CN105244249A - Graphene sheet-carbon nanotube film flexible composite material, preparation method and application thereof - Google Patents
Graphene sheet-carbon nanotube film flexible composite material, preparation method and application thereof Download PDFInfo
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- CN105244249A CN105244249A CN201510681497.2A CN201510681497A CN105244249A CN 105244249 A CN105244249 A CN 105244249A CN 201510681497 A CN201510681497 A CN 201510681497A CN 105244249 A CN105244249 A CN 105244249A
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Abstract
The invention discloses a graphene sheet-carbon nanotube film flexible composite material, preparation method and application thereof. Graphene sheets are prepared by employing the microwave plasma-enhanced chemical vapor deposition method on a carbon nanotube film, and a graphene sheet-carbon nanotube film flexible composite material obtained is used to manufacture a cathode assembly field emitter. The graphene sheet-carbon nanotube film flexible composite material prepared by the method of the invention has the flexible characteristic. 1-10 layers of graphene sheets having a width of 0.5-1.2 micrometers are distributed on the carbon nanotube in an array manner, with a distribution density of 8-12 piece/[mu]m2. Compared with graphene sheets grown on a planar silicon substrate, the graphene sheet-carbon nanotube film flexible composite material prepared by the method of the invention has lower turn-on field and higher field emission current density and is able to work stably under relatively high field emission current density, thereby achieving great application values.
Description
The present invention obtains state natural sciences fund-youth fund funded projects (bullets 51302187).Obtain Tianjin application foundation and cutting edge technology research plan key project is subsidized (bullets 14JCZDJC32100).
Technical field
The invention belongs to the preparation and application technical field of nano material, relate to and utilize plasma enhanced chemical vapor deposition method with commercially available carbon nano-tube film for a kind of flexible compound nano material of structure uniqueness is prepared in substrate, and it is used for the preparation method of vacuum field electron emission device.
Background technology
Since being found from 2004, Graphene, because of the electricity of its excellence, mechanical performance and chemical stability, presents good application prospect in all many-sides, wherein just comprises the exploitation of vacuum field electronic device.Graphene has the sharp edge of atomic scale and beyond challenge good electric conductivity, under DC Electric Field, can form great local electric field in edge, thus impel electronics more easily to escape in vacuum.In addition, compared with this traditional one dimension field emmision material of carbon nano-tube, the Joule heat that unique two-dimensional structure of Graphene is conducive to producing in Flied emission is at its surperficial Quick diffusing, effectively prevent effective field launch point to burn because of the accumulation of Joule heat, thus make graphene-based filed emission cathode material have field emission stability more better than carbon nano-tube.Research shows, traditional is generally lain low in substrate by the epitaxially grown Graphene of deposited catalyst, efficient Flied emission point can not be become in the sharp edge emission process on the scene of its atomic scale, this is that array status is distributed in substrate with regard to the Graphene prepared by needing, and namely prepares array graphene film.Plasma reinforced chemical vapour deposition method prepares the main stream approach of array graphene film now, this method does not need to introduce catalyst, the dependence of growth to substrate of graphene film is lower, thus makes graphene film suprabasilly be grown to serve as possibility various.The substrate being used to graphene film growth is at present mainly the hard substrate such as silicon chip, sheet metal, and this just limits the application of field emission device to a certain extent, and flexible substrates field-electron emission device then well can make up the defect in this application.The exploitation of flexible substrates field emission electron components and parts is focuses now, and it likely brings a revolution in Performance Monitor field.Just think a mobile phone or computer is flexible, arbitrarily can be folded and put pocket into, this just needs its display unit to be flexible foldable (this also needs flexibility, the miniaturization of corresponding hardware device certainly), and this prospect is charming beyond doubt.In the research of flexible substrates field emission device carried out now, such as Graphene/carbon nanotube composite material and ZnO nano-wire/graphene composite material etc., in these materials, Graphene uses as just excellent electric conductivity, folding flexible substrates, and its sharp edge is not excavated out as the advantage of efficient Flied emission point.The present invention proposes based on exploitation high performance graphite thiazolinyl filed emission cathode material just, we are using carbon nano-tube film as substrate, with the graphene film grown thereon for Flied emission main body, make full use of carbon nano-tube film conductivity good, flexible, surface irregularity (Flied emission point affects little by electric field shielding) and the good structural advantage of graphene film field emission stability, prepared composite material is made to have lower operating voltage than the graphene film prepared on general hard plate material, under higher current density, also there is good field emission stability simultaneously, thus significantly improve its using value.
