges from 1 to 20 μm.
Preferably, the particle size of the nano silver powder ranges from 50 nm to 500nm.
Preferably, the structure of the bisphenol A epoxy resin containing polar groups is as follows:
wherein X-is Cl-, br-, HS-, H 2 N-, RHN-or R 2 N-, preferably HS-containing bisphenol A epoxy treeAnd (3) grease.
Preferably, the solvent is selected from one or more of terpineol, turpentine, butyl carbitol, benzyl alcohol, ethanol, cyclohexanone, acetic acid, acetone, butanone and n-butyl acetate.
Preferably, the other additives include a curing agent, a dispersing agent, an anti-settling agent and a leveling agent for effecting curing during heating of the resin and improving dispersibility and leveling of the slurry.
The invention also provides a preparation method of the low-temperature sintered silver paste, which comprises the following preparation steps:
s1, mixing and stirring the high molecular polymer, the solvent and other additives in proportion to obtain an organic phase mixture;
s2, mixing and stirring the spherical silver powder, the flake silver powder and the nano silver powder with the machine phase mixture according to a proportion to obtain semi-finished slurry;
s3, grinding the semi-finished product slurry to obtain roller grinding mixture semi-finished product slurry;
and S4, defoaming the mixture semi-finished product slurry to obtain the low-temperature sintered silver slurry.
Preferably, the stirring temperature in the step S1 is room temperature, the rotating speed is 500-1000 rpm, and the stirring time is 15-20 min.
Preferably, the stirring temperature in the step S2 is 25-30 ℃, the rotating speed is 300-500 rpm, and the stirring time is 5-10 min.
The invention also provides application of the low-temperature sintered silver paste in semiconductor packaging.
In the process of solidifying silver paste, under the action of bisphenol A epoxy resin high polymer of polar groups, solvent and catalyst, when two nano particles are contacted, a concave surface is generated in the neck-shaped area between the two particles, so that the surface pressure of the area is reduced. Atoms diffuse from a convex surface region with positive curvature to a concave surface region with negative curvature, resulting in the polymerization of the two nanoparticles and the disappearance of the sintered neck region. The nano silver paste is sintered at a temperature much lower than that of the traditional powder metallurgy sintering temperature by utilizing the small-size effect of nano silver particles and through the mutual diffusion of atoms between the nano silver paste and an interconnection material, so that the interconnection between a chip or a component and a substrate is realized.
Further, as no pressure is applied during sintering and the sintering temperature is low, nano-scale or submicron-scale pores are uniformly distributed in the internal tissue of the nano-silver paste interconnection joint, obvious holes appear at the bottom contacted with the base material, the insufficient adhesion force can be caused by excessive holes, silver nano particles can bear certain extrusion in the process of solidifying and shrinking the resin, and the particles which are originally contacted with each other can deform to a certain extent under the extrusion action, so that the contact area is increased, and the contact resistance is further reduced; on the other hand, silver powders with different morphologies, which are far away from each other, are close to each other, so that the probability of tunnel effect is greatly increased.
In the curing process of bisphenol A epoxy resin with polar groups, the polar groups can polarize atoms on the surface of silver, so that the reactivity of silver is improved, the melting temperature of silver powder is reduced, and low-temperature sintering is realized; and the covalent bond formed by the silver powder also chemically bonds the silver filler into the resin network structure, so that the dispersion and bonding strength of the silver can be improved, the interaction between the silver and the resin matrix is enhanced, the contact area between the silver powder is increased, and the gap generated by the nano silver powder is reduced.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts bisphenol A epoxy resin containing strong polar groups, and the special strong polar groups can attract silver ions to migrate to the surface of silver powder, so that good combination is formed with the silver powder, and further the reaction activity of the silver is improved, thereby reducing gaps, improving bonding strength, reducing the melting temperature of the silver powder and realizing low-temperature sintering. Meanwhile, the polar groups are combined with the silver powder, so that holes generated in the sintering process of the nano silver powder are reduced.
2. The preparation method disclosed by the invention is simple in process, pressureless in sintering, low in sintering temperature, and capable of obtaining excellent adhesion capability and conductivity without adding extra steps or pressure.
