CN113481491B - Copper/graphene composite film material and preparation method and application thereof - Google Patents
Copper/graphene composite film material and preparation method and application thereof Download PDFInfo
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- CN113481491B CN113481491B CN202110778303.6A CN202110778303A CN113481491B CN 113481491 B CN113481491 B CN 113481491B CN 202110778303 A CN202110778303 A CN 202110778303A CN 113481491 B CN113481491 B CN 113481491B
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Abstract
The invention discloses a copper/graphene composite film material prepared by newly adding a single-layer graphene dispersion liquid in a basic chemical copper plating solution by adopting an ultrasonic-assisted chemical plating method to ensure that metal copper and single-layer graphene are co-deposited on the surface of a substrate, wherein the metal copper on the surface of the material is tightly stacked with the single-layer graphene, the surface has no holes, the compactness is high, and the shape of crystal grains is uniform; when the weight of copper sulfate pentahydrate is 5-14g, the weight of double complexing agent is 17-51g, the weight of sodium hydroxide is 10-13g, and the weight of formaldehyde is 10-25mL and 2,2，The mass of bipyridyl is 10-30mg, the mass of single-layer graphene is 0.1-2g, and the balance of deionized water is, the highest thermal conductivity can reach 501.45W/(m.K). The copper/graphene composite film material disclosed by the invention is uniform in growth distribution, good in stability and wide in application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical copper plating, and particularly relates to a copper/graphene composite film material and a preparation method and application thereof.
Background
Electroless Plating, also known as Electroless Plating (electrolessly Plating), is a surface treatment technique in which metal ions are reduced by a reducing agent in a solution on the surface of a substrate having catalytic activity without applying an electric current, thereby forming a metal layer on the surface of the substrate. Due to the specific performance of electroless copper plating, the electroless copper plating is widely applied to metallization of the surface of a non-metal material, preparation of a composite material, a printed circuit board and an electromagnetic shielding material. As is well known, copper metal has high thermal and electrical conductivity and excellent ductility, and is an indispensable material in the fields of aerospace, electronic and electric power, building industry, transportation and the like. Compared with electroplating, chemical plating has the characteristics of simple equipment, uniform plating layer, no edge effect, no influence of substrate conductivity and the like, so that the chemical plating is favored by researchers. However, pure copper has low strength and poor thermal stability, and it is desirable to improve its performance by adding reinforcement. Wherein the graphene is formed by passing sp through carbon atoms2The two-dimensional material with the thickness of the monoatomic layer formed by combining the hybrid orbitals has excellent thermal properties due to a unique two-dimensional structure, the thermal conductivity of the two-dimensional material is as high as 5300W/(m.K), the material is the material with the highest thermal conductivity found at present, and graphene has excellent physical properties, good chemical stability and structural stability, and is an ideal choice for a composite material reinforcement. The method can uniformly disperse the single-layer graphene in the basic chemical copper plating solution, so that the obtained composite plated copper layer is firm and compact, and the thermal conductivity of the surface of the composite film is favorably improved, thereby improving the application value of the composite film in the fields of electronic packaging, microelectronic industry, national defense aerospace and the like.
Disclosure of Invention
The invention aims to provide a copper/graphene composite film material and a preparation method and application thereof.
Firstly, according to one aspect of the present invention, the present invention provides a copper/graphene composite thin film material, wherein the copper/graphene composite thin film material is a copper/graphene composite thin film material prepared by adding a single-layer graphene dispersion liquid in a basic chemical copper plating solution by an ultrasonic-assisted chemical plating method to co-deposit metal copper and single-layer graphene on a substrate surface, and the metal copper and the single-layer graphene on the surface of the copper/graphene composite thin film material are tightly stacked, and have no holes on the surface, high compactness and uniform crystal grain shape.
Preferably, when the weight of copper sulfate pentahydrate, the weight of a double complexing agent, the weight of sodium hydroxide, the weight of formaldehyde, the weight of 2, 2' -bipyridine, the weight of single-layer graphene and the balance of deionized water are 5-14g, 17-51g, 10-13g, 10-25mL and 0.1-2g respectively, and 10-30mg respectively in each liter of basic electroless copper plating solution, the copper/graphene composite film material with the thermal conductivity up to 501.45W/(m.K) is obtained, wherein the double complexing agent is composed of sodium potassium tartrate and ethylene diamine tetraacetic acid in a mass ratio of (1:2) - (1:1), and the sheet diameter of the single-layer graphene is 0.5-5 μm.
