CN108821264B - Nano-scale sound wave generator - Google Patents
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
- B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
- B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
- B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
The invention discloses a nanoscale sound wave generator which comprises a substrate with the thermal conductivity lower than 200W/mK, a sound wave generating film paved on the substrate, two silver colloid electrodes for audio current input and an electric signal input unit, wherein the two silver colloid electrodes are respectively arranged at two ends of the sound wave generating film; the sound wave generating film is a graphene film, the thickness of the sound wave generating film is not more than 60nm, and the density of the sound wave generating film is 2.0-2.2 g/cm3The graphene layers are crosslinked, the degree of crosslinking is 1-5%, and the graphene film has excellent electric heating performance and thermal conductivity and can effectively cause thermal shock of air at the position of the film. The sound production device has good sound quality and high sound definition.
Description
Technical Field
The invention relates to a high-performance nano material and a preparation method thereof, in particular to a nano sound wave generator.
Background
In 2010, Andre GeiM and Konstantin Novoselov, two professors of Manchester university in England, raised the worldwide hot trend of graphene research because of the first successful separation of stable graphene to obtain the Nobel prize of physics. Graphene has excellent electrical properties (the electron mobility can reach 2 multiplied by 105cM2/Vs at room temperature), outstanding properties (5000W/(MK), extraordinary specific surface area (2630M2/g), Young modulus (1100GPa) and breaking strength (125GPa), excellent electric conduction and heat conduction properties of graphene completely exceed metal, meanwhile, graphene has the advantages of high temperature resistance and corrosion resistance, and good mechanical properties and lower density of graphene enable the graphene to have the potential of replacing metal in the field of electric heating materials. The portable electronic device can be widely applied to portable electronic devices such as sound production, sound wave detection, smart phones, intelligent portable hardware, tablet computers and notebook computers.
However, due to the existence of edge defects and the weak interaction force between graphene layers, the strength of the graphene film sintered at high temperature is generally not too high, less than 100MPa, which is not favorable for practical application. In addition, the cross-linked structure between graphene layers is similar to that of a diamond structure, so that heat conduction is not damaged, and the heat conduction performance of the graphene film is not seriously influenced.
To date, graphene films have begun to be applied to sound-producing devices, such as laser-produced PI-based graphene films, chemically reduced graphene films. However, the films of the two have inevitable defects, namely large structural defects and low heating speed; secondly, the thickness is very high, the cooling speed is slow, and therefore the sound production definition is poor; thirdly, the film has poor temperature resistance and poor sound adjustment. To address the above issues, this patent designed a nano-thick crosslinked graphene membrane. The film is applied to sound wave detection and has the following advantages: firstly, the film structure is perfect, the structure and stacking defects are few, the conductivity is high, and the temperature rise speed is high; secondly, the thickness of the film is below 60nm, the heat conductivity is high, and the heat dissipation is fast; the graphene film has high temperature rise and fall rate, so that the graphene film has excellent tone quality and high sound definition. Thirdly, the graphene film has few defects, internal crosslinking, good thermal stability, high temperature resistance of 520 ℃ in the air and good sound volume adjustability; and fourthly, the graphene film has high thermal conductivity and lower sound production voltage.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a nano-scale sound wave generator.
The purpose of the invention is realized by the following technical scheme: a nanometer-scale sound wave generator is characterized by comprising a substrate with the thermal conductivity lower than 200W/mK, a sound wave generating film paved on the substrate, an electric signal input unit and two silver colloid electrodes for audio current input, wherein the two silver colloid electrodes are respectively arranged at two ends of the sound wave generating film; the sound wave generation film is a graphene film, the thickness of the sound wave generation film is not more than 60nm, the density of the sound wave generation film is 2.0-2.2 g/cm3, the graphene layers are crosslinked, the degree of crosslinking is 1-5%, and the graphene film is prepared by the following method:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10ug/mL, and performing suction filtration to form a film;
(2) putting the graphene oxide film attached to the suction filtration substrate into a closed container, and fumigating at the high temperature of 80-100 ℃ from the bottom to the top for 0.1-1 h;
(3) uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film, and slowly cooling at room temperature until the film is separated from the substrate;
(4) heating the reduced graphene oxide film treated in the step 3 to sublimate or volatilize the solid transfer agent;
(5) spraying a layer of metal such as titanium, molybdenum or cobalt on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of sputtered metal nanoparticles is not more than 30% of the molar weight of carbon atoms in the graphene film;
(6) chloridizing the graphene film sputtered with the metal at 800-1200 ℃, and dissipating the metal nanoparticles in the form of chloride;
(7) and (3) placing the chlorinated graphene film in a high-temperature furnace, heating to 1500 ℃ at 5-20 ℃ per minute, and then heating to 2000 ℃ at 2-5 ℃ per minute to obtain the interlayer crosslinked graphene film.
