CN110379540B - Organic silver/carbon nano tube composite slurry and preparation method and application thereof - Google Patents
Organic silver/carbon nano tube composite slurry and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electronic paste, in particular to organic silver/carbon nano tube composite paste and a preparation method and application thereof. The organic silver/carbon nano tube composite slurry is an organic composite slurry consisting of an organic solvent, a carbon nano tube, a silver compound and ethylamine; the silver compound and ethylamine in the organic silver/carbon nano tube composite slurry form an organic silver complex. The composite slurry is convenient to prepare, and can be quickly and efficiently prepared by a two-step method; the prepared composite slurry has the advantages of convenient transportation and storage; the composite slurry is used for perforating the hole on the printed circuit board, and the nano conductive composite film layer formed on the inner wall of the hole has the advantages of high bonding strength, low resistivity and the like.
Description
Technical Field
The invention relates to the technical field of electronic paste, in particular to organic silver/carbon nano tube composite paste and a preparation method and application thereof.
Background
With the gradual trend of miniaturization and portability of electronic devices, printed circuit boards are developed toward high precision, slimness, high-density assembly and environmental protection. In addition, price limits and profits of electronic devices are also being reduced. Under the background, a new process for silver paste through holes is generated. The silver conductive paste mainly takes micron-sized silver powder as a conductive medium, takes a resin special curing agent as a main binder, is added with a small amount of diluent, and utilizes the shrinkage of the silver paste in a hole to the hole wall by heating, so as to conduct the upper layer and the lower layer. However, the physical coating method has the problems that the resin binder is easy to age, the silver film layer is easy to break and fall off, the resistivity is high, and the like, and in addition, when the viscosity of the silver paste is too high, the through hole capability is poor, even the through hole cannot be penetrated, and the like. In order to solve the above problems, studies on organic silver inks/pastes containing no resin binder have been conducted by several scholars and research institutes at home and abroad. For example, the organic silver compound and the preparation method thereof, the organic silver ink and the invention patent authorization of the direct wiring method thereof, which are disclosed by the Chinese patent office on 4/2/2008, and the publication number of the invention is CN100377891C, in the technical scheme of the invention, silver oxide is reacted with an amine compound and a lactone compound, the amine compound and the lactone compound are dissolved in the latter, and alcohols, a surfactant and the like are added to prepare the organic silver ink. The organic silver ink can be coated on a substrate or a guide hole of a printed circuit board in a spin coating, direct ink writing, fine nozzle printing and spray gun spraying mode, and is heated to obtain the conductive silver film layer. Also, as the invention patent of the preparation method of the low-temperature sintering particle-free silver conductive ink disclosed by the chinese patent office on 2016, 4, 6, the publication number is CN105462366A, in the technical scheme of the invention, insoluble silver salt generated by the reaction of sodium carbonate, sodium acetate, sodium citrate and silver nitrate is dissolved in a mixed solvent composed of methanol, isopropanol, isopropylamine and the like respectively or in a combined manner, the viscosity is adjusted by terpineol to form organic silver ink, and the organic silver ink is subjected to inkjet printing and low-temperature sintering to form a conductive silver film layer.
The patent achievement mainly utilizes the complexation of silver salt and organic amine to form a complex, can obviously reduce the thermal decomposition temperature of the silver salt, and can effectively avoid the damage of a printed circuit board substrate caused by the generation of a silver film layer due to the high-temperature thermal decomposition of the silver salt. In addition, due to the conductive paste containing the organic silver complex, when the conductive paste is heated at low temperature, the complex precursor is thermally decomposed, nano silver particles are generated in situ in the hole wall, and a nano silver film layer is further grown and formed. Therefore, compared with the silver film layer prepared by the traditional silver paste which takes silver powder, resin binder and the like as main components, the nano silver film layer prepared by the method has the advantages of high film-substrate binding force, good surface smoothness, difficult falling-off of the film layer and the like. However, the conductive film layer connected by the nano silver particles still shows relatively high resistivity, about 2-10 times that of the bulk metallic silver, compared with the resistivity of the bulk metallic silver. The high resistivity of the silver film layer is caused mainly by problems such as grain boundaries and structural defects, residual additives of the silver film layer, different thermal expansion coefficients between the silver film layer and the substrate, and the like. These problems affect the performance of the electronic device.