Further, the copper/graphene composite film material is prepared by the following steps:
(1) cleaning, roughening and activating the surface of the red copper sheet substrate: placing the copper sheet substrate into a beaker filled with deionized water for ultrasonic cleaning for 3-5min, soaking in alkaline washing solution at 50-60 ℃ for 3-5min after cleaning, taking out and washing with deionized water, placing into dilute hydrochloric acid at room temperature for standing for 20-40s, and finally washing with deionized water and drying; wherein, the formula of the alkaline washing liquid is that 10-30g of trisodium phosphate, 10-30g of sodium carbonate and 5-10g of sodium hydroxide are added into each liter of deionized water; the concentration of the dilute hydrochloric acid is 0.05-0.1 mol/L.
(2) Preparing a basic electroless copper plating solution: weighing 5-14g of blue vitriol, 17-51g of double complexing agent, 10-13g of sodium hydroxide and 10-30mg of stabilizer per liter of deionized water, and placing the weighed materials in a beaker filled with the deionized water to obtain a basic chemical copper plating solution;
(3) preparing a single-layer graphene dispersion liquid: weighing 0.1-2g of single-layer graphene per liter of deionized water, placing the single-layer graphene in a beaker filled with the deionized water, performing ultrasonic treatment and stirring for 2 hours, adding a mixed dispersant, performing ultrasonic treatment and stirring for 2 hours for later use, wherein the mixed dispersant is a combination of two or more of polyvinylpyrrolidone, chloroform, dimethylformamide and tetrahydrofuran, and the mass of the added dispersant can be set to be 3-8 times of that of the single-layer graphene according to the type of the mixed dispersant, so as to obtain a single-layer graphene dispersion liquid;
(4) preheating a basic chemical copper plating solution: placing the beaker of the basic electroless copper plating solution prepared in the step (2) in a constant-temperature water bath kettle at the temperature of 45-75 ℃ and stirring for 1-3min to enable the beaker to reach the corresponding electroless copper plating temperature;
(5) preparing a mixed electroless copper plating solution: adding 10mL of the dispersion liquid of the g single-layer graphene prepared in the step (3) into 240mL of the preheated basic chemical copper plating solution in the step (4), stirring at the rotating speed of 200-400rpm to fully mix the dispersion liquid with the basic chemical copper plating solution, then carrying out ultrasonic stirring on the mixed plating solution for 3-7min, and then placing the mixed plating solution back into a constant-temperature water bath kettle at the temperature of 45-75 ℃ for chemical copper plating;
(6) chemical plating treatment: clamping the copper sheet substrate treated in the step (1) by using a clamp, putting the copper sheet substrate into the mixed chemical copper plating solution in the step (5), adding 10-25mL of reducing agent into each liter of basic chemical copper plating solution while stirring, wherein the chemical copper plating time is 20-40 min;
(7) and (4) washing the copper/graphene composite film on the surface of the red copper sheet obtained in the step (6) with deionized water, and drying the copper/graphene composite film by using a blower to obtain the copper/graphene composite film material.
Further, the invention relates to an application of the copper/graphene composite film material as a high-heat-conducting material.
On the other hand, the invention also provides a method for preparing the copper/graphene composite film material by utilizing an ultrasonic-assisted chemical plating method, which comprises the following steps:
(1) cleaning, roughening and activating the surface of the red copper sheet substrate: placing the copper sheet substrate into a beaker filled with deionized water for ultrasonic cleaning for 3-5min, soaking in alkaline washing solution at 50-60 ℃ for 3-5min after cleaning, taking out and washing with deionized water, placing into dilute hydrochloric acid at room temperature for standing for 20-40s, and finally washing with deionized water and drying; wherein, the formula of the alkaline washing liquid is that 10-30g of trisodium phosphate, 10-30g of sodium carbonate and 5-10g of sodium hydroxide are added into each liter of deionized water; the concentration of the dilute hydrochloric acid is 0.05-0.1 mol/L.
