CN112480848B - Electric and heat conducting silver adhesive for chip bonding and preparation method thereof - Google Patents
Electric and heat conducting silver adhesive for chip bonding and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/023—Silicon
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- C08K2003/0831—Gold
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- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The application relates to the field of semiconductor chip packaging materials, and particularly discloses an electric and heat conducting silver adhesive for chip bonding and a preparation method thereof. An electric and heat conducting silver adhesive for chip bonding is prepared from the following raw materials in parts by weight: epoxy resin, acrylic resin, a curing agent, an ester flexibilizer, a coupling agent, an antioxidant, a dispersing agent, silver powder and silicon powder; the preparation method comprises the following steps: s1, heating and mixing epoxy resin, acrylic resin, a curing agent, an ester flexibilizer, a coupling agent, an antioxidant and a dispersing agent, heating to 70-85 ℃, and mixing for 1-2 hours to obtain a premix; s2, mixing the pre-mixed body, the silver powder and the silicon powder at the mixing temperature of 80-90 ℃ to obtain a mixed body; and S3, stirring the mixed mixture at room temperature for 0.5-2 h, and performing vacuum drying and degassing to obtain the electric and heat conductive silver adhesive. The electric and heat conducting silver adhesive has the advantage of improving the operation performance of the electric adhesive.
Description
Technical Field
The application relates to the field of semiconductor chip packaging materials, in particular to an electric and heat conducting silver adhesive for chip bonding and a preparation method thereof.
Background
Packaging technology is an important part of the IC chip industry, and as electronic products are driven by light, thin, short, and small market demands and technologies, various new packaging forms put higher demands on packaging materials, and as packaging structures have improved heat dissipation performance, advanced IC packaging technologies have gradually become the key point of technical research and development in various packaging factories, wherein conductive adhesives used for electronic chip packaging are widely researched.
The conductive adhesive used for packaging the electronic chip is generally called conductive silver adhesive, is an adhesive with certain conductive performance after being cured or dried, generally takes matrix resin and conductive particles as main components, and combines the conductive particles together through the bonding action of the matrix resin to form a conductive path to realize the conductive connection of the bonded material.
The related conductive adhesive generally takes epoxy resin and silver powder as main materials, wherein the epoxy resin is used as matrix resin, the silver powder is used as conductive particles, and an epoxy diluent and a curing agent are added to prepare the conductive adhesive.
Disclosure of Invention
In order to improve the overall strength and the conductivity of the conductive adhesive, the application provides the conductive and heat-conductive silver adhesive for chip bonding and the preparation method thereof.
In a first aspect, the application provides an electrically and thermally conductive silver paste for chip bonding, which adopts the following technical scheme:
an electric and heat conducting silver adhesive for chip bonding is prepared from the following raw materials in parts by weight:
20-40 parts of epoxy resin;
10-20 parts of acrylic resin;
5-10 parts of phenolic resin;
0.4-0.8 part of curing agent;
0.6-1 part of a plasticizer;
0.8-1.4 parts of an ion complexing agent;
0.8-1.2 parts of a coupling agent;
0.05-0.1 part of antioxidant;
0.3-0.5 part of a dispersing agent;
0.05-0.1 part of catalyst;
70-85 parts of silver powder;
2.5-3.5 parts of silicon powder.
By adopting the technical scheme, as the acrylic resin and the epoxy resin are matched, the acrylic resin and the epoxy resin form an interpenetrating network, the defect of brittleness of the cured epoxy resin is overcome, the heat conductivity of the colloid is improved, and the flexibility of the epoxy resin can be improved by the plasticizer, so that the shearing strength of the colloid is improved, and the operating performance of the colloid is improved; in addition, the interpenetrating grids are beneficial to the uniform dispersion of the silver powder in the colloid, so that the conductive capacity of the colloid is improved, the addition of the phenolic resin can promote the crosslinking of the epoxy resin, the silver powder is better arranged, and the conductive performance and the overall strength of the colloid are improved.
