CN105244249B - A kind of graphene film carbon nano-tube film flexible composite and preparation method and application - Google Patents
A kind of graphene film carbon nano-tube film flexible composite and preparation method and application Download PDFInfo
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- CN105244249B CN105244249B CN201510681497.2A CN201510681497A CN105244249B CN 105244249 B CN105244249 B CN 105244249B CN 201510681497 A CN201510681497 A CN 201510681497A CN 105244249 B CN105244249 B CN 105244249B
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Abstract
The invention discloses a kind of graphene film carbon nano-tube film flexible composite and preparation method and application.It, over the carbon nanotube film using microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece, is cathode assembling field emission device with the graphene film carbon nano-tube film flexible composite for being obtained that it is.The characteristics of graphene film carbon nano-tube film flexible composite prepared by this method has flexible, graphene film is distributed on the carbon nanotubes in array status, and the graphene film number of plies is 1 10 layers, distribution density over the carbon nanotube film is 8 12/square micron, width is 0.5 1.2 microns.Compared with the graphene film grown on planar silicon substrate, graphene film carbon nano-tube film flexible composite prepared by this method has lower threshold electric field and bigger Flied emission current density, and can under high field emission steady operation, with application value higher.
Description
The present invention obtains state natural sciences fund-youth fund funded projects（Bullets 51302187）.Obtain day
Jinshi City's application foundation is subsidized with cutting edge technology research plan key project（Bullets 14JCZDJC32100）.
Technical field
The invention belongs to the preparation and application technical field of nano material, relate to the use of PECVD and sink
Area method prepares a kind of flexible compound nano material of unique structure with commercially available carbon nano-tube film as substrate, and it is used for into vacuum
The preparation method of field-electron emission device.
Background technology
Since being found from 2004, Graphene because of its excellent electricity, mechanical performance and chemical stability, all multi-party
Face presents good application prospect, wherein just including the exploitation of vacuum field electronic device.Graphene has the cutting edge of a knife or a sword of atomic scale
Sharp edge and unmatched good electric conductivity, under DC Electric Field, can form great local electricity in edge
, so as in promoting electronics to be more easy to escape into vacuum.Additionally, compared with this traditional one-dimensional field emmision material of CNT,
Unique two-dimensional structure of Graphene is conducive to the Joule heat produced in Flied emission in its surface Quick diffusing, effectively prevent effectively
Flied emission point burns because of the accumulation of Joule heat, so that graphene-based filed emission cathode material is with more preferable than CNT
Field emission stability.Research shows that traditional Graphene by deposited catalyst epitaxial growth typically lies low in substrate,
Efficient Flied emission point can not be turned into the sharp edge emission process on the scene of its atomic scale, this is accomplished by prepared stone
Black alkene is distributed in substrate in array status, that is, prepare array graphene film.Plasma reinforced chemical vapour deposition method is now
The main stream approach of array graphene film is prepared, this method simultaneously need not introduce catalyst, and the growth of graphene film is to substrate
Dependence is relatively low, so that graphene film is grown to serve as possibility in various substrates.Have been used for graphene film at present
The substrate of growth is mainly the hard substrates such as silicon chip, sheet metal, and this limits the application of field emission device to a certain extent, soft
Property substrate field-electron emission device then can well make up the defect in this application field.Flexible substrates field emission electron unit device
The exploitation of part is focus now, and it is possible to bring a revolution in Performance Monitor field.Just think a mobile phone or
Computer is flexible, can put pocket into by being arbitrarily folded, and it is flexible foldable that this is accomplished by its display device（This is certain
It is also required to flexibility, the miniaturization of corresponding hardware device）, this prospect is undoubtedly charming.The flexible substrates carried out now
In the research of field emission device, such as Graphene/carbon nanotube composite material and ZnO nano-wire/graphene composite material etc., these
Graphene is used as just excellent electric conductivity, folding flexible substrates in material, and its sharp edge is sent out as efficient field
The advantage of exit point is not exploited out.The present invention is based on exploitation high performance graphite alkenyl filed emission cathode material and carries
Go out, we, using carbon nano-tube film as substrate, are Flied emission main body with the graphene film for growing thereon, make full use of carbon
Nanotube films electric conductivity is good, flexible, surface irregularity（Flied emission point is influenceed small by electric field shielding）Sent out with Graphene film studio
Penetrate the structural advantage of good stability so that graphene film of the prepared composite than the preparation on general hard plate material
With lower operating voltage, while also there is good field emission stability under higher current density, so as to be substantially improved
Its application value.
The content of the invention
It is an object of the invention to overcome existing hard plate field emission device limitation, planar substrates stone in the application
Black alkene piece filed emission cathode material opens field deficiency higher, using a kind of simple plasma enhanced chemical vapor deposition work
Skill prepares the graphene film of dense distribution, effective integration carbon nano-tube film good conductivity, flexibility in carbon nano-tube film substrate
Foldable, surface irregularity and the advantage such as graphene film field emission stability is good, so as to provide a kind of low-work voltage, great Chang
Emission, high field emission stability, flexible filed emission cathode material.