Summary of the invention
The object of the invention is to overcome existing hard plate field emission device limitation in the application, planar substrates graphene film filed emission cathode material opens the higher deficiency in field, utilize a kind of simple plasma enhanced chemical vapor deposition technique in carbon nano-tube film substrate, prepare the graphene film of dense distribution, effective integration carbon nano-tube film good conductivity, flexible foldable, surface irregularity and the advantage such as graphene film field emission stability is good, thus a kind of low-work voltage is provided, large Flied emission current density, high field emission stability, flexible filed emission cathode material.
The invention discloses following technology contents for achieving the above object:
A kind of graphene sheet-carbon nanotube film flexible composite, it is that the graphene film of 1-10 layer forms by carbon nano-tube film depositing the edge number of plies; Wherein on carbon nano-tube film, the distribution density of deposited graphite alkene sheet is 8-12 sheet/square micron, and graphene film width is 0.5-1.2 micron.
The present invention further discloses the preparation method of graphene sheet-carbon nanotube film flexible composite, it is characterized in that carrying out as follows:
(1) commercially available carbon nano-tube film is put on the graphite sample platform of Microwave Plasma Torch Atomic Emission Spect rometry device, pass into 15sccm high-purity hydrogen (5N), adjustable pressure is 1.5kPa, being heated to temperature stabilization to the sample stage being loaded with carbon nano-tube film was 600 DEG C, to carbon nano-tube film heat treatment 30 minutes;
(2) on the basis of step (1), promote sample stage temperature to stabilizing to 750 DEG C, and adjustable pressure is 1kPa;
(3) on the basis of step (2), microwave source is started, adjustment microwave power is 200-300W, and pass into 1-3sccm high purity acetylene gas (5N), rapid adjustment reative cell air pressure is 1kPa, start the deposition of graphene film, sedimentation time is 2 hours, and the distribution density of deposited graphite alkene sheet is 8-12 sheet/square micron, and graphene film width is 0.5-1.2 micron.The method preparing graphene film can be Microwave Plasma Torch Atomic Emission Spect rometry, also can be the method such as radio frequency sputtering deposition, radio frequency plasma enhancing chemical vapour deposition (CVD).
The present invention further discloses graphene sheet-carbon nanotube film flexible composite for the preparation of the application in vacuum field electron emission device, and experimental result shows:
(1) threshold electric field of the graphene sheet-carbon nanotube film flexible composite prepared by the present invention only has 1.78-3.38V/ μm;
(2) the maximum field emission of the graphene sheet-carbon nanotube film flexible composite prepared by the present invention can reach 7.10mA/cm
2;
(3) the graphene sheet-carbon nanotube film flexible composite prepared by the present invention in mean field emission up to 3.62mA/cm
2, corresponding electric field strength shows good field emission stability when being only 2.30V/ μm: 20 hours internal field emission current densities without obviously declining, current fluctuation is less than 3%.
Graphene sheet-carbon nanotube film flexible composite disclosed by the invention and preparation method and compared with prior art the had good effect of application are:
Carbon nano-tube film has excellent conductivity, is conducive to electronics and flows to graphene film from carbon nano-tube film; Carbon nano-tube film has flexible feature, makes prepared filed emission cathode material have the advantage of flexible foldable; Compared with the substrate of the planar structure such as silicon chip, sheet metal, carbon nano-tube film surface irregularity, effectively can reduce the impact of Electric field shielding effect on graphene film Flied emission, thus reduces the operating voltage of graphene sheet-carbon nanotube film flexible composite; The thickness of graphene film is controlled by experiment parameter, and the prepared graphene film with sharp edge (1-10 layer) can promote field-electron emission; The structural advantage of above carbon nano-tube film and graphene film makes prepared graphene sheet-carbon nanotube film flexible Field Emission cathode material have lower unlatching field (1.78-3.38V/ μm) and larger Flied emission current density (7.10mA/cm
2), also remain the good field emission stability of grapheme material, these indexs compare the graphene film prepared on planar silicon substrate lifting simultaneously.In addition, Microwave Plasma Torch Atomic Emission Spect rometry method of the present invention, technique is simple, and can not introduce impurity in prepared material, and practical value is high.