Preferably, the ionic complexing agent is selected from one or more of dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide ], sebacic acid bis-salicyloyl hydrazide, m-nitrobenzoyl hydrazide, 3-aminophthalic acid dihydrazide, terephthalic acid dihydrazide or adipic acid dihydrazide.
By adopting the technical scheme, the ion complexing agent can complex metal ions such as sodium, copper and the like in the colloid, and the influence of the metal ions such as sodium, copper and the like on the stability and the conductivity of the colloid is reduced.
Preferably, the curing agent is selected from methyl ethyl ketone peroxide.
By adopting the technical scheme, the curing effect of the methyl ethyl ketone peroxide on the epoxy resin and the acrylic resin is better.
Preferably, the plasticizer is selected from polybutadiene epoxy resins.
By adopting the technical scheme, the polybutadiene epoxy resin can better improve the flexibility of colloid.
Preferably, the coupling agent is selected from titanate coupling agents.
By adopting the technical scheme, the titanate coupling agent is beneficial to promoting the combination of the silicon powder, the epoxy resin and the acrylic resin, and the strength of the colloid is improved.
Preferably, the dispersant is selected from one of polyvinylpyrrolidone or polyethylene glycol.
By adopting the technical scheme, the polyvinylpyrrolidone and the polyethylene glycol are beneficial to reducing the surface tension of the colloid and improving the bonding effect.
Preferably, the antioxidant is selected from 2, 6-di-tert-butyl-p-cresol.
Preferably, the silver powder has an average particle diameter of 100 μm and an average specific surface area of 10.5m2/g。
By adopting the technical scheme, the high specific surface area of the silver powder is beneficial to improving the connection stability of the phenolic resin and the silver powder, further promoting the silver powder to be better arranged and improving the bonding effect and the conductive effect of the colloid.
Preferably, the raw material also comprises 0.4-0.8 part by weight of conductive gold balls, and the average particle size of the conductive gold balls is 20 microns.
By adopting the technical scheme, the conductive gold balls are doped in the space formed by the silver powder, so that the conductivity of the colloid is further improved.
Preferably, the raw material also comprises 0.7-0.9 part by weight of indium tin oxide, and the average particle size of the indium tin oxide is 1 μm.
By adopting the technical scheme, the indium tin oxide is doped in the space formed by the silver powder, so that the conductivity of the colloid is further improved.
Preferably, the catalyst is selected from bis [ (OC-6-11) -hexafluoroantimonate (1-) ].
By adopting the technical scheme, the curing temperature of the colloid is reduced to 120 ℃, and the convenience of operation is improved.
In a second aspect, the present application provides a method for preparing an electrically and thermally conductive silver paste for chip bonding, which adopts the following technical scheme:
a preparation method of electric and heat conducting silver adhesive for chip bonding comprises the following steps:
s1, mixing epoxy resin, acrylic resin, phenolic resin, a plasticizer, an ion complexing agent, a coupling agent, an antioxidant and a dispersing agent, heating to 70-85 ℃, mixing for 1-2 hours, and extruding at 105-115 ℃ to obtain a premix;
s2, mixing the pre-mixture, the silver powder and the silicon powder at the mixing temperature of 80-90 ℃ for 15-25 min to obtain a mixed body;
and S3, stirring the mixed body, the catalyst and the curing agent at room temperature for 0.5-2 h, and performing vacuum drying and degassing to obtain the electric and heat conductive silver colloid.
By adopting the technical scheme, the premixed body mixed to a certain degree is prepared, and the silver powder and the silicon powder are added for mixing, so that the dispersibility of the silver powder and the silicon powder in the colloid is improved, and the conductivity is improved.
Preferably, in step S2, conductive gold balls are further added for kneading.
Preferably, before the step of S2, the method further comprises the step of S2A: and immersing the silver powder in acrylic acid, and performing ultrasonic dispersion to obtain the pretreated silver powder.
