CN108987215A - A method of promoting graphene film-carbon nano-tube array composite material field emission performance - Google Patents
A method of promoting graphene film-carbon nano-tube array composite material field emission performance Download PDFInfo
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- CN108987215A CN108987215A CN201810096763.9A CN201810096763A CN108987215A CN 108987215 A CN108987215 A CN 108987215A CN 201810096763 A CN201810096763 A CN 201810096763A CN 108987215 A CN108987215 A CN 108987215A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/30—Cold cathodes, e.g. field-emissive cathode
- H01J1/304—Field-emissive cathodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
Abstract
The invention discloses a kind of promotion graphene film-carbon nano-tube array composite material field emission performance methods, belong to the preparation and application field of nano material.Including following preparation process: (1) utilizing silver ion bombardment pretreatment silicon single crystal flake；(2) carbon nano pipe array is prepared using thermal chemical vapor deposition method and the high temperature anneal is carried out to it；(3) thin graphene piece is prepared on carbon nano pipe array using microwave plasma enhanced chemical vapour deposition technique；(4) nitrogen, hydrogen plasma process are carried out at room temperature to gained graphene film-carbon nano pipe array.Compared with prior art, the piece of nitrogen-doped graphene prepared by this method-carbon nano-tube array composite material has good field emission stability with extremely low applied electric field, high current density and under high current density, there is very high application value.
Description
Technical field
The invention belongs to the preparation and application technical fields of nano material, and in particular to a kind of to utilize corona treatment system
Standby nitrogen-doped graphene piece-carbon nano-tube array composite material and the method for promoting field emission performance.
Background technique
Flied emission refers to that cathode material internal electron is reinforced under electric field action outside, escapes into vacuum from material surface
Process, excellent field emission performance generally requires cathode with lower applied electric field and biggish current density and good
Stability.Carbon nanotube becomes as a kind of quasi-one-dimensional nanometer material, great draw ratio and excellent electric conductivity
A kind of ideal filed emission cathode material, in vacuum fields such as New-generation vacuum pipe, X-ray tube, field-emission plane displays
Electronic device preparation aspect has shown good application prospect.But simple carbon nanotube is when as field-transmitting cathode, past
Lead to its maximum field emission current toward because of the characteristics of contacting not good enough (contact surface is small) with substrate and easily being burnt by Joule heat
Density is less than 10mA/cm2, this just greatly limits its application.In addition, threshold field (the field of carbon nanotube base field-transmitting cathode
Emission reaches 10mA/cm2When corresponding electric field strength) be generally higher than 2.0 V/ μm, in practical application
In be equivalent to spacing be 1 millimeter yin-yang interpolar apply 2000V high pressure, it is contemplated that yin-yang interpolar also need keep height it is true
Sky, this is technically undoubtedly than device relatively difficult to achieve.After the processing such as ion irradiation, doping, chemical modification
The threshold field of carbon nanotube base field-transmitting cathode is also difficult to be higher than 10mA/ in current density generally also above 1.5V/ μm
cm2The field-electron emission of Shi Shixian long-time stable, this just proposes reduction applied electric field and promotion Flied emission current density
It is required that.Due to carbon nanotube base field-transmitting cathode maximum field emission and pipe base junction resultant force and be applied to carbon nanotube
On electrostatic field intensity have relationship, we can close and reduce applied electric field the two aspects from reinforced pipe base junction and start with
Promote the field emission performance of material.Wherein, carbon nanotube and other low-dimension nano materials are carried out compound being to promote its Flied emission
One quantum jump mouth of performance, wherein compound with this quasi- two-dimension nano materials of graphene film with good field emission stability
It is the emphasis of research.This one-dimensional/Two-dimensional Composites can have both the big L/D ratio and two-dimentional stone of one-dimensional carbon nanotube simultaneously
The good field emission stability of black alkene piece, so that the field emission performance of gained composite material is increased dramatically.In the prior art
In, graphene film-carbon nano tube compound material maximum field emission is up to 49.60mA/cm2, threshold field can be down to
1.51V/ μm, and there is good field emission stability, these indexs have compared with original carbon nanotubes significantly to be promoted.
But undeniably, graphene film-carbon nano tube compound material field emission performance is still not excellent enough.Firstly, its maximum field is sent out
Still there are also huge rooms for promotion for radio current density, can just better meet high current density field-electron emission device system in this way
Standby demand, such as the preparation of high current density field emission lamp；Secondly, realizing steady operation under big Flied emission current density
Target is not also reached still, this is just promoted to further using graphene film-carbon nano tube compound material as the Flied emission of base yin
The performance of pole is put forward new requirements.
Summary of the invention
It is an object of the invention to overcome existing arrange with graphene film-carbon nano-pipe array to work for the field-transmitting cathode of base
Electric field is relatively high, Flied emission current density is smaller, high current density Flied emission when the bad deficiency of stability, pass through silver ion
Bombardment processing introduces transition zone to reinforce the binding force between carbon nanotube and silicon single crystal flake, at microwave nitrogen, hydrogen plasma
Reason, obtains that work function is low, nitrogen-doped graphene piece-carbon nano-tube array composite material more than Flied emission point number, and finally obtains
It a kind of must have both low applied electric field, big Flied emission current density and under high current density with the field of good field emission stability
Emitting cathode composite material.