Accompanying drawing illustrates:
Fig. 1 is the process flow diagram that the present invention prepares graphene sheet-carbon nanotube film flexible composite, and its core procedure is that Microwave Plasma Torch Atomic Emission Spect rometry method prepares graphene film on carbon nano-tube film;
Fig. 2 is optics and the scanning electron microscopic picture of the present invention's carbon nano-tube film used, comprising: the optics picture of 21. carbon nano-tube films; The low power ESEM top view of 22. carbon nano-tube films;
Fig. 3 is the structural representation of the present invention's Microwave Plasma Torch Atomic Emission Spect rometry device reaction used chamber; The purity of acetylene gas used and hydrogen is 5N, heats substrate with homemade graphite heater, vacuumizes reative cell with " mechanical pump+molecular pump " combination unit;
Fig. 4 is ESEM and the transmission electron microscope picture of graphene sheet-carbon nanotube film flexible composite prepared by embodiment 1, comprising:
41. by embodiment 1 condition (microwave power: 200W; Acetylene gas flow: 2sccm) prepared by the low power ESEM top view of graphene sheet-carbon nanotube film flexible composite;
42. by embodiment 1 condition (microwave power: 200W; Acetylene gas flow: 2sccm) prepared by the high power ESEM top view of graphene sheet-carbon nanotube film flexible composite;
43. by embodiment 1 condition (microwave power: 200W; Acetylene gas flow: 2sccm) prepared by the low power transmission electron microscope picture of graphene sheet-carbon nanotube film flexible composite;
44. by embodiment 1 condition (microwave power: 200W; Acetylene gas flow: 2sccm) prepared by the high power transmission electron microscope picture of graphene sheet-carbon nanotube film flexible composite;
Figure 5 shows that the structural representation of the present invention's high vacuum Flied emission used tester, for testing the field emission performance of the graphene sheet-carbon nanotube film flexible composite of gained in each embodiment; This device is Flied emission test conventional equipment, and with prepared graphene sheet-carbon nanotube film flexible composite for negative electrode, corresponding anode is the corrosion resistant plate that diameter is about 10 centimetres, and cathode and anode spacing remains 1 millimeter; During test, in the adjustable positive bias of plate-load 0-10kV, and by minus earth, test result is by the automatic record of computer;
Fig. 6 is the field emission performance figure of the graphene sheet-carbon nanotube film flexible composite prepared at different conditions, characterize the Flied emission current density variation relation with electric field strength, specifically comprise the field emission performance of the four class samples such as graphene sheet-carbon nanotube film flexible composite prepared in embodiment 1, embodiment 2, embodiment 3 and the graphene film prepared on planar silicon substrate;
Fig. 7 is graphene sheet-carbon nanotube film flexible composite prepared by the embodiment 1 field emission stability figure in 20 hours, when Flied emission current density is about 1/2 of maximum field emission, under being characterized in constant DC Electric Field, Flied emission current density relation over time.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, but the invention is not restricted to these embodiments.Wherein used carbon nano-tube film, silicon single crystal flake, high-purity hydrogen, high purity acetylene gas, Microwave Plasma Torch Atomic Emission Spect rometry device, Flied emission tester etc. all have commercially available.
Be the process flow diagram that the present invention prepares graphene sheet-carbon nanotube film flexible composite shown in Fig. 1, its core procedure is that Microwave Plasma Torch Atomic Emission Spect rometry method prepares graphene film on carbon nano-tube film.
Optics picture and the scanning electron microscopic picture of the present invention's carbon nano-tube film used (having commercially available) is shown in Fig. 2; Wherein Figure 21 is depicted as the optics picture of carbon nano-tube film, can find out that carbon nano-tube film is that flexibility can free bend; Figure 22 is depicted as the low power ESEM top view of carbon nano-tube film, and can find out that carbon nano-tube is densely distributed, surface impurity is few, and film surface presents rough state due to carbon nano-tube skewness.
Embodiment 1
Heat treated carbon nanotube films in atmosphere of hydrogen:
Be placed on after carbon nano-tube film being cut into 1cm × 1cm small pieces with blade on the graphite sample platform of Microwave Plasma Torch Atomic Emission Spect rometry device (having commercially available), shown in Fig. 3, be the structural representation of this device reaction room; Start pumped vacuum systems, reative cell vacuum is evacuated to about 1.0 × 10
-3pass into 15sccm hydrogen (purity is 5N) after Pa, air pressure adjustment is 1.5kPa, being 600 DEG C, continuing process 30 minutes, for removing adsorbate and the pollutant on carbon nano-tube film surface with making graphite heater specimen heating holder by oneself to temperature stabilization.
Microwave Plasma Torch Atomic Emission Spect rometry legal system is for graphene film:
In atmosphere of hydrogen after heat treated carbon nanotube films, and then 750 DEG C are warming up to substrate, adjustable pressure is 1kPa, after temperature and air pressure are all stablized, start microwave source, microwave power set is 200W, pass into the acetylene gas (purity is 5N) of 2sccm immediately, and adjustable pressure is to stabilizing to 1kPa rapidly, namely start the growth of graphene film, growth time is 2 hours; Low power and the high power ESEM top view of graphene sheet-carbon nanotube film flexible composite prepared in the present embodiment is respectively shown in Figure 41 and Figure 42 in Fig. 4, can find out, graphene film is in carbon nano tube surface dense distribution, distribution density is about 10/square micron, graphene film width is 0.7-1.1 micron, and the rough surface of carbon nano-tube film causes the surface of gained composite material also uneven; Figure 43 in Fig. 4 is depicted as the low power transmission electron microscope picture of graphene sheet-carbon nanotube film flexible composite prepared in the present embodiment, can find out that graphene film dense distribution is in carbon nano-tube, the underlapped part of graphene film is close to transparent state, show that the lamellar spacing of prepared graphene film is little, the thickness of graphene film can be found out further from the high power transmission electron microscope picture shown in the Figure 44 Fig. 4, and only there is 3-4 layer at the edge of shown graphene film.In the present embodiment, the number of plies of gained graphene film is layer 1-7.