To achieve the above object the invention discloses following technology contents：
A kind of graphene sheet-carbon nanotube film flexible composite, it is to be by depositing the edge number of plies on carbon nano-tube film
1-10 layers of graphene film composition；The distribution density of deposited graphite alkene piece is 8-12 pieces/square micron wherein on carbon nano-tube film,
Graphene film width is 0.5-1.2 microns.
The present invention further discloses the preparation method of graphene sheet-carbon nanotube film flexible composite, its feature exists
Carried out in as follows：
（1）Commercially available carbon nano-tube film is put into the graphite sample platform of microwave plasma enhanced chemical vapor deposition unit
On, it is passed through 15sccm high-purity hydrogens（5N）, regulation air pressure is 1.5kPa, and the sample stage to being loaded with carbon nano-tube film is heated to temperature
600 DEG C are stabilized to, carbon nano-tube film is heat-treated 30 minutes；
（2）In step（1）On the basis of, lifting sample stage temperature adjusts air pressure for 1kPa to stabilizing to 750 DEG C；
（3）In step（2）On the basis of start microwave source, regulation microwave power is 200-300W, and it is high to be passed through 1-3sccm
Pure acetylene gas（5N）, rapid regulation reative cell air pressure is 1kPa, starts the deposition of graphene film, and sedimentation time is 2 hours, deposition
The distribution density of graphene film is 8-12 pieces/square micron, and graphene film width is 0.5-1.2 microns.Prepare graphene film
Method can be microwave plasma enhanced chemical vapor deposition, or radio frequency sputtering deposition, radio frequency plasma enhancing
The methods such as chemical vapor deposition.
The present invention further discloses graphene sheet-carbon nanotube film flexible composite for preparing vacuum field electricity
Application in terms of sub- ballistic device, experimental result shows：
（1）The threshold electric field of the graphene sheet-carbon nanotube film flexible composite prepared by the present invention only has 1.78-
3.38 V/μm；
（2）The maximum field emission of the graphene sheet-carbon nanotube film flexible composite prepared by the present invention
Up to 7.10 mA/cm2；
（3）Graphene sheet-carbon nanotube film flexible composite prepared by the present invention is in mean field emission
Up to 3.62 mA/cm2, correspondence electric field strength show good field emission stability when being only 2.30 V/ μm：
20 hours internal field emission current densities are without being decreased obviously, current fluctuation is less than 3%.
Graphene sheet-carbon nanotube film flexible composite disclosed by the invention and preparation method and application and prior art
It is compared to the good effect having：
Carbon nano-tube film has excellent electric conductivity, is conducive to electronics to be flowed in graphene film from carbon nano-tube film；Carbon is received
The characteristics of mitron film has flexible so that prepared filed emission cathode material has the advantage of flexible foldable；With silicon chip, gold
The planar structure substrates such as category piece are compared, and carbon nano-tube film surface irregularity can effectively reduce Electric field shielding effect to Graphene
The influence of piece Flied emission, so as to reduce the operating voltage of graphene sheet-carbon nanotube film flexible composite；The thickness of graphene film
Degree can be controlled by by experiment parameter, prepared with sharp edge（1-10 layers）Graphene film can promote approach electronic
Transmitting；The structural advantage of above carbon nano-tube film and graphene film causes prepared graphene sheet-carbon nanotube film flexibility field
Emitting cathode material has relatively low unlatching（1.78-3.38 V/μm）With larger Flied emission current density（7.10 mA/
cm2）, while also remaining the good field emission stability of grapheme material, these indexs are compared and prepared on planar silicon substrate
Graphene film have lifting.Additionally, microwave plasma enhanced chemical vapour deposition technique of the present invention, technique letter
It is single, and impurity will not be introduced into in prepared material, practical value is high.
