CN108987214A - A method of promoting carbon nano pipe array field emission performance - Google Patents
A method of promoting carbon nano pipe array field emission performance Download PDFInfo
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- CN108987214A CN108987214A CN201810096701.8A CN201810096701A CN108987214A CN 108987214 A CN108987214 A CN 108987214A CN 201810096701 A CN201810096701 A CN 201810096701A CN 108987214 A CN108987214 A CN 108987214A
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/30—Cold cathodes
- H01J2201/304—Field emission cathodes
- H01J2201/30403—Field emission cathodes characterised by the emitter shape
- H01J2201/30434—Nanotubes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/30—Cold cathodes
- H01J2201/304—Field emission cathodes
- H01J2201/30446—Field emission cathodes characterised by the emitter material
- H01J2201/30453—Carbon types
- H01J2201/30469—Carbon nanotubes (CNTs)
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2201/00—Electrodes common to discharge tubes
- H01J2201/30—Cold cathodes
- H01J2201/304—Field emission cathodes
- H01J2201/30446—Field emission cathodes characterised by the emitter material
- H01J2201/30484—Carbides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2209/00—Apparatus and processes for manufacture of discharge tubes
- H01J2209/02—Manufacture of cathodes
- H01J2209/022—Cold cathodes
- H01J2209/0223—Field emission cathodes
Abstract
The invention discloses a kind of methods for promoting carbon nano pipe array field emission performance, belong to the preparation and application field of nano material.Including following preparation process: (1) carrying out carrying energy silver ion bombardment pretreatment to monocrystalline silicon piece；(2) carbon nano pipe array and high annealing are prepared with conventional thermal chemical vapor deposition method；(3) carbon nano pipe array is handled at room temperature with nitrogen, hydrogen plasma in microwave plasma system；(4) carbon nanotube is carried out in a manner of the injection of inclination angle carrying energy silicon ion bombardment processing.Compared to the prior art with simple carbon nano pipe array, nitrogen doped silicon carbide-carbon nano pipe array prepared by this method has fabulous field emission stability with extremely low applied electric field and high Flied emission current density and under high field emission 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 silicon carbide-carbon nano pipe array and the method for promoting its field-electron emission performance.
Background technique
Carbon nanotube has good electric conductivity and mechanical strength and higherization as a kind of quasi-one-dimensional nanometer material
Inertia is learned, has all shown good application prospect in numerous areas such as energy storage, transistor, Material cladding enhancing, detectors.Together
When, the great draw ratio of carbon nanotube has also become a kind of ideal filed emission cathode material, in vacuum field electronic device
Exploitation aspect shows good application potential.Flied emission refers to that cathode material internal electron reinforces electric field action outside
Under, the process in vacuum is escaped into from material surface, excellent field emission performance generally requires cathode with lower threshold field
With biggish current density and good stability, wherein threshold field refers to that Flied emission current density reaches 10mA/cm2When
Corresponding electric field strength, 10mA/cm2Also it is known as being minimum current required when vacuum field electronic device is routinely applied
Density.Carbon nanotube base field-transmitting cathode is compared to other low-dimensional nanometers such as silicon nanowires, array graphene film, zinc oxide nanowires
Material has the advantages that applied electric field is low and current density is big.However, the threshold value electricity of carbon nanotube base field-transmitting cathode
Field is generally higher than 2.0V/ μm, is equivalent to apply the height of 2000V in the yin-yang interpolar that spacing is 1 millimeter in practical applications
Pressure, it is contemplated that yin-yang interpolar also needs to keep high vacuum, this is technically undoubtedly than device relatively difficult to achieve.Even across
Ion irradiation, doping, chemical modification etc. processing after carbon nanotube base field-transmitting cathode threshold field generally also above 1.5V/ μm,
It is also difficult to be higher than 10mA/cm in current density simultaneously2The field-electron emission of Shi Shixian long-time stable, this is just electric to work is reduced
Field and promotion Flied emission current density are put forward new requirements.
Summary of the invention
It is an object of the invention to overcome, existing carbon nanotube base field-transmitting cathode applied electric field is relatively high, Flied emission
Current density is smaller, high current density field-electron emission when the bad deficiency of stability, utilize that carry can Si ion implantation and microwave
Nitrogen, hydrogen plasma process, obtain that work function is low, nitrogen doped silicon carbide-carbon nano pipe array more than Flied emission point number is compound
Material, and finally obtain one kind and have both good field under ultralow applied electric field, super large Flied emission current density and high current density and send out
Penetrate the carbon nanotube base filed emission cathode material of stability.
