CN108890170A - A kind of graphene-nano mattisolda Heat Conduction Material and preparation method thereof - Google Patents
A kind of graphene-nano mattisolda Heat Conduction Material and preparation method thereof Download PDFInfo
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- CN108890170A CN108890170A CN201811002610.XA CN201811002610A CN108890170A CN 108890170 A CN108890170 A CN 108890170A CN 201811002610 A CN201811002610 A CN 201811002610A CN 108890170 A CN108890170 A CN 108890170A
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- graphene
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- hydrazine hydrate
- graphene oxide
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
Abstract
The invention discloses a kind of graphene-nano mattisolda Heat Conduction Materials and preparation method thereof, the Heat Conduction Material is mixed by graphene oxide dispersion with silver nitrate solution, it is prepared by the way that redox reaction occurs with reducing agent hydrazine hydrate, the addition of multilayer graphene oxide is configured into certain density graphene dispersing solution in distilled water first, then it is mixed again with silver nitrate solution as oxidation solution, a certain amount of hydrazine hydrate and stabilizer are added dropwise after shaken well, the reducing solution of dispersant, until reaction is completed, mixed slurry is prepared after local reduction way, pass through washing, centrifugation obtains graphene-nano mattisolda material.The graphene added in the present invention has biggish specific surface area, nano-Ag particles can be allowed preferably to adsorb, and improves dispersibility, improves nano silver densified sintering product deficiency problem, improves the heating conduction of nano mattisolda.
Description
Technical field
The present invention relates to the preparation technical field of composite nano materials more particularly to a kind of graphene-nano mattisoldas
Preparation process.
Background technique
The interconnection material of current chip and substrate mainly has solder alloy, conducting resinl, frit silver paste and novel-section
Expect nano mattisolda.However, solder alloy there is high temperature reliabilities not high, conducting resinl thermal conductivity is low, frit silver paste
The critical defect of own materials such as sintering temperature height and be difficult to meet the growth requirement of high-power component.Therefore, in order to meet
The growth requirement of power device, it is necessary to go to probe into a kind of interconnection material that can be used in power device and low-temperature sintering skill
Art, with the heat of hoisting power device interconnection encapsulating structure, electricity, mechanical performance, but for current present Research, power device is new
The preparation of type nano mattisolda and its sintering process are still not yet completely apparent, and there are still be difficult to realize 200 DEG C of low temperature below
The dispersion of sintering temperature, the non-densifying dispersal behavior in low-temperature sintering area and nano particle and enhancing base two end number mixing storeroom is not
The significant defect such as uniformly.It would therefore be highly desirable to further investigate preparation and its low temperature sintering technology of novel nano silver paste.
The method of the hot property and mechanical performance that improve nano mattisolda sintering at present is few, mainly improvement sintering process
With doping metals particle, the former process flow is complicated, and energy consumption is bigger, and the latter can increase the sintering temperature of nano mattisolda.
Therefore, novel high molecular material is developed, there is important value as the reinforced phase in nano mattisolda.
Summary of the invention
The object of the present invention is to provide a kind of graphene-nano mattisolda preparation methods being simple and efficient, to aoxidize stone
Black alkene is entrained in nano mattisolda as reinforced phase by the way that surface is modified, synthesizes the nano silver with good adhesion
Soldering paste；The method is simple, practical application value with higher.
To solve above-mentioned technical problem, technical solution provided by the invention is：
A kind of graphene-nano mattisolda preparation method, includes the following steps：
(1) hydrazine hydrate mixing reducing solution is prepared：Hydrazine hydrate, stabilizer and dispersing agent are added to water by certain mass ratio
In, ultrasonic disperse is uniform, then dilute nitric acid solution is added dropwise, and adjusts the pH value of solution between 4~7；
(2) the mixed oxidization liquid of silver nitrate and graphene oxide is prepared：By silver nitrate solution and graphene oxide dispersion
Mixing, ultrasonic disperse are uniform；
(3) graphene-nano silver slurry is prepared：By step (2) the mixed oxidization liquid agitating and heating, then thereto with one
Fixed speed a dropping step (1) the hydrazine hydrate mixing reducing solution terminates until reacting, washs, is centrifugated, obtain graphite
Alkene-nano mattisolda.
Further, in step (1), stabilizer is polyvinylpyrrolidone (PVP), and dispersing agent is 12-3-12 type
Gemini (Shuangzi) quaternary ammonium salt.
Further, in step (1), the mass ratio of hydrazine hydrate, stabilizer and dispersing agent is 3~7:1:2.
Further, in step (2), in the mixed oxidization liquid of silver nitrate and graphene oxide, the mass concentration of silver nitrate
For 8.2~9.4g/L, the mass concentration of graphene oxide is 0.1~0.12g/L.