The purpose of the present invention is what is reached by following measure:
First with energy silver ion bombardment pretreatment silicon single crystal flake is carried, carbon nanometer then is prepared using thermal chemical vapor deposition method
Pipe array simultaneously carries out the high temperature anneal, and microwave plasma enhanced chemical vapour deposition technique is recycled to prepare thin graphene
Piece, it is micro- by adjusting finally at normal temperature using graphene film-carbon nano pipe array obtained by microwave nitrogen, hydrogen plasma process
Wave power is 100~140W, chamber pressure 1.5kPa, processing time are 0.5~2 hour to control its pattern, is finally obtained
Obtain nitrogen-doped graphene piece-carbon nano-tube array composite material；Nitrogen-doped graphene piece-carbon nano pipe array the composite wood
By on carbon nano pipe array, the deposition edge number of plies is 1-5 layers to material, the graphene film of rich defect, N doping forms；Prepared
Nitrogen-doped graphene piece-carbon nano-tube array composite material threshold field averagely only has 1.09-1.21V/ μm, maximum Flied emission electricity
Current density is average up to 101.79-120.56mA/cm2, 45.46mA/cm is up in mean field emission2, 20 hours
Interior current attenuation only has 3.86%.
It is further open to promote graphene film-carbon nano-tube array composite material field emission performance in above-mentioned technical proposal
Specific step is as follows for method:
Step (1) pre-processes silicon single crystal flake: silicon single crystal flake is first cut into 2cm × 2cm small pieces, then successively in deionized water and
Each ultrasound (50W) is cleaned 5 minutes in dehydrated alcohol, and then the silicon single crystal flake is immersed in 5 in the hydrofluoric acid that volume ratio is 4%
Minute, it takes out dry later, then by the silicon single crystal flake of obtained clean surface in metal vapor vacuum arc source
Carry out carrying in (source MEVVA) can silver ion bombardment pretreatment, when bombardment, sample stage is kept at the uniform velocity to rotate, sample stage biased voltage setting
For -15kV, line is 10 milliamperes, and bombardment time is 10 minutes；
Step (2) thermal chemical vapor deposition method prepares carbon nano pipe array and the high temperature anneal: step (1) is obtained
Silicon single crystal flake is placed in the iron catalyst film that deposition thickness is 5 nanometers in magnetic control sputtering device, is then placed in the silicon single crystal flake high
Carbon nano pipe array is prepared with conventional thermal chemical vapor deposition method in warm quartz tube furnace, when growing carbon nanotube, will first be sunk
Product there is the silicon single crystal flake of iron catalyst to be heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after 150sccm ammonia,
It is handled under 750 degrees Celsius 10 minutes, carbon nanometer is finally grown under 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure
Pipe array, growth time are 30 minutes, increase the temperature to 1000 degrees Celsius later, life is handled under 400sccm hydrogen, normal pressure
At carbon nanotube, processing the time be 2 hours；
Step (3) microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece: the carbon that step (2) obtains is received
Mitron array is placed on the graphite sample platform in microwave plasma system, and reaction chamber vacuum is evacuated to 1.0 × 10-3Lead to after Pa
Enter 10sccm hydrogen, air pressure adjusting section is 1kPa, stabilizes to 800 degrees Celsius with heater specimen heating holder to temperature, starts microwave
Source, adjusting microwave power is 150W, and is passed through the acetylene gas of 3sccm, and adjusting air pressure again is 1kPa, that is, starts graphene film
Growth, growth time are 3 hours, finally obtain graphene film-carbon nano pipe array；
Step (4) nitrogen, hydrogen plasma process graphene film-carbon nano pipe array: on the basis of step (3),
Cooling sample carries out nitrogen, hydrogen plasma to gained graphene film-carbon nano pipe array to room temperature in 10sccm atmosphere of hydrogen
Processing, the mixed gas that the gas for generating plasma is made of nitrogen and hydrogen, nitrogen, hydrogen flow be respectively
5,10sccm, adjusting air pressure is 1.5kPa, after stable gas pressure, starts microwave source, adjusting microwave power is 100~140W, place
Managing the time is 0.5~2 hour to get nitrogen-doped graphene piece-carbon nano pipe array.
In above-mentioned technical proposal, various gas purities used are 5N.
Nitrogen-doped graphene piece-the carbon nano-tube array composite material obtained is by carbon nanometer using the above scheme
The pipe deposited over arrays edge number of plies is 1-5 layers, the graphene film of rich defect, N doping forms；Prepared nitrogen-doped graphene
Piece-carbon nano-tube array composite material threshold field averagely only has 1.09-1.21V/ μm, and maximum field emission averagely may be used
Up to 101.79-120.56mA/cm2, 45.46mA/cm is up in mean field emission2, current attenuation in 20 hours only
Have 3.86%.
It is disclosed by the invention to bombard to form transition zone and room temperature nitrogen, hydrogen plasma process for being promoted by silver ion
Graphene film-carbon nano-tube array composite material field emission performance method compared with prior art its be advantageous in that: (1)
Using energy silver ion bombardment pretreatment silicon base is carried, silver-silicon transition zone, this transition zone one side energy are formed on silicon single crystal flake
Enough promote the transmission of electronics, it on the other hand, can be by the way that silver be precipitated in having grown the high temperature anneal after carbon nanotube
Mode forms effective cladding to the root of carbon nanotube, the binding force between carbon nanotube and silicon wafer is promoted, to promote material
Maximum field emission；(2) by carrying out nitrogen to graphene film-carbon nano pipe array, hydrogen plasma irradiates, can be with
Play the role of reducing work function, the electronics in filed emission cathode material made to be easier tunneling barrier and escape into vacuum,
It is secondary to introduce a large amount of defects, efficient Flied emission point can be become in these defects emission process on the scene, the present invention is why
Handled using normal-temperature plasma rather than high-temperature process in the prior art, also for preferably retaining these defects.In short,
The enhancing of binding force, the reduction of work function and Flied emission points purpose increase are nitrogen-doped graphenes between carbon nanotube and silicon base
Piece-carbon nano pipe array has the key of excellent field emission performance, also where superiority exactly of the invention.Silver ion bombardment and
The introducing of N doping is so that present invention gained nitrogen-doped graphene piece-carbon nano-tube array composite material has extremely low unlatching field
(1.09V/ μm), high Flied emission current density (120.56mA/cm2) and splendid high current density Flied emission stabilization
Property (is up to 45.46mA/cm in mean field emission2, the current attenuation in 20 hours only have 3.86%), these indexs
Compared with prior art, have greatly improved.