Brief description of the drawings
Fig. 1 is the process flow diagram that the present invention prepares graphene sheet-carbon nanotube film flexible composite, its core
Step prepares graphene film for microwave plasma enhanced chemical vapour deposition technique on carbon nano-tube film；
Fig. 2 is the optics and scanning electron microscopic picture of carbon nano-tube film used by the present invention, including：
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 microwave plasma enhanced chemical vapor deposition unit reaction chamber used by the present invention；
The purity of acetylene gas used and hydrogen is 5N, substrate is heated with homemade graphite heater, with " mechanical pump+molecular pump "
Combination unit is vacuumized to reative cell；
Fig. 4 is the ESEM and transmission electron microscope of graphene sheet-carbon nanotube film flexible composite prepared by embodiment 1
Picture, including：
41. press the condition of embodiment 1（Microwave power：200W；Acetylene throughput：2sccm）Prepared graphene film-carbon is received
The low power ESEM top view of mitron film flexible composite；
42. press the condition of embodiment 1（Microwave power：200W；Acetylene throughput：2sccm）Prepared graphene film-carbon is received
The high power ESEM top view of mitron film flexible composite；
43. press the condition of embodiment 1（Microwave power：200W；Acetylene throughput：2sccm）Prepared graphene film-carbon is received
The low power transmission electron microscope picture of mitron film flexible composite；
44. press the condition of embodiment 1（Microwave power：200W；Acetylene throughput：2sccm）Prepared graphene film-carbon is received
The high power transmission electron microscope picture of mitron film flexible composite；
Fig. 5 show the structural representation of high vacuum Flied emission tester used by the present invention, for testing in each embodiment
The field emission performance of the graphene sheet-carbon nanotube film flexible composite of gained；The device is that Flied emission tests conventional equipment,
With prepared graphene sheet-carbon nanotube film flexible composite as negative electrode, correspondence anode is about 10 centimetres not for diameter
Rust steel plate, cathode and anode spacing remains 1 millimeter；During test, in the adjustable positive biases of plate-load 0-10kV, and by minus earth,
Test result is recorded automatically by computer；
Fig. 6 is the field emission performance figure of the graphene sheet-carbon nanotube film flexible composite for preparing at different conditions,
Variation relation of the Flied emission current density with electric field strength is characterized, in specifically including embodiment 1, embodiment 2, embodiment 3
Prepared graphene sheet-carbon nanotube film flexible composite and four classes such as graphene film of preparation on planar silicon substrate
The field emission performance of sample；
Fig. 7 is graphene sheet-carbon nanotube film flexible composite prepared by embodiment 1 in 20 hours, Flied emission
Current density is about field emission stability figure during the 1/2 of maximum field emission, is characterized in constant DC Electric Field
Under, Flied emission current density changes with time relation.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples, but the invention is not restricted to these realities
Apply example.Wherein used carbon nano-tube film, silicon single crystal flake, high-purity hydrogen, high purity acetylene gas, microwave plasma enhanced chemistry
Vapor phase growing apparatus, Flied emission tester etc. are commercially available.
The process flow diagram that the present invention prepares graphene sheet-carbon nanotube film flexible composite is shown in Fig. 1,
Its core procedure prepares graphene film for microwave plasma enhanced chemical vapour deposition technique on carbon nano-tube film.
Present invention carbon nano-tube film used is shown in Fig. 2（It is commercially available）Optics picture and scanning electron microscopic picture；Wherein
In Fig. 2 the 21 optics pictures for showing carbon nano-tube film, it can be seen that carbon nano-tube film is that flexibility can free bend；Fig. 2
In the 22 low power ESEM top views for showing carbon nano-tube film, it can be seen that CNT is densely distributed, surface impurity
Few, film surface is presented rough state due to CNT skewness.
Embodiment 1
（1）Heat treated carbon nanotube films in atmosphere of hydrogen：
Carbon nano-tube film is cut into blade microwave plasma enhanced chemical vapor deposition is placed on after 1cm × 1cm small pieces
Product device（It is commercially available）Graphite sample platform on, the structural representation of the device reaction room is shown in Fig. 3；Startup vacuumizes and is
System, about 1.0 × 10 are evacuated to by reative cell vacuum-315sccm hydrogen is passed through after Pa（Purity is 5N）, air pressure adjustment is 1.5kPa, is used
Self-control graphite heater specimen heating holder to temperature stabilization is 600 DEG C, is persistently processed 30 minutes, for removing carbon nano-tube film table
The adsorbate and pollutant in face.
（2）Microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece：
In atmosphere of hydrogen after heat treated carbon nanotube films, 750 DEG C are and then warming up to substrate, regulation air pressure is 1kPa,
After temperature and air pressure are stablized, start microwave source, microwave power set is 200W, and the acetylene gas of 2sccm is passed through immediately（Purity
It is 5N）, and regulation air pressure to 1kPa is stabilized to, that is, starts the growth of graphene film rapidly, growth time is 2 hours；In Fig. 4
The low power of graphene sheet-carbon nanotube film flexible composite prepared in 42 shown respectively the present embodiment in 41 and Fig. 4
With high power ESEM top view, it can be seen that graphene film is about 10 in carbon nano tube surface dense distribution, distribution density
Piece/square micron, graphene film width is 0.7-1.1 microns, and the rough surface of carbon nano-tube film causes gained composite wood
The surface of material is also uneven；43 show prepared graphene sheet-carbon nanotube film flexible compound in the present embodiment in Fig. 4
The low power transmission electron microscope picture of material, it can be seen that graphene film dense distribution on CNT, the underlapped portion of graphene film
Divide almost transparent state, show that the lamellar spacing of prepared graphene film is small, the thickness of graphene film can further from Fig. 4
Find out in high power transmission electron microscope picture shown in 44, the edge of shown graphene film only has 3-4 layers.Gained graphite in the present embodiment
The number of plies of alkene piece is layer 1-7.