Disclosure of Invention
The invention provides organic silver/carbon nano tube composite slurry and a preparation method and application thereof, aiming at solving the problems that resin is easy to age and fall off when the conventional silver paste is matched with the resin to carry out through holes on a printed circuit board, and the resistivity is higher when the conventional organic silver paste is adopted to carry out through holes. It firstly achieves the following purposes: firstly, ensuring that the composite slurry can be used for through holes of the printed circuit board, and realizing the purpose of film formation and conduction of upper and lower layers of the printed circuit board; secondly, the composite slurry can form a film at low temperature after the through holes are formed, so that the damage to the printed circuit board is avoided; thirdly, the bonding strength of the film layer formed by the composite slurry after the through hole is formed and the inner wall of the through hole is improved, and the problem of film layer falling off is avoided; fourthly, the conductivity of a film layer formed by the composite slurry is improved, and the influence on the performance of the printed circuit board is avoided; and fifthly, the preparation process of the composite slurry and the film layer is simplified, and the composite slurry is easier to store.
In order to achieve the purpose, the invention adopts the following technical scheme.
An organic silver/carbon nano tube composite slurry,
the organic silver/carbon nano tube composite slurry is an organic composite slurry consisting of an organic solvent, a carbon nano tube, a silver compound and ethylamine;
the silver compound and ethylamine in the organic silver/carbon nano tube composite slurry form an organic silver complex.
As a preference, the first and second liquid crystal compositions are,
the organic solvent is an organic solvent which is liquid at normal temperature, and includes, but is not limited to, ethylene glycol.
In the composite slurry, the organic solvent is selected as a liquid carrier, so that the problems of oxidation of the printed circuit board or large amount of aggregation and precipitation of the organic silver complex and the like caused by the galvanic cell effect generated during film preparation of the through hole on the printed circuit board when water is used as the carrier can be avoided, and a better protection effect can be generated on the printed circuit board and the organic silver complex;
and when the slurry is used for preparing a film layer by perforating on a printed circuit board, the organic silver complex can generate thermal decomposition, and the film layer is formed by in-situ deposition in a hole wall, but the pyrolysis and film-forming process is different from the traditional organic silver complex film-forming process, the traditional organic silver complex film-forming process is only a pyrolysis film-forming process, and the carbon nano tube can enter the film layer together when the composite slurry is used for forming the film in the hole of the printed circuit board in the technical scheme, the silver film formed in the traditional process is a silver film in a micro-splitting state, and still has higher resistivity due to the existence of nano silver particle boundaries, structural defects and the like, in the technical scheme, the nano conductive composite film is prepared by doping the carbon nano tube, so that the conductivity of the nano conductive composite film can be greatly improved, because the carbon nano tube can play a role similar to a wire in the nano conductive composite film, the separated nano silver is bridged, so that the effect of communicating the nano silver is achieved, the adverse effect of the boundary of nano silver particles and the structural defects of the nano silver particles on the conductivity is reduced and avoided, the conductivity is improved, and the resistivity is reduced;
in addition, in the traditional process, because the thermal expansion coefficients of the silver film layer and the printed circuit board are different, the problems that the structural defects of the silver film layer are amplified and the resistivity is rapidly increased after thermal shock or cold shock are also easily caused, and the composite slurry adopting the technical scheme can not only play a role of a wire but also play a role of a bandage to a certain extent because the carbon nano tube bridges the nano silver, so that the structural stability of the nano conductive composite film layer can be well kept after thermal shock or cold shock is received, and the good conductivity of the nano conductive composite film layer is further ensured.