Field emission performance is tested:
High vacuum Flied emission tester (having commercially available) is used to the field emission performance of the graphene sheet-carbon nanotube film flexible composite tested prepared by the present embodiment, be the structural representation of this device shown in Fig. 5, this device is conventional field emission performance testing apparatus.Test house vacuum maintains about 1 × 10 by titanium getter pump
-7pa.Be bonded at as negative electrode on copper sample platform using the graphene sheet-carbon nanotube film flexible composite conducting resinl prepared by the present embodiment, be about the corrosion resistant plate of 10 centimetres as anode with a diameter, cathode and anode spacing is 1 millimeter; During test, by adjustable for 0-10kV positive bias load on anode, and bias voltage increases with constant speed (500V/min), and grounded cathode, test result is by the automatic record of computer.The field emission performance figure of different-shape graphene film sample is shown in Fig. 6, characterize the Flied emission current density variation relation with electric field strength, specifically comprise the field emission performance of the four class samples such as graphene sheet-carbon nanotube film flexible composite prepared in embodiment 1, embodiment 2, embodiment 3 and the graphene film prepared on planar silicon substrate.Can find out, unlatching field and the maximum field emission of graphene sheet-carbon nanotube film flexible composite prepared in the present embodiment are respectively 1.78V/ μm and 7.10mA/cm
2, 4.29V/ μm and 1.67mA/cm of prepared graphene film on silicon single crystal flake be far superior to
2.The reason that field emission performance strengthens mainly carbon nano-tube film is compared silicon single crystal flake and is had better conductivity, and surface irregularity reduces the impact of Electric field shielding effect.To Figure 7 shows that in the present embodiment prepared graphene sheet-carbon nanotube film flexible composite in 20 hours, (mean field emission is 3.62mA/cm to Flied emission current density when being about 1/2 of maximum field emission
2) field emission stability figure, under being characterized in constant DC Electric Field, Flied emission current density relation over time.Can find out, Flied emission current density changed minimum in 20 hours, did not obviously decline, and fluctuation is less than 3%, and applied electric field also only has 2.30V/ μm, and these results have all shown good application prospect.
Field emission device assembling (conventional sectional method):
Prepared graphene sheet-carbon nanotube film flexible composite conducting resinl being sticked to thickness is as negative electrode on the copper electrode of 2 millimeters, anode is the copper coin that a thickness is about 2 millimeters, and the ring-type polytetrafluoroethylene film that two interpolars are 200 microns by thickness is isolated; In Flied emission process, in plate-load positive bias, minus earth, can obtain stable field-electron emission, and Flied emission size of current controls by regulating anodic bias.
Embodiment 2
Heat treated carbon nanotube films in atmosphere of hydrogen:
Be placed on after carbon nano-tube film being cut into 1cm × 1cm small pieces with blade on the graphite sample platform of Microwave Plasma Torch Atomic Emission Spect rometry device (having commercially available), shown in Fig. 3, be the structural representation of this device reaction room; Start pumped vacuum systems, reative cell vacuum is evacuated to about 1.0 × 10
-3pass into 15sccm hydrogen (purity is 5N) after Pa, air pressure adjustment is 1.5kPa, being 600 DEG C, continuing process 30 minutes, for removing adsorbate and the pollutant on carbon nano-tube film surface with making graphite heater specimen heating holder by oneself to temperature stabilization.
Microwave Plasma Torch Atomic Emission Spect rometry legal system is for graphene film:
In atmosphere of hydrogen after heat treated carbon nanotube films, and then 750 DEG C are warming up to substrate, adjustable pressure is 1kPa, after temperature and air pressure are all stablized, start microwave source, microwave power set is 200W, pass into the acetylene gas (purity is 5N) of 1sccm immediately, and adjustable pressure is to stabilizing to 1kPa rapidly, namely start the growth of graphene film, growth time is 2 hours.The distribution density of gained graphene film is about 8/square micron, width is 0.6-0.9 micron, the number of plies is 1-6 layer.