By adopting the technical scheme, the acrylic acid can promote the connection among the silver powder particles, and the heat conduction and electric conduction effects of the silver powder are improved.
Preferably, before the step of S2, the method further comprises the step of S2B: adding indium tin oxide into a mixed solvent consisting of ethanol and water at 50-60 ℃, stirring, dropwise adding aminopropyltriethoxysilane, continuing stirring for 0.5-1 h, wherein the weight ratio of the indium tin oxide to the ethanol to the water to the aminopropyltriethoxysilane is 10 (20-30) to (3-5) to (0.3-0.6), filtering after stirring is finished, collecting solids and drying to obtain modified indium tin oxide; in step S2, modified indium tin oxide was further added and kneaded.
By adopting the technical scheme, the modified indium tin oxide is combined with the silver powder, so that the indium tin oxide is promoted to be mixed in the space formed by the silver powder, the contact between the indium tin oxide and the silver powder is good, and the conductive effect of the colloid is improved.
In summary, the present application has the following beneficial effects:
1. due to the matching of the acrylic resin and the epoxy resin, the defect of brittleness of the cured epoxy resin is overcome, the heat conductivity of the colloid is improved, and the flexibility of the epoxy resin can be improved by the plasticizer, so that the shear strength of the colloid is improved, and the operating performance of the colloid is improved; in addition, the interpenetrating grids are beneficial to uniform dispersion of the silver powder in the colloid and improvement of the conductive capability of the colloid, and the addition of the phenolic resin can promote the crosslinking of the epoxy resin and better arrange the silver powder, so that the colloid has good strength, heat-conducting property and conductive performance.
2. In the application, indium tin oxide is preferably added, and the conductivity of the colloid is improved by modifying aminopropyltriethoxysilane and pretreating silver powder by acrylic acid.
Detailed Description
The present application will be described in further detail with reference to examples.
The epoxy resin was selected from biphenyl type epoxy resin, model NC-3000, available from Nippon chemical Co., Ltd;
the acrylic resin was selected from Mitsubishi chemical corporation, model BR-116;
the phenolic resin was selected from Nippon Sumitomo chemical corporation, model PR-55147;
the conductive gold balls are purchased from waterlogging chemical industry Co., Ltd, and have an average particle size of 15-20 μm;
silver powder was selected from Nippon Hokko, K.K., having an average particle diameter of 100 μm and a specific surface area of 6m2G and 10.5m2/g；
Titanate coupling agents are commercially available from Kenrechi, USA, model KR-38S.
Examples
Example 1
A preparation method of electric and heat conducting silver adhesive for chip bonding comprises the following steps:
s1, adding 2kg of epoxy resin, 1kg of acrylic resin, 0.5kg of phenolic resin, 0.06kg of polybutadiene epoxy resin, 0.08kg of sebacic acid bis-salicylyl hydrazide, 0.08kg of titanate coupling agent, 0.005kg of 2, 6-di-tert-butyl-p-cresol and 0.03kg of polyvinylpyrrolidone into a reaction kettle, mixing and stirring, heating to 70 ℃, mixing for 1h, and then extruding in a screw extruder at 105 ℃ to obtain a premix;
s2, adding the pre-mixture, 5kg of silver powder and 0.25kg of silicon powder into a mixing roll for mixing at the mixing temperature of 80 ℃ for 15min to obtain a mixed body;
s3, stirring the mixed body, 0.005kg of bis [ (OC-6-11) -hexafluoroantimonate (1-) ] and 0.06kg of methyl ethyl ketone peroxide at room temperature for 0.5h, filtering through a 500-mesh screen, drying in vacuum, and degassing to obtain the conductive and heat-conductive silver adhesive.