A method for preparing organic silver/carbon nano tube composite slurry,
the preparation method comprises the following preparation steps:
1) selecting a silver compound as a silver source, dissolving the silver compound in an organic solution containing ethylamine, and reacting in the organic solution to form an organic silver complex to obtain a precursor liquid;
2) adding the functionalized carbon nano tube into the precursor liquid, and uniformly dispersing to obtain the organic silver/carbon nano tube composite slurry.
As a preference, the first and second liquid crystal compositions are,
step 1) the silver compound comprises any one or more of silver acetate, silver carbonate and silver citrate;
the organic solution in the step 1) is an ethylamine and ethylene glycol solution, and the mass ratio of ethylamine to ethylene glycol in the ethylamine and ethylene glycol solution is (15-25): (40-65);
the mass ratio of the silver compound used in the step 1) to the organic solution is (10-46): (55-90).
As a preference, the first and second liquid crystal compositions are,
the silver compound of step 1) is preferably silver acetate;
the mass ratio of ethylamine to ethylene glycol in the ethylamine-ethylene glycol solution in the step 1) is (20-25): (40-53);
when the silver compound in the step 1) is silver acetate, the mass ratio of the silver acetate to the organic solution is (12-15): (60-78).
As a preference, the first and second liquid crystal compositions are,
the functionalized carbon nanotube in the step 2) comprises but is not limited to any one of a carboxylated carbon nanotube, a hydroxylated carbon nanotube and an aminated carbon nanotube;
the mass ratio of the functionalized carbon nano tube used in the step 2) to the silver compound used in the step 1) is (10-20): (10-46).
As a preference, the first and second liquid crystal compositions are,
when the silver compound in the step 1) is silver acetate, the mass ratio of the functionalized carbon nanotube used in the step 2) to the silver acetate is (15-20): (12-15).
In the preparation method, the composite slurry is prepared by a simple two-step method, firstly, an organic solution containing ethylamine is prepared and combined with a silver source to form a silver compound-ethylamine complex, and then, the carbon nano-particles are subjected to surface modificationThe tube is mixed and added into the precursor liquid, the silver compound can be dispersed and uniformly mixed with ethylamine in the step 1) in a mode of ultrasonic vibration for 30-40 min to form a complex, and the carbon nano tube and the organic silver complex can be uniformly mixed in the step 2) in a mode of ultrasonic vibration for 40-60 min and mechanical stirring for 6-10 h to form the composite slurry. The preparation method is simple and efficient, the functionalized carbon nanotube can be carboxylated multi-wall or single-wall nanotube, and the surface of the carbon nanotube is coated with-COOH, -OH or-NH through an acid oxidation method or a polymer such as poly-4-sodium styrene sulfonate (PPS) or Polyethyleneimine (PEI)2And the preparation is simple and convenient due to the anchoring groups. In addition, the prepared composite slurry has silver in a high valence state, and is free from worrying about oxidation in the transportation and storage processes, so that the transportation and the storage are more convenient.
An application of organic silver/carbon nano tube composite slurry,
the organic silver/carbon nano tube composite slurry is used for preparing a nano conductive composite film on a printed circuit board.
As a preference, the first and second liquid crystal compositions are,
the method for preparing the nano conductive composite film on the printed circuit board comprises the following steps:
and dropwise adding the organic silver/carbon nanotube composite slurry into the guide hole of the printed circuit board, heating and preserving heat until the slurry is dried to form a film, and thus preparing the nano conductive composite film on the printed circuit board.
As a preference, the first and second liquid crystal compositions are,
the heating and heat preservation process comprises the following steps: the heating temperature is 100-160 ℃, and the heat preservation time is 30-60 min.
As a preference, the first and second liquid crystal compositions are,
the heating and heat preservation process comprises the following steps: the heating temperature is 120-150 ℃, and the heat preservation time is 40-60 min.