(2) Preparing a basic electroless copper plating solution: weighing 5-14g of blue vitriol, 17-51g of double complexing agent, 10-13g of sodium hydroxide and 10-30mg of stabilizer per liter of deionized water, and placing the weighed materials in a beaker filled with the deionized water to obtain a basic chemical copper plating solution;
(3) preparing a single-layer graphene dispersion liquid: weighing 0.1-2g of single-layer graphene per liter of deionized water, placing the single-layer graphene in a beaker filled with the deionized water, performing ultrasonic treatment and stirring for 2 hours, adding a mixed dispersant, performing ultrasonic treatment and stirring for 2 hours for later use, wherein the mixed dispersant is a combination of two or more of polyvinylpyrrolidone, chloroform, dimethylformamide and tetrahydrofuran, and the mass of the added dispersant can be set to be 3-8 times of that of the single-layer graphene according to the type of the mixed dispersant, so as to obtain a single-layer graphene dispersion liquid;
(4) preheating a basic electroless copper plating solution: placing the beaker of the basic electroless copper plating solution prepared in the step (2) in a constant-temperature water bath kettle at the temperature of 45-75 ℃ and stirring for 1-3min to enable the beaker to reach the corresponding electroless copper plating temperature;
(5) preparing a mixed electroless copper plating solution: adding 10mL of the dispersion liquid of the single-layer graphene prepared in the step (3) into 240mL of the preheated basic chemical copper plating solution in the step (4), stirring at the rotating speed of 200-400rpm to fully mix the dispersion liquid with the basic chemical copper plating solution, performing ultrasonic treatment and stirring treatment on the mixed plating solution for 3-7min, and then placing the mixed plating solution back into a constant-temperature water bath kettle at the temperature of 45-75 ℃ for chemical copper plating;
(6) chemical plating treatment: clamping the copper sheet substrate treated in the step (1) by using a clamp, putting the copper sheet substrate into the mixed chemical copper plating solution in the step (5), adding 10-25mL of reducing agent into each liter of basic chemical copper plating solution while stirring, wherein the chemical copper plating time is 20-40 min;
(7) and (4) washing the copper/graphene composite film on the surface of the red copper sheet obtained in the step (6) with deionized water, and drying the copper/graphene composite film by using a blower to obtain the copper/graphene composite film material.
Finally, the invention also relates to the application of the method for preparing the copper/graphene composite film material by utilizing the ultrasonic-assisted chemical plating method in the chemical copper plating industry.
Compared with the prior art, the invention has the beneficial effects that:
1. the method comprises the steps of uniformly mixing a basic chemical copper plating solution and a quantitative single-layer graphene dispersion solution, and then carrying out chemical composite deposition to uniformly co-deposit metal copper and single-layer graphene on the surface of a substrate to form the copper/graphene composite film. The introduction of the highly dispersed single-layer graphene enables the surface of the composite film to be more tightly stacked, the surface has no holes, the compactness is high, the shape of crystal grains is uniform, and the interface combination of a plating layer and a substrate is good.
2. According to the invention, an ultrasonic-assisted chemical plating method is adopted, the mixed chemical copper plating solution is subjected to ultrasonic stirring before chemical copper plating, copper ions are adsorbed on the surface of highly dispersed single-layer graphene through selection and adjustment of a dispersing agent, and the copper ions and the single-layer graphene are jointly deposited on the surface of a substrate under the action of a reducing agent, so that the thermal conductivity of the surface of the obtained copper/graphene composite film is effectively improved.
3. The preparation method of the copper/graphene composite film is simple, equipment is easy to operate, the repeatability is good, the production period is short, the process cost is low, and the large-scale industrial production is facilitated.
Drawings
FIG. 1 is a SEM photograph of a copper layer film deposited on a substrate surface with copper metal prepared in example 1 of the present invention;
FIG. 2 is a SEM photograph of the Cu/graphene composite thin film prepared in example 2;
FIG. 3 is a SEM photograph of the Cu/graphene composite thin film prepared in example 3;
FIG. 4 is a SEM photograph of the Cu/graphene composite thin film prepared in example 4;
FIG. 5 is an X-ray diffraction analysis chart of a copper layer thin film deposited on the surface of a substrate by the metallic copper prepared in example 1;
fig. 6 is an X-ray diffraction analysis chart of the copper/graphene composite thin film materials prepared in examples 2 to 4 of the present invention.
Detailed Description
The present invention will be described in detail and with reference to specific examples thereof, which are set forth to illustrate, but are not to be construed as the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention, in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
In the present invention, all parts and percentages are by weight unless otherwise specified; all equipment and raw materials are commercially available or commonly used in the industry unless otherwise specified; the methods in the following examples are conventional in the art unless otherwise specified.