3. The main component of the invention adopts the flaky silver powder spherical silver powder to be mixed with the nanometer silver powder, and compared with the pure nanometer silver powder, the cost is lower.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of a silver paste of bisphenol A epoxy resin with polar groups after sintering in an embodiment of the invention;
FIG. 2 is a scanning electron microscope image of a cross section of a silver paste of bisphenol A epoxy resin without polar groups in a comparative example of the present invention after sintering.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
The present invention will be described in detail below with reference to specific embodiments shown in the drawings. These embodiments are not intended to limit the invention and structural, methodological, or functional modifications of these embodiments that may be made by one of ordinary skill in the art are included within the scope of the invention.
Example 1
A low-temperature sintered conductive silver paste was prepared by taking 25g of spherical silver powder having a D50 of 5 μm, 30g of plate-like silver powder having a D50 of 10 μm, 25g of nano powder having a particle diameter of 50 to 500nm, 10g of HS-bisphenol A epoxy resin, 5g of solvent, and 5g of other additives, as follows:
s1, mixing 10g of HS-bisphenol A epoxy resin, 5g of solvent and 5g of other additives according to the component proportion, mechanically stirring at 25 ℃ at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 25g of spherical silver powder with the D50 of 5 mu m, 30g of flaky silver powder with the D50 of 10 mu m, 25g of nano powder with the particle size of 50-500nm and the organic phase mixture in proportion, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 60 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The scanning electron microscope image of the section of the sintered conductive silver paste prepared by the method is shown in figure 1, and the conductive silver paste can be coated on a glass substrate to test the electrical property, and the specific method comprises the following steps: according to the measurement of its resistance R using a two-terminal resistance meter, the actual length L of the coated sample is measured, as well as the cross-sectional area S, according to the volume resistivity formula:the actual volume resistivity was calculated to be 8.8E-06. Omega. Cm.
And (3) dispensing the silver paste prepared by the method by using a dispensing machine, detecting push-pull force by using a universal tension tester, and calculating the shearing strength to be 15Mpa according to the detection thrust of N, the bonding area of S and the shearing strength of N/S. In the conductive silver paste of the embodiment, the bisphenol A epoxy resin containing polar groups is added, so that the paste with low resistance and high shear strength is obtained.
Example 2
A low-temperature sintered conductive silver paste was prepared by taking 25g of spherical silver powder having a D50 of 5 μm, 30g of plate-like silver powder having a D50 of 10 μm, 25g of nano powder having a particle diameter of 50 to 500nm, and 10g of Cl-bisphenol A epoxy resin, 7g of a solvent, and 3g of other additives, as follows:
s1, mixing 10g of Cl-bisphenol A epoxy resin with 7g of solvent and 3g of other additives in proportion, mechanically stirring at 25 ℃ at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 25g of spherical silver powder with the D50 of 5 mu m, 30g of flaky silver powder with the D50 of 10 mu m, 25g of nano powder with the particle size of 50-500nm and the organic phase mixture according to a certain mass ratio, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 60 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The conductive silver paste prepared by the method can be coated on a glass substrate to test electrical properties, and is calculated by adopting the volume resistivity calculation method which is the same as that of the embodiment 1, so that the actual volume resistivity is calculated to be 9.2E-06 Ω & cm.
Meanwhile, the silver paste obtained by the method is dispensed by a dispensing machine, then is subjected to push-pull force detection by a universal tensile force tester, and is calculated by adopting the same method for calculating the shear strength as in the embodiment 1, so that the shear strength is calculated to be 13Mpa. In the conductive silver paste of the embodiment, the bisphenol A epoxy resin containing polar groups is added, so that the paste with low resistance and high shear strength is obtained.