（5）Field emission performance is tested：
High vacuum Flied emission tester（It is commercially available）It is used in testing for the graphene film-CNT prepared by the present embodiment
The field emission performance of film flexible composite, is the structural representation of the device shown in Fig. 5, the device is conventional Flied emission
Performance testing device.Test house vacuum maintains about 1 × 10 by titanium getter pump-7Pa.By the graphite prepared by the present embodiment
Alkene piece-carbon nano-tube film flexible composite conduction is adhesive on copper sample platform as negative electrode, and 10 centimetres are about with a diameter
Stainless steel plate as anode, cathode and anode spacing is 1 millimeter；During test, the adjustable positive biases of 0-10kV are supported on anode,
And it is biased to constant speed（500 V/min）Increase, and grounded cathode, test result are recorded automatically by computer.Shown in Fig. 6 i.e.
It is the field emission performance figure of different-shape graphene film sample, characterizes Flied emission current density and closed with the change of electric field strength
System, specifically include prepared graphene sheet-carbon nanotube film flexible composite in embodiment 1, embodiment 2, embodiment 3 with
And the field emission performance of the four class samples such as graphene film prepared on planar silicon substrate.As can be seen that made in the present embodiment
The unlatching of standby graphene sheet-carbon nanotube film flexible composite and maximum field emission are respectively 1.78 V/ μ
M and 7.10 mA/cm2, to be far superior to 4.29 V/ μm and 1.67 mA/cm of prepared graphene film on silicon single crystal flake2.Field hair
The reason for penetrating performance enhancement mainly carbon nano-tube film has more preferable electric conductivity compared to silicon single crystal flake, and surface irregularity drops
The low influence of Electric field shielding effect.Fig. 7 show prepared graphene sheet-carbon nanotube film flexible compound in the present embodiment
When material is in 20 hours, Flied emission current density is about the 1/2 of maximum field emission（Mean field emission
It is 3.62 mA/cm2）Field emission stability figure, be characterized under constant DC Electric Field, Flied emission current density is with the time
Variation relation.As can be seen that Flied emission current density was changed very little in 20 hours, it is not decreased obviously, fluctuation is less than 3%,
And also only 2.30 V/ μm of applied electric field, these results have all shown good application prospect.
（6）Field emission device is assembled（Conventional sectional method）：
It is 2 millimeters that prepared graphene sheet-carbon nanotube film flexible composite conducting resinl is sticked into thickness
As negative electrode on copper electrode, anode is the copper coin that a thickness is about 2 millimeters, and two interpolars are gathered by the ring-type that thickness is 200 microns
Tetrafluoroethene film is isolated；During Flied emission, in plate-load positive bias, minus earth, you can obtain the field of stabilization
Electron emission, Flied emission size of current can be controlled by adjusting anodic bias.
Embodiment 2
（1）Heat treated carbon nanotube films in atmosphere of hydrogen：
Carbon nano-tube film is cut into blade microwave plasma enhanced chemical vapor deposition is placed on after 1cm × 1cm small pieces
Product device（It is commercially available）Graphite sample platform on, the structural representation of the device reaction room is shown in Fig. 3；Startup vacuumizes and is
System, about 1.0 × 10 are evacuated to by reative cell vacuum-315sccm hydrogen is passed through after Pa（Purity is 5N）, air pressure adjustment is 1.5kPa, is used
Self-control graphite heater specimen heating holder to temperature stabilization is 600 DEG C, is persistently processed 30 minutes, for removing carbon nano-tube film table
The adsorbate and pollutant in face.
（2）Microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece：
In atmosphere of hydrogen after heat treated carbon nanotube films, 750 DEG C are and then warming up to substrate, regulation air pressure is 1kPa,
After temperature and air pressure are stablized, start microwave source, microwave power set is 200W, and the acetylene gas of 1sccm is passed through immediately（Purity
It is 5N）, and regulation air pressure to 1kPa is stabilized to, that is, starts the growth of graphene film rapidly, growth time is 2 hours.Gained stone
The distribution density of black alkene piece is about 8/square micron, width for 0.6-0.9 microns, the number of plies are 1-6 layers.
（5）Field emission performance is tested：
High vacuum Flied emission tester（It is commercially available）It is used in testing for the graphene film-CNT prepared by the present embodiment
The field emission performance of film flexible composite, is the structural representation of the device shown in Fig. 5, the device is conventional Flied emission
Performance testing device.Test house vacuum maintains about 1 × 10 by titanium getter pump-7Pa.By the graphite prepared by the present embodiment
Alkene piece-carbon nano-tube film flexible composite conduction is adhesive on copper sample platform as negative electrode, and 10 centimetres are about with a diameter
Stainless steel plate as anode, cathode and anode spacing is 1 millimeter；During test, the adjustable positive biases of 0-10kV are supported on anode,
And it is biased to constant speed（500 V/min）Increase, and grounded cathode, test result are recorded automatically by computer.Can be with from Fig. 6
Find out, the unlatching of graphene sheet-carbon nanotube film flexible composite prepared in the present embodiment is electric with maximum Flied emission
Current density is respectively 2.80 V/ μm and 4.16 mA/cm2, to be far superior to 4.29 of prepared graphene film on silicon single crystal flake
V/ μm and 1.67 mA/cm2.The reason for field emission performance strengthens mainly carbon nano-tube film has more preferable compared to silicon single crystal flake
Electric conductivity, and surface irregularity reduces the influence of Electric field shielding effect.