The purpose of the present invention is what is reached by following measure:
A method of promoting carbon nano pipe array field emission performance, comprising: in the silicon single crystal that load energy silver ion bombarded
On piece prepares carbon nano pipe array and high annealing with thermal chemical vapor deposition method, is then existed using microwave nitrogen, hydrogen plasma
Handle carbon nano pipe array under room temperature, by adjust microwave power be 150~200W, chamber pressure 1.5kPa, processing when
Between for 0.5~1 hour come the pattern that controls carbon nanotube, then by gained nitrogen-doped carbon nanometer pipe array in metallic vapour vacuum
Si ion implantation processing is carried out in arc ion source (source MEVVA), finally obtains nitrogen doped silicon carbide-carbon nano pipe array.
It further include that silicon single crystal flake is successively respectively used in deionized water and dehydrated alcohol to 50W function in above-mentioned technical proposal
Rate is cleaned by ultrasonic 5 minutes preprocessing process.
It further include the hydrofluoric acid leaching that the silicon single crystal flake merging volume ratio after being cleaned by ultrasonic is 4% in above-mentioned technical proposal
The step of steeping 5 minutes.
In above-mentioned technical proposal, further disclosure promotes the specific steps of carbon nano pipe array field emission performance method such as
Under: 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, which can be used for being promoted between carbon nanotube and substrate
Binding force；
Step (2) thermal chemical vapor deposition method prepares carbon nano pipe array and high annealing: 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) nitrogen, hydrogen plasma process carbon nano pipe array: the carbon nano pipe array that step (2) is obtained is placed in
Nitrogen, hydrogen plasma process are carried out in microwave plasma system at normal temperature, the gas for generating plasma is by nitrogen
The mixed gas of gas and hydrogen composition, nitrogen, hydrogen flow be respectively 5,10sccm, adjustings air pressure is 1.5kPa, to air pressure
After stabilization, start microwave source, set microwave power as 150~200W, the processing time is 0.5~1 hour, is obtained by the process
Nitrogen-doped carbon nanometer pipe array；
Step (4) Si ion implantation nitrogen-doped carbon nanometer pipe array: the nitrogen-doped carbon nanometer pipe array that step (3) is obtained
Si ion implantation processing is carried out in the source MEVVA, when injection, silicon ion incident direction and axial resistivity are in about 10 degree of folder
Angle, and sample stage is kept at the uniform velocity to rotate, sample stage biased voltage is set as -20kV, and line is set as 5 milliamperes, and injection length is 15 points
Clock is to get nitrogen doped silicon carbide-carbon nano-tube array composite material.
In above-mentioned technical proposal, various gas purities used are 5N.
Corona treatment disclosed by the invention prepares nitrogen doped silicon carbide-carbon nano pipe array for promoting Flied emission
Can method compared with prior art its be advantageous in that: (1) silicon base pretreatment in, bombarded using silver ion, compared to original
There is the iron ion bombardment in technology to will not influence carbon nanometer since silver itself does not have catalytic action to carbon nano tube growth
The pattern of pipe array, but iron ion bombardment can influence the iron catalyst film that subsequent magnetron sputtering is deposited to a certain extent
Thickness, and then influence the pattern of carbon nano pipe array；(2) aspect is combined between enhancing carbon nanotube and substrate, silver exists compared to iron
Subsequent high temperature is easier to be precipitated and be coated on the root of carbon nanotube when making annealing treatment, and receives so as to significantly more efficient enhancing carbon
Binding force between mitron and substrate, and then promote the maximum field emission of carbon nanotube；(3) by introducing silicon ion note
Enter with N doping both post-processing to obtain nitrogen doped silicon carbide-carbon nano tube compound material, compare original technology, N doping
Formation with silicon carbide each contributes to reduce the evolution work function of carbon nanotube, and the electronics in carbon nanotube is made to be easier tunnelling gesture
It builds and escapes into vacuum, i.e., so that the field-electron emission ability of carbon nanotube is enhanced；(4) normal-temperature plasma handles phase
High-temperature plasma processing than in the prior art helps preferably to retain a large amount of defects in carbon nanotube, because these are lacked
Efficient Flied emission point can be become in the process by being trapped in Flied emission.In short, pipe base junction close further enhance, the reduction of work function
It is the key that nitrogen doped silicon carbide-carbon nano pipe array has excellent field emission performance with Flied emission points purpose increase, also just
It is superiority place of the invention.The introducing of Si ion implantation and N doping is so that present invention gained nitrogen doped silicon carbide-carbon is received
Mitron array has extremely low threshold field (1.10V/ μm), high Flied emission current density (110.96mA/cm2) and it is splendid
High current density field emission stability (be up to 31.31mA/cm in mean field emission2, the electric current in 50 hours declines
Subtract only 3.4%), these indexs compared with prior art, have greatly improved.