Example 3
A low-temperature sintered conductive silver paste was prepared by taking 30g of spherical silver powder having a D50 of 5 μm, 25g of plate-like silver powder having a D50 of 10 μm, 25g of nano powder having a particle diameter of 50 to 500nm, and 8g of Br-bisphenol a epoxy resin with 10g of solvent, 2g of other additives, as follows:
s1, mixing 8g of Br-bisphenol A epoxy resin with 10g of solvent and 5g of other additives in proportion, mechanically stirring at 25 ℃ at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 30g of spherical silver powder with the D50 of 5 mu m, 25g of flaky silver powder with the D50 of 10 mu m, 25g of nano powder with the particle size of 50-500nm and an organic phase according to a certain mass ratio, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 60 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The conductive silver paste prepared in the mode can be coated on a glass substrate to test electrical properties. The actual volume resistivity was calculated to be 9.8E-06. Omega. Cm by the same method for calculating volume resistivity as in example 1.
After the silver paste obtained in the above manner is dispensed by a dispensing machine, the push-pull force is detected by a universal tensile tester, and the shear strength is calculated by the same method for calculating the shear strength as in example 1, so that the shear strength is calculated to be 12Mpa. In the embodiment, the bisphenol A epoxy resin containing polar groups is added, so that the slurry with low resistance and high shear strength is obtained.
Example 4
A low-temperature sintered conductive silver paste was prepared by taking 30g of spherical silver powder having a D50 of 5 μm, 25g of plate-like silver powder having a D50 of 10 μm, 25g of nano powder having a particle diameter of 50 to 500nm, and 8g of H2N-bisphenol a epoxy resin with 10g of solvent, 2g of other additives, as follows:
s1, 8g of H 2 Mixing N-bisphenol A epoxy resin with 10g of solvent and 5g of other additives in proportion, mechanically stirring at 25 ℃ and rotating at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 30g of spherical silver powder with the D50 of 5 mu m, 25g of flaky silver powder with the D50 of 10 mu m, 25g of nano powder with the particle size of 50-500nm and an organic phase according to a certain mass ratio, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 60 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The conductive silver paste prepared by the method can be coated on a glass substrate to test electrical properties. Calculation was performed by the same method for calculating volume resistivity as in example 1, and the actual volume resistivity was calculated to be 9.5E-06. Omega. Cm.
After the silver paste obtained in the above manner is dispensed by a dispensing machine, the push-pull force is detected by a universal tensile tester, and the shear strength is calculated by the same method for calculating the shear strength as in example 1, so that the shear strength is calculated to be 13Mpa. In the embodiment, the bisphenol A epoxy resin containing polar groups is added, so that the slurry with low resistance and high shear strength is obtained.
Example 5
A low-temperature sintered conductive silver paste was prepared by taking 35g of spherical silver powder having a D50 of 5 μm, 20g of plate-like silver powder having a D50 of 10 μm, 20g of nano powder having a particle diameter of 50 to 500nm, and 6g of RHN-bisphenol a epoxy resin with 18.5g of solvent, 0.5g of other additives, according to the following steps:
s1, mixing 6g of RHN-bisphenol A epoxy resin with 18.5g of solvent and 0.5g of other additive components in proportion, mechanically stirring at 25 ℃ at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 35g of spherical silver powder with the D50 of 5 mu m, 20g of flaky silver powder with the D50 of 10 mu m, 20g of nano powder with the particle size of 50-500nm and an organic phase according to a certain mass ratio, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 60 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The conductive silver paste prepared in the mode can be coated on a glass substrate to test electrical properties. The actual volume resistivity was calculated to be 10.1E-06. Omega. Cm by performing the calculation in the same manner as in example 1.
After the silver paste obtained in the above manner is dispensed by a dispensing machine, the push-pull force is detected by a universal tensile tester, and the shear strength is calculated by the same method for calculating the shear strength as in example 1, so that the shear strength is calculated to be 12Mpa. In the embodiment, the bisphenol A epoxy resin containing polar groups is added, so that the slurry with low resistance and high shear strength is obtained.