（6）Field emission device is assembled（Conventional sectional method）：
It is 2 millimeters that prepared graphene sheet-carbon nanotube film flexible composite conducting resinl is sticked into thickness
As negative electrode on copper electrode, anode is the copper coin that a thickness is about 2 millimeters, and two interpolars are gathered by the ring-type that thickness is 200 microns
Tetrafluoroethene film is isolated；During Flied emission, in plate-load positive bias, minus earth, you can obtain the field of stabilization
Electron emission, Flied emission size of current can be controlled by adjusting anodic bias.
Embodiment 3
（1）Heat treated carbon nanotube films in atmosphere of hydrogen：
Carbon nano-tube film is cut into blade microwave plasma enhanced chemical vapor deposition is placed on after 1cm × 1cm small pieces
Product device（It is commercially available）Graphite sample platform on, the structural representation of the device reaction room is shown in Fig. 3；Startup vacuumizes and is
System, about 1.0 × 10 are evacuated to by reative cell vacuum-315sccm hydrogen is passed through after Pa（Purity is 5N）, air pressure adjustment is 1.5kPa, is used
Self-control graphite heater specimen heating holder to temperature stabilization is 600 DEG C, is persistently processed 30 minutes, for removing carbon nano-tube film table
The adsorbate and pollutant in face.
（2）Microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece：
In atmosphere of hydrogen after heat treated carbon nanotube films, 750 DEG C are and then warming up to substrate, regulation air pressure is 1kPa,
After temperature and air pressure are stablized, start microwave source, microwave power set is 200W, and the acetylene gas of 3sccm is passed through immediately（Purity
It is 5N）, and regulation air pressure to 1kPa is stabilized to, that is, starts the growth of graphene film rapidly, growth time is 2 hours.Gained stone
The distribution density of black alkene piece is about 12/square micron, width for 0.9-1.2 microns, the number of plies are 1-10 layers.
（5）Field emission performance is tested：
High vacuum Flied emission tester（It is commercially available）It is used in testing for the graphene film-CNT prepared by the present embodiment
The field emission performance of film flexible composite, is the structural representation of the device shown in Fig. 5, the device is conventional Flied emission
Performance testing device.Test house vacuum maintains about 1 × 10 by titanium getter pump-7Pa.By the graphite prepared by the present embodiment
Alkene piece-carbon nano-tube film flexible composite conduction is adhesive on copper sample platform as negative electrode, and 10 centimetres are about with a diameter
Stainless steel plate as anode, cathode and anode spacing is 1 millimeter；During test, the adjustable positive biases of 0-10kV are supported on anode,
And it is biased to constant speed（500 V/min）Increase, and grounded cathode, test result are recorded automatically by computer.Can be with from Fig. 6
Find out, the unlatching of graphene sheet-carbon nanotube film flexible composite prepared in the present embodiment is electric with maximum Flied emission
Current density is respectively 2.33 V/ μm and 6.99 mA/cm2, to be far superior to 4.29 of prepared graphene film on silicon single crystal flake
V/ μm and 1.67 mA/cm2.The reason for field emission performance strengthens mainly carbon nano-tube film has more preferable compared to silicon single crystal flake
Electric conductivity, and surface irregularity reduces the influence of Electric field shielding effect.
（6）Field emission device is assembled（Conventional sectional method）：
It is 2 millimeters that prepared graphene sheet-carbon nanotube film flexible composite conducting resinl is sticked into thickness
As negative electrode on copper electrode, anode is the copper coin that a thickness is about 2 millimeters, and two interpolars are gathered by the ring-type that thickness is 200 microns
Tetrafluoroethene film is isolated；During Flied emission, in plate-load positive bias, minus earth, you can obtain the field of stabilization
Electron emission, Flied emission size of current can be controlled by adjusting anodic bias.
Embodiment 4
（1）Heat treated carbon nanotube films in atmosphere of hydrogen：
Carbon nano-tube film is cut into blade microwave plasma enhanced chemical vapor deposition is placed on after 1cm × 1cm small pieces
Product device（It is commercially available）Graphite sample platform on, the structural representation of the device reaction room is shown in Fig. 3；Startup vacuumizes and is
System, about 1.0 × 10 are evacuated to by reative cell vacuum-315sccm hydrogen is passed through after Pa（Purity is 5N）, air pressure adjustment is 1.5kPa, is used
Self-control graphite heater specimen heating holder to temperature stabilization is 600 DEG C, is persistently processed 30 minutes, for removing carbon nano-tube film table
The adsorbate and pollutant in face.