The composite slurry has the advantages of simple and convenient use and rapidness, and can realize through holes on the surface of a printed circuit board and prepare a high-conductivity nano conductive composite film layer on the surface of the inner wall of the hole by adopting a one-step method. In addition, the temperature is lower and the duration is shorter in the heating and heat preservation process, so that the damage of the printed circuit board caused by high temperature can be effectively avoided, and the use effect is good.
The invention has the beneficial effects that:
1) the composite slurry is convenient to prepare, and can be quickly and efficiently prepared by a two-step method;
2) the prepared composite slurry has the advantages of convenient transportation and storage;
3) the composite slurry is used for perforating the hole on the printed circuit board, and the nano conductive composite film layer formed on the inner wall of the hole has the advantages of high bonding strength, low resistivity and the like;
4) the composite slurry is convenient to use, and the nano conductive composite film layer can be prepared by pyrolysis at low temperature;
5) the prepared nano conductive composite film layer has excellent thermal shock resistance and cold shock resistance.
Drawings
FIG. 1 is a thermogravimetric plot of an organic silver/carbon nanotube composite slurry prepared in example 3 of the present invention;
FIG. 2 is an XRD spectrum of the nano-conductive composite film prepared in example 3 of the present invention;
FIG. 3 is a macroscopic view of a cross section of a nano-conductive composite film prepared in example 3 of the present invention;
FIG. 4 is an SEM image of the internal fracture morphology of the nano conductive composite film layer prepared in example 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1
Preparing organic silver/carbon nano tube composite slurry:
1) preparing materials: preparing a carboxylated carbon nanotube, silver acetate, ethylamine and ethylene glycol according to a mass ratio of 15:12:20: 53;
2) mixing ethylamine and ethylene glycol to form an organic solution, adding silver acetate serving as a silver source into the organic solution, and ultrasonically vibrating for 40min to form precursor liquid containing a silver acetate-ethylamine complex;
3) adding the carboxylated carbon nano tube into the precursor liquid, carrying out ultrasonic vibration for 60min, and then mechanically stirring for 8h to obtain organic silver/carbon nano tube composite slurry;
preparing a nano conductive composite film:
dripping the prepared organic silver/carbon nano tube composite slurry into a guide hole of a printed circuit board, heating for 40min at 120 ℃, and directly depositing a nano conductive composite film consisting of nano silver and carbon nano tubes on the inner wall of the guide hole in situ so as to conduct the upper layer and the lower layer of the printed circuit board;
and (3) detection:
testing a guide hole of the nano conductive composite film formed on the surface of the printed circuit board after the through hole by using a TH2513 low resistance tester, wherein the single-hole resistance of the nano conductive composite film is only 18m omega;
measuring the adhesion grade of the product to be 5B by adopting an adhesive tape test method;
the hardness was measured according to GB/T6739-1996 using the film hardness pencil method and was H6.
Example 2
Preparing organic silver/carbon nano tube composite slurry:
1) preparing materials: preparing a carboxylated carbon nanotube, silver acetate, ethylamine and ethylene glycol according to the mass ratio of 20:15:25: 40;
2) mixing ethylamine and ethylene glycol to form an organic solution, adding silver acetate serving as a silver source into the organic solution, and ultrasonically vibrating for 40min to form precursor liquid containing a silver acetate-ethylamine complex;
3) adding the carboxylated carbon nano tube into the precursor liquid, carrying out ultrasonic vibration for 60min, and then mechanically stirring for 8h to obtain organic silver/carbon nano tube composite slurry;
preparing a nano conductive composite film:
dripping the prepared organic silver/carbon nano tube composite slurry into a guide hole of a printed circuit board, heating for 60min at 150 ℃, and directly depositing a nano conductive composite film consisting of nano silver and carbon nano tubes on the inner wall of the guide hole in situ so as to conduct the upper layer and the lower layer of the printed circuit board;
and (3) detection:
testing a guide hole of the nano conductive composite film formed on the surface of the printed circuit board after the through hole by using a TH2513 low resistance tester, wherein the single-hole resistance of the test hole is only 17m omega;
measuring the adhesion grade of the product to be 5B by adopting an adhesive tape test method;
the hardness was measured according to GB/T6739-1996 using the film hardness pencil method and was H6.