Further, the substrate with the thermal conductivity lower than 200W/mK is selected from a polymer substrate and a silicon substrate.
Further, the solid transfer agent is selected from the group consisting of paraffin, naphthalene, arsenic trioxide, camphor, sulfur, norbornene, rosin, and other small molecule solid substances insoluble in water that can sublime or volatilize under certain conditions.
Further, the sublimation temperature of the solid transfer agent is controlled below 320 ℃.
Further, the chlorination treatment means: and (3) placing the graphene film sputtered with the metal nano particles in an environment with the chlorine content of 0.5-10% for heating treatment for 0.1-4 h.
The invention has the beneficial effects that: according to the invention, firstly, an ultrathin graphene film is obtained in a solid transfer mode, so that a foundation is laid for the high resistance of a device; further, the surface wrinkles of the graphene film are increased through slow heating (1 ℃/min), and the area of the graphene film in a unit space is expanded; and then heating at a speed of 10 ℃/min and placing at 2000 ℃ to remove most of atomic defects in the graphene, but not recovering the stacking structure in the graphene. Further sputtering metal particles on the surface of the ultrathin graphene film, and reacting the metal particles with the graphene at high temperature to form metal carbide; then the metal carbide forms metal chloride under the action of chlorine and escapes, meanwhile, the carbon structure is converted to the diamond structure, the strength (reaching 7-20GPa) and the thermal stability of the film are greatly improved, the graphene film structure is recovered to a great extent by high-temperature treatment at 2000 ℃, but the interlayer cross-linking structure is not influenced and an AB accumulation structure is not formed. The invention sacrifices partial electric conduction and heat conduction performance of the graphene film, introduces an interlayer crosslinking structure into the graphene sheet layers, greatly improves the strength of the graphene film, and improves the strength by more than 80 times. The film is applied to sound wave detection and has the following advantages: firstly, the film structure is perfect, the structure and stacking defects are few, the conductivity is high, and the temperature rise speed is high; secondly, the thickness of the film is below 60nm, the heat conductivity is high, and the heat dissipation is fast; the graphene film has high temperature rise and fall rate, so that the graphene film has excellent tone quality and high sound definition. Thirdly, the graphene film has few defects, internal crosslinking, good thermal stability, high temperature resistance of 520 ℃ in the air and good sound volume adjustability; and fourthly, the graphene film has high thermal conductivity and lower sound production voltage.
Drawings
Fig. 1 is a raman spectrum of a non-crosslinked graphene film after treatment at 2000 degrees celsius.
Fig. 2 is a raman spectrum of the cross-linked graphene film after 2000 degrees celsius treatment.
Fig. 3 is a transmission spectrum of a non-crosslinked graphene film at 2000 degrees celsius treatment.
Fig. 4 is a transmission spectrum of a cross-linked graphene film processed at 2000 degrees celsius.
Fig. 5 is a graph of tensile strength testing of a cross-linked graphene film at 2000 degrees celsius treatment.
Fig. 6 is a temperature increase and decrease curve of the graphene film obtained in example 1.
Fig. 7 is a temperature curve of the graphene film along the direction of the straight line where the two electrodes are located at the time T ═ 1 s.
Detailed Description
Example 1:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5ug/mL, and performing suction filtration to form a membrane by taking the hydrophilic polytetrafluoroethylene membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the hydrophilic polytetrafluoroethylene membrane in a closed container, and fumigating the graphene oxide membrane from the bottom to the top for 1h at a high temperature of 80 ℃.
(3) And uniformly coating the melted solid transfer agent camphor on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, slowly cooling at room temperature, and separating the film from the substrate.
(4) And slowly volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at 40 ℃ to obtain the independent self-supported graphene film.
(5) And spraying a layer of metallic titanium on the surface of the chemically reduced graphene film in a magnetron sputtering mode. By controlling the sputtering parameters, the molar weight of the finally sputtered metal nanoparticles is 28.6% of the molar weight of carbon atoms in the graphene film.