Detailed description of the invention
Fig. 1 is that corona treatment prepares nitrogen doped silicon carbide-carbon nano pipe array method flow schematic diagram；
The scanning electron microscopic picture of gained carbon nano pipe array and transmission electricity after Fig. 2 is unprocessed in embodiment 1 and processing
Mirror picture, comprising:
21. being the scanning electron microscope top view of untreated original carbon nanotubes；
22. being nitrogen-doped carbon nanometer pipe scanning electron microscope top view；
23. being nitrogen doped silicon carbide-carbon nano tube compound material scanning electron microscope top view；
24. being nitrogen doped silicon carbide-carbon nano tube compound material high-resolution-ration transmission electric-lens picture；
Fig. 3 is the structural schematic diagram of microwave plasma system used in the present invention；
Fig. 4 is the structural schematic diagram of diode-type high vacuum Flied emission tester used in the present invention；
Fig. 5 is in untreated original carbon nanotubes, the prior art, embodiment 1 and embodiment 2 by plasma
Gained nitrogen doped silicon carbide-carbon nano tube compound material field emission performance figure after reason；
Fig. 6 is that gained nitrogen doped silicon carbide-carbon nano-pipe array is listed in the field emission stability in 50 hours in embodiment 1
Figure, 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 pure nitrogen, high purity acetylene gas, high-purity ammonia, height
Pure iron target, high purity silver target, high-purity silicon target etc. are commercially available.Ultrasonic cleaning, metal vapor vacuum arc source (source MEVVA), magnetic
The devices such as control sputtering, high temperature process furnances, microwave plasma system, diode-type high vacuum Flied emission tester are commercially available.
Carbon nano pipe array preparation thermal chemical vapor deposition method used, iron catalyst deposition magnetron sputtering method and resulting materials used
The method of field emission performance test belongs to conventional method.Material field transmitting property test uses diode-type high vacuum Flied emission
Tester is 10 centimetres stainless with the diameter of parallel face using prepared material as cathode, and minus earth when test
Steel plate is anode, and anode and cathode spacing is 2 millimeters, sending out cathode material by way of the adjustable positive bias of plate-load 0-10kV
Radio.
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, finally obtains carbon nano pipe array.Its
Threshold field and maximum field emission are respectively 1.39V/ μm and 74.74mA/cm2。
Fig. 1 is that nitrogen doped silicon carbide-carbon nano-tube array composite material flow diagram is prepared in the present invention, main point
It prepares carbon to carry energy silver ion bombardment pretreatment silicon base, magnetron sputtering method Precipitated iron catalyst, thermal chemical vapor deposition method and receives
Mitron array, hydrogen plasma process carbon nanotube, carries five parts such as energy Si ion implantation carbon nanotube at microwave nitrogen, below
This step is pressed in relation to the preparation of nitrogen doped silicon carbide-carbon nano pipe array in embodiment to carry out.
Embodiment 1
(1) silicon single crystal flake is pre-processed:
N-shaped (100) silicon single crystal flakes of 2cm × 2cm small pieces each ultrasound in deionized water and dehydrated alcohol will be first cut into
(50W) is cleaned 5 minutes, is then immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, is taken out dry later, then will obtain
The silicon single crystal flake of clean surface carry out carrying in metal vapor vacuum arc source (source MEVVA) can the pre- place of silver ion bombardment
Reason 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 10
Minute, which can be used for being promoted the binding force between carbon nanotube and substrate.
(2) thermal chemical vapor deposition method prepares carbon nano pipe array and high annealing:
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 it is put into high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method.Growth carbon is received
When mitron, first the silicon single crystal flake for being deposited with iron catalyst is heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after
150sccm ammonia is handled 10 minutes under 750 degrees Celsius, finally in 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure
Lower growth carbon nano pipe array, growth time are 30 minutes, increase the temperature to 1000 degrees Celsius later, in 400sccm hydrogen, often
The carbon nanotube that high-temperature heat treatment generates is depressed, the processing time is 2 hours, which also can be used for promoting carbon nanometer
Binding force between pipe and substrate, above-mentioned gases used purity is 5N.Be shown in Figure 21 in the present embodiment original carbon used receive
The scanning electron microscope top view of mitron.
(3) nitrogen, hydrogen plasma process carbon nano pipe array:
(Fig. 3 is the structural representation of the device to the carbon nano pipe array merging microwave plasma system that step (2) is obtained
Figure) in carry out nitrogen, hydrogen plasma process at normal temperature, what the gas for generating plasma was made of nitrogen and hydrogen
Mixed gas, nitrogen, hydrogen flow be respectively 5,10sccm, adjusting air pressure is 1.5kPa, after stable gas pressure, starts microwave
Source sets microwave power as 150W, and the processing time is 1 hour.X-ray photoelectron spectroscopic analysis shows to mix in carbon nano pipe array
Miscellaneous a certain amount of nitrogen-atoms, that is, obtain nitrogen-doped carbon nanometer pipe array, scanning electron microscopic picture is as shown in figure 22.