（2）Microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece：
In atmosphere of hydrogen after heat treated carbon nanotube films, 750 DEG C are and then warming up to substrate, regulation air pressure is 1kPa,
After temperature and air pressure are stablized, start microwave source, microwave power set is 250W, and the acetylene gas of 1sccm is passed through immediately（Purity
It is 5N）, and regulation air pressure to 1kPa is stabilized to, that is, starts the growth of graphene film rapidly, growth time is 2 hours.Gained stone
The distribution density of black alkene piece is about 8/square micron, width for 0.5-0.9 microns, the number of plies are 1-5 layers.
（5）Field emission performance is tested：
High vacuum Flied emission tester（It is commercially available）It is used in testing for the graphene film-CNT prepared by the present embodiment
The field emission performance of film flexible composite, is the structural representation of the device shown in Fig. 5, the device is conventional Flied emission
Performance testing device.Test house vacuum maintains about 1 × 10 by titanium getter pump-7Pa.By the graphite prepared by the present embodiment
Alkene piece-carbon nano-tube film flexible composite conduction is adhesive on copper sample platform as negative electrode, and 10 centimetres are about with a diameter
Stainless steel plate as anode, cathode and anode spacing is 1 millimeter；During test, the adjustable positive biases of 0-10kV are supported on anode,
And it is biased to constant speed（500 V/min）Increase, and grounded cathode, test result are recorded automatically by computer.The present embodiment
In prepared graphene sheet-carbon nanotube film flexible composite unlatching and maximum field emission be respectively
3.38 V/ μm and 3.35 mA/cm2, to be far superior to 4.29 V/ μm and 1.67 of prepared graphene film on silicon single crystal flake
mA/cm2.The reason for field emission performance strengthens mainly carbon nano-tube film has more preferable electric conductivity, and table compared to silicon single crystal flake
The uneven influence for reducing Electric field shielding effect in face.
（6）Field emission device is assembled（Conventional sectional method）：
It is 2 millimeters that prepared graphene sheet-carbon nanotube film flexible composite conducting resinl is sticked into thickness
As negative electrode on copper electrode, anode is the copper coin that a thickness is about 2 millimeters, and two interpolars are gathered by the ring-type that thickness is 200 microns
Tetrafluoroethene film is isolated；During Flied emission, in plate-load positive bias, minus earth, you can obtain the field of stabilization
Electron emission, Flied emission size of current can be controlled by adjusting anodic bias.
Embodiment 5
（1）Heat treated carbon nanotube films in atmosphere of hydrogen：
Carbon nano-tube film is cut into blade microwave plasma enhanced chemical vapor deposition is placed on after 1cm × 1cm small pieces
Product device（It is commercially available）Graphite sample platform on, the structural representation of the device reaction room is shown in Fig. 3；Startup vacuumizes and is
System, about 1.0 × 10 are evacuated to by reative cell vacuum-315sccm hydrogen is passed through after Pa（Purity is 5N）, air pressure adjustment is 1.5kPa, is used
Self-control graphite heater specimen heating holder to temperature stabilization is 600 DEG C, is persistently processed 30 minutes, for removing carbon nano-tube film table
The adsorbate and pollutant in face.
（2）Microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece：
In atmosphere of hydrogen after heat treated carbon nanotube films, 750 DEG C are and then warming up to substrate, regulation air pressure is 1kPa,
After temperature and air pressure are stablized, start microwave source, microwave power set is 250W, and the acetylene gas of 3sccm is passed through immediately（Purity
It is 5N）, and regulation air pressure to 1kPa is stabilized to, that is, starts the growth of graphene film rapidly, growth time is 2 hours.Gained stone
The distribution density of black alkene piece is about 11/square micron, width for 0.8-1.1 microns, the number of plies are 1-8 layers.
（5）Field emission performance is tested：
High vacuum Flied emission tester（It is commercially available）It is used in testing for the graphene film-CNT prepared by the present embodiment
The field emission performance of film flexible composite, is the structural representation of the device shown in Fig. 5, the device is conventional Flied emission
Performance testing device.Test house vacuum maintains about 1 × 10 by titanium getter pump-7Pa.By the graphite prepared by the present embodiment
Alkene piece-carbon nano-tube film flexible composite conduction is adhesive on copper sample platform as negative electrode, and 10 centimetres are about with a diameter
Stainless steel plate as anode, cathode and anode spacing is 1 millimeter；During test, the adjustable positive biases of 0-10kV are supported on anode,
And it is biased to constant speed（500 V/min）Increase, and grounded cathode, test result are recorded automatically by computer.The present embodiment
In prepared graphene sheet-carbon nanotube film flexible composite unlatching and maximum field emission be respectively
2.00 V/ μm and 6.16 mA/cm2, to be far superior to 4.29 V/ μm and 1.67 of prepared graphene film on silicon single crystal flake
mA/cm2.The reason for field emission performance strengthens mainly carbon nano-tube film has more preferable electric conductivity, and table compared to silicon single crystal flake
The uneven influence for reducing Electric field shielding effect in face.