Example 1 (comparative example, without addition of graphene Dispersion)
The preparation method of the basic electroless copper plating film material comprises the following specific steps:
(1) firstly, ultrasonically cleaning a copper sheet for 3min, then soaking the copper sheet in alkaline washing liquid at 60 ℃ for 4min, taking out the copper sheet, washing the copper sheet by using deionized water, then placing the copper sheet into 0.1mol/L diluted hydrochloric acid at room temperature, standing the copper sheet for 30s, and finally simply washing the copper sheet by using deionized water and drying the copper sheet;
(2) preparing an alkaline washing solution: weighing 20g of trisodium phosphate, 20g of sodium carbonate and 8g of sodium hydroxide in per liter of deionized water, respectively, putting the weighed materials into 100mL of deionized water, and stirring the materials at a constant temperature of 60 ℃ until the materials are clear;
(3) preparing a basic electroless copper plating solution: weighing 10g of copper sulfate pentahydrate, 14g of potassium sodium tartrate, 20g of disodium ethylene diamine tetraacetate, 12g of sodium hydroxide and 20mg of 2, 2' -bipyridyl in each liter of deionized water and placing the weighed materials into a beaker filled with 250mL of deionized water;
(4) placing the beaker of the basic electroless copper plating solution prepared in the step (3) in a constant-temperature water bath kettle at 60 ℃ and stirring for 2min to reach the corresponding electroless copper plating temperature;
(5) clamping the red copper sheet treated in the step (1) by using a clamp, putting the red copper sheet into the preheated basic chemical copper plating solution in the step (4), stirring by adopting a cantilever type electric stirrer at a rotating speed of 300rpm, adding 5mL of formaldehyde, and carrying out chemical copper plating for 30 min;
(6) washing the sample obtained in the step (5) with deionized water, and drying the sample with a blower to obtain the copper deposit on the surface of the red copper sheet substrate, and recording as S1。
Example 2
A preparation method of a copper/graphene composite film comprises the following specific steps:
(1) firstly, ultrasonically cleaning a copper sheet for 3min, then soaking the copper sheet in alkaline washing liquid at 50 ℃ for 4min, taking out the copper sheet, washing the copper sheet by using deionized water, then placing the copper sheet into 0.1mol/L diluted hydrochloric acid at room temperature, standing for 30s, and finally simply washing the copper sheet by using deionized water and drying the copper sheet;
(2) preparing an alkaline washing solution: weighing 10g of trisodium phosphate, 10g of sodium carbonate and 8g of sodium hydroxide in each liter of deionized water, respectively, putting the weighed materials into 100mL of deionized water, and stirring the materials at a constant temperature of 50 ℃ until the materials are clear;
(3) preparing 0.1g/L of single-layer graphene dispersion liquid: weighing 1mg of single-layer graphene, dissolving the single-layer graphene in 10mL of deionized water, ultrasonically stirring the graphene for 2 hours, then weighing 3mg of mixed dispersant, adding the mixed dispersant, wherein the mixed dispersant consists of polyvinylpyrrolidone and chloroform in a mass ratio of 2:1, ultrasonically stirring the graphene for 2 hours again for later use, and stirring the graphene for 3 minutes before use;
(4) preparing a basic electroless copper plating solution: weighing 5g of copper sulfate pentahydrate, 10g of potassium sodium tartrate, 20g of disodium ethylene diamine tetraacetate, 8g of sodium hydroxide and 20mg of 2, 2' -bipyridyl in each liter of deionized water and placing the weighed materials in a beaker filled with 240mL of deionized water;
(5) placing the beaker of the basic electroless copper plating solution prepared in the step (4) in a constant-temperature water bath kettle at 50 ℃ and stirring for 2min to reach the corresponding electroless copper plating temperature;
(6) adding 10mL of the single-layer graphene dispersion liquid prepared in the step (3) into 240mL of the basic electroless copper plating solution prepared in the step (5), stirring to fully mix the single-layer graphene dispersion liquid with the basic electroless copper plating solution, taking out the mixed plating solution, performing ultrasonic treatment for 7min, and then putting the mixed plating solution back into a 50 ℃ constant-temperature water bath kettle;
(7) clamping the red copper sheet treated in the step (1) by using a clamp, putting the red copper sheet into the mixed electroless copper plating solution treated in the step (6), stirring by adopting a cantilever type electric stirrer at a rotating speed of 400rpm, adding 5mL of formaldehyde, and performing electroless copper plating for 40 min;
(8) washing the sample obtained in the step (7) with deionized water, and drying the sample with a blower to obtain the copper/graphene composite film, wherein the S is recorded2。
Example 3
A preparation method of a copper/graphene composite film comprises the following specific steps:
(1) firstly, ultrasonically cleaning a copper sheet for 3min, then soaking the copper sheet in alkaline washing liquid at 60 ℃ for 4min, taking out the copper sheet, washing the copper sheet by using deionized water, then placing the copper sheet into 0.1mol/L diluted hydrochloric acid at room temperature, standing the copper sheet for 30s, and finally simply washing the copper sheet by using deionized water and drying the copper sheet;
(2) preparing an alkaline solution: 30g of trisodium phosphate, 30g of sodium carbonate and 5g of sodium hydroxide are respectively weighed according to per liter of deionized water, put into 100mL of deionized water, and stirred at the constant temperature of 60 ℃ until the mixture is clear;
(3) preparing 0.5g/L of single-layer graphene dispersion liquid: weighing 5mg of single-layer graphene, dissolving the single-layer graphene in 10mL of deionized water, ultrasonically stirring the graphene for 2 hours, then weighing 25mg of mixed dispersant, adding the mixed dispersant, ultrasonically stirring the mixed dispersant again for 2 hours for later use, wherein the mixed dispersant is composed of polyvinylpyrrolidone, chloroform, dimethylformamide and tetrahydrofuran in a mass ratio of 2:1:1:1, and stirring the mixed dispersant for 3 minutes before use;
(4) preparing a basic electroless copper plating solution: weighing 14g of copper sulfate pentahydrate, 20g of potassium sodium tartrate, 20g of disodium ethylene diamine tetraacetate, 13g of sodium hydroxide and 30mg of 2, 2' -bipyridyl in each liter of deionized water and placing the weighed materials in a beaker filled with 240mL of deionized water;
(5) placing the beaker of the basic electroless copper plating solution prepared in the step (4) in a constant-temperature water bath kettle at 45 ℃ and stirring for 2min to reach the corresponding electroless copper plating temperature;
(6) adding 10mL of the single-layer graphene dispersion liquid prepared in the step (3) into 240mL of the basic electroless copper plating solution prepared in the step (5), stirring to fully mix the single-layer graphene dispersion liquid with the electroless copper plating solution, taking out the mixed plating solution, performing ultrasonic treatment for 3min, and then putting the mixed plating solution back into a45 ℃ constant-temperature water bath kettle;
(7) clamping the red copper sheet treated in the step (1) by using a clamp, putting the red copper sheet into the mixed chemical copper plating solution treated in the step (6), stirring by adopting a cantilever type electric stirrer at a rotating speed of 200rpm, adding 6mL of formaldehyde, and carrying out chemical copper plating for 30 min;
(8) washing the sample obtained in the step (7) with deionized water, and drying the sample with a blower to obtain the copper/graphene composite film, wherein the S is recorded3。
Example 4
A preparation method of a copper/graphene composite film comprises the following specific steps:
(1) firstly, ultrasonically cleaning a copper sheet for 3min, then soaking the copper sheet in alkaline solution at 55 ℃ for 4min, taking out the copper sheet, washing the copper sheet by using deionized water, then placing the copper sheet into 0.1mol/L diluted hydrochloric acid at room temperature, standing for 30s, and finally simply washing the copper sheet by using deionized water and drying the copper sheet;
(2) preparing an alkaline washing solution: weighing 20g of trisodium phosphate, 20g of sodium carbonate and 10g of sodium hydroxide in per liter of deionized water, respectively, putting the weighed materials into 100mL of deionized water, and stirring the materials at a constant temperature of 55 ℃ until the materials are clear;
(3) preparing 1g/L of single-layer graphene dispersion liquid: weighing 10mg of single-layer graphene, dissolving the single-layer graphene in 10mL of deionized water, ultrasonically stirring the solution for 2 hours, then weighing 80mg of mixed dispersant, adding the mixed dispersant, ultrasonically stirring the mixed dispersant again for 2 hours for later use, wherein the mixed dispersant is composed of polyvinylpyrrolidone, chloroform, dimethylformamide and tetrahydrofuran in a mass ratio of 1:1:1:1, and stirring the mixture for 3 minutes before use;
(4) preparing a basic electroless copper plating solution: weighing 10g of copper sulfate pentahydrate, 14g of potassium sodium tartrate, 20g of disodium ethylene diamine tetraacetate, 10g of sodium hydroxide and 10mg of 2, 2' -bipyridyl in each liter of deionized water and placing the weighed materials into a beaker filled with 240mL of deionized water;
(5) placing the beaker of the basic electroless copper plating solution prepared in the step (4) in a constant-temperature water bath kettle at 75 ℃ and stirring for 2min to reach the corresponding electroless copper plating temperature;
(6) adding 10mL of the single-layer graphene dispersion liquid prepared in the step (3) into 240mL of the basic electroless copper plating solution prepared in the step (5), stirring to fully mix the single-layer graphene dispersion liquid with the electroless copper plating solution, taking out the mixed plating solution, carrying out ultrasonic treatment for 5min, and then putting the mixed plating solution back into a 75-DEG C constant-temperature water bath kettle;