(4) Si ion implantation nitrogen-doped carbon nanometer pipe array and field emission performance characterization:
The nitrogen-doped carbon nanometer pipe array that step (3) is obtained carries out Si ion implantation processing in the source MEVVA, injection
When, silicon ion incident direction and axial resistivity are in about 10 degree of angle, and sample stage is kept at the uniform velocity to rotate, sample stage biased voltage
It is set as -20kV, line is set as 5 milliamperes, and injection length is 15 minutes.X-ray photoelectron spectroscopic analysis shows resulting materials
In have a certain amount of silicon carbide contents, i.e., nitrogen doped silicon carbide-carbon nano-tube array composite material has been obtained by processing, swept
It is as shown in figure 23 to retouch electron microscopic picture.Figure 24 show the transmission of nitrogen doped silicon carbide-carbon nano-tube array composite material high-resolution
Electron microscopic picture.As can be seen that the outer about 5 layers of carbon atom of the tube wall of carbon nanotube are becoming rich after Si ion implantation is handled
The structure of defect, but internal layer still maintains preferable layer structure.It is with resulting nitrogen doped silicon carbide-carbon nano-pipe array column
Cathode, with the field emission performance of diode-type high vacuum Flied emission tester test material shown in Fig. 4.Fig. 5 show this reality
Apply composite material obtained by example and original carbon nanotubes array and in the prior art the Flied emission current density of carbon nano pipe array
With the increased variation relation of electric field strength, corresponding Flied emission test result is as shown in table 1.As can be seen that N doping carbonization
The threshold field and maximum field emission of silico-carbo nano-tube array are respectively 1.10V/ μm and 110.96mA/cm2, much
Better than 1.72V/ μm (present invention reduces 0.62V/ μm) of unprocessed original carbon nanotubes and 20.71mA/cm2(the present invention
It is its 5.36 times), also far superior to 1.39V/ μm (present invention reduces 0.29V/ μm) of the prior art and 74.74mA/cm2
(present invention improves 48.5%).Fig. 6 show nitrogen doped silicon carbide-carbon nano-pipe array obtained by the present embodiment and is listed in sustained field feelings
Under condition, after aging process 1 hour, Flied emission current density changes with time relationship.As can be seen that adding sustained field strong outside
Only 1.30V/ μm of degree, mean field emission are up to 31.31mA/cm2(22.86mA/ far superior in the prior art
cm2, corresponding to additional sustained field intensity is 1.54V/ μm) in the case where, decaying of the Flied emission current density in 50 hours is only
Have 3.4%, shows fabulous application prospect.
Embodiment 2
(1) silicon single crystal flake is pre-processed:
N-shaped (100) silicon single crystal flakes of 2cm × 2cm small pieces each ultrasound in deionized water and dehydrated alcohol will be first cut into
(50W) is cleaned 5 minutes, is then immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, is taken out dry later, then will obtain
The silicon single crystal flake of clean surface carry out carrying in metal vapor vacuum arc source (source MEVVA) can the pre- place of silver ion bombardment
Reason 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 10
Minute.
(2) chemical vapor deposition for carbon nanotubes array:
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 it is put into high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method.Growth carbon is received
When mitron, first the silicon single crystal flake for being deposited with iron catalyst is heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after
150sccm ammonia is handled 10 minutes under 750 degrees Celsius, finally in 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure
Lower growth carbon nano pipe array, growth time are 30 minutes, increase the temperature to 1000 degrees Celsius later, in 400sccm hydrogen, often
The carbon nanotube that high-temperature heat treatment generates is depressed, the processing time is 2 hours.
(3) nitrogen, hydrogen plasma process carbon nano pipe array:
The carbon nano pipe array that step (2) obtains is placed in microwave plasma system and carries out nitrogen, hydrogen etc. at normal temperature
Gas ions processing, the mixed gas that the gas for generating plasma is made of nitrogen and hydrogen, the flow of nitrogen, hydrogen
Respectively 5,10sccm, adjusting air pressure is 1.5kPa, after stable gas pressure, starts microwave source, sets microwave power as 175W, locates
Managing the time is 1 hour, i.e. acquisition nitrogen-doped carbon nanometer pipe array.
(4) Si ion implantation nitrogen-doped carbon nanometer pipe array and field emission performance characterization:
The nitrogen-doped carbon nanometer pipe array that step (3) is obtained carries out Si ion implantation processing in the source MEVVA, injection
When, silicon ion incident direction and axial resistivity are in about 10 degree of angle, and sample stage is kept at the uniform velocity to rotate, sample stage biased voltage
It is set as -20kV, line is set as 5 milliamperes, and injection length is 15 minutes multiple to get nitrogen doped silicon carbide-carbon nano pipe array
Condensation material.Flied emission test result shows (table 1), nitrogen doped silicon carbide-carbon nano pipe array threshold field obtained by the present embodiment
It is respectively 1.15V/ μm and 98.38mA/cm with maximum field emission2, far superior to unprocessed original carbon nanotubes
1.72V/ μm and 20.71mA/cm2, also far superior to 1.39V/ μm (present invention reduces 0.24V/ μm) of the prior art and
74.74mA/cm2(present invention improves 31.6%).