Example 6
Taking 35g of spherical silver powder with the D50 of 5 mu m, 20g of flaky silver powder with the D50 of 10 mu m, 20g of nano powder with the particle size of 50-500nm and 6g of R 2 N-bisphenol A epoxy resin, 18.5g of solvent, 0.5g of other additives, and the conductive silver paste sintered at low temperature was prepared according to the following steps:
s1, R is 6g 2 Mixing N-bisphenol A epoxy resin, 18.5g of solvent and 0.5g of other additives in proportion, mechanically stirring at 25 ℃ at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 35g of spherical silver powder with the D50 of 5 mu m, 20g of flaky silver powder with the D50 of 10 mu m, 20g of nano powder with the particle size of 50-500nm and an organic phase according to a certain mass ratio, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 60 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The conductive silver paste prepared in the mode can be coated on a glass substrate to test electrical properties. The actual volume resistivity was calculated to be 9.4E-06. Omega. Cm by performing the calculation in the same manner as in example 1.
After the silver paste obtained in the above manner is dispensed by a dispensing machine, the push-pull force is detected by a universal tensile tester, and the shear strength is calculated by the same method for calculating the shear strength as in example 1, so that the shear strength is calculated to be 13Mpa. In the embodiment, the bisphenol A epoxy resin containing polar groups is added, so that the slurry with low resistance and high shear strength is obtained.
Comparative example 1
S1, mixing 1g of HS-bisphenol A epoxy resin with 16g of solvent and 3g of other additive components in proportion, mechanically stirring at 25 ℃ at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 25g of spherical silver powder with the D50 of 5 mu m, 30g of flaky silver powder with the D50 of 10 mu m, 25g of nano powder with the particle size of 50-500nm and an organic phase according to a certain mass ratio, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 60 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The conductive silver paste prepared in the mode can be coated on a glass substrate to test electrical properties. The actual volume resistivity was calculated to be 20.5E-06. Omega. Cm by performing the calculation in the same manner as in example 1.
After the silver paste obtained in the above manner was dispensed by the dispenser, the push-pull force was detected by the universal tensile tester, and the shear strength was calculated by the same method as in example 1, to calculate that the shear strength was 4Mpa. In the embodiment, as the added bisphenol A epoxy resin containing polar groups is less, the obtained slurry has higher resistance and lower shear strength.
Comparative example 2
S1, mixing 12g of HS-bisphenol A epoxy resin with 5g of solvent and 3g of other additives in proportion, mechanically stirring at 25 ℃ at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 25g of spherical silver powder with the D50 of 5 mu m, 30g of flaky silver powder with the D50 of 10 mu m, 25g of nano powder with the particle size of 50-500nm and an organic phase according to a certain mass ratio, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 70 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The conductive silver paste prepared in the mode can be coated on a glass substrate to test electrical properties. The actual volume resistivity was calculated to be 12.6E-06. Omega. Cm by performing the calculation in the same manner as in example 1.
After the silver paste is dispensed by a dispenser, the push-pull force is detected by a universal tensile tester, and the shear strength is calculated by the same method for calculating the shear strength as in the embodiment 1, so that the shear strength is calculated to be 5Mpa. In the embodiment, the added bisphenol A epoxy resin containing polar groups is excessive, so that the obtained slurry has higher resistance and lower shear strength.
Comparative example 3
S1, mixing 4g of HS-bisphenol A epoxy resin with 11g of solvent and 5g of other additives in proportion, mechanically stirring at 25 ℃ at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 25g of spherical silver powder with the D50 of 5 mu m, 30g of flaky silver powder with the D50 of 10 mu m, 25g of nano powder with the particle size of 50-500nm and an organic phase according to a certain mass ratio, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 60 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The conductive silver paste prepared in the mode can be coated on a glass substrate to test electrical properties. The actual volume resistivity was calculated to be 11.4E-06. Omega. Cm by performing the calculation in the same manner as in example 1.
After the silver paste is dispensed by a dispenser, the push-pull force is detected by a universal tensile tester, and the shear strength is calculated by the same method for calculating the shear strength as in the embodiment 1, so that the shear strength is calculated to be 7Mpa. In the embodiment, as the added bisphenol A epoxy resin containing polar groups is less, the obtained slurry has higher resistance and lower shear strength.