Example 3
Preparing organic silver/carbon nano tube composite slurry:
1) preparing materials: preparing a carboxylated carbon nanotube, silver acetate, ethylamine and ethylene glycol according to a mass ratio of 18:15:22: 45;
2) mixing ethylamine and ethylene glycol to form an organic solution, adding silver acetate serving as a silver source into the organic solution, and ultrasonically vibrating for 40min to form precursor liquid containing a silver acetate-ethylamine complex;
3) adding the carboxylated carbon nano tube into the precursor liquid, carrying out ultrasonic vibration for 60min, and then mechanically stirring for 8h to obtain organic silver/carbon nano tube composite slurry;
preparing a nano conductive composite film:
dripping the prepared organic silver/carbon nanotube composite slurry into a guide hole of a printed circuit board, heating for 50min at 130 ℃, and directly depositing a nano conductive composite film consisting of nano silver and carbon nanotubes on the inner wall of the guide hole in situ so as to conduct the upper layer and the lower layer of the printed circuit board;
and (3) detection:
testing a guide hole of the nano conductive composite film formed on the surface of the printed circuit board after the through hole by using a TH2513 low resistance tester, wherein the single-hole resistance of the test hole is only 17m omega;
measuring the adhesion grade of the product to be 5B by adopting an adhesive tape test method;
the hardness is H6 according to GB/T6739-1996 by adopting a film hardness pencil determination method;
the thermogravimetric test is carried out on the prepared organic silver/carbon nanotube composite slurry, the test result is shown in figure 1, and the main thermal decomposition area of the composite slurry prepared by the technical scheme is 60-165 ℃ as is obvious from the figure, so that the composite slurry has good low-temperature thermal decomposition property;
XRD characterization analysis is carried out on the prepared nano composite conductive film layer, the analysis result is shown in figure 2, the characteristic peaks of four crystal faces of metal silver (111), (200), (220) and (311) appear in the prepared film layer can be seen from the figure, in addition, a diffraction peak at 25.96 degrees corresponds to a carbon nano tube (002) crystal face, and no other substance diffraction peak exists on the spectrogram, which indicates that the purity of the prepared composite film layer is high under the process condition;
the positions of the guide holes of the printed circuit board are cut, and a high-definition macroscopic picture of the printed circuit board is shot as shown in figure 3, so that the nano conductive composite film is uniformly and smoothly deposited and tightly combined, and the measured average film thickness is about 25 micrometers;
SEM observation is carried out on the nano conductive composite film at the cut part after cutting, as shown in figure 4, the particle size of the prepared nano silver particles is between dozens of nanometers and hundreds of nanometers, partial nano silver particles are aggregated to form a sphere, and the nano silver particles and the carbon nano tubes are mutually staggered, wound and connected, so that the shape structure can effectively reduce the resistance of the nano conductive composite film.