Embodiment 3
(1) silicon single crystal flake is pre-processed:
N-shaped (100) silicon single crystal flakes of 2cm × 2cm small pieces each ultrasound in deionized water and dehydrated alcohol will be first cut into
(50W) is cleaned 5 minutes, is then immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, is taken out dry later, then will obtain
The silicon single crystal flake of clean surface carry out carrying in metal vapor vacuum arc source (source MEVVA) can the pre- place of silver ion bombardment
Reason 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 10
Minute.
(2) chemical vapor deposition for carbon nanotubes array:
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 it is put into high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method.Growth carbon is received
When mitron, first the silicon single crystal flake for being deposited with iron catalyst is heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after
150sccm ammonia is handled 10 minutes under 750 degrees Celsius, finally in 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure
Lower growth carbon nano pipe array, growth time are 30 minutes, increase the temperature to 1000 degrees Celsius later, in 400sccm hydrogen, often
The carbon nanotube that high-temperature heat treatment generates is depressed, the processing time is 2 hours.
(3) nitrogen, hydrogen plasma process carbon nano pipe array:
The carbon nano pipe array that step (2) obtains is placed in microwave plasma system and carries out nitrogen, hydrogen etc. at normal temperature
Gas ions processing, the mixed gas that the gas for generating plasma is made of nitrogen and hydrogen, the flow of nitrogen, hydrogen
Respectively 5,10sccm, adjusting air pressure is 1.5kPa, after stable gas pressure, starts microwave source, sets microwave power as 200W, locates
Managing the time is 1 hour, i.e. acquisition nitrogen-doped carbon nanometer pipe array.
(4) Si ion implantation nitrogen-doped carbon nanometer pipe array and field emission performance characterization:
The nitrogen-doped carbon nanometer pipe array that step (3) is obtained carries out Si ion implantation processing in the source MEVVA, injection
When, silicon ion incident direction and axial resistivity are in about 10 degree of angle, and sample stage is kept at the uniform velocity to rotate, sample stage biased voltage
It is set as -20kV, line is set as 5 milliamperes, and injection length is 15 minutes multiple to get nitrogen doped silicon carbide-carbon nano pipe array
Condensation material.Flied emission test result shows (table 1), nitrogen doped silicon carbide-carbon nano pipe array threshold field obtained by the present embodiment
It is respectively 1.27V/ μm and 83.54mA/cm with maximum field emission2, far superior to unprocessed original carbon nanotubes
1.72V/ μm and 20.71mA/cm2, also superior to the prior art 1.39V/ μm (present invention reduces 0.12V/ μm) and
74.74mA/cm2(present invention improves 11.8%).
Embodiment 4
(1) silicon single crystal flake is pre-processed:
N-shaped (100) silicon single crystal flakes of 2cm × 2cm small pieces each ultrasound in deionized water and dehydrated alcohol will be first cut into
(50W) is cleaned 5 minutes, is then immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, is taken out dry later, then will obtain
The silicon single crystal flake of clean surface carry out carrying in metal vapor vacuum arc source (source MEVVA) can the pre- place of silver ion bombardment
Reason 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 10
Minute.
(2) chemical vapor deposition for carbon nanotubes array:
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 it is put into high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method.Growth carbon is received
When mitron, first the silicon single crystal flake for being deposited with iron catalyst is heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after
150sccm ammonia is handled 10 minutes under 750 degrees Celsius, finally in 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure
Lower growth carbon nano pipe array, growth time are 30 minutes, increase the temperature to 1000 degrees Celsius later, in 400sccm hydrogen, often
The carbon nanotube that high-temperature heat treatment generates is depressed, the processing time is 2 hours.
(3) nitrogen, hydrogen plasma process carbon nano pipe array:
The carbon nano pipe array that step (2) obtains is placed in microwave plasma system and carries out nitrogen, hydrogen etc. at normal temperature
Gas ions processing, the mixed gas that the gas for generating plasma is made of nitrogen and hydrogen, the flow of nitrogen, hydrogen
Respectively 5,10sccm, adjusting air pressure is 1.5kPa, after stable gas pressure, starts microwave source, sets microwave power as 150W, locates
Managing the time is 0.5 hour, i.e. acquisition nitrogen-doped carbon nanometer pipe array.