(6) The graphene film sputtered with the metal is chlorinated at 1200 degrees celsius, allowing the titanium nanoparticles to escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 0.5% for heating treatment for 4 h.
(7) And (3) carrying out 2000-degree high-temperature treatment on the chlorinated graphene film, wherein the temperature rise process in the 2000-degree high-temperature process is as follows: below 1500 ℃ and 20 ℃ per minute; above 1500 ℃, 5 ℃ per minute; graphene films with a thickness of 59nm were obtained.
Comparing FIGS. 1 and 2, the graphene film having a plurality of crosslinked structures has a stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 4.8%; in fig. 3 and 4, the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The strength of the prepared graphene film is 7GPa (shown in figure 5), and the thermal stability of the graphene film can be ensured. The density of the graphene film is 2.0g/cm3。
Two electrodes are connected to the left side and the right side of the graphene film, the temperature change of the graphene electrothermal film is measured by using a temperature control sensor, the stable temperature 519 ℃ of the graphene film is achieved only by 0.5 second under the direct current voltage of 10V in the atmospheric environment, and after the graphene film is powered off, the temperature of the graphene film is reduced to be close to the room temperature within 0.5 second due to the excellent thermal conductivity of the graphene film, as shown in figure 6. And (3) acquiring a surface temperature distribution graph of the film by using an infrared detector at the moment T-1 s, wherein the temperature of the graphene film is stable along the direction of the straight line where the two electrodes are located, and the temperature is about 519 ℃.
2 x 2cm of the graphene film2The nano-scale acoustic wave generator is formed by paving the graphene film on a polyimide substrate (with the thermal conductivity of 0.35W/mK), coating silver colloid electrodes at two ends of the graphene film, and respectively connecting the two silver colloid electrodes with the positive electrode and the negative electrode of an electric signal input unit. Because the film has high electrical conductivity, the film can release heat and raise temperature violently under the condition of external voltage, the external voltage is removed, the heat dissipation speed of the film is extremely high due to good thermal conductivity and thin thickness, and the film can quickly raise and lower the temperature under the combined action, so that the thermal shock of the air at the film is caused, and the film can sound. Therefore, a certain air thermal vibration amplitude, namely pitch, can be obtained by auxiliary loading of a direct current voltage of 10V and additionally inputting a specified audio signal through the electric signal input unit to adjust the overall input voltage and change frequency; the thermal vibration frequency of the air can be adjusted by adjusting the frequency of the input signal, so that the frequency of the sounding is changed to send different sounds.
Example 2:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 10ug/mL, and performing suction filtration to form a film by taking the PC film as a substrate.
(2) And (3) putting the graphene oxide film attached to the PC film into a closed container, and fumigating the graphene oxide film at the high temperature of 100 ℃ from the bottom to the top for 0.1 h.
(3) And uniformly coating the melted solid transfer agent naphthalene on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the graphene film supported by the solid transfer agent at 80 ℃ to obtain the independent self-supporting graphene film.
(5) And spraying a layer of metallic titanium on the surface of the chemically reduced graphene film in a magnetron sputtering mode. By controlling the sputtering parameters, the molar weight of the finally sputtered metal nanoparticles is 18.4% of the molar weight of carbon atoms in the graphene film.
(6) The graphene film sputtered with the metal is chlorinated at 800 degrees celsius, so that the titanium nanoparticles escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 10% for heating treatment for 0.1 h.
(7) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃, 5 ℃ per minute; above 1500 ℃, 2 ℃ per minute; keeping the temperature at 2000 ℃ for 1 h; obtaining the graphene film with the thickness of 48 nm.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 1.1%; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The prepared graphene film has the strength of 7.6GPa and the density of 2.0g/cm3。
The left side and the right side of the graphene film are connected with two electrodes, the temperature change of the graphene electrothermal film is measured by using a temperature control sensor, the stable temperature of the graphene film reaches 514 ℃ in only 0.5 second under the direct current voltage of 10V in the atmospheric environment, and the temperature of the graphene film is reduced to be close to the room temperature in 0.5 second due to the excellent thermal conductivity of the graphene film after power failure. The graphene film is stable in temperature along the linear direction of the two electrodes, and the temperature is about 514 ℃.
