CN106847648A - A kind of preparation method of the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure - Google Patents
A kind of preparation method of the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure Download PDFInfo
- Publication number
- CN106847648A CN106847648A CN201710116167.8A CN201710116167A CN106847648A CN 106847648 A CN106847648 A CN 106847648A CN 201710116167 A CN201710116167 A CN 201710116167A CN 106847648 A CN106847648 A CN 106847648A
- Authority
- CN
- China
- Prior art keywords
- graphene
- zinc oxide
- sandwich structure
- zno
- field emission
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Cold Cathode And The Manufacture (AREA)
Abstract
The invention belongs to microelectronic vacuum and display technology field, and in particular to a kind of preparation method of the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure, comprise the following steps：S10, with graphene oxide powder as raw material, on a monocrystaline silicon substrate using the layer graphene film of electrostatic spray techniques of deposition one；S20, penetrates magnetron sputtering technique and sputters layer of ZnO film as seed crystal on graphene film surface by the use of frequency, and with zinc salt and hexa as raw material, hydrothermal growth ZnO nano pin array obtains Graphene on silicon substrate/ZnO nano pin array composite material；S30, a layer graphene is deposited using electrostatic spray deposition technique on ZnO surfaces, and the Graphene/zinc oxide/Graphene composite cathode material with sandwich structure is obtained.Preparation technology of the invention is workable, equipment requirement is not high, cost is relatively low, large area can be carried out quickly to prepare, be expected to use for field emission Graphene/zinc oxide/Graphene sandwich structure compatible with large-scale production process, to obtain composite cathode material Flied emission Turn-on voltage is relatively low and emitting performance stabilization.
Description
Technical field
The invention belongs to microelectronic vacuum and display technology field, and in particular to a kind of use for field emission Graphene/zinc oxide/
The preparation method of the composite cathode material of Graphene sandwich structure.
Background technology
In the information age of current high speed development, to improve " portability " of electronic equipment, the flat board of display unit is realized
Change and minimize, the more traditional hot cathode ray tube Display Technique of development cold-cathode field lift-off technology has a clear superiority.Cold the moon
Pole Field Emission Display is beaten to cause on fluorescent screen using the electron beam that cold cathode sends and lighted come display image, is keeping excellent
Pre-heating system is avoided while as matter, with low Turn-on voltage, the features such as low-power consumption, small volume, structure ultrathin.
It is the cold-cathode material for being developed for Flied emission that cold-cathode field launches most crucial technology.In recent ten years, have many
Plant material and be found to have this potentiality, such as, and the GaN and AlN of early stage, subsequent CNT (CNTs), diamond/eka-gold
Hard rock or ZnO, or even the Graphene for occurring recently etc..Wherein, to be generally considered luminescent lifetime most long for ZnO, is currently the only energy
Enough steady operations within thousands of hours low pressure (<Cold-cathode material in 500V).In addition, ZnO can be easily by doping
Change material work functions, to reduce the purpose of threshold field strength.Recent studies have shown that, the unlatching of acicular nanometer ZnO emitters
Strong and threshold field strength is minimum, and it aligns and has more excellent field emission performance, within the specific limits, battle array than disordered structure
Row density is bigger, and emission current is bigger, but if density exceedes certain limit, the screen effect between pin and pin can cause field again
Enhancer reduces.But by the end of current, on orienting the preparation technology of ZnO sodium rice pin arrays in stability and controllability side
Face is also immature, and understanding on the affecting laws between array density and Flied emission enhancer is also insufficient.
Graphene (Graphene, G) also there is field emission cold-cathode material required for many unique properties, such as very
Electron mobility high (at room temperature 2, such as electron transfer very high is 100 times of Si), high current density patience (2), electricity high
Current density patience, is 100 times of Cu), high thermal conductivity (3-5 high thermal conductivities (patience (, suitable with CNTs) and superpower chemistry
With mechanical strength (suitable with diamond) etc., it is expected to play important in fields such as high-performance nano electronic device, field emmision materials
Effect.