(4) Si ion implantation nitrogen-doped carbon nanometer pipe array and field emission performance characterization:
The nitrogen-doped carbon nanometer pipe array that step (3) is obtained carries out Si ion implantation processing in the source MEVVA, injection
When, silicon ion incident direction and axial resistivity are in about 10 degree of angle, and sample stage is kept at the uniform velocity to rotate, sample stage biased voltage
It is set as -20kV, line is set as 5 milliamperes, and injection length is 15 minutes multiple to get nitrogen doped silicon carbide-carbon nano pipe array
Condensation material.Flied emission test result shows (table 1), nitrogen doped silicon carbide-carbon nano pipe array threshold field obtained by the present embodiment
It is respectively 1.30V/ μm and 87.93mA/cm with maximum field emission2, far superior to unprocessed original carbon nanotubes
1.72V/ μm and 20.71mA/cm2, also superior to the prior art 1.39V/ μm (present invention reduces 0.07V/ μm) and
74.74mA/cm2(present invention improves 4.3%).
Embodiment 5
(1) silicon single crystal flake is pre-processed:
N-shaped (100) silicon single crystal flakes of 2cm × 2cm small pieces each ultrasound in deionized water and dehydrated alcohol will be first cut into
(50W) is cleaned 5 minutes, is then immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, is taken out dry later, then will obtain
The silicon single crystal flake of clean surface carry out carrying in metal vapor vacuum arc source (source MEVVA) can the pre- place of silver ion bombardment
Reason 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 10
Minute.
(2) chemical vapor deposition for carbon nanotubes array:
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 it is put into high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method.Growth carbon is received
When mitron, first the silicon single crystal flake for being deposited with iron catalyst is heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after
150sccm ammonia is handled 10 minutes under 750 degrees Celsius, finally in 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure
Lower growth carbon nano pipe array, growth time are 30 minutes, increase the temperature to 1000 degrees Celsius later, in 400sccm hydrogen, often
The carbon nanotube that high-temperature heat treatment generates is depressed, the processing time is 2 hours.
(3) nitrogen, hydrogen plasma process carbon nano pipe array:
The carbon nano pipe array that step (2) obtains is placed in microwave plasma system and carries out nitrogen, hydrogen etc. at normal temperature
Gas ions processing, the mixed gas that the gas for generating plasma is made of nitrogen and hydrogen, the flow of nitrogen, hydrogen
Respectively 5,10sccm, adjusting air pressure is 1.5kPa, after stable gas pressure, starts microwave source, sets microwave power as 200W, locates
Managing the time is 0.5 hour, i.e. acquisition nitrogen-doped carbon nanometer pipe array.
(4) Si ion implantation nitrogen-doped carbon nanometer pipe array and field emission performance characterization:
The nitrogen-doped carbon nanometer pipe array that step (3) is obtained carries out Si ion implantation processing in the source MEVVA, injection
When, silicon ion incident direction and axial resistivity are in about 10 degree of angle, and sample stage is kept at the uniform velocity to rotate, sample stage biased voltage
It is set as -20kV, line is set as 5 milliamperes, and injection length is 15 minutes multiple to get nitrogen doped silicon carbide-carbon nano pipe array
Condensation material.Flied emission test result shows (table 1), nitrogen doped silicon carbide-carbon nano pipe array threshold field obtained by the present embodiment
It is respectively 1.19V/ μm and 96.57mA/cm with maximum field emission2, far superior to unprocessed original carbon nanotubes
1.72V/ μm and 20.71mA/cm2, also superior to the prior art 1.39V/ μm (present invention reduces 0.20V/ μm) and
74.74mA/cm2(present invention improves 29.2%).
Embodiment 6
(1) silicon single crystal flake is pre-processed:
N-shaped (100) silicon single crystal flakes of 2cm × 2cm small pieces each ultrasound in deionized water and dehydrated alcohol will be first cut into
(50W) is cleaned 5 minutes, is then immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, is taken out dry later, then will obtain
The silicon single crystal flake of clean surface carry out carrying in metal vapor vacuum arc source (source MEVVA) can the pre- place of silver ion bombardment
Reason 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 10
Minute.
(2) chemical vapor deposition for carbon nanotubes array:
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 it is put into high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method.Growth carbon is received
When mitron, first the silicon single crystal flake for being deposited with iron catalyst is heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after
150sccm ammonia is handled 10 minutes under 750 degrees Celsius, finally in 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure
Lower growth carbon nano pipe array, growth time are 30 minutes, increase the temperature to 1000 degrees Celsius later, in 400sccm hydrogen, often
The carbon nanotube that high-temperature heat treatment generates is depressed, the processing time is 2 hours.