Field emission performance is tested:
High vacuum Flied emission tester (having commercially available) is used to the field emission performance of the graphene sheet-carbon nanotube film flexible composite tested prepared by the present embodiment, be the structural representation of this device shown in Fig. 5, this device is conventional field emission performance testing apparatus.Test house vacuum maintains about 1 × 10 by titanium getter pump
-7pa.Be bonded at as negative electrode on copper sample platform using the graphene sheet-carbon nanotube film flexible composite conducting resinl prepared by the present embodiment, be about the corrosion resistant plate of 10 centimetres as anode with a diameter, cathode and anode spacing is 1 millimeter; During test, by adjustable for 0-10kV positive bias load on anode, and bias voltage increases with constant speed (500V/min), and grounded cathode, test result is by the automatic record of computer.As can be seen from Figure 6, unlatching field and the maximum field emission of prepared in the present embodiment graphene sheet-carbon nanotube film flexible composite are respectively 2.80V/ μm and 4.16mA/cm
2, 4.29V/ μm and 1.67mA/cm of prepared graphene film on silicon single crystal flake be far superior to
2.The reason that field emission performance strengthens mainly carbon nano-tube film is compared silicon single crystal flake and is had better conductivity, and surface irregularity reduces the impact of Electric field shielding effect.
Field emission device assembling (conventional sectional method):
Prepared graphene sheet-carbon nanotube film flexible composite conducting resinl being sticked to thickness is as negative electrode on the copper electrode of 2 millimeters, anode is the copper coin that a thickness is about 2 millimeters, and the ring-type polytetrafluoroethylene film that two interpolars are 200 microns by thickness is isolated; In Flied emission process, in plate-load positive bias, minus earth, can obtain stable field-electron emission, and Flied emission size of current controls by regulating anodic bias.
Embodiment 3
Heat treated carbon nanotube films in atmosphere of hydrogen:
Be placed on after carbon nano-tube film being cut into 1cm × 1cm small pieces with blade on the graphite sample platform of Microwave Plasma Torch Atomic Emission Spect rometry device (having commercially available), shown in Fig. 3, be the structural representation of this device reaction room; Start pumped vacuum systems, reative cell vacuum is evacuated to about 1.0 × 10
-3pass into 15sccm hydrogen (purity is 5N) after Pa, air pressure adjustment is 1.5kPa, being 600 DEG C, continuing process 30 minutes, for removing adsorbate and the pollutant on carbon nano-tube film surface with making graphite heater specimen heating holder by oneself to temperature stabilization.
Microwave Plasma Torch Atomic Emission Spect rometry legal system is for graphene film:
In atmosphere of hydrogen after heat treated carbon nanotube films, and then 750 DEG C are warming up to substrate, adjustable pressure is 1kPa, after temperature and air pressure are all stablized, start microwave source, microwave power set is 200W, pass into the acetylene gas (purity is 5N) of 3sccm immediately, and adjustable pressure is to stabilizing to 1kPa rapidly, namely start the growth of graphene film, growth time is 2 hours.The distribution density of gained graphene film is about 12/square micron, width is 0.9-1.2 micron, the number of plies is 1-10 layer.
Field emission performance is tested:
High vacuum Flied emission tester (having commercially available) is used to the field emission performance of the graphene sheet-carbon nanotube film flexible composite tested prepared by the present embodiment, be the structural representation of this device shown in Fig. 5, this device is conventional field emission performance testing apparatus.Test house vacuum maintains about 1 × 10 by titanium getter pump
-7pa.Be bonded at as negative electrode on copper sample platform using the graphene sheet-carbon nanotube film flexible composite conducting resinl prepared by the present embodiment, be about the corrosion resistant plate of 10 centimetres as anode with a diameter, cathode and anode spacing is 1 millimeter; During test, by adjustable for 0-10kV positive bias load on anode, and bias voltage increases with constant speed (500V/min), and grounded cathode, test result is by the automatic record of computer.As can be seen from Figure 6, unlatching field and the maximum field emission of prepared in the present embodiment graphene sheet-carbon nanotube film flexible composite are respectively 2.33V/ μm and 6.99mA/cm
2, 4.29V/ μm and 1.67mA/cm of prepared graphene film on silicon single crystal flake be far superior to
2.The reason that field emission performance strengthens mainly carbon nano-tube film is compared silicon single crystal flake and is had better conductivity, and surface irregularity reduces the impact of Electric field shielding effect.
Field emission device assembling (conventional sectional method):
Prepared graphene sheet-carbon nanotube film flexible composite conducting resinl being sticked to thickness is as negative electrode on the copper electrode of 2 millimeters, anode is the copper coin that a thickness is about 2 millimeters, and the ring-type polytetrafluoroethylene film that two interpolars are 200 microns by thickness is isolated; In Flied emission process, in plate-load positive bias, minus earth, can obtain stable field-electron emission, and Flied emission size of current controls by regulating anodic bias.