Detailed description of the invention
Fig. 1 is that prepare nitrogen-doped graphene piece-carbon nano pipe array compound for silver ion bombardment and nitrogen, hydrogen plasma process
The method flow schematic diagram of material；
Fig. 2 is the structural schematic diagram of microwave plasma enhanced chemical gas-phase deposition system used in the present invention；
Fig. 3 is in embodiment 1 by silver ion bombardment and gained nitrogen-doped graphene piece-after nitrogen, hydrogen plasma process
The scanning electron microscope and high-resolution-ration transmission electric-lens picture of carbon nano pipe array, comprising:
A is nitrogen-doped graphene piece-carbon nano pipe array scanning electron microscope side view；
B is the high-resolution-ration transmission electric-lens picture of graphene film in nitrogen-doped graphene piece-carbon nano pipe array；
Fig. 4 is the structural schematic diagram of diode-type high vacuum Flied emission tester used in the present invention；
Fig. 5 is embodiment 1, gained nitrogen-doped graphene piece-carbon nano-tube array composite material and existing skill in embodiment 2
The field emission performance figure of sample in art 1, the prior art 2；
Fig. 6 be in embodiment 1 after silver ion bombards gained nitrogen-doped graphene piece-carbon nano-tube array composite material
Field emission stability figure in 20 hours, wherein " E ", " Jmean" respectively indicate additional sustained field intensity and average Flied emission
Current density；
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but the present invention is not limited to these Examples.
Wherein used silicon single crystal flake, dehydrated alcohol, hydrofluoric acid, high-purity hydrogen, high-purity ammonia, high pure nitrogen, high purity acetylene gas, height
Pure iron target, high purity silver target etc. are commercially available.Ultrasonic cleaning, metal vapor vacuum arc source (source MEVVA), high temperature process furnances,
The devices such as microwave plasma system, diode-type high vacuum Flied emission tester are commercially available.Used in carbon nanotube preparation
Thermal chemical vapor deposition method, graphene film preparation plasma enhanced chemical vapor deposition method used, the source MEVVA silver ion
Blast technique and the method for resulting materials field emission performance test belong to conventional method.Material field transmitting property test uses two poles
Cast high vacuum Flied emission tester, when test, using prepared material as cathode, and minus earth, with the straight of parallel face
The stainless steel plate that diameter is 10 centimetres is anode, and anode and cathode spacing is 2 millimeters, by the adjustable positive bias of plate-load 0-10kV
Mode makes cathode material launching electronics.
In specific implementation, using " a kind of nanometer of carbon plate-composite structure of carbon nano tube field-transmitting cathode preparation method "
(number of patent application 201510152592.3) is compared as the prior art 1, and maximum field emission is reachable
49.60mA/cm2, threshold field is 13.46mA/cm down to 1.51V/ μm, and in mean field emission2When show compared with
Good field emission stability.
In specific implementation, using " a kind of method that microwave hydrogen plasma processing promotes Field Emission of Carbon Nanotubes "
(Chinese patent, patent No. ZL201510153273.4) is compared as the prior art 2, threshold field and maximum Flied emission electricity
Current density is respectively 1.39V/ μm and 74.74mA/cm2, and be 22.86 mA/cm in mean field emission2When show
Preferable field emission stability.
Fig. 1 is that nitrogen-doped graphene piece-carbon nano-tube array composite material flow diagram is prepared in the present invention, mainly
It is divided into pretreatment silicon single crystal flake, thermal chemical vapor deposition method prepares carbon nano pipe array and the high temperature anneal, microwave plasma
Body enhances chemical vapour deposition technique and prepares thin graphene piece, microwave nitrogen, hydrogen plasma process graphene film-carbon nano-pipe array
This is pressed in relation to the preparation of nitrogen-doped graphene piece-carbon nano-tube array composite material in following embodiment in four parts such as column
Step carries out.
Embodiment 1
(1) silicon single crystal flake is pre-processed:
Silicon single crystal flake is first cut into 2cm × 2cm small pieces, then successively each ultrasound (50W) in deionized water and dehydrated alcohol
Then the silicon single crystal flake is immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, takes out dry later by cleaning 5 minutes, then
The silicon single crystal flake of obtained clean surface is carried out to carry energy silver ion in metal vapor vacuum arc source (source MEVVA)
Bombardment pretreatment when bombardment, keeps sample stage at the uniform velocity to rotate, and sample stage biased voltage is set as -15kV, and line is 10 milliamperes, bombardment
Time is 10 minutes.