2 x 2cm of the graphene film2The nano-scale acoustic wave generator is formed by paving the graphene film on a polyimide substrate (with the thermal conductivity of 0.35W/mK), coating silver colloid electrodes at two ends of the graphene film, and respectively connecting the two silver colloid electrodes with the positive electrode and the negative electrode of an electric signal input unit.
Example 3:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 1ug/mL, and performing suction filtration to form a membrane by taking the hydrophilic polytetrafluoroethylene membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the hydrophilic polytetrafluoroethylene in a closed container, and fumigating at high temperature of 90 ℃ for 0.5h from the bottom to the top.
(3) And uniformly coating the molten solid transfer agent sulfur on the surface of the reduced graphene oxide film by using a method such as evaporation, casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the graphene film supported by the solid transfer agent at 120 ℃ to obtain the independent self-supporting graphene film.
(5) And (2) spraying a layer of metal cobalt on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of the finally sputtered metal nanoparticles is 15.9% of the molar weight of carbon atoms in the graphene film by controlling sputtering parameters.
(6) The graphene film sputtered with the metal is chlorinated at 1000 degrees celsius, allowing the cobalt nanoparticles to escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 5% for heating treatment for 1 h.
(7) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃ and 10 ℃ per minute; above 1500 ℃, 3 ℃ per minute; keeping the temperature at 2000 ℃ for 0.5 h; graphene films with a thickness of 28nm were obtained.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 1.9%; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The prepared graphene film has the strength of 11GPa and the density of 2.1g/cm3。
The left side and the right side of the graphene film are connected with two electrodes, the temperature change of the graphene electrothermal film is measured by using a temperature control sensor, the stable temperature of the graphene film can reach 518 ℃ only in 0.5 second under the direct current voltage of 10V in the atmospheric environment, and after the graphene film is powered off, the temperature of the graphene film can be reduced to be close to the room temperature in 0.5 second due to the excellent thermal conductivity of the graphene film. The graphene film is stable in temperature along the linear direction of the two electrodes.
2 x 2cm of the graphene film2The nano-scale acoustic wave generator is formed by paving the graphene film on a polyimide substrate (with the thermal conductivity of 0.35W/mK), coating silver colloid electrodes at two ends of the graphene film, and respectively connecting the two silver colloid electrodes with the positive electrode and the negative electrode of an electric signal input unit.
Example 4:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 3ug/mL, and performing suction filtration to form a film by taking the AAO film as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating the graphene oxide membrane at the high temperature of 100 ℃ from the bottom to the top for 0.2 h.
(3) And uniformly coating the melted solid transfer agent paraffin on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the graphene film supported by the solid transfer agent at 200 ℃ to obtain the independent self-supporting graphene film.
(5) And (2) spraying a layer of metal titanium on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of the finally sputtered metal nanoparticles is 25.4% of the molar weight of carbon atoms in the graphene film by controlling sputtering parameters.
(5) The graphene film sputtered with the metal is chlorinated at 1100 degrees celsius, allowing the titanium nanoparticles to escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 2% for heating treatment for 2 hours.
(6) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃, 12 ℃ per minute; above 1500 ℃, 4 ℃ per minute; and keeping the temperature at 2000 ℃ for 1h to obtain the graphene film with the thickness of 33 nm.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 2.2%; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The prepared graphene film has the strength of 9.6GPa and the density of 2.0g/cm3。
The left side and the right side of the graphene film are connected with two electrodes, the temperature change of the graphene electrothermal film is measured by using a temperature control sensor, the stable temperature of the graphene film is 506 ℃ only needing 0.5 second under the direct current voltage of 10V in the atmospheric environment, and after the graphene film is powered off, the temperature of the graphene film is reduced to be close to the room temperature within 0.5 second due to the excellent thermal conductivity of the graphene film. The graphene film is stable in temperature along the linear direction of the two electrodes.
2 x 2cm of the graphene film2The nano-scale acoustic wave generator is formed by paving the graphene film on a polyimide substrate (with the thermal conductivity of 0.35W/mK), coating silver colloid electrodes at two ends of the graphene film, and respectively connecting the two silver colloid electrodes with the positive electrode and the negative electrode of an electric signal input unit.
Example 5:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 10ug/mL, and performing suction filtration to form a membrane by taking the hydrophilic polytetrafluoroethylene membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the hydrophilic polytetrafluoroethylene membrane in a closed container, and fumigating at high temperature of 80 ℃ HI from the bottom to the top for 0.8 h.