In order to give full play to the advantage of respective emissive material, nearest people attempt by various field emmision materials be combined with
As novel cold cathode emitter.The Preliminary Results of ZnO/CNTs complexs show that some field emission performances are obtained really
Certain improvement.Nearest part research institution of China is to the complex of ZnO nano-wire or nanometer rods and Graphene in cold-cathode field
Research in terms of transmitting has been also carried out preliminary trial, and proves than single ZnO or grapheme material with lower unlatching
By force.The new field emission body for being to prepare a kind of Graphene/ZnO nano pin array/Graphene sandwich structure proposed by the present invention,
Using process optimization with obtain it is a kind of there is high current density, Low threshold field intensity, and long lifespan, good stability novel cold cathode
Field emission material.Preparation method of the invention is workable, and equipment requirement is not high, and cost is relatively low, can carry out large area fast
Prepared by speed, with emission effciency and emissive porwer higher, can provide a kind of new approaches for correlative study.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of use for field emission Graphene/zinc oxide/Graphene sandwich knot
The preparation method of the composite cathode material of structure.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：
A kind of system of the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure of the invention
Preparation Method, comprises the following steps：
S10, with graphene oxide powder as raw material, on a monocrystaline silicon substrate using one layer of electrostatic spray techniques of deposition
Graphene film；
S20, penetrates magnetron sputtering technique and sputters layer of ZnO film as seed crystal, with zinc on graphene film surface by the use of frequency
Salt and hexa are raw material, and hydrothermal growth ZnO nano pin array obtains Graphene on silicon substrate/ZnO nano pin array
Composite；
S30, a layer graphene is deposited using electrostatic spray deposition technique on ZnO surfaces, is obtained with sandwich structure
Graphene/zinc oxide/Graphene composite cathode material.
Preferably, S10 is specifically included：
S101, graphene oxide powder is dissolved in the mixed liquor of 1,2-PD and absolute ethyl alcohol by 0.1~0.5mmol/L
In, ultrasonic wave obtains the suspended precursor liquid that electrostatic spray deposits (ESD) after stirring 1~2h；
S102, monocrystalline silicon piece is fixed on substrate clamping plate, and substrate temperature then is heated into 100~250 DEG C；
S103, it is 5~7cm to adjust the distance between capillary nozzle and substrate of ESD devices, added DC voltage is 9~
12kV；
The suspended precursor liquid of S104, the ESD that step S101 is obtained adds the liquid stream that ESD devices are set to ESD devices
Spray speed is the liquid of 600~800 μ 00, opens switch, and ESD devices start to be sprayed to ESD precursor liquids on backing material；
S105, after 1~2h of spraying, closes ESD devices；Normal temperature is cooled to, graphene film material on silicon substrate is obtained.
Preferably, S20 is specifically included：
S201, used as substrate, ZnO ceramics are target to graphene film on the silicon substrate that step S105 is obtained, using penetrating
Frequency magnetron sputtering technique, sputters 10~30min in the argon gas atmosphere of 0.1~1Pa, the ZnO film thickness of deposition for 100~
200nm；
S202, takes 0.5~4mmol zinc salts and 0.25~2mmol hexas are dissolved in 30ml deionized waters, machinery
0.1~2h of stirring mixing；
S203, is transferred to the stainless steel high pressure with polytetrafluoroethyllining lining that volume is 50ml anti-by above-mentioned mixed solution
The ZnO film sample deposited in answering kettle, then on the graphene substrate that step S201 is obtained is inverted in autoclave；
S204, after autoclave is sealed after 8~24h of hydro-thermal reaction under 70~150 DEG C of temperature conditionss, takes out sample
18~36h is dried in 60 DEG C of thermostatic drying chambers, Graphene on silicon substrate/ZnO nano pin array composite material is obtained.
Preferably, S30 is specifically included：The step of repeating S101-S105, wherein substrate surface are ZnO nano pin array, are obtained
Graphene/zinc oxide/Graphene composite cathode material with sandwich structure.
Preferably, graphene oxide powder, 1,2-PD and absolute ethyl alcohol are and analyze pure, and mass percent is respectively
99%th, 99.5% and 99.8%.
Preferably, 1,2-PD is 1 with the volume ratio of absolute ethyl alcohol with 1,2-PD in the mixed liquor of absolute ethyl alcohol：
2~2：1.
Preferably, monocrystalline silicon piece is N-type or p-type<100>、<111>Or<001>Monocrystalline silicon buffing sheet, resistivity is 3~10
The silicon of Ω 0.
Preferably, the mass percent of ZnO target material is 99.99%, and the mass percent of argon gas is 99.995%.
Preferably, zinc salt is the pure two water zinc acetate of analysis or zinc nitrate hexahydrate, mass percent be respectively 99.99% or
99%, hexa is pure for analysis, and mass percent is 99.5%.