(2) thermal chemical vapor deposition method prepares carbon nano pipe array and the high temperature anneal:
The iron catalyst film that deposition thickness is 5 nanometers in the silicon single crystal flake merging magnetic control sputtering device that step (1) is obtained,
Then the silicon single crystal flake is placed in high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method,
When growing carbon nanotube, it is small that the silicon single crystal flake for being deposited with iron catalyst is first heat-treated 1 under 400sccm hydrogen, 580 degrees Celsius
When, after handled under 150sccm ammonia, 750 degrees Celsius 10 minutes, finally taken the photograph in 87sccm acetylene, 600sccm hydrogen, 750
Carbon nano pipe array is grown under family name's degree, normal pressure, growth time is 30 minutes, 1000 degrees Celsius are increased the temperature to later,
The carbon nanotube of generation is handled under 400sccm hydrogen, normal pressure, the processing time is 2 hours.
(3) microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece:
The graphite sample carbon nano pipe array that step (2) obtains being placed in microwave plasma system shown in Fig. 2
In sample platform, reaction chamber vacuum is evacuated to 1.0 × 10-310sccm hydrogen is passed through after Pa, air pressure adjusting section is 1kPa, is heated with heater
Sample stage to temperature stabilizes to 800 degrees Celsius, starts microwave source, adjusting microwave power is 150W, and is passed through the acetylene of 3sccm
Gas, adjusting air pressure again is 1kPa, that is, starts the growth of graphene film, and growth time is 3 hours, and final gained is graphene
Piece-carbon nano pipe array.
(4) nitrogen, hydrogen plasma process graphene film-carbon nano pipe array:
On the basis of step (3), cooling sample is to room temperature in 10sccm atmosphere of hydrogen, to gained graphene film-carbon
Nano-tube array carries out nitrogen, hydrogen plasma process, and the gas for generating plasma is mixed by what nitrogen and hydrogen formed
Close gas, nitrogen, hydrogen flow be respectively 5,10sccm, adjustings air pressure is 1.5kPa, after stable gas pressure, starting microwave
Source, adjusting microwave power is 120W, the processing time is 1 hour.X-ray photoelectron spectroscopic analysis shows graphene film-carbon nanometer
It is doped with a certain amount of nitrogen-atoms in pipe array composite material, that is, obtains nitrogen-doped graphene piece-carbon nano pipe array.Fig. 3
A and the B of Fig. 3 be respectively gained nitrogen-doped graphene piece-carbon nano pipe array scanning electron microscope side view and high-resolution transmission
Electron microscopic picture.As can be seen that the graphene edge number of plies is less and surface enrichment defect, these design features can promote material
Field-electron emission.It is emphasized that the number of plies of present invention gained graphene film is mostly 1-5 layers.
(5) the field emission performance characterization of resulting materials:
Using resulting nitrogen-doped graphene piece-carbon nano-tube array composite material as cathode, with diode-type shown in Fig. 4
The field emission performance of high vacuum Flied emission tester test material.Fig. 5 show nitrogen-doped graphene piece-carbon obtained by the present embodiment
The field emission performance of sample compares figure in nanotube array composite material and the prior art 1, the prior art 2, and characterization is yin
For pole yard of material emission with the increased variation relation of electric field strength, corresponding test result is as shown in table 1.It can be with
Find out, in the nitrogen-doped graphene piece-carbon nanotube threshold for introducing silver ion bombardment with obtaining after nitrogen, hydrogen plasma process
Value field only has 1.14V/ μm, and maximum field emission is up to 120.56mA/cm2, compared with the prior art 1, the two refer to
Target situation of change is respectively as follows: 2.43 times (tables 1) for reducing 0.37V/ μm, the prior art；Compared with the prior art 2, this two
The situation of change of a index is respectively as follows: 1.61 times (tables 1) for reducing 0.25V/ μm, the prior art, illustrates nitrogen obtained by the present invention
Doped graphene piece-carbon nano-tube array composite material field emission performance is substantially improved compared with prior art.Fig. 6 is shown
Nitrogen-doped graphene piece-carbon nano-pipe array obtained by the present embodiment be listed in sustained field in the case of, after aging process 1 hour, field hair
Radio current density changes with time relationship.As can be seen that adding sustained field intensity to only have 1.42V/ μm, average Flied emission electricity outside
Current density is up to 45.46mA/cm2In the case where, decaying of the Flied emission current density in 20 hours only has 3.86%, much
Better than the 13.86mA/cm of the prior art 12(it is 1.57V/ μm that it, which corresponds to additional sustained field intensity) and the prior art 2
22.86mA/cm2(it is 1.54V/ μm that it, which corresponds to additional sustained field intensity), shows fabulous application prospect.
Embodiment 2
(1) silicon single crystal flake is pre-processed:
Silicon single crystal flake is first cut into 2cm × 2cm small pieces, then successively each ultrasound (50W) in deionized water and dehydrated alcohol
Then the silicon single crystal flake is immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, takes out dry later by cleaning 5 minutes, then
The silicon single crystal flake of obtained clean surface is carried out to carry energy silver ion in metal vapor vacuum arc source (source MEVVA)
Bombardment pretreatment when bombardment, keeps sample stage at the uniform velocity to rotate, and sample stage biased voltage is set as -15kV, and line is 10 milliamperes, bombardment
Time is 10 minutes.
(2) thermal chemical vapor deposition method prepares carbon nano pipe array and the high temperature anneal:
The iron catalyst film that deposition thickness is 5 nanometers in the silicon single crystal flake merging magnetic control sputtering device that step (1) is obtained,
Then the silicon single crystal flake is placed in high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method,
When growing carbon nanotube, it is small that the silicon single crystal flake for being deposited with iron catalyst is first heat-treated 1 under 400sccm hydrogen, 580 degrees Celsius
When, after handled under 150sccm ammonia, 750 degrees Celsius 10 minutes, finally taken the photograph in 87sccm acetylene, 600sccm hydrogen, 750
Carbon nano pipe array is grown under family name's degree, normal pressure, growth time is 30 minutes, 1000 degrees Celsius are increased the temperature to later,
The carbon nanotube of generation is handled under 400sccm hydrogen, normal pressure, the processing time is 2 hours.