(7) clamping the red copper sheet treated in the step (1) by using a clamp, putting the red copper sheet into the mixed chemical copper plating solution treated in the step (6), stirring by adopting a cantilever type electric stirrer at a rotating speed of 300rpm, adding 5mL of formaldehyde, and carrying out chemical copper plating for 30 min;
(8) washing the sample obtained in the step (7) with deionized water, and drying the sample with a blower to obtain the copper/graphene composite film, wherein the S is recorded4。
Example 5
Each sample was tested for thermal conductivity at room temperature using a laser thermal conductivity apparatus (LFA 457):
1. preparation of a sample: cutting the red copper sheet into a round sample with the diameter of 12.7mm by utilizing wire cutting, and plating a film on the round sample;
2. treatment before sample testing: in order to reduce the reflection of a sample material to a laser pulse and increase the absorption of a sample surface film to the energy of the laser pulse, graphite coatings can be uniformly sprayed on two surfaces of a sample to be detected (the graphite coatings can prevent laser rays and the thermal radiation of observable wavelength bands from penetrating, can resist the heating of the laser pulse without melting and evaporating at a high temperature stage, and do not react with a sample);
3. and (3) determination of a sample: after the sample is processed, it can be placed in an instrument for testing, and the thermal conductivity values can be measured, to obtain table 1.
And observing the microstructure of each sample by using a cold field emission Scanning Electron Microscope (SEM), and adhering each sample on a sample table by using a conductive adhesive and observing by using an instrument. The used scanning electron microscope model is Hitachi, SU8020 field emission scanning electron microscope, the used accelerating voltage is 5kV or 15kV, and the test result is shown in fig. 1-4.
The phase composition of each sample material was analyzed by X-ray diffractometry (XRD). The sample was fixed on a sample stage using plasticine and then placed in an X-ray diffractometer. The XRD model used was X' Pert PRO MPD with a source of Cu ka (λ ═ 0.15406nm), a scan range of 10 ° -90 °, a scan rate of 5 °/min, a tube voltage of 20-60kV, a tube current of 10-300mA, and the results of the tests gave figures 5-6.
As shown in fig. 1, in the copper layer film prepared in example 1, the surface structure of the copper layer film is relatively flat, copper particles can be uniformly deposited, the crystallization is relatively fine, and the accumulation is relatively compact. As shown in the X-ray diffraction analysis chart of fig. 5, the S1 spectrum has only 3 diffraction peaks of copper and no other impurity phases, indicating that the copper layer thin film exists in the form of elemental copper. As shown by the thermal conductivity values of the samples in table 1, the thermal conductivity of S1 was increased by only 0.72% compared to that of red copper, indicating that the thermal conductivity of the copper layer film was substantially the same as that of red copper.
As shown in fig. 2, in the copper/graphene composite film prepared in example 2, the surface structure of the copper/graphene composite film is flat, and the single-layer graphene and the copper particles are uniformly deposited, so that the crystal is finer and finer, and the two are firmly and tightly combined. As shown in the X-ray diffraction analysis chart of fig. 6, the S2 spectrum has only 3 diffraction peaks of copper, and no diffraction peak of single-layer graphene appears, and the detection limit of X-ray diffraction may not be reached due to too small content of single-layer graphene. The thermal conductivity values of the samples in table 1 show that the thermal conductivity of S2 is improved by 36.0% and 35.0% respectively compared with that of red copper and S1, which indicates that the thermal conductivity of the composite film can be effectively improved by introducing single-layer graphene.
As shown in fig. 3, the copper/graphene composite film prepared in example 3 has a significantly increased amount of single-layer graphene deposited on the surface of the substrate as the concentration of the single-layer graphene increases. As shown in the X-ray diffraction analysis chart of fig. 6, the S3 spectrum has only 3 diffraction peaks of copper, and no diffraction peak of single-layer graphene appears yet, indicating that the detection limit of X-rays has not been reached yet. As shown by the thermal conductivity values of the samples in table 1, the thermal conductivity of S3 is increased by 35.3% and 34.3% respectively compared with that of red copper and S1, but is reduced by 0.5% compared with that of S2, which indicates that the increase of the content of single-layer graphene is not beneficial to the improvement of the thermal conductivity of the composite film. This is because the increase of the content of the single-layer graphene reduces the relative density of the composite film, which leads to the increase of internal defects of the material, and the increase of the deposition amount of the single-layer graphene in the composite film leads to the increase of grain boundaries between the single-layer graphene and copper, which both hinder the transmission and transfer of electrons and phonons, thereby affecting the thermal conductivity of the composite film.