There is following beneficial effect using the present invention：
1st, preparation technology of the invention is workable, and equipment requirement is not high, and cost is relatively low, can carry out large area and quickly make
It is standby, it is expected to answering for use for field emission Graphene/zinc oxide/Graphene sandwich structure compatible with large-scale production process, to obtain
Conjunction cathode material Flied emission Turn-on voltage is relatively low and emitting performance is stable；
2nd, ZnO nano pin array structure is controllable, by adjusting hydrothermal temperature, reactant concentration, acid-base value and reaction time
Controllable nanoneedle draw ratio, array density etc.；
3rd, compound the moon of use for field emission Graphene/zinc oxide/Graphene sandwich structure is obtained by the method for the present invention
Pole material field transmitting property is excellent, and transmitting Turn-on voltage is relatively low and emitting performance is stable.
Brief description of the drawings
Fig. 1 be the present invention be rational use for field emission Graphene/zinc oxide/Graphene sandwich structure composite cathode material
The preparation technology flow chart of material；
Fig. 2 is the composite cathode material of the use for field emission Graphene/zinc oxide/Graphene sandwich structure of the embodiment of the present invention
The SEM figures of material；
Fig. 3 is the composite cathode material of the use for field emission Graphene/zinc oxide/Graphene sandwich structure of the embodiment of the present invention
The Flied emission I-V curve of material.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is a part of embodiment of the invention, rather than whole embodiments.Based on this hair
Embodiment in bright, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to the scope of protection of the invention.
Embodiment 1：
As shown in figure 1, measuring the pure 1,2-PD 33.33ml of analysis and quality hundred that mass percent is 99.5% respectively
Divide than the pure absolute ethyl alcohol 66.67ml of analysis for 99.8%, after both are sufficiently mixed, obtain 1,2-PD and absolute ethyl alcohol
Volume ratio is 1：2 mixed liquor 100ml, the analysis pure zirconia graphene powder that 0.05mmol mass percents are 99% is dissolved in
In the mixed liquor, after ultrasonic wave stirring 1h, the suspended precursor liquid of electrostatic spray deposition (ESD) is obtained；Then by N-type<001>
Monocrystalline silicon buffing sheet (resistivity is 3 silicon polishings) is fixed on substrate clamping plate, and substrate temperature is heated into 100 DEG C, regulation ESD dresses
The distance between capillary nozzle for putting and substrate are 5cm, plus DC voltage is 12kV, the ESD precursor liquids that will be prepared add to
ESD devices, the liquid stream spray speed for setting ESD devices is 600ml/h, opens switch, and ESD devices start to be sprayed to ESD precursor liquids
On backing material, after spraying 2h, ESD devices are closed, be cooled to normal temperature, obtain graphene film material on silicon substrate；To obtain
Silicon substrate on graphene film as substrate, mass percent be 99.99% ZnO ceramics for target, using radio-frequency magnetic
Control sputtering technology, 10min, the ZnO film thickness of deposition are sputtered in argon gas (mass percent is 99.995%) atmosphere of 1Pa
It is 100nm；The pure two water zinc acetate of analysis that 0.5mmol mass percents are 99.99% is taken again and 2mmol mass percents are
The 99.5% pure hexa of analysis is dissolved in 30ml deionized waters, and after mechanical agitation mixing 0.5h, being transferred to volume is
In the stainless steel autoclave with polytetrafluoroethyllining lining of 50ml, then deposition obtained above there is ZnO film seed crystal
Graphene substrate be inverted in autoclave, after autoclave is sealed under 70 DEG C of temperature conditionss hydro-thermal reaction 24h
Afterwards, take out sample and dry 18h in 60 DEG C of thermostatic drying chambers, obtain Graphene on silicon substrate/ZnO nano pin array composite wood
Material；The composite is fixed on substrate clamping plate again finally, identical electrostatic is used with suspended precursor liquid using above-mentioned ESD
Mist depositing operation, i.e. 100 DEG C of substrate temperature, distance is 5cm between capillary nozzle and substrate, and added DC voltage is 9kV, the spray of liquid stream
Speed is 600ml/h, after spraying 1h, obtains final sample -- the Graphene with sandwich structure/ZnO nano pin battle array on silicon substrate
The composite of row/Graphene.