（6）Field emission device is assembled（Conventional sectional method）：
It is 2 millimeters that prepared graphene sheet-carbon nanotube film flexible composite conducting resinl is sticked into thickness
As negative electrode on copper electrode, anode is the copper coin that a thickness is about 2 millimeters, and two interpolars are gathered by the ring-type that thickness is 200 microns
Tetrafluoroethene film is isolated；During Flied emission, in plate-load positive bias, minus earth, you can obtain the field of stabilization
Electron emission, Flied emission size of current can be controlled by adjusting anodic bias.
Embodiment 6
（1）Heat treated carbon nanotube films in atmosphere of hydrogen：
Carbon nano-tube film is cut into blade microwave plasma enhanced chemical vapor deposition is placed on after 1cm × 1cm small pieces
Product device（It is commercially available）Graphite sample platform on, the structural representation of the device reaction room is shown in Fig. 3；Startup vacuumizes and is
System, about 1.0 × 10 are evacuated to by reative cell vacuum-315sccm hydrogen is passed through after Pa（Purity is 5N）, air pressure adjustment is 1.5kPa, is used
Self-control graphite heater specimen heating holder to temperature stabilization is 600 DEG C, is persistently processed 30 minutes, for removing carbon nano-tube film table
The adsorbate and pollutant in face.
（2）Microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece：
In atmosphere of hydrogen after heat treated carbon nanotube films, 750 DEG C are and then warming up to substrate, regulation air pressure is 1kPa,
After temperature and air pressure are stablized, start microwave source, microwave power set is 300W, and the acetylene gas of 2sccm is passed through immediately（Purity
It is 5N）, and regulation air pressure to 1kPa is stabilized to, that is, starts the growth of graphene film rapidly, growth time is 2 hours.Gained stone
The distribution density of black alkene piece is about 10/square micron, width for 0.6-1.0 microns, the number of plies are layer 1-7.
（5）Field emission performance is tested：
High vacuum Flied emission tester（It is commercially available）It is used in testing for the graphene film-CNT prepared by the present embodiment
The field emission performance of film flexible composite, is the structural representation of the device shown in Fig. 5, the device is conventional Flied emission
Performance testing device.Test house vacuum maintains about 1 × 10 by titanium getter pump-7Pa.By the graphite prepared by the present embodiment
Alkene piece-carbon nano-tube film flexible composite conduction is adhesive on copper sample platform as negative electrode, and 10 centimetres are about with a diameter
Stainless steel plate as anode, cathode and anode spacing is 1 millimeter；During test, the adjustable positive biases of 0-10kV are supported on anode,
And it is biased to constant speed（500 V/min）Increase, and grounded cathode, test result are recorded automatically by computer.The present embodiment
In prepared graphene sheet-carbon nanotube film flexible composite unlatching and maximum field emission be respectively
2.97 V/ μm and 3.74 mA/cm2, to be far superior to 4.29 V/ μm and 1.67 of prepared graphene film on silicon single crystal flake
mA/cm2.The reason for field emission performance strengthens mainly carbon nano-tube film has more preferable electric conductivity, and table compared to silicon single crystal flake
The uneven influence for reducing Electric field shielding effect in face.
（6）Field emission device is assembled（Conventional sectional method）：
It is 2 millimeters that prepared graphene sheet-carbon nanotube film flexible composite conducting resinl is sticked into thickness
As negative electrode on copper electrode, anode is the copper coin that a thickness is about 2 millimeters, and two interpolars are gathered by the ring-type that thickness is 200 microns
Tetrafluoroethene film is isolated；During Flied emission, in plate-load positive bias, minus earth, you can obtain the field of stabilization
Electron emission, Flied emission size of current can be controlled by adjusting anodic bias.
Embodiment 7
（1）Heat treated carbon nanotube films in atmosphere of hydrogen：
Carbon nano-tube film is cut into blade microwave plasma enhanced chemical vapor deposition is placed on after 1cm × 1cm small pieces
Product device（It is commercially available）Graphite sample platform on, the structural representation of the device reaction room is shown in Fig. 3；Startup vacuumizes and is
System, about 1.0 × 10 are evacuated to by reative cell vacuum-315sccm hydrogen is passed through after Pa（Purity is 5N）, air pressure adjustment is 1.5kPa, is used
Self-control graphite heater specimen heating holder to temperature stabilization is 600 DEG C, is persistently processed 30 minutes, for removing carbon nano-tube film table
The adsorbate and pollutant in face.