(3) And uniformly coating the melted solid transfer agent norbornene on the surface of the reduced graphene oxide film by using methods such as evaporation, tape casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the obtained graphene film supported by the solid transfer agent at 60 ℃ under 2 atmospheric pressures to obtain the independent self-supported graphene film.
(4) And spraying a layer of metal molybdenum on the surface of the chemically reduced graphene film in a magnetron sputtering mode. By controlling the sputtering parameters, the molar weight of the finally sputtered metal nanoparticles is 22.8% of the molar weight of carbon atoms in the graphene film.
(5) The graphene film sputtered with the metal is chlorinated at 800 degrees celsius, so that the molybdenum nanoparticles escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with chlorine content of 6% for heating treatment for 3 h.
(6) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃, 7 ℃ per minute; and (3) preserving heat for 1h at the temperature of more than 1500 ℃, 2 ℃ per minute and 2000 ℃, so as to obtain the graphene film with the thickness of 36 nm.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 3.7%; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The prepared graphene film has the strength of 9.8GPa and the density of 2.2g/cm3。
The left side and the right side of the graphene film are connected with two electrodes, the temperature change of the graphene electrothermal film is measured by using a temperature control sensor, the stable temperature of the graphene film reaches 503 ℃ in 0.5 second under the direct current voltage of 10V in the atmospheric environment, and the temperature of the graphene film is reduced to be close to the room temperature in 0.5 second due to the excellent thermal conductivity of the graphene film after power failure. The graphene film is stable in temperature along the linear direction of the two electrodes.
2 x 2cm of the graphene film2The nano-scale acoustic wave generator is formed by paving the graphene film on a polyimide substrate (with the thermal conductivity of 0.35W/mK), coating silver colloid electrodes at two ends of the graphene film, and respectively connecting the two silver colloid electrodes with the positive electrode and the negative electrode of an electric signal input unit.
Claims (5)
1. A nanometer-scale sound wave generator is characterized by comprising a substrate with the thermal conductivity lower than 200W/mK, a sound wave generating film paved on the substrate, an electric signal input unit and two silver colloid electrodes for audio current input, wherein the two silver colloid electrodes are respectively arranged at two ends of the sound wave generating film; the sound wave generating film is a graphene film, the thickness of the sound wave generating film is not more than 60nm, and the density of the sound wave generating film is 2.0-2.2 g/cm3The graphene layers are crosslinked, the degree of crosslinking is 1-5%, and the graphene film is prepared by the following method:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10 mug/mL, and filtering to form a film;
(2) putting the graphene oxide film attached to the suction filtration substrate into a closed container, and fumigating the graphene oxide film from the bottom to the top at the HI high temperature of 80-100 ℃ for 0.1-1 h;
(3) uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film, and slowly cooling at room temperature until the film is separated from the substrate;
(4) heating the reduced graphene oxide film treated in the step (3) to sublimate or volatilize the solid transfer agent;
(5) spraying a layer of metal titanium, molybdenum or cobalt on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of sputtered metal nanoparticles is not more than 30% of the molar weight of carbon atoms in the graphene film;
(6) chloridizing the graphene film sputtered with the metal at 800-1200 ℃, and dissipating the metal nanoparticles in the form of chloride;
(7) and (3) placing the chlorinated graphene film in a high-temperature furnace, heating to 1500 ℃ at 5-20 ℃ per minute, and then heating to 2000 ℃ at 2-5 ℃ per minute to obtain the interlayer crosslinked graphene film.
2. The nano-scale acoustic wave generator of claim 1, wherein the substrate having a thermal conductivity of less than 200W/mK is selected from a polymer substrate, a silicon substrate.
3. The nano-scale acoustic wave generator of claim 1, wherein the solid transfer agent is selected from the group consisting of paraffin, naphthalene, camphor, norbornene, rosin.
4. The nano-scale acoustic-wave generator of claim 1, wherein the sublimation temperature of the solid transfer agent is controlled to be below 320 ℃.
5. The nanoscale acoustic-wave generator of claim 1, wherein the chlorination treatment is: and (3) placing the graphene film sputtered with the metal nano particles in an environment with the chlorine content of 0.5-10% for heating treatment for 0.1-4 h.
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