Final composite sample is made into negative electrode, copper sheet does anode, is placed in high voltage direct current pressure, test its field emission performance,
Obtain I-V curve.The sample surfaces ZnO nano pin draw ratio 8:1, Graphene is distributed in that array is more uniform, and Turn-on voltage is
10.4V/μm。
Embodiment 2
As shown in figure 1, measuring the pure 1,2-PD 50ml of analysis and quality percentage that mass percent is 99.5% respectively
Than the pure absolute ethyl alcohol 50ml of analysis for 99.8%, after both are sufficiently mixed, 1,2-PD and absolute ethyl alcohol volume are obtained
Than being 1:1 mixed liquor 100ml, is dissolved in the analysis pure zirconia graphene powder that 0.03mmol mass percents are 99% this and mixes
Close in liquid, after ultrasonic wave stirring 1.5h, obtain the suspended precursor liquid of electrostatic spray deposition (ESD)；Then by N-type<111>It is single
(resistivity is fixed on substrate clamping plate crystal silicon polished silicon wafer for 8.1 mating plates (), and substrate temperature is heated into 150 DEG C, regulation ESD dresses
The distance between capillary nozzle for putting and substrate are 6cm, plus DC voltage is 11kV, the ESD precursor liquids that will be prepared add to
ESD devices, the liquid stream spray speed for setting ESD devices is 650ml/h, opens switch, and ESD devices start to be sprayed to ESD precursor liquids
On backing material, after spraying 1.5h, ESD devices are closed, be cooled to normal temperature, obtain graphene film material on silicon substrate；Will
Graphene film is used as substrate on the silicon substrate of acquisition, and mass percent is that 99.99% ZnO ceramics are target, using radio frequency
Magnetron sputtering technique, 15min, the ZnO film of deposition are sputtered in argon gas (mass percent is 99.995%) atmosphere of 0.5Pa
Thickness is 120nm；The pure two water zinc acetate of analysis and 0.5mmol mass percents that 2mmol mass percents are 99.99% are taken again
The pure hexa of analysis for 99.5% is dissolved in 30ml deionized waters, after mechanical agitation mixing 0.1h, is transferred to volume
In for the stainless steel autoclave with polytetrafluoroethyllining lining of 50ml, then deposition obtained above there is ZnO film seed
Brilliant graphene substrate is inverted in autoclave, after autoclave is sealed under 120 DEG C of temperature conditionss hydro-thermal reaction
After 16h, take out sample and dry 30h in 60 DEG C of thermostatic drying chambers, obtain Graphene on silicon substrate/ZnO nano pin array and be combined
Material.
The composite is fixed on substrate clamping plate again finally, identical is used with suspended precursor liquid using above-mentioned ESD
Electrostatic spray depositing operation, i.e. 150 DEG C of substrate temperature, distance is 6cm between capillary nozzle and substrate, and added DC voltage is
11kV, liquid stream spray speed is 650ml/h, after spraying 1.5h, obtains final sample -- the graphite with sandwich structure on silicon substrate
The composite of alkene/ZnO nano pin array/Graphene；Final composite sample is made into negative electrode, copper sheet does anode, be placed in straightening high
Under stream voltage, its field emission performance is tested, obtain I-V curve.The sample surfaces ZnO nano pin draw ratio 10:1, Graphene point
It is distributed in array more uniform, Turn-on voltage is 5.7V/ μm.