Wherein the silver powder has an average particle diameter of 100 μm and an average specific surface area of 6m2/g。
Example 2
A preparation method of electric and heat conducting silver adhesive for chip bonding comprises the following steps:
s1, adding 4kg of epoxy resin, 0.5kg of acrylic resin, 0.8kg of phenolic resin, 0.08kg of methyl ethyl ketone peroxide, 0.1kg of polybutadiene epoxy resin, 0.12kg of m-nitrophenyl hydrazide, 0.1kg of titanate coupling agent, 0.01kg of 2, 6-di-tert-butyl-p-cresol and 0.05kg of polyethylene glycol into a reaction kettle, mixing and stirring, heating to 85 ℃, mixing for 2 hours, and then extruding at 115 ℃ in a screw extruder to obtain a premix;
s2, adding the premixed body, 7.5kg of silver powder and 0.3kg of silicon powder into a mixing roll for mixing at the mixing temperature of 90 ℃ for 25min to obtain a mixed body;
s3, stirring the mixed body, 0.01kg of bis [ (OC-6-11) -hexafluoroantimonate (1-) ] and 0.08kg of methyl ethyl ketone peroxide at room temperature for 2 hours, filtering through a 500-mesh screen, drying in vacuum, and degassing to obtain the conductive and heat-conductive silver colloid.
Wherein the silver powder has an average particle diameter of 100 μm and an average specific surface area of 6m2/g。
Example 3
A preparation method of electric and heat conducting silver adhesive for chip bonding comprises the following steps:
s1, adding 3kg of epoxy resin, 0.8kg of acrylic resin, 1kg of phenolic resin, 0.04kg of methyl ethyl ketone peroxide, 0.08kg of polybutadiene epoxy resin, 0.14kg of 3-aminophthalide, 0.12kg of titanate coupling agent, 0.007kg of 2, 6-di-tert-butyl-p-cresol and 0.04kg of polyvinylpyrrolidone into a reaction kettle, mixing and stirring, heating to 80 ℃, mixing for 1h, and then extruding in a screw extruder at 110 ℃ to obtain a premix;
s2, adding the premixed body, 6.5kg of silver powder and 0.35kg of silicon powder into a mixing roll for mixing at the mixing temperature of 85 ℃ for 25min to obtain a mixed body;
s3, stirring the mixed body, 0.005kg of bis [ (OC-6-11) -hexafluoroantimonate (1-) ] and 0.04kg of methyl ethyl ketone peroxide at room temperature for 1h, filtering through a 500-mesh screen, vacuum drying and degassing to obtain the conductive and heat-conductive silver colloid.
Wherein the silver powder has an average particle diameter of 100 μm and an average specific surface area of 6m2/g。
The differences between examples 1 and 3 are shown in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| Epoxy resin (kg) | 2 | 4 | 3 |
| Acrylic resin (kg) | 1 | 0.5 | 0.8 |
| Phenolic resin (kg) | 0.5 | 0.8 | 1 |
| Methyl ethyl ketone peroxide (kg) | 0.06 | 0.08 | 0.04 |
| Bis [ (OC-6-11) -hexafluoroantimonate (1-)](kg) | 0.005 | 0.01 | 0.005 |
| Polybutadiene epoxy resin (kg) | 0.06 | 0.1 | 0.08 |
| Sebacic acid bis-salicyloyl hydrazide (kg) | 0.08 | 0 | 0 |
| M-nitrophenyl hydrazide (kg) | 0 | 0.12 | 0 |
| 3-Aminophthalhydrazide (kg) | 0 | 0 | 0.14 |
| Titanate coupling agent (kg) | 0.08 | 0.1 | 0.12 |
| 2, 6-Di-tert-butyl-p-cresol (kg) | 0.005 | 0.01 | 0.007 |
| Polyvinylpyrrolidone (kg) | 0.03 | 0 | 0.04 |
| Polyethylene glycol (kg) | 0 | 0.05 | 0 |
| Silver powder (kg) | 5 | 7.5 | 6.5 |
| Silicon powder (kg) | 0.25 | 0.3 | 0.35 |
| Heating temperature (. degree.C.) in S1 | 70 | 85 | 80 |
| Mixing time (h) in S1 | 1 | 2 | 1 |
| Extrusion temperature (. degree.C.) in S1 | 105 | 115 | 110 |
| Mixing temperature (. degree.C.) in S2 | 80 | 90 | 85 |
| Mixing time (min) in S2 | 15 | 25 | 25 |
| Stirring time (h) in S3 | 0.5 | 2 | 1 |
Example 4
This example is different from example 3 in that the average specific surface area of the silver powder was 10.5m2/g。
Example 5
This example is different from example 4 in that 0.04kg of conductive gold balls was further added to the kneader in step S2.