Further, in step (3), the mixed oxidization liquid is placed in 30~50 DEG C of water-baths and is heated.
Further, in step (3), with revolving speed 20~50min/s magnetic agitation mixed oxidization liquid, after stirring 5min,
Hydrazine hydrate mixing reducing solution is added dropwise with the speed of 1.5~3.5ml/min thereto again.
Compared with prior art, it is an advantage of the invention that：
Graphene-nano mattisolda prepared by the present invention, densified sintering product is good, and thermal conductivity is high, has and preferably actually answers
With value；The preparation process is simple, and the period is shorter, economic and environment-friendly.
Detailed description of the invention
Fig. 1 is graphene-nano mattisolda Heat Conduction Material preparation technology flow chart.
Fig. 2 is the TEM electron microscope of graphene nanometer sheet liquid phase in-situ reducing nano-Ag particles.
Specific embodiment
The contents of the present invention are further elaborated with reference to the accompanying drawings and examples, but are not to of the invention
It limits.
Inventor's trial prepares the nano mattisolda Heat Conduction Material of graphene oxide doped, can be compared with to nano-Ag particles
Good is dispersed on graphene sheet layer, improves the sintered compactness of nano mattisolda and hot property, develops a kind of unique more
The chip interconnection materials of function.However, in this application, inventor is it was unexpectedly observed that dopen Nano is golden in nano mattisolda
Hard rock, there is no as the expected apparent sintering temperature for reducing nano mattisolda, but graphene oxide and nano-Ag particles
Between realize and be effectively combined, densified sintering product performance is significantly improved, while improving thermal conductivity.The application is to prepare high property
Energy nano mattisolda Heat Conduction Material provides a kind of unique new approaches, has both science and practical value.
In conjunction with Fig. 1, graphene of the present invention-nano mattisolda Heat Conduction Material preparation method includes the following steps：
(1) hydrazine hydrate mixing reducing solution is prepared：By hydrazine hydrate, stabilizer, dispersing agent is added to steaming by certain mass ratio
In distilled water, then by supersonic oscillations 30min, uniform mixed solution is obtained, then adds the dilute nitre of 8~12ml in the solution
Acid solution adjusts the pH value of mixing reducing solution between 4~7.
(2) the mixed oxidization liquid of silver nitrate and graphene oxide is prepared：Silver nitrate solution and graphene oxide solution 1 are mixed
It closes, by supersonic oscillations 10min, obtains evenly dispersed mixed oxidization liquid；
(3) graphene-nano silver slurry is prepared：Mixed oxidization liquid is placed in water-bath and is heated, with revolving speed 20min/s magnetic
Power stirring stirs 5min and then hydrazine hydrate mixing reducing solution is added dropwise with the speed of 1.5ml/min thereto, until reaction is tied
Beam, then repeatedly washed with deionized water and dehydrated alcohol, finally by centrifuge separation, obtain graphene-nano mattisolda.
Embodiment 1
(1) hydrazine hydrate mixing reducing solution is configured, by hydrazine hydrate, polyvinylpyrrolidone (PVP), 12-3-12 type
Gemini (Shuangzi) quaternary ammonium salt in mass ratio 4:1:2 are added in distilled water, then by supersonic oscillations 30min, obtain
Even mixed solution, it is 2% dilute nitric acid solution that 8ml concentration is then added in the solution, and the pH value for adjusting mixing reducing solution is
6；
(2) the mixed oxidization liquid for configuring silver nitrate and graphene oxide, silver nitrate solution and graphene oxide solution are mixed
It closes, by supersonic oscillations 30min, obtains evenly dispersed mixed oxidization liquid；
(3) graphene-nano silver slurry is prepared, mixed oxidization liquid is placed in water-bath and heats 30 DEG C, with revolving speed
30min/s magnetic agitation stirs 5min and then hydrazine hydrate mixing reducing solution is added dropwise with the speed of 1.5ml/min thereto, directly
Terminate to reaction, then carries out 3 washings with deionized water and dehydrated alcohol and obtain graphene-nanometer finally by centrifuge separation
Silver paste.
Graphene-nano mattisolda microscopic appearance (TEM) projects electron microscope as indicated with 2, according to TEM test result table
It is bright：The high-visible load on graphene sheet layer has an a large amount of metallic silver particles in figure, and silver-colored simple substance present it is spherical, dispersibility compared with
It is good, there is not apparent agglomeration.Performance is carried out to graphene manufactured in the present embodiment-nano mattisolda Heat Conduction Material
Detection, measuring thermal conductivity by Hot Disk thermal constant analyzer is 62.5W/mK.
Embodiment 2
Other conditions examine material prepared by the mass ratio of different hydrazine hydrates, stabilizer and dispersing agent with embodiment 1
Performance, experimental result is shown in Table 1.
The performance of material prepared by the mass ratio of the different hydrazine hydrates of table 1, stabilizer and dispersing agent
From the above results, the mass ratio of hydrazine hydrate, stabilizer and dispersing agent preferably 4:1:2 (embodiments 1).
Embodiment 3
Other conditions examine the performance of material prepared by the pH value of different mixing reducing solutions, experimental result with embodiment 1
It is shown in Table 2.
The performance of material prepared by the pH value of the different mixing reducing solutions of table 2
| Serial number | Mix the pH value of reducing solution | Thermal conductivity (W/mk) |
| 1 | 4 | 52.8 |
| 2 | 5 | 56.4 |
| 3 | 6 (embodiments 1) | 62.5 |
| 4 | 7 | 0.23 |
| 5 | 8 | 1.45 |
From the above results, the pH value preferred value for mixing reducing solution is 6 (embodiments 1).
Embodiment 4
Other conditions examine the performance of material prepared by different mixed oxidization liquid water bath heating temperatures with embodiment 1, real
It tests and the results are shown in Table 3.
The performance of material prepared by the different mixed oxidization liquid water bath heating temperatures of table 3
| Serial number | Mixed oxidization liquid water bath heating temperature (DEG C) | Thermal conductivity (W/mk) |
| 1 | 30 (embodiments 1) | 62.5 |
| 2 | 35 | 59.4 |
| 3 | 40 | 50.7 |
| 4 | 45 | 45.6 |
| 5 | 50 | 41.5 |
From the above results, preferably 30 DEG C (embodiment 1) of mixed oxidization liquid water bath heating temperature.
Embodiment 5
Other conditions examine the performance of material prepared by the different drop rates of reducing solution, experimental result with embodiment 1
It is shown in Table 4.
The performance of material prepared by the different drop rates of 4 reducing solution of table
From the above results, the preferred 1.5ml/min of different drop rates (embodiment 1) of reducing solution.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to the above reality
Any simple modifications, equivalent substitutions and improvements etc. made by example are applied, it is fallen within the scope of protection of the technical scheme of the present invention
It is interior.
Claims (9)
1. graphene-nano mattisolda Heat Conduction Material preparation method, which is characterized in that include the following steps：
（1）Prepare hydrazine hydrate mixing reducing solution：Hydrazine hydrate, stabilizer and dispersing agent are added to the water by certain mass ratio,
Ultrasonic disperse is uniform, then dilute nitric acid solution is added dropwise, and adjusts the pH value of solution between 4 ~ 7；
（2）Prepare the mixed oxidization liquid of silver nitrate and graphene oxide：Silver nitrate solution and graphene oxide dispersion are mixed,
Ultrasonic disperse is uniform；
（3）Prepare graphene-nano silver slurry：By step（2）The mixed oxidization liquid agitating and heating, then thereto with certain
Speed a dropping step（1）The hydrazine hydrate mixing reducing solution terminates until reacting, washs, is centrifugated, obtain graphene-and receive
Rice silver paste.
2. the method as described in claim 1, which is characterized in that stabilizer is polyvinylpyrrolidone, dispersing agent 12-3-12
Type gemini quaternary ammonium salt.
3. the method as described in claim 1, which is characterized in that step（1）In, the quality of hydrazine hydrate, stabilizer and dispersing agent
Than being 3 ~ 7:1:2.
4. the method as described in claim 1, which is characterized in that in the mixed oxidization liquid of silver nitrate and graphene oxide, nitric acid
The mass concentration of silver is 8.2 ~ 9.4g/L, and the mass concentration of graphene oxide is 0.1 ~ 0.12g/L.
5. the method as described in claim 1, which is characterized in that step（3）In, the mixed oxidization liquid is placed in 30 ~ 50 DEG C
It is heated in water-bath.
6. the method as described in claim 1, which is characterized in that step（3）In, with the mixing of revolving speed 20 ~ 50min/s magnetic agitation
Oxidation solution stirs 5min and then hydrazine hydrate mixing reducing solution is added dropwise with the speed of 1.5 ~ 3.5ml/min thereto.
7. the method as described in claim 1, which is characterized in that graphene oxide is multilayer graphene oxide, and the number of plies is 4 ~ 6
Layer, partial size are 500nm ~ 50um.
8. the method as described in claim 1, which is characterized in that the mass concentration of silver nitrate solution is 80 ~ 98%.
9. graphene-nano mattisolda Heat Conduction Material of method preparation a method as claimed in any one of claims 1-8.
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| CN111360452A (en) * | 2020-03-17 | 2020-07-03 | 深圳第三代半导体研究院 | Preparation method of graphite-nano silver composite soldering paste sintering material |
| CN114260460A (en) * | 2021-12-24 | 2022-04-01 | 陕西煤业化工技术研究院有限责任公司 | Submicron graphene silver powder suitable for 5G field and preparation method and application thereof |
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