Embodiment 4
Heat treated carbon nanotube films in atmosphere of hydrogen:
Be placed on after carbon nano-tube film being cut into 1cm × 1cm small pieces with blade on the graphite sample platform of Microwave Plasma Torch Atomic Emission Spect rometry device (having commercially available), shown in Fig. 3, be the structural representation of this device reaction room; Start pumped vacuum systems, reative cell vacuum is evacuated to about 1.0 × 10
-3pass into 15sccm hydrogen (purity is 5N) after Pa, air pressure adjustment is 1.5kPa, being 600 DEG C, continuing process 30 minutes, for removing adsorbate and the pollutant on carbon nano-tube film surface with making graphite heater specimen heating holder by oneself to temperature stabilization.
Microwave Plasma Torch Atomic Emission Spect rometry legal system is for graphene film:
In atmosphere of hydrogen after heat treated carbon nanotube films, and then 750 DEG C are warming up to substrate, adjustable pressure is 1kPa, after temperature and air pressure are all stablized, start microwave source, microwave power set is 250W, pass into the acetylene gas (purity is 5N) of 1sccm immediately, and adjustable pressure is to stabilizing to 1kPa rapidly, namely start the growth of graphene film, growth time is 2 hours.The distribution density of gained graphene film is about 8/square micron, width is 0.5-0.9 micron, the number of plies is 1-5 layer.
Field emission performance is tested:
High vacuum Flied emission tester (having commercially available) is used to the field emission performance of the graphene sheet-carbon nanotube film flexible composite tested prepared by the present embodiment, be the structural representation of this device shown in Fig. 5, this device is conventional field emission performance testing apparatus.Test house vacuum maintains about 1 × 10 by titanium getter pump
-7pa.Be bonded at as negative electrode on copper sample platform using the graphene sheet-carbon nanotube film flexible composite conducting resinl prepared by the present embodiment, be about the corrosion resistant plate of 10 centimetres as anode with a diameter, cathode and anode spacing is 1 millimeter; During test, by adjustable for 0-10kV positive bias load on anode, and bias voltage increases with constant speed (500V/min), and grounded cathode, test result is by the automatic record of computer.Unlatching field and the maximum field emission of graphene sheet-carbon nanotube film flexible composite prepared in the present embodiment are respectively 3.38V/ μm and 3.35mA/cm
2, 4.29V/ μm and 1.67mA/cm of prepared graphene film on silicon single crystal flake be far superior to
2.The reason that field emission performance strengthens mainly carbon nano-tube film is compared silicon single crystal flake and is had better conductivity, and surface irregularity reduces the impact of Electric field shielding effect.
Field emission device assembling (conventional sectional method):
Prepared graphene sheet-carbon nanotube film flexible composite conducting resinl being sticked to thickness is as negative electrode on the copper electrode of 2 millimeters, anode is the copper coin that a thickness is about 2 millimeters, and the ring-type polytetrafluoroethylene film that two interpolars are 200 microns by thickness is isolated; In Flied emission process, in plate-load positive bias, minus earth, can obtain stable field-electron emission, and Flied emission size of current controls by regulating anodic bias.
Embodiment 5
Heat treated carbon nanotube films in atmosphere of hydrogen:
Be placed on after carbon nano-tube film being cut into 1cm × 1cm small pieces with blade on the graphite sample platform of Microwave Plasma Torch Atomic Emission Spect rometry device (having commercially available), shown in Fig. 3, be the structural representation of this device reaction room; Start pumped vacuum systems, reative cell vacuum is evacuated to about 1.0 × 10
-3pass into 15sccm hydrogen (purity is 5N) after Pa, air pressure adjustment is 1.5kPa, being 600 DEG C, continuing process 30 minutes, for removing adsorbate and the pollutant on carbon nano-tube film surface with making graphite heater specimen heating holder by oneself to temperature stabilization.
Microwave Plasma Torch Atomic Emission Spect rometry legal system is for graphene film:
In atmosphere of hydrogen after heat treated carbon nanotube films, and then 750 DEG C are warming up to substrate, adjustable pressure is 1kPa, after temperature and air pressure are all stablized, start microwave source, microwave power set is 250W, pass into the acetylene gas (purity is 5N) of 3sccm immediately, and adjustable pressure is to stabilizing to 1kPa rapidly, namely start the growth of graphene film, growth time is 2 hours.The distribution density of gained graphene film is about 11/square micron, width is 0.8-1.1 micron, the number of plies is 1-8 layer.