(3) microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece:
The carbon nano pipe array that step (2) obtains is placed on the graphite sample platform in microwave plasma system, it will
Reaction chamber vacuum is evacuated to 1.0 × 10-310sccm hydrogen is passed through after Pa, air pressure adjusting section is 1kPa, extremely with heater specimen heating holder
Temperature stabilizes to 800 degrees Celsius, starts microwave source, and adjusting microwave power is 150W, and is passed through the acetylene gas of 3sccm, is adjusted again
Solar term pressure is 1kPa, that is, starts the growth of graphene film, and growth time is 3 hours, and final gained is graphene film-carbon nanometer
Pipe array.
(4) nitrogen, hydrogen plasma process graphene film-carbon nano pipe array:
On the basis of step (3), cooling sample is to room temperature in 10sccm atmosphere of hydrogen, to gained graphene film-carbon
Nano-tube array carries out nitrogen, hydrogen plasma process, and the gas for generating plasma is mixed by what nitrogen and hydrogen formed
Close gas, nitrogen, hydrogen flow be respectively 5,10sccm, adjustings air pressure is 1.5kPa, after stable gas pressure, starting microwave
Source, adjusts that microwave power is 140W, the processing time is 0.5 hour to get to nitrogen-doped graphene piece-carbon nano pipe array.
(5) the field emission performance characterization of resulting materials:
Flied emission test shows (Fig. 5) that nitrogen-doped graphene piece-carbon nanotube threshold field obtained by the present embodiment only has
1.09V/ μm, maximum field emission is up to 112.56mA/cm2, compared with the prior art 1, the variation of the two indexs
Situation is respectively as follows: 2.27 times (tables 1) for reducing 0.42V/ μm, the prior art；Compared with the prior art 2, the two indexs
Situation of change is respectively as follows: 1.51 times (tables 1) for reducing 0.20V/ μm, the prior art, illustrates N doping graphite obtained by the present invention
Alkene piece-carbon nano-tube array composite material field emission performance is substantially improved compared with prior art.
Embodiment 3
(1) silicon single crystal flake is pre-processed:
Silicon single crystal flake is first cut into 2cm × 2cm small pieces, then successively each ultrasound (50W) in deionized water and dehydrated alcohol
Then the silicon single crystal flake is immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, takes out dry later by cleaning 5 minutes, then
The silicon single crystal flake of obtained clean surface is carried out to carry energy silver ion in metal vapor vacuum arc source (source MEVVA)
Bombardment pretreatment when bombardment, keeps sample stage at the uniform velocity to rotate, and sample stage biased voltage is set as -15kV, and line is 10 milliamperes, bombardment
Time is 10 minutes.
(2) thermal chemical vapor deposition method prepares carbon nano pipe array and the high temperature anneal:
The iron catalyst film that deposition thickness is 5 nanometers in the silicon single crystal flake merging magnetic control sputtering device that step (1) is obtained,
Then the silicon single crystal flake is placed in high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method,
When growing carbon nanotube, it is small that the silicon single crystal flake for being deposited with iron catalyst is first heat-treated 1 under 400sccm hydrogen, 580 degrees Celsius
When, after handled under 150sccm ammonia, 750 degrees Celsius 10 minutes, finally taken the photograph in 87sccm acetylene, 600sccm hydrogen, 750
Carbon nano pipe array is grown under family name's degree, normal pressure, growth time is 30 minutes, 1000 degrees Celsius are increased the temperature to later,
The carbon nanotube of generation is handled under 400sccm hydrogen, normal pressure, the processing time is 2 hours.
(3) microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece:
The carbon nano pipe array that step (2) obtains is placed on the graphite sample platform in microwave plasma system, it will
Reaction chamber vacuum is evacuated to 1.0 × 10-310sccm hydrogen is passed through after Pa, air pressure adjusting section is 1kPa, extremely with heater specimen heating holder
Temperature stabilizes to 800 degrees Celsius, starts microwave source, and adjusting microwave power is 150W, and is passed through the acetylene gas of 3sccm, is adjusted again
Solar term pressure is 1kPa, that is, starts the growth of graphene film, and growth time is 3 hours, and final gained is graphene film-carbon nanometer
Pipe array.
(4) nitrogen, hydrogen plasma process graphene film-carbon nano pipe array:
On the basis of step (3), cooling sample is to room temperature in 10sccm atmosphere of hydrogen, to gained graphene film-carbon
Nano-tube array carries out nitrogen, hydrogen plasma process, and the gas for generating plasma is mixed by what nitrogen and hydrogen formed
Close gas, nitrogen, hydrogen flow be respectively 5,10sccm, adjustings air pressure is 1.5kPa, after stable gas pressure, starting microwave
Source, adjusts that microwave power is 100W, the processing time is 1 hour to get to nitrogen-doped graphene piece-carbon nano pipe array.
(5) the field emission performance characterization of resulting materials:
Flied emission test shows that nitrogen-doped graphene piece-carbon nanotube threshold field obtained by the present embodiment only has 1.17V/ μ
M, maximum field emission are up to 105.25mA/cm2, compared with the prior art 1, the situation of change of the two indexs is distinguished
Are as follows: reduce 2.12 times (tables 1) of 0.34V/ μm, the prior art；Compared with the prior art 2, the situation of change of the two indexs
It is respectively as follows: 1.41 times (tables 1) for reducing 0.22V/ μm, the prior art, illustrates that nitrogen-doped graphene piece-carbon obtained by the present invention is received
The field emission performance of mitron array composite material is substantially improved compared with prior art.