(3) nitrogen, hydrogen plasma process carbon nano pipe array:
The carbon nano pipe array that step (2) obtains is placed in microwave plasma system and carries out nitrogen, hydrogen etc. at normal temperature
Gas ions processing, the mixed gas that the gas for generating plasma is made of nitrogen and hydrogen, the flow of nitrogen, hydrogen
Respectively 5,10sccm, adjusting air pressure is 1.5kPa, after stable gas pressure, starts microwave source, sets microwave power as 175W, locates
Managing the time is 0.75 hour, i.e. acquisition nitrogen-doped carbon nanometer pipe array.
(4) Si ion implantation nitrogen-doped carbon nanometer pipe array and field emission performance characterization:
The nitrogen-doped carbon nanometer pipe array that step (3) is obtained carries out Si ion implantation processing in the source MEVVA, injection
When, silicon ion incident direction and axial resistivity are in about 10 degree of angle, and sample stage is kept at the uniform velocity to rotate, sample stage biased voltage
It is set as -20kV, line is set as 5 milliamperes, and injection length is 15 minutes multiple to get nitrogen doped silicon carbide-carbon nano pipe array
Condensation material.Flied emission test result shows (table 1), nitrogen doped silicon carbide-carbon nano pipe array threshold field obtained by the present embodiment
It is respectively 1.22V/ μm and 84.36mA/cm with maximum field emission2, far superior to unprocessed original carbon nanotubes
1.72V/ μm and 20.71mA/cm2, also superior to the prior art 1.39V/ μm (present invention reduces 0.17V/ μm) and
74.74mA/cm2(present invention improves 12.9%).
Embodiment 7
(1) silicon single crystal flake is pre-processed:
N-shaped (100) silicon single crystal flakes of 2cm × 2cm small pieces each ultrasound in deionized water and dehydrated alcohol will be first cut into
(50W) is cleaned 5 minutes, is then immersed in the hydrofluoric acid that volume ratio is 4% 5 minutes, is taken out dry later, then will obtain
The silicon single crystal flake of clean surface carry out carrying in metal vapor vacuum arc source (source MEVVA) can the pre- place of silver ion bombardment
Reason 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 10
Minute.
(2) chemical vapor deposition for carbon nanotubes array:
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 it is put into high quartz tube furnace and prepares carbon nano pipe array with conventional thermal chemical vapor deposition method.Growth carbon is received
When mitron, first the silicon single crystal flake for being deposited with iron catalyst is heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after
150sccm ammonia is handled 10 minutes under 750 degrees Celsius, finally in 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure
Lower growth carbon nano pipe array, growth time are 30 minutes, increase the temperature to 1000 degrees Celsius later, in 400sccm hydrogen, often
The carbon nanotube that high-temperature heat treatment generates is depressed, the processing time is 2 hours.
(3) nitrogen, hydrogen plasma process carbon nano pipe array:
The carbon nano pipe array that step (2) obtains is placed in microwave plasma system and carries out nitrogen, hydrogen etc. at normal temperature
Gas ions processing, the mixed gas that the gas for generating plasma is made of nitrogen and hydrogen, the flow of nitrogen, hydrogen
Respectively 5,10sccm, adjusting air pressure is 1.5kPa, after stable gas pressure, starts microwave source, sets microwave power as 200W, locates
Managing the time is 0.75 hour, i.e. acquisition nitrogen-doped carbon nanometer pipe array.
(4) Si ion implantation nitrogen-doped carbon nanometer pipe array and field emission performance characterization:
The nitrogen-doped carbon nanometer pipe array that step (3) is obtained carries out Si ion implantation processing in the source MEVVA, injection
When, silicon ion incident direction and axial resistivity are in about 10 degree of angle, and sample stage is kept at the uniform velocity to rotate, sample stage biased voltage
It is set as -20kV, line is set as 5 milliamperes, and injection length is 15 minutes multiple to get nitrogen doped silicon carbide-carbon nano pipe array
Condensation material.Flied emission test result shows (table 1), nitrogen doped silicon carbide-carbon nano pipe array threshold field obtained by the present embodiment
It is respectively 1.26V/ μm and 87.74mA/cm with maximum field emission2, far superior to unprocessed original carbon nanotubes
1.72V/ μm and 20.71mA/cm2, also superior to the prior art 1.39V/ μm (present invention reduces 0.13V/ μm) and
74.74mA/cm2(present invention improves 17.4%).
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 and performance boost of the achievable carbon nano pipe array of number, gained nitrogen doped silicon carbide-carbon nano pipe array threshold field are flat
Only have 1.10-1.32V/ μm, maximum field emission is average up to 77.93-110.96mA/cm2, in average Flied emission
Current density is up to 31.31mA/cm2, the current attenuation in 50 hours only have 3.4%, be significantly better than that original carbon nanotubes and
The prior art.It is apparent that there are many more other experiment parameter combined methods, this researchs the present invention is not limited to above-described embodiment
The relevant situation that those of ordinary skill in field directly can export or associate from present disclosure, should all recognize
To be protection scope of the present invention.