Embodiment 3
As shown in figure 1, measuring the pure 1,2-PD 33.33ml of analysis and quality hundred that mass percent is 99.5% respectively
Divide than the pure absolute ethyl alcohol 66.67ml of analysis for 99.8%, after both are sufficiently mixed, obtain 1,2-PD and absolute ethyl alcohol
Volume ratio is 1：2 mixed liquor 100ml, the analysis pure zirconia graphene powder that 0.02mmol mass percents are 99% is dissolved in
In the mixed liquor, after ultrasonic wave stirring 1h, the suspended precursor liquid of electrostatic spray deposition (ESD) is obtained；Then by N-type<100>
(resistivity is fixed on substrate clamping plate monocrystalline silicon buffing sheet for 5.8 mating plates (), and substrate temperature is heated into 200 DEG C, adjusts ESD
The distance between capillary nozzle and substrate of device are 6cm, plus DC voltage is 10kV, and the ESD precursor liquids that will be prepared are added
To ESD devices, the liquid stream spray speed for setting ESD devices is 700ml/h, opens switch, and ESD devices start to spray ESD precursor liquids
To backing material, after spraying 1h, ESD devices are closed, be cooled to normal temperature, obtain graphene film material on silicon substrate；Will
Graphene film is used as substrate on the silicon substrate of acquisition, and mass percent is that 99.99% ZnO ceramics are target, using radio frequency
Magnetron sputtering technique, 20min, the ZnO film of deposition are sputtered in argon gas (mass percent is 99.995%) atmosphere of 0.3Pa
Thickness is 150nm；The pure two water zinc acetate of analysis that 1mmol mass percents are 99.99% is taken again and 1mmol mass percents are
The 99.5% pure hexa of analysis is dissolved in 30ml deionized waters, and after mechanical agitation mixing 1h, being transferred to volume is
In the stainless steel autoclave with polytetrafluoroethyllining lining of 50ml, then deposition obtained above there is ZnO film seed crystal
Graphene substrate be inverted in autoclave, after autoclave is sealed under 90 DEG C of temperature conditionss hydro-thermal reaction 12h
Afterwards, take out sample and dry 36h in 60 DEG C of thermostatic drying chambers, obtain Graphene on silicon substrate/ZnO nano pin array composite wood
Material；The composite is fixed on substrate clamping plate again finally, identical electrostatic is used with suspended precursor liquid using above-mentioned ESD
Mist depositing operation, i.e. 200 DEG C of substrate temperature, distance is 6cm between capillary nozzle and substrate, and added DC voltage is 10kV, liquid stream
Spray speed is 700ml/h, after spraying 1h, obtains final sample -- the Graphene/ZnO nano pin with sandwich structure on silicon substrate
The composite of array/Graphene.
Final composite sample is made into negative electrode, copper sheet does anode, is placed in high voltage direct current pressure, test its field emission performance,
Obtain I-V curve.The sample surfaces ZnO nano pin draw ratio 15:1, Graphene is distributed in array uniformly, as shown in accompanying drawing 2.It is multiple
The minimum Turn-on voltage of compound is 2.8V/ μm, sees accompanying drawing 3.
Embodiment 4
As shown in figure 1, measuring the pure 1,2-PD 40ml of analysis and quality percentage that mass percent is 99.5% respectively
Than the pure absolute ethyl alcohol 60ml of analysis for 99.8%, after both are sufficiently mixed, 1,2-PD and absolute ethyl alcohol volume are obtained
Than being 1:1.5 mixed liquor 100ml, this is dissolved in by the analysis pure zirconia graphene powder that 0.04mmol mass percents are 99%
In mixed liquor, after ultrasonic wave stirring 2h, the suspended precursor liquid of electrostatic spray deposition (ESD) is obtained；Then by p-type<100>It is single
Crystal silicon polished silicon wafer (resistivity is 6.9 polished silicon wafers) is fixed on substrate clamping plate, and substrate temperature is heated into 180 DEG C, regulation ESD dresses
The distance between capillary nozzle and substrate for putting are 5.5cm, plus DC voltage is 10kV, and the ESD precursor liquids that will be prepared are added
To ESD devices, the liquid stream spray speed for setting ESD devices is 750ml/h, opens switch, and ESD devices start to spray ESD precursor liquids
To backing material, after spraying 1h, ESD devices are closed, be cooled to normal temperature, obtain graphene film material on silicon substrate；Will
Graphene film is used as substrate on the silicon substrate of acquisition, and mass percent is that 99.99% ZnO ceramics are target, using radio frequency
Magnetron sputtering technique, 25min, the ZnO film of deposition are sputtered in argon gas (mass percent is 99.995%) atmosphere of 0.8Pa
Thickness is 180nm；The pure two water zinc acetate of analysis and 1.5mmol mass percents that 3mmol mass percents are 99.99% are taken again
The pure hexa of analysis for 99.5% is dissolved in 30ml deionized waters, after mechanical agitation mixing 1.5h, is transferred to volume
In for the stainless steel autoclave with polytetrafluoroethyllining lining of 50ml, then deposition obtained above there is ZnO film seed
Brilliant graphene substrate is inverted in autoclave, after autoclave is sealed under 110 DEG C of temperature conditionss hydro-thermal reaction
After 20h, take out sample and dry 24h in 60 DEG C of thermostatic drying chambers, obtain Graphene on silicon substrate/ZnO nano pin array and be combined
Material；The composite is fixed on substrate clamping plate again finally, identical electrostatic is used with suspended precursor