（2）Microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece：
In atmosphere of hydrogen after heat treated carbon nanotube films, 750 DEG C are and then warming up to substrate, regulation air pressure is 1kPa,
After temperature and air pressure are stablized, start microwave source, microwave power set is 300W, and the acetylene gas of 3sccm is passed through immediately（Purity
It is 5N）, and regulation air pressure to 1kPa is stabilized to, that is, starts the growth of graphene film rapidly, growth time is 2 hours.Gained stone
The distribution density of black alkene piece is about 9/square micron, width for 0.7-1.0 microns, the number of plies are 1-8 layers.
（5）Field emission performance is tested：
High vacuum Flied emission tester（It is commercially available）It is used in testing for the graphene film-CNT prepared by the present embodiment
The field emission performance of film flexible composite, is the structural representation of the device shown in Fig. 5, the device is conventional Flied emission
Performance testing device.Test house vacuum maintains about 1 × 10 by titanium getter pump-7Pa.By the graphite prepared by the present embodiment
Alkene piece-carbon nano-tube film flexible composite conduction is adhesive on copper sample platform as negative electrode, and 10 centimetres are about with a diameter
Stainless steel plate as anode, cathode and anode spacing is 1 millimeter；During test, the adjustable positive biases of 0-10kV are supported on anode,
And it is biased to constant speed（500 V/min）Increase, and grounded cathode, test result are recorded automatically by computer.The present embodiment
In prepared graphene sheet-carbon nanotube film flexible composite unlatching and maximum field emission be respectively
2.27 V/ μm and 5.65 mA/cm2, to be far superior to 4.29 V/ μm and 1.67 of prepared graphene film on silicon single crystal flake
mA/cm2.The reason for field emission performance strengthens mainly carbon nano-tube film has more preferable electric conductivity, and table compared to silicon single crystal flake
The uneven influence for reducing Electric field shielding effect in face.
（6）Field emission device is assembled（Conventional sectional method）：
It is 2 millimeters that prepared graphene sheet-carbon nanotube film flexible composite conducting resinl is sticked into thickness
As negative electrode on copper electrode, anode is the copper coin that a thickness is about 2 millimeters, and two interpolars are gathered by the ring-type that thickness is 200 microns
Tetrafluoroethene film is isolated；During Flied emission, in plate-load positive bias, minus earth, you can obtain the field of stabilization
Electron emission, Flied emission size of current can be controlled by adjusting anodic bias.
It is last it should be noted that, the above only lists exemplary embodiments of the invention.It is apparent that the present invention is not limited to
State embodiment, also many other experiment parameter combined methods, the those of ordinary skill in this research field can be from the present invention
The relevant situation for directly being derived in disclosure or being associated, is considered to be protection scope of the present invention.
Claims (1)
1. a kind of preparation method of graphene sheet-carbon nanotube film flexible composite, it is characterised in that carry out as follows：
（1）Heat treated carbon nanotube films in atmosphere of hydrogen：Carbon nano-tube film is cut into microwave etc. is placed on after 1cm × 1cm small pieces
On the graphite sample platform of gas ions enhancing chemical vapor deposition unit, reative cell vacuum is evacuated to 1.0 × 10-3It is passed through after Pa
15sccm hydrogen, purity is 5N, and air pressure adjustment is 1.5kPa, is with self-control graphite heater specimen heating holder to temperature stabilization
600 DEG C, persistently process 30 minutes；
（2）Microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece：In step（1）On the basis of, to substrate liter
To 750 DEG C, regulation air pressure is 1kPa to temperature, after temperature and air pressure are stablized, starts microwave source, and microwave power set is 200W,
The acetylene gas of 2sccm is passed through immediately, and purity is 5N, and regulation air pressure to 1kPa is stabilized to, that is, starts the life of graphene film rapidly
Long, growth time is 2 hours, and final gained is graphene sheet-carbon nanotube film flexible composite, and as field hair
Penetrate cathode material assembling flexible field electron emission device；
Prepared graphene sheet-carbon nanotube film flexible composite is 1-10 layers by depositing the edge number of plies on carbon nano-tube film
Graphene film composition；The distribution density of deposited graphite alkene piece is 8-12 pieces/square micron, Graphene wherein on carbon nano-tube film
Piece width is 0.5-1.2 microns.
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| CN106847648B (en) * | 2017-03-01 | 2019-01-08 | 杭州电子科技大学 | A kind of preparation method of use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material |
| CN107146889B (en) * | 2017-04-24 | 2019-06-28 | 西北工业大学 | A kind of graphene/CNTs hybrid does lithium metal battery collector and preparation method thereof |
| CN107416808B (en) * | 2017-08-23 | 2020-01-17 | 中山大学 | Preparation method of graphene-carbon nanotube nano composite structure |
| CN108987217B (en) * | 2018-01-31 | 2019-12-31 | 天津师范大学 | Method for improving field emission performance of graphene sheet-carbon nanotube film flexible composite material |
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