As shown in fig. 4, in the copper/graphene composite film prepared in this example, as the concentration of single-layer graphene is further increased, the deposition amount of single-layer graphene in the composite film is the highest compared with S2 and S3. As shown in the X-ray diffraction analysis chart of fig. 6, the S4 spectrum has only 3 diffraction peaks of copper, and no diffraction peak of single-layer graphene still appears, indicating that the single-layer graphene deposited on the substrate surface cannot be detected by X-rays. As shown by the thermal conductivity values of the samples in table 1, the thermal conductivity of S4 is increased by 34.1% and 33.1% compared with that of red copper and S1, but is decreased by 1.4% and 0.9% compared with that of S2 and S3, respectively, which further proves that the increase of the content of the single-layer graphene is not beneficial to the improvement of the thermal conductivity of the composite film.
TABLE 1
| Sample (I) | Red copper | S1 | S2 | S3 | S4 |
| Thermal conductivity (W/(m.K)) | 368.72 | 371.38 | 501.45 | 498.92 | 494.38 |
The above-described embodiments of the present invention do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (5)
1. A copper/graphene composite film material is characterized in that: the copper/graphene composite film material is prepared by adding a single-layer graphene dispersion liquid in a basic chemical copper plating solution by adopting an ultrasonic-assisted chemical plating method so that metal copper and single-layer graphene are co-deposited on the surface of a substrate; when the mass of copper sulfate pentahydrate, the mass of a double complexing agent and the mass of sodium hydroxide are respectively 5-14g, 10-13g, the volume of formaldehyde is 10-25mL, 10-30mg of 2, 2' -bipyridine and 0.1-2g of single-layer graphene and the balance is deionized water in each liter of basic chemical copper plating solution, the copper/graphene composite film material with the highest thermal conductivity of 501.45W/(m.K) is obtained, wherein the double complexing agent is composed of sodium potassium tartrate and disodium ethylene diamine tetraacetate with the mass ratio of 1/2-1, and the sheet diameter of the single-layer graphene is 0.5-5 mu m.
2. The copper/graphene composite thin film material according to claim 1, wherein: the copper/graphene composite film material is prepared by the following steps:
(1) cleaning, roughening and activating the surface of the red copper sheet substrate: placing the copper sheet substrate into a beaker filled with deionized water for ultrasonic cleaning for 3-5min, soaking in alkaline washing solution at 50-60 ℃ for 3-5min after cleaning, taking out and washing with deionized water, placing into dilute hydrochloric acid at room temperature for standing for 20-40s, and finally washing with deionized water and drying; wherein, the alkaline washing liquid is prepared by adding 10-30g of trisodium phosphate, 10-30g of sodium carbonate and 5-10g of sodium hydroxide into each liter of deionized water; the concentration of the dilute hydrochloric acid is 0.05-0.1 mol/L;
(2) preparing a basic electroless copper plating solution: weighing 5-14g of blue vitriol, 17-51g of double complexing agent, 10-13g of sodium hydroxide and 10-30mg of stabilizer per liter of deionized water, and placing the weighed materials in a beaker filled with the deionized water to obtain a basic chemical copper plating solution;
(3) preparing a single-layer graphene dispersion liquid: weighing 0.1-2g of single-layer graphene per liter of deionized water, placing the single-layer graphene in a beaker filled with the deionized water, performing ultrasonic treatment and stirring for 2 hours, adding a mixed dispersant, performing ultrasonic treatment and stirring for 2 hours for later use, wherein the mixed dispersant is a combination of two or more of polyvinylpyrrolidone, chloroform, dimethylformamide and tetrahydrofuran, and the mass of the added dispersant can be set to be 3-8 times of that of the single-layer graphene according to the type of the mixed dispersant, so as to obtain a single-layer graphene dispersion liquid;
(4) preheating a basic electroless copper plating solution: placing the beaker of the basic electroless copper plating solution prepared in the step (2) in a constant-temperature water bath kettle at the temperature of 45-75 ℃ and stirring for 1-3min to enable the beaker to reach the corresponding electroless copper plating temperature;
(5) preparing a mixed chemical copper plating solution: adding 10mL of the dispersion liquid of the single-layer graphene prepared in the step (3) into 240mL of the preheated basic chemical copper plating solution in the step (4), stirring at the rotating speed of 200-400rpm to fully mix the dispersion liquid with the basic chemical copper plating solution, then carrying out ultrasonic stirring on the mixed plating solution for 3-7min, and then placing the mixed plating solution back into a constant-temperature water bath kettle at the temperature of 45-75 ℃ for chemical copper plating;
(6) chemical plating treatment: clamping the copper sheet substrate treated in the step (1) by using a clamp, putting the copper sheet substrate into the mixed chemical copper plating solution in the step (5), adding 10-25mL of reducing agent into each liter of basic chemical copper plating solution while stirring, wherein the chemical copper plating time is 20-40 min;
(7) and (4) washing the copper/graphene composite film on the surface of the red copper sheet obtained in the step (6) with deionized water, and drying the copper/graphene composite film by using a blower to obtain the copper/graphene composite film material.