Embodiment 4
(1) silicon single crystal flake is pre-processed:
Silicon single crystal flake is first cut into 2cm × 2cm small pieces, then successively each ultrasound (50W) in deionized water and dehydrated alcohol
Then the silicon single crystal flake is immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, takes out dry later by cleaning 5 minutes, then
The silicon single crystal flake of obtained clean surface is carried out to carry energy silver ion in metal vapor vacuum arc source (source MEVVA)
Bombardment pretreatment when bombardment, keeps sample stage at the uniform velocity to rotate, and sample stage biased voltage is set as -15kV, and line is 10 milliamperes, bombardment
Time is 10 minutes.
(2) thermal chemical vapor deposition method prepares carbon nano pipe array and the high temperature anneal:
The iron catalyst film that deposition thickness is 5 nanometers in the silicon single crystal flake merging magnetic control sputtering device that step (1) is obtained,
Then the silicon single crystal flake is placed in high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method,
When growing carbon nanotube, it is small that the silicon single crystal flake for being deposited with iron catalyst is first heat-treated 1 under 400sccm hydrogen, 580 degrees Celsius
When, after handled under 150sccm ammonia, 750 degrees Celsius 10 minutes, finally taken the photograph in 87sccm acetylene, 600sccm hydrogen, 750
Carbon nano pipe array is grown under family name's degree, normal pressure, growth time is 30 minutes, 1000 degrees Celsius are increased the temperature to later,
The carbon nanotube of generation is handled under 400sccm hydrogen, normal pressure, the processing time is 2 hours.
(3) microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece:
The carbon nano pipe array that step (2) obtains is placed on the graphite sample platform in microwave plasma system, it will
Reaction chamber vacuum is evacuated to 1.0 × 10-310sccm hydrogen is passed through after Pa, air pressure adjusting section is 1kPa, extremely with heater specimen heating holder
Temperature stabilizes to 800 degrees Celsius, starts microwave source, and adjusting microwave power is 150W, and is passed through the acetylene gas of 3sccm, is adjusted again
Solar term pressure is 1kPa, that is, starts the growth of graphene film, and growth time is 3 hours, and final gained is graphene film-carbon nanometer
Pipe array.
(4) nitrogen, hydrogen plasma process graphene film-carbon nano pipe array:
On the basis of step (3), cooling sample is to room temperature in 10sccm atmosphere of hydrogen, to gained graphene film-carbon
Nano-tube array carries out nitrogen, hydrogen plasma process, and the gas for generating plasma is mixed by what nitrogen and hydrogen formed
Close gas, nitrogen, hydrogen flow be respectively 5,10sccm, adjustings air pressure is 1.5kPa, after stable gas pressure, starting microwave
Source, adjusts that microwave power is 100W, the processing time is 2 hours to get to nitrogen-doped graphene piece-carbon nano pipe array.
(5) the field emission performance characterization of resulting materials:
Flied emission test shows that nitrogen-doped graphene piece-carbon nanotube threshold field obtained by the present embodiment only has 1.11V/ μ
M, maximum field emission are up to 114.73mA/cm2, compared with the prior art 1, the situation of change of the two indexs is distinguished
Are as follows: reduce 2.31 times (tables 1) of 0.40V/ μm, the prior art；Compared with the prior art 2, the situation of change of the two indexs
It is respectively as follows: 1.54 times (tables 1) for reducing 0.28V/ μm, the prior art, illustrates that nitrogen-doped graphene piece-carbon obtained by the present invention is received
The field emission performance of mitron array composite material is substantially improved compared with prior art.
Embodiment 5
(1) silicon single crystal flake is pre-processed:
Silicon single crystal flake is first cut into 2cm × 2cm small pieces, then successively each ultrasound (50W) in deionized water and dehydrated alcohol
Then the silicon single crystal flake is immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, takes out dry later by cleaning 5 minutes, then
The silicon single crystal flake of obtained clean surface is carried out to carry energy silver ion in metal vapor vacuum arc source (source MEVVA)
Bombardment pretreatment when bombardment, keeps sample stage at the uniform velocity to rotate, and sample stage biased voltage is set as -15kV, and line is 10 milliamperes, bombardment
Time is 10 minutes.
(2) thermal chemical vapor deposition method prepares carbon nano pipe array and the high temperature anneal:
The iron catalyst film that deposition thickness is 5 nanometers in the silicon single crystal flake merging magnetic control sputtering device that step (1) is obtained,
Then the silicon single crystal flake is placed in high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method,
When growing carbon nanotube, it is small that the silicon single crystal flake for being deposited with iron catalyst is first heat-treated 1 under 400sccm hydrogen, 580 degrees Celsius
When, after handled under 150sccm ammonia, 750 degrees Celsius 10 minutes, finally taken the photograph in 87sccm acetylene, 600sccm hydrogen, 750
Carbon nano pipe array is grown under family name's degree, normal pressure, growth time is 30 minutes, 1000 degrees Celsius are increased the temperature to later,
The carbon nanotube of generation is handled under 400sccm hydrogen, normal pressure, the processing time is 2 hours.