Example 6
This example is different from example 4 in that 0.08kg of conductive gold balls were further added to the kneader in the step of S2.
Example 7
The present embodiment is different from embodiment 4 in that before the step of S2, the present embodiment further includes a step of S2A, and the step of S2A specifically includes: and pouring acrylic acid into the first reaction bottle, immersing the silver powder into the acrylic acid, and performing ultrasonic dispersion for 30min to obtain the pretreated silver powder.
Example 8
This example is different from example 7 in that 0.07kg of indium tin oxide having an average particle diameter of 1 μm was further added to the kneader in the step of S2.
Example 9
This example is different from example 7 in that 0.09kg of indium tin oxide having an average particle diameter of 1 μm was further added to the kneader in the step of S2.
Example 10
The present embodiment is different from embodiment 8 in that before the step of S2, the method further includes a step of S2B, and the step of S2B specifically includes: at 50 ℃, 0.4kg of ethanol and 0.06kg of water are poured into a second reaction bottle to form a mixed solvent, then 0.2kg of indium tin oxide is added into the mixed solvent, 0.006kg of aminopropyltriethoxysilane is dripped while stirring, the mixture is continuously stirred for 0.5h, after the stirring is finished, the mixture is filtered, and the solid is collected and dried in an oven at 55 ℃ for 1h to obtain the modified indium tin oxide.
In step S2, 0.07kg of modified indium tin oxide was added to the mixer in place of an equivalent amount of indium tin oxide.
Example 11
The present embodiment is different from embodiment 9 in that before the step of S2, the present embodiment further includes a step of S2B, and the step of S2B specifically includes: and at the temperature of 60 ℃, 0.6kg of ethanol and 0.1kg of water are poured into a second reaction bottle to form a mixed solvent, then 0.2kg of indium tin oxide is added into the mixed solvent, 0.012kg of aminopropyltriethoxysilane is dripped while stirring, the mixture is continuously stirred for 1h, after the stirring is finished, the mixture is filtered, and the solid is collected and dried in an oven at the temperature of 55 ℃ for 1h to obtain the modified indium tin oxide.
In step S2, 0.09kg of modified indium tin oxide was substituted for an equivalent amount of indium tin oxide and added to the mixer.
Comparative example
Comparative example 1
This comparative example is different from example 3 in that in the step of S1, an equal amount of epoxy resin was used instead of the acrylic resin, phenolic resin and 3-aminophthalic hydrazide.
Comparative example 2
This comparative example is different from example 3 in that in the step of S1, the acrylic resin and 3-aminophthalic hydrazide are replaced with the same amount of epoxy resin.
Comparative example 3
This comparative example is different from example 3 in that in the step of S1, an equal amount of epoxy resin was used instead of the phenol resin and 3-aminophthalic hydrazide.
Comparative example 4
This comparative example is different from example 3 in that 3-aminophthalic hydrazide is replaced with the same amount of epoxy resin in the step of S1.
Performance test
According to GB/T35494.1-2017 'testing method for isotropic conductive adhesives', the shear strength and the thermal conductivity of the conductive and heat conductive silver adhesive of each example and comparative example of the application are tested, and the test results are shown in Table 2.