Field emission performance is tested:
High vacuum Flied emission tester (having commercially available) is used to the field emission performance of the graphene sheet-carbon nanotube film flexible composite tested prepared by the present embodiment, be the structural representation of this device shown in Fig. 5, this device is conventional field emission performance testing apparatus.Test house vacuum maintains about 1 × 10 by titanium getter pump
-7pa.Be bonded at as negative electrode on copper sample platform using the graphene sheet-carbon nanotube film flexible composite conducting resinl prepared by the present embodiment, be about the corrosion resistant plate of 10 centimetres as anode with a diameter, cathode and anode spacing is 1 millimeter; During test, by adjustable for 0-10kV positive bias load on anode, and bias voltage increases with constant speed (500V/min), and grounded cathode, test result is by the automatic record of computer.Unlatching field and the maximum field emission of graphene sheet-carbon nanotube film flexible composite prepared in the present embodiment are respectively 2.00V/ μm and 6.16mA/cm
2, 4.29V/ μm and 1.67mA/cm of prepared graphene film on silicon single crystal flake be far superior to
2.The reason that field emission performance strengthens mainly carbon nano-tube film is compared silicon single crystal flake and is had better conductivity, and surface irregularity reduces the impact of Electric field shielding effect.
Field emission device assembling (conventional sectional method):
Prepared graphene sheet-carbon nanotube film flexible composite conducting resinl being sticked to thickness is as negative electrode on the copper electrode of 2 millimeters, anode is the copper coin that a thickness is about 2 millimeters, and the ring-type polytetrafluoroethylene film that two interpolars are 200 microns by thickness is isolated; In Flied emission process, in plate-load positive bias, minus earth, can obtain stable field-electron emission, and Flied emission size of current controls by regulating anodic bias.
Embodiment 6
Heat treated carbon nanotube films in atmosphere of hydrogen:
Be placed on after carbon nano-tube film being cut into 1cm × 1cm small pieces with blade on the graphite sample platform of Microwave Plasma Torch Atomic Emission Spect rometry device (having commercially available), shown in Fig. 3, be the structural representation of this device reaction room; Start pumped vacuum systems, reative cell vacuum is evacuated to about 1.0 × 10
-3pass into 15sccm hydrogen (purity is 5N) after Pa, air pressure adjustment is 1.5kPa, being 600 DEG C, continuing process 30 minutes, for removing adsorbate and the pollutant on carbon nano-tube film surface with making graphite heater specimen heating holder by oneself to temperature stabilization.
Microwave Plasma Torch Atomic Emission Spect rometry legal system is for graphene film:
In atmosphere of hydrogen after heat treated carbon nanotube films, and then 750 DEG C are warming up to substrate, adjustable pressure is 1kPa, after temperature and air pressure are all stablized, start microwave source, microwave power set is 300W, pass into the acetylene gas (purity is 5N) of 2sccm immediately, and adjustable pressure is to stabilizing to 1kPa rapidly, namely start the growth of graphene film, growth time is 2 hours.The distribution density of gained graphene film is about 10/square micron, width is 0.6-1.0 micron, the number of plies is layer 1-7.
Field emission performance is tested:
High vacuum Flied emission tester (having commercially available) is used to the field emission performance of the graphene sheet-carbon nanotube film flexible composite tested prepared by the present embodiment, be the structural representation of this device shown in Fig. 5, this device is conventional field emission performance testing apparatus.Test house vacuum maintains about 1 × 10 by titanium getter pump
-7pa.Be bonded at as negative electrode on copper sample platform using the graphene sheet-carbon nanotube film flexible composite conducting resinl prepared by the present embodiment, be about the corrosion resistant plate of 10 centimetres as anode with a diameter, cathode and anode spacing is 1 millimeter; During test, by adjustable for 0-10kV positive bias load on anode, and bias voltage increases with constant speed (500V/min), and grounded cathode, test result is by the automatic record of computer.Unlatching field and the maximum field emission of graphene sheet-carbon nanotube film flexible composite prepared in the present embodiment are respectively 2.97V/ μm and 3.74mA/cm
2, 4.29V/ μm and 1.67mA/cm of prepared graphene film on silicon single crystal flake be far superior to
2.The reason that field emission performance strengthens mainly carbon nano-tube film is compared silicon single crystal flake and is had better conductivity, and surface irregularity reduces the impact of Electric field shielding effect.
Field emission device assembling (conventional sectional method):
Prepared graphene sheet-carbon nanotube film flexible composite conducting resinl being sticked to thickness is as negative electrode on the copper electrode of 2 millimeters, anode is the copper coin that a thickness is about 2 millimeters, and the ring-type polytetrafluoroethylene film that two interpolars are 200 microns by thickness is isolated; In Flied emission process, in plate-load positive bias, minus earth, can obtain stable field-electron emission, and Flied emission size of current controls by regulating anodic bias.
Embodiment 7
Heat treated carbon nanotube films in atmosphere of hydrogen:
Be placed on after carbon nano-tube film being cut into 1cm × 1cm small pieces with blade on the graphite sample platform of Microwave Plasma Torch Atomic Emission Spect rometry device (having commercially available), shown in Fig. 3, be the structural representation of this device reaction room; Start pumped vacuum systems, reative cell vacuum is evacuated to about 1.0 × 10
-3pass into 15sccm hydrogen (purity is 5N) after Pa, air pressure adjustment is 1.5kPa, being 600 DEG C, continuing process 30 minutes, for removing adsorbate and the pollutant on carbon nano-tube film surface with making graphite heater specimen heating holder by oneself to temperature stabilization.