(3) microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece:
The carbon nano pipe array that step (2) obtains is placed on the graphite sample platform in microwave plasma system, it will
Reaction chamber vacuum is evacuated to 1.0 × 10-310sccm hydrogen is passed through after Pa, air pressure adjusting section is 1kPa, extremely with heater specimen heating holder
Temperature stabilizes to 800 degrees Celsius, starts microwave source, and adjusting microwave power is 150W, and is passed through the acetylene gas of 3sccm, is adjusted again
Solar term pressure is 1kPa, that is, starts the growth of graphene film, and growth time is 3 hours, and final gained is graphene film-carbon nanometer
Pipe array.
(4) nitrogen, hydrogen plasma process graphene film-carbon nano pipe array:
On the basis of step (3), cooling sample is to room temperature in 10sccm atmosphere of hydrogen, to gained graphene film-carbon
Nano-tube array carries out nitrogen, hydrogen plasma process, and the gas for generating plasma is mixed by what nitrogen and hydrogen formed
Close gas, nitrogen, hydrogen flow be respectively 5,10sccm, adjustings air pressure is 1.5kPa, after stable gas pressure, starting microwave
Source, adjusts that microwave power is 140W, the processing time is 1 hour to get to nitrogen-doped graphene piece-carbon nano pipe array.
(5) the field emission performance characterization of resulting materials:
Flied emission test shows that nitrogen-doped graphene piece-carbon nanotube threshold field obtained by the present embodiment only has 1.21V/ μ
M, maximum field emission are up to 101.79mA/cm2, compared with the prior art 1, the situation of change of the two indexs is distinguished
Are as follows: reduce 2.05 times (tables 1) of 0.30V/ μm, the prior art；Compared with the prior art 2, the situation of change of the two indexs
It is respectively as follows: 1.36 times (tables 1) for reducing 0.17V/ μm, the prior art, illustrates that nitrogen-doped graphene piece-carbon obtained by the present invention is received
The field emission performance of mitron array composite material is substantially improved compared with prior art.
Embodiment 6
(1) silicon single crystal flake is pre-processed:
Silicon single crystal flake is first cut into 2cm × 2cm small pieces, then successively each ultrasound (50W) in deionized water and dehydrated alcohol
Then the silicon single crystal flake is immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, takes out dry later by cleaning 5 minutes, then
The silicon single crystal flake of obtained clean surface is carried out to carry energy silver ion in metal vapor vacuum arc source (source MEVVA)
Bombardment pretreatment when bombardment, keeps sample stage at the uniform velocity to rotate, and sample stage biased voltage is set as -15kV, and line is 10 milliamperes, bombardment
Time is 10 minutes.
(2) thermal chemical vapor deposition method prepares carbon nano pipe array and the high temperature anneal:
The iron catalyst film that deposition thickness is 5 nanometers in the silicon single crystal flake merging magnetic control sputtering device that step (1) is obtained,
Then the silicon single crystal flake is placed in high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method,
When growing carbon nanotube, it is small that the silicon single crystal flake for being deposited with iron catalyst is first heat-treated 1 under 400sccm hydrogen, 580 degrees Celsius
When, after handled under 150sccm ammonia, 750 degrees Celsius 10 minutes, finally taken the photograph in 87sccm acetylene, 600sccm hydrogen, 750
Carbon nano pipe array is grown under family name's degree, normal pressure, growth time is 30 minutes, 1000 degrees Celsius are increased the temperature to later,
The carbon nanotube of generation is handled under 400sccm hydrogen, normal pressure, the processing time is 2 hours.
(3) microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece:
The carbon nano pipe array that step (2) obtains is placed on the graphite sample platform in microwave plasma system, it will
Reaction chamber vacuum is evacuated to 1.0 × 10-310sccm hydrogen is passed through after Pa, air pressure adjusting section is 1kPa, extremely with heater specimen heating holder
Temperature stabilizes to 800 degrees Celsius, starts microwave source, and adjusting microwave power is 150W, and is passed through the acetylene gas of 3sccm, is adjusted again
Solar term pressure is 1kPa, that is, starts the growth of graphene film, and growth time is 3 hours, and final gained is graphene film-carbon nanometer
Pipe array.
(4) nitrogen, hydrogen plasma process graphene film-carbon nano pipe array:
On the basis of step (3), cooling sample is to room temperature in 10sccm atmosphere of hydrogen, to gained graphene film-carbon
Nano-tube array carries out nitrogen, hydrogen plasma process, and the gas for generating plasma is mixed by what nitrogen and hydrogen formed
Close gas, nitrogen, hydrogen flow be respectively 5,10sccm, adjustings air pressure is 1.5kPa, after stable gas pressure, starting microwave
Source, adjusts that microwave power is 120W, the processing time is 2 hours to get to nitrogen-doped graphene piece-carbon nano pipe array.
(5) the field emission performance characterization of resulting materials:
Flied emission test shows that nitrogen-doped graphene piece-carbon nanotube threshold field obtained by the present embodiment only has 1.15V/ μ
M, maximum field emission are up to 109.75mA/cm2, compared with the prior art 1, the situation of change of the two indexs is distinguished
Are as follows: reduce 2.21 times (tables 1) of 0.36V/ μm, the prior art；Compared with the prior art 2, the situation of change of the two indexs
It is respectively as follows: 1.47 times (tables 1) for reducing 0.24V/ μm, the prior art, illustrates that nitrogen-doped graphene piece-carbon obtained by the present invention is received
The field emission performance of mitron array composite material is substantially improved compared with prior art.