Comparative example 4
S1, mixing 10g of bisphenol A epoxy resin without polar groups, 5g of solvent and 5g of other additives in proportion, mechanically stirring at 25 ℃ at 500rpm for 20min to obtain an organic phase mixture;
s2, mixing 25g of spherical silver powder with the D50 of 5 mu m, 30g of flaky silver powder with the D50 of 10 mu m, 25g of nano powder with the particle size of 50-500nm and an organic phase according to a certain mass ratio, mechanically stirring at the temperature of 25 ℃ at the speed of 500rpm for 5min to obtain semi-finished product slurry;
s3, grinding the semi-finished product slurry by a three-roller mill, wherein the roller grinding speed is 200rpm/min, and filtering by using a 400-mesh screen plate to obtain roller grinding mixture semi-finished product slurry;
and S4, placing the slurry with the viscosity of 60 Pa.s into a vacuum deaerator for deaeration treatment, and obtaining the low-temperature pressureless sintering silver slurry.
The scanning electron microscope image of the section of the sintered conductive silver paste prepared in the mode is shown in figure 2, and the conductive silver paste can be coated on a glass substrate to test the electrical property. The actual volume resistivity was calculated to be 13.6E-06. Omega. Cm by performing the calculation in the same manner as in example 1.
After the silver paste obtained in the manner is dispensed by the dispensing machine, the push-pull force is detected by the universal tensile force tester, the shear strength is calculated by adopting the method for calculating the shear strength, which is the same as that of the embodiment 1, and the calculated shear strength is 6 Mpa.
The description of specific exemplary embodiments of the invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. The low-temperature sintered silver paste is characterized by comprising the following raw materials in percentage by weight:
spherical silver powder: 25-35%;
flake silver powder: 20-30%;
nano silver powder: 20-25%;
high molecular polymer: 6-10%;
solvent: 3-20%;
other additives: 0.5 to 5 percent;
wherein the high molecular polymer is bisphenol A epoxy resin containing polar groups.
2. The low-temperature sintered silver paste according to claim 1, wherein the spherical silver powder has a particle diameter ranging from 1 to 20 μm and the plate-like silver powder has a particle diameter ranging from 1 to 20 μm.
3. The low temperature sintered silver paste of claim 1, wherein the nano silver powder has a particle size ranging from 50 to 500nm.
4. The low temperature sintered silver paste of claim 1, wherein the polar group-containing bisphenol a epoxy resin has the structure:
wherein X-is Cl-,Br-，HS-，H 2 n-, RHN-or R 2 N-。
5. The low temperature sintered silver paste of claim 1, wherein the solvent is selected from one or more of terpineol, turpentine, butyl carbitol, benzyl alcohol, ethanol, cyclohexanone, acetic acid, acetone, butanone, n-butyl acetate.
6. The low temperature sintered silver paste of claim 1, wherein the other additives include a curing agent, a dispersing agent, an anti-settling agent and a leveling agent for effecting curing during heating of the resin and improving dispersibility and leveling of the paste.
7. A method for producing the low-temperature sintered silver paste according to any one of claims 1 to 6, comprising the steps of:
s1, mixing and stirring the high molecular polymer, the solvent and other additives in proportion to obtain an organic phase mixture;
s2, mixing and stirring the spherical silver powder, the flake silver powder and the nano silver powder with the machine phase mixture according to a proportion to obtain semi-finished slurry;
s3, grinding the semi-finished product slurry to obtain roller grinding mixture semi-finished product slurry;
and S4, defoaming the mixture semi-finished product slurry to obtain the low-temperature sintered silver slurry.
8. The method for preparing low temperature sintered silver paste according to claim 7, wherein the stirring temperature in the step S1 is room temperature, the rotation speed is 500 to 1000rpm, and the stirring time period is 15 to 20 minutes.
9. The method for preparing low temperature sintered silver paste according to claim 7, wherein the stirring temperature in the step S2 is 25 to 30 ℃, the rotation speed is 300 to 500rpm, and the stirring time is 5 to 10 minutes.
10. Use of a low temperature sintered silver paste according to any one of claims 1 to 6 in semiconductor packaging.
CN202310763087.7A 2023-06-27 2023-06-27 Low-temperature sintered conductive silver paste and preparation method and application thereof Pending CN116779213A (en)

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