The volume resistivity of the thermally and electrically conductive silver paste of the examples and comparative examples of the present application was measured according to CNS 13727-1996 volume resistivity measurement of electrically conductive paste, and the results are shown in Table 2.
TABLE 2
| Shear strength (MPa) | Thermal conductivity (W/MK) | Volume resistivity (. times.10)-5Ω·m) | |
| Example 1 | 8.63 | 11.6 | 3.2 |
| Example 2 | 8.66 | 11.8 | 3.5 |
| Example 3 | 8.72 | 11.5 | 3.4 |
| Example 4 | 8.65 | 12.1 | 2.6 |
| Example 5 | 8.69 | 12.4 | 1.9 |
| Example 6 | 8.66 | 12.2 | 1.7 |
| Example 7 | 8.68 | 12.1 | 2.4 |
| Example 8 | 8.75 | 12.3 | 3 |
| Example 9 | 8.61 | 12.3 | 3.1 |
| Example 10 | 8.66 | 12.5 | 1.8 |
| Example 11 | 8.71 | 12.2 | 1.9 |
| Comparative example 1 | 4.52 | 7.8 | 7.3 |
| Comparative example 2 | 5.34 | 8.3 | 6.2 |
| Comparative example 3 | 5.62 | 9.5 | 6.5 |
| Comparative example 4 | 8.64 | 11.4 | 5.1 |
According to table 2, comparative example 1 is a related method for preparing conductive adhesive in background art, compared with example 3, the obtained conductive adhesive has larger shear strength and thermal conductivity coefficient and smaller volume resistivity, which illustrates that the conductive adhesive of example 3 has good operation performance, good thermal conductivity and good electrical conductivity, probably because the acrylic resin and the epoxy resin form interpenetrating grids which form stable thermal conductive channels, and the defect of brittleness of the cured epoxy resin is improved, and the silver powder is uniformly dispersed in the colloid, thereby improving the electrical conductivity of the colloid; the addition of the phenolic resin can promote the crosslinking of the epoxy resin, improve the dispersibility of the silver powder and enable the silver powder to be better arranged, thereby improving the overall strength and the conductivity of the colloid.
The shear strength and the heat conductivity of the embodiment 3 are higher than those of the comparative example 2, the volume resistivity is lower than that of the comparative example 2, and the fact that the phenolic resin can better improve the strength, the heat conductivity and the electric conductivity of the colloid when only the phenolic resin is added is shown.
The shear strength and the thermal conductivity of the example 3 are higher than those of the comparative example 3, and the volume resistivity is lower than that of the comparative example 3, which shows that when only the acrylic resin is added, the acrylic resin can better improve the strength, the thermal conductivity and the electric conductivity of the colloid, and the interpenetrating grids formed by the acrylic resin and the epoxy resin can improve the thermal conductivity.
The shear strength and the thermal conductivity of example 3 are similar to those of comparative example 4, and the volume resistivity is lower than that of comparative example 3, because the 3-aminophthalic hydrazide is probably used as an ion complexing agent to complex metal ions such as sodium and copper in the colloid, so that the interference of the metal ions is reduced, and the conductivity is improved.
The conductive performance of example 4 is better than that of example 3, probably because the specific surface area of the silver powder is increased, which facilitates the connection of the silver powder and the phenolic resin, promotes the better arrangement of the silver powder, and improves the conductive performance of the colloid.
The conductive performance of examples 5-6 was superior to that of example 3, probably because the conductive gold balls were added, the conductive gold balls were mixed in the spaces of the silver powder particles, and the conductive gold balls were in good contact with the silver powder, improving the conductive performance of the colloid.
The conductive performance of example 7 is superior to that of example 3, probably because acrylic acid is bonded to the surface of silver powder, facilitating the connection between particles of silver powder, and improving the heat and electric conductive effects of silver powder.