It is last it should be noted that, it is above only to list exemplary embodiments of the invention；Join by adjusting technique of the invention
The preparation of nitrogen-doped graphene piece-carbon nano-tube array composite material can be achieved in number and field emission performance is promoted, and threshold field is flat
Only have 1.09-1.21V/ μm, maximum field emission is average up to 101.79-120.56A/cm2, in high field emission electricity
It can be achieved to stablize field-electron emission under current density.It is apparent that there are many more other real the present invention is not limited to above-described embodiment
Parameter combination method is tested, the those of ordinary skill in this research field directly can export or associate from present disclosure
The relevant situation arrived should all be considered protection scope of the present invention.
Table 1 is the prior art 1, the Flied emission result of sample compares in the prior art 2 and various embodiments of the present invention, wherein
“Eth" indicate threshold field, " Jmax" indicate maximum field emission, " ↓ " indicates decline.
Claims (4)
1. a kind of promotion graphene film-carbon nano-tube array composite material field emission performance method characterized by comprising
First with energy silver ion bombardment pretreatment silicon single crystal flake is carried, carbon nano pipe array then is prepared simultaneously using thermal chemical vapor deposition method
The high temperature anneal is carried out, recycles microwave plasma enhanced chemical vapour deposition technique to prepare thin graphene piece, finally exists
Microwave nitrogen, the resulting graphene film-carbon nano pipe array of hydrogen plasma process are utilized under room temperature, are by adjusting microwave power
100~140W, chamber pressure 1.5kPa, processing time are 0.5~2 hour to control its pattern, finally obtain N doping
Graphene film-carbon nano-tube array composite material；Nitrogen-doped graphene piece-the carbon nano-tube array composite material is by carbon
The deposition edge number of plies is 1-5 layers on nano-tube array, the graphene film of rich defect, N doping forms；Prepared N doping stone
The threshold field of black alkene piece-carbon nano-tube array composite material averagely only has 1.09-1.21V/ μm, and maximum field emission is flat
Up to 101.79-120.56mA/cm2, 45.46mA/cm is up in mean field emission2, the electric current in 20 hours declines
Subtract only 3.86%.
2. a kind of promotion graphene film-carbon nano-tube array composite material field emission performance side according to claim 1
Method, which is characterized in that carry out as follows:
Step (1) pre-processes silicon single crystal flake: silicon single crystal flake being first cut into 2cm × 2cm small pieces, then successively in deionized water and anhydrous
Each ultrasound (50W) is cleaned 5 minutes in ethyl alcohol, and the silicon single crystal flake is then immersed in the hydrofluoric acid that volume ratio is 4% 5 points
Clock takes out dry later, then by the silicon single crystal flake of obtained clean surface in metal vapor vacuum arc source (MEVVA
Source) in carry can silver ion bombardment pretreatment, when bombardment, sample stage is kept at the uniform velocity to rotate, sample stage biased voltage is set as-
15kV, line are 10 milliamperes, and bombardment time is 10 minutes；
Step (2) thermal chemical vapor deposition method prepares carbon nano pipe array and the high temperature anneal: the silicon list that step (1) is obtained
Chip is placed in the iron catalyst film that deposition thickness is 5 nanometers in magnetic control sputtering device, and the silicon single crystal flake is then placed in high fire stons
Carbon nano pipe array is prepared with conventional thermal chemical vapor deposition method in English tube furnace, when growing carbon nanotube, will be first deposited with
The silicon single crystal flake of iron catalyst is heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after taken the photograph in 150sccm ammonia, 750
It is handled 10 minutes under family name's degree, finally grows carbon nano-pipe array under 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure
Column, growth time are 30 minutes, increase the temperature to 1000 degrees Celsius later, the carbon of generation is handled under 400sccm hydrogen, normal pressure
Nanotube, processing time are 2 hours；
Step (3) microwave plasma enhanced process for preparing graphenes by chemical vapour deposition piece: the carbon nanotube that step (2) is obtained
Array is placed on the graphite sample platform in microwave plasma system, and reaction chamber vacuum is evacuated to 1.0 × 10-3It is passed through after Pa
10sccm hydrogen, air pressure adjusting section are 1kPa, stabilize to 800 degrees Celsius with heater specimen heating holder to temperature, start microwave source,
Adjusting microwave power is 150W, and is passed through the acetylene gas of 3sccm, and adjusting air pressure again is 1kPa, that is, starts the life of graphene film
Long, growth time is 3 hours, finally obtains graphene film-carbon nano pipe array；
Step (4) nitrogen, hydrogen plasma process graphene film-carbon nano pipe array: on the basis of step (3), in 10sccm
Cooling sample carries out nitrogen, hydrogen plasma process to gained graphene film-carbon nano pipe array, uses to room temperature in atmosphere of hydrogen
In the mixed gas that is made of nitrogen and hydrogen of gas for generating plasma, nitrogen, hydrogen flow be respectively 5,
10sccm, adjusting air pressure is 1.5kPa, after stable gas pressure, starts microwave source, adjusting microwave power is 100~140W, processing
Time is 0.5~2 hour to get nitrogen-doped graphene piece-carbon nano pipe array.
3. a kind of promotion graphene film-carbon nano-tube array composite material field emission performance side according to claim 2
Method, which is characterized in that various gas purities used are 5N.
4. graphene film-carbon nano-tube array composite material that one kind is prepared method according to claim 1, feature
It is, the nitrogen-doped graphene piece-carbon nano-tube array composite material on carbon nano pipe array by depositing the edge number of plies
For 1-5 layers, rich defect, N doping graphene film composition；Prepared nitrogen-doped graphene piece-carbon nano pipe array composite wood
The threshold field of material averagely only has 1.09-1.21V/ μm, and maximum field emission is average up to 101.79-120.56mA/
cm2, 45.46mA/cm is up in mean field emission2, the current attenuation in 20 hours only have 3.86%.
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