Table 1 is that the field emission performance of sample in the prior art and various embodiments of the present invention compares, wherein " Eth" indicate threshold value
, " Jmax" indicate maximum field emission, " ↓ " indicates decline, and " ↑ " indicates to rise.
Table 1.
Claims (5)
1. a kind of method for promoting carbon nano pipe array field emission performance characterized by comprising bombarded carrying energy silver ion
Silicon single crystal flake on thermal chemical vapor deposition method prepare carbon nano pipe array and high annealing, then utilize microwave nitrogen, hydrogen etc.
Gas ions handle carbon nano pipe array at normal temperature, are 150~200W by adjusting microwave power, chamber pressure is
The pattern that 1.5kPa, processing time are 0.5~1 hour to control carbon nanotube, then by gained nitrogen-doped carbon nanometer pipe array
Si ion implantation processing is carried out in metal vapor vacuum arc source (source MEVVA), is finally obtained nitrogen doped silicon carbide-carbon and is received
Mitron array；Gained nitrogen doped silicon carbide-carbon nano pipe array threshold field averagely only has 1.10-1.32V/ μm, maximum field hair
Radio current density is average up to 77.93-110.96mA/cm2, 31.31mA/cm is up in mean field emission2, it is 50 small
When in current attenuation only have 3.4%.
2. the method according to claim 1, wherein further including by silicon single crystal flake successively in deionized water and anhydrous
Respectively it is cleaned by ultrasonic 5 minutes preprocessing process in ethyl alcohol using 50W power.
3. the method according to claim 1, wherein further including the silicon single crystal flake merging volume after being cleaned by ultrasonic
Than the step of being hydrofluoric acid dips 5 minutes of 4%.
4. a kind of method for promoting carbon nano pipe array field emission performance according to claim 1, which is characterized in that by such as
Lower step carries out:
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 high annealing: the silicon single crystal flake that step (1) is obtained
It is placed in the iron catalyst film that deposition thickness is 5 nanometers in magnetic control sputtering device, the silicon single crystal flake is then placed in high quartz pipe
Carbon nano pipe array is prepared with conventional thermal chemical vapor deposition method in formula furnace, when growing carbon nanotube, iron will be first deposited with and urge
The silicon single crystal flake of agent is heat-treated 1 hour under 400sccm hydrogen, 580 degrees Celsius, after in 150sccm ammonia, 750 degrees Celsius
Lower processing 10 minutes, finally grows carbon nano pipe array under 87sccm acetylene, 600sccm hydrogen, 750 degrees Celsius, normal pressure, raw
For a long time it is 30 minutes, increases the temperature to 1000 degrees Celsius later, the carbon nanometer of generation is handled under 400sccm hydrogen, normal pressure
Pipe, processing time are 2 hours；
Step (3) nitrogen, hydrogen plasma process carbon nano pipe array: the carbon nano pipe array that step (2) is obtained is placed in microwave
Nitrogen, hydrogen plasma process are carried out in plasma system at normal temperature, the gas for generating plasma be by nitrogen and
The mixed gas of hydrogen composition, nitrogen, hydrogen flow be respectively 5,10sccm, adjustings air pressure is 1.5kPa, to stable gas pressure
Afterwards, start microwave source, set microwave power as 150~200W, the processing time is 0.5~1 hour, is that nitrogen is mixed obtained by the process
Miscellaneous carbon nano pipe array；
Step (4) Si ion implantation nitrogen-doped carbon nanometer pipe array: the nitrogen-doped carbon nanometer pipe array that step (3) obtains is existed
Si ion implantation processing is carried out in the source MEVVA, when injection, silicon ion incident direction and axial resistivity are in about 10 degree of folder
Angle, and sample stage is kept at the uniform velocity to rotate, sample stage biased voltage is set as -20kV, and line is set as 5 milliamperes, and injection length is 15 points
Clock is to get nitrogen doped silicon carbide-carbon nano-tube array composite material.
5. a kind of method for promoting carbon nano pipe array field emission performance according to claim 4, which is characterized in that used
Various gas purities are 5N.
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| CN110950323A (en) * | 2019-12-19 | 2020-04-03 | 湖南德智新材料有限公司 | Carbon nanotube-silicon carbide nanowire composite material and preparation method thereof |
| CN111392762A (en) * | 2020-04-09 | 2020-07-10 | 沈阳师范大学 | Preparation method of copper oxide nanowire array field emission cathode material based on metal ion implantation |
| CN113697812A (en) * | 2021-09-30 | 2021-11-26 | 中国航发北京航空材料研究院 | Preparation method of silicon carbide nanotube based on high-frequency electromagnetic field excitation |
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| CN1861521A (en) * | 2006-05-30 | 2006-11-15 | 浙江理工大学 | Synthesis process of needle shape nano silicon carbide |
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