The conductive properties of examples 8-9 were slightly inferior to those of example 4, probably because the indium tin oxide was not well dispersed after addition, and could not form a good conductive system with the colloid and silver powder, and the conductivity between part of the silver powder was hindered, affecting the conductive properties of the colloid.
The conductive performance of examples 10-11 is better than that of example 6, probably because the aminopropyltriethoxysilane of the indium tin oxide is combined with the acrylic acid of the silver powder after the indium tin oxide is modified, so that the indium tin oxide is stably mixed in the space formed by the silver powder, the dispersibility of the indium tin oxide is improved, the contact between the indium tin oxide and the silver powder is good, and the conductive effect of the colloid is improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (4)
1. The electric and heat conducting silver adhesive for chip bonding is characterized by being prepared from the following raw materials in parts by weight:
20-40 parts of epoxy resin;
10-20 parts of acrylic resin;
5-10 parts of phenolic resin;
0.4-0.8 part of curing agent;
0.6-1 part of a plasticizer;
0.8-1.4 parts of an ion complexing agent;
0.8-1.2 parts of a coupling agent;
0.05-0.1 part of antioxidant;
0.3-0.5 part of a dispersing agent;
0.05-0.1 part of catalyst;
70-85 parts of silver powder;
2.5-3.5 parts of silicon powder;
the silver powder has an average particle diameter of 100 μm and an average specific surface area of 6m2G and 10.5m2/g；
The raw materials also comprise 0.7-0.9 part by weight of modified indium tin oxide, and the average particle size of the modified indium tin oxide is 1 mu m;
the preparation of the electric and heat conductive silver adhesive comprises the following steps:
s1, mixing epoxy resin, acrylic resin, phenolic resin, a plasticizer, an ion complexing agent, a coupling agent, an antioxidant and a dispersing agent, heating to 70-85 ℃, mixing for 1-2 hours, and extruding at 105-115 ℃ to obtain a premix;
s2, mixing the pre-mixture, the silver powder and the silicon powder at the mixing temperature of 80-90 ℃ for 15-25 min to obtain a mixed body;
s3, stirring the mixed body, the catalyst and the curing agent at room temperature for 0.5-2 h, and performing vacuum drying and degassing to obtain the electric and heat conductive silver colloid;
before the step of S2, the method further comprises the step of S2A: immersing silver powder in acrylic acid, and performing ultrasonic dispersion to obtain pretreated silver powder;
before the step of S2, the method further comprises the step of S2B: adding indium tin oxide into a mixed solvent consisting of ethanol and water at 50-60 ℃, stirring, dropwise adding aminopropyltriethoxysilane, continuing stirring for 0.5-1 h, wherein the weight ratio of the indium tin oxide to the ethanol to the water to the aminopropyltriethoxysilane is 10 (20-30) to (3-5) to (0.3-0.6), filtering after stirring is finished, collecting solids and drying to obtain modified indium tin oxide; in step S2, modified indium tin oxide was further added and kneaded.
2. The silver paste for chip bonding according to claim 1, wherein: the ionic complexing agent is selected from one or more of sebacic acid disalicyl hydrazide, m-nitrophenyl hydrazide, 3-aminophthalic hydrazide, dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide ], terephthalic acid dihydrazide or adipic acid dihydrazide.
3. The silver paste for chip bonding according to claim 1, wherein: the raw materials also comprise 0.4-0.8 part by weight of conductive gold balls, the average particle size of the conductive gold balls is 20 microns, and the conductive gold balls are added in the step S2.
4. The silver paste for chip bonding according to claim 1, wherein: the catalyst is selected from bis [ (OC-6-11) -hexafluoroantimonate (1-) ].
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| JP6091019B2 (en) * | 2015-02-02 | 2017-03-08 | 田中貴金属工業株式会社 | Thermally conductive conductive adhesive composition |
| CN105238314B (en) * | 2015-11-13 | 2017-11-07 | 深圳先进技术研究院 | A kind of wet-heat resisting high reliability epoxy conductive silver glue and preparation method and application |
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