Example 4
Preparing organic silver/carbon nano tube composite slurry:
1) preparing materials: preparing a hydroxylated carbon nanotube, silver carbonate, ethylamine and ethylene glycol according to a mass ratio of 20:25:25: 65;
2) mixing ethylamine and ethylene glycol to form an organic solution, adding silver acetate serving as a silver source into the organic solution, and performing ultrasonic vibration for 30min to form precursor liquid containing a silver acetate-ethylamine complex;
3) adding the carboxylated carbon nano tube into the precursor liquid, performing ultrasonic vibration for 40min, and then mechanically stirring for 10h to obtain organic silver/carbon nano tube composite slurry;
preparing a nano conductive composite film:
dropping the prepared organic silver/carbon nanotube composite slurry into a guide hole of a printed circuit board, heating for 30min at 160 ℃, and directly depositing a nano conductive composite film consisting of nano silver and carbon nanotubes on the inner wall of the guide hole in situ so as to conduct the upper layer and the lower layer of the printed circuit board;
and (3) detection:
testing a guide hole of the nano conductive composite film formed on the surface of the printed circuit board after the through hole by using a TH2513 low resistance tester, wherein the single-hole resistance of the test hole is only 19m omega;
measuring the adhesion grade of the product to be 5B by adopting an adhesive tape test method;
the hardness was measured according to GB/T6739-1996 using the film hardness pencil method and was H6.
Example 5
Preparing organic silver/carbon nano tube composite slurry:
1) preparing materials: preparing a hydroxylated carbon nanotube, silver citrate, ethylamine and ethylene glycol according to a mass ratio of 10:46:15: 40;
2) mixing ethylamine and ethylene glycol to form an organic solution, adding silver acetate serving as a silver source into the organic solution, and performing ultrasonic vibration for 30min to form precursor liquid containing a silver acetate-ethylamine complex;
3) adding the carboxylated carbon nano tube into the precursor liquid, performing ultrasonic vibration for 40min, and then mechanically stirring for 10h to obtain organic silver/carbon nano tube composite slurry;
preparing a nano conductive composite film:
dripping the prepared organic silver/carbon nano tube composite slurry into a guide hole of a printed circuit board, heating for 60min at 100 ℃, and directly depositing a nano conductive composite film consisting of nano silver and carbon nano tubes on the inner wall of the guide hole in situ so as to conduct the upper layer and the lower layer of the printed circuit board;
and (3) detection:
testing a guide hole of the nano conductive composite film formed on the surface of the printed circuit board after the through hole by using a TH2513 low resistance tester, wherein the single-hole resistance of the nano conductive composite film is only 18m omega;
measuring the adhesion grade of the product to be 5B by adopting an adhesive tape test method;
the hardness was measured according to GB/T6739-1996 using the film hardness pencil method and was H6.
Example 6
Preparing organic silver/carbon nano tube composite slurry:
1) preparing materials: preparing an aminated carbon nanotube, silver acetate, ethylamine and ethylene glycol according to the mass ratio of 10:10:20: 40;
2) mixing ethylamine and ethylene glycol to form an organic solution, adding silver acetate serving as a silver source into the organic solution, and performing ultrasonic vibration for 30min to form precursor liquid containing a silver acetate-ethylamine complex;
3) adding the carboxylated carbon nano tube into the precursor liquid, carrying out ultrasonic vibration for 60min, and then mechanically stirring for 6h to obtain organic silver/carbon nano tube composite slurry;
preparing a nano conductive composite film:
dripping the prepared organic silver/carbon nanotube composite slurry into a guide hole of a printed circuit board, heating for 50min at 130 ℃, and directly depositing a nano conductive composite film consisting of nano silver and carbon nanotubes on the inner wall of the guide hole in situ so as to conduct the upper layer and the lower layer of the printed circuit board;
and (3) detection:
testing a guide hole of the nano conductive composite film formed on the surface of the printed circuit board after the through hole by using a TH2513 low resistance tester, wherein the single-hole resistance of the test hole is only 17m omega;
measuring the adhesion grade of the product to be 5B by adopting an adhesive tape test method;
the hardness was measured according to GB/T6739-1996 using the film hardness pencil method and was H6.