3. Use of the copper/graphene composite thin film material according to any one of claims 1-2 as a high thermal conductive material.
4. A method for preparing a copper/graphene composite film material by utilizing an ultrasonic-assisted chemical plating method is characterized by comprising the following steps:
(1) cleaning, roughening and activating the surface of the red copper sheet substrate: placing the copper sheet substrate into a beaker filled with deionized water for ultrasonic cleaning for 3-5min, soaking in alkaline washing solution at 50-60 ℃ for 3-5min after cleaning, taking out and washing with deionized water, placing into dilute hydrochloric acid at room temperature for standing for 20-40s, and finally washing with deionized water and drying; wherein, the alkaline washing liquid is prepared by adding 10-30g of trisodium phosphate, 10-30g of sodium carbonate and 5-10g of sodium hydroxide into per liter of deionized water; the concentration of the dilute hydrochloric acid is 0.05-0.1 mol/L;
(2) preparing a basic electroless copper plating solution: weighing 5-14g of blue vitriol, 17-51g of double complexing agent, 10-13g of sodium hydroxide and 10-30mg of stabilizer per liter of deionized water, and placing the weighed materials in a beaker filled with the deionized water to obtain a basic chemical copper plating solution;
(3) preparing a single-layer graphene dispersion liquid: weighing 0.1-2g of single-layer graphene per liter of deionized water, placing the single-layer graphene in a beaker filled with the deionized water, performing ultrasonic treatment and stirring for 2 hours, adding a mixed dispersant, performing ultrasonic treatment and stirring for 2 hours for later use, wherein the mixed dispersant is a combination of two or more of polyvinylpyrrolidone, chloroform, dimethylformamide and tetrahydrofuran, and the mass of the added dispersant can be set to be 3-8 times of that of the single-layer graphene according to the type of the mixed dispersant, so as to obtain a single-layer graphene dispersion liquid;
(4) preheating a basic electroless copper plating solution: placing the beaker of the basic electroless copper plating solution prepared in the step (2) in a constant-temperature water bath kettle at the temperature of 45-75 ℃ and stirring for 1-3min to enable the beaker to reach the corresponding electroless copper plating temperature;
(5) preparing a mixed electroless copper plating solution: adding 10mL of the dispersion liquid of the single-layer graphene prepared in the step (3) into 240mL of the preheated basic chemical copper plating solution in the step (4), stirring at the rotating speed of 200-400rpm to fully mix the dispersion liquid with the basic chemical copper plating solution, performing ultrasonic treatment and stirring treatment on the mixed plating solution for 3-7min, and then placing the mixed plating solution back into a constant-temperature water bath kettle at the temperature of 45-75 ℃ for chemical copper plating;
(6) chemical plating treatment: clamping the copper sheet substrate treated in the step (1) by using a clamp, putting the copper sheet substrate into the mixed chemical copper plating solution in the step (5), adding 10-25mL of reducing agent into each liter of basic chemical copper plating solution while stirring, wherein the chemical copper plating time is 20-40 min;
(7) and (4) washing the copper/graphene composite film on the surface of the red copper sheet obtained in the step (6) with deionized water, and drying the copper/graphene composite film by using a blower to obtain the copper/graphene composite film material.
5. The use of the method of claim 4 for preparing a copper/graphene composite thin film material using ultrasound assisted electroless plating in the electroless copper plating industry.
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