Microwave Plasma Torch Atomic Emission Spect rometry legal system is for graphene film:
In atmosphere of hydrogen after heat treated carbon nanotube films, and then 750 DEG C are warming up to substrate, adjustable pressure is 1kPa, after temperature and air pressure are all stablized, start microwave source, microwave power set is 300W, pass into the acetylene gas (purity is 5N) of 3sccm immediately, and adjustable pressure is to stabilizing to 1kPa rapidly, namely start the growth of graphene film, growth time is 2 hours.The distribution density of gained graphene film is about 9/square micron, width is 0.7-1.0 micron, the number of plies is 1-8 layer.
Field emission performance is tested:
High vacuum Flied emission tester (having commercially available) is used to the field emission performance of the graphene sheet-carbon nanotube film flexible composite tested prepared by the present embodiment, be the structural representation of this device shown in Fig. 5, this device is conventional field emission performance testing apparatus.Test house vacuum maintains about 1 × 10 by titanium getter pump
-7pa.Be bonded at as negative electrode on copper sample platform using the graphene sheet-carbon nanotube film flexible composite conducting resinl prepared by the present embodiment, be about the corrosion resistant plate of 10 centimetres as anode with a diameter, cathode and anode spacing is 1 millimeter; During test, by adjustable for 0-10kV positive bias load on anode, and bias voltage increases with constant speed (500V/min), and grounded cathode, test result is by the automatic record of computer.Unlatching field and the maximum field emission of graphene sheet-carbon nanotube film flexible composite prepared in the present embodiment are respectively 2.27V/ μm and 5.65mA/cm
2, 4.29V/ μm and 1.67mA/cm of prepared graphene film on silicon single crystal flake be far superior to
2.The reason that field emission performance strengthens mainly carbon nano-tube film is compared silicon single crystal flake and is had better conductivity, and surface irregularity reduces the impact of Electric field shielding effect.
Field emission device assembling (conventional sectional method):
Prepared graphene sheet-carbon nanotube film flexible composite conducting resinl being sticked to thickness is as negative electrode on the copper electrode of 2 millimeters, anode is the copper coin that a thickness is about 2 millimeters, and the ring-type polytetrafluoroethylene film that two interpolars are 200 microns by thickness is isolated; In Flied emission process, in plate-load positive bias, minus earth, can obtain stable field-electron emission, and Flied emission size of current controls by regulating anodic bias.
Finally it should be noted that, only list exemplary embodiments of the present invention above.But obviously the present invention is not limited to above-described embodiment; also have other experiment parameter combined methods many; the relevant situation that those of ordinary skill in this research field can directly derive or associate from content disclosed by the invention, is all considered to be protection scope of the present invention.
Claims (4)
1. a graphene sheet-carbon nanotube film flexible composite, is characterized in that it is that the graphene film of 1-10 layer forms by carbon nano-tube film depositing the edge number of plies; Wherein on carbon nano-tube film, the distribution density of deposited graphite alkene sheet is 8-12 sheet/square micron, and graphene film width is 0.5-1.2 micron.
2. graphene sheet-carbon nanotube film flexible composite according to claim 1 is for the preparation of vacuum field electron emission device.
3. the preparation method of graphene sheet-carbon nanotube film flexible composite according to claim 1, is characterized in that carrying out as follows:
(1) commercially available carbon nano-tube film is put on the graphite sample platform of Microwave Plasma Torch Atomic Emission Spect rometry device, pass into 15sccm high-purity hydrogen (5N), adjustable pressure is 1.5kPa, being heated to temperature stabilization to the sample stage being loaded with carbon nano-tube film was 600 DEG C, to carbon nano-tube film heat treatment 30 minutes;
(2) on the basis of step (1), promote sample stage temperature to stabilizing to 750 DEG C, and adjustable pressure is 1kPa;
(3) on the basis of step (2), microwave source is started, adjustment microwave power is 200-300W, and pass into 1-3sccm high purity acetylene gas (5N), rapid adjustment reative cell air pressure is 1kPa, start the deposition of graphene film, sedimentation time is 2 hours, and the distribution density of deposited graphite alkene sheet is 8-12 sheet/square micron, and graphene film width is 0.5-1.2 micron.
4. the preparation method of graphene sheet-carbon nanotube film flexible composite according to claim 3, the method wherein preparing graphene film is that Microwave Plasma Torch Atomic Emission Spect rometry, radio frequency sputtering deposition or radio frequency plasma strengthen chemical vapour deposition (CVD).
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