Example 7
Preparing organic silver/carbon nano tube composite slurry:
1) preparing materials: preparing an aminated carbon nanotube, silver acetate, ethylamine and ethylene glycol according to the mass ratio of 18:15:25: 53;
2) mixing ethylamine and ethylene glycol to form an organic solution, adding silver acetate serving as a silver source into the organic solution, and performing ultrasonic vibration for 30min to form precursor liquid containing a silver acetate-ethylamine complex;
3) adding the carboxylated carbon nano tube into the precursor liquid, carrying out ultrasonic vibration for 60min, and then mechanically stirring for 8h to obtain organic silver/carbon nano tube composite slurry;
preparing a nano conductive composite film:
dripping the prepared organic silver/carbon nano tube composite slurry into a guide hole of a printed circuit board, heating for 55min at 135 ℃, and directly depositing a nano conductive composite film consisting of nano silver and carbon nano tubes on the inner wall of the guide hole in situ so as to conduct the upper layer and the lower layer of the printed circuit board;
and (3) detection:
testing a guide hole of the nano conductive composite film formed on the surface of the printed circuit board after the through hole by using a TH2513 low resistance tester, wherein the single-hole resistance of the nano conductive composite film is only 18m omega;
measuring the adhesion grade of the product to be 5B by adopting an adhesive tape test method;
the hardness was measured according to GB/T6739-1996 using the film hardness pencil method and was H6.
As is obvious from the above examples 1-7, the resistance of the nano conductive composite film prepared by applying the composite slurry in the technical scheme is 17-19 m omega, the adhesion grade can reach 5B grade, the hardness can reach H6 grade, and the nano conductive composite film has excellent use effect.
Claims (7)
1. An organic silver/carbon nano tube composite slurry is characterized in that,
the organic silver/carbon nano tube composite slurry is an organic composite slurry consisting of an organic solvent, a carbon nano tube, a silver compound and ethylamine;
forming an organic silver complex by a silver compound and ethylamine in the organic silver/carbon nanotube composite slurry;
the silver compound is any one or more of silver acetate, silver carbonate and silver citrate;
the carbon nano tube is any one or more of a carboxylated carbon nano tube, a hydroxylated carbon nano tube and an aminated carbon nano tube.
2. A method for preparing the organic silver/carbon nanotube composite paste according to claim 1,
the preparation method comprises the following preparation steps:
1) selecting a silver compound as a silver source, dissolving the silver compound in an organic solution containing ethylamine, and reacting in the organic solution to form an organic silver complex to obtain a precursor liquid;
2) adding the functionalized carbon nano tube into the precursor liquid, and uniformly dispersing to obtain the organic silver/carbon nano tube composite slurry.
3. The method for preparing organic silver/carbon nanotube composite paste according to claim 2,
the silver compound in the step 1) comprises silver acetate, silver carbonate and silver citrate;
the organic solution in the step 1) is an ethylamine and ethylene glycol solution, and the mass ratio of ethylamine to ethylene glycol in the ethylamine and ethylene glycol solution is (15-25): (40-65);
the mass ratio of the silver compound used in the step 1) to the organic solution is (10-46): (55-90).
4. The method for preparing organic silver/carbon nanotube composite paste according to claim 2,
the functionalized carbon nano tube in the step 2) comprises a carboxylated carbon nano tube, a hydroxylated carbon nano tube and an aminated carbon nano tube;
the mass ratio of the functionalized carbon nano tube used in the step 2) to the silver compound used in the step 1) is (10-20): (10-46).
5. The use of the organic silver/carbon nanotube composite paste according to claim 1,
the organic silver/carbon nano tube composite slurry is used for preparing a nano conductive composite film on a printed circuit board.
6. The use according to claim 5,
the method for preparing the nano conductive composite film on the printed circuit board comprises the following steps:
and dropwise adding the organic silver/carbon nanotube composite slurry into the guide hole of the printed circuit board, heating and preserving heat until the slurry is dried to form a film, and thus preparing the nano conductive composite film on the printed circuit board.
7. The use according to claim 6,
the heating and heat preservation process comprises the following steps: the heating temperature is 100-160 ℃, and the heat preservation time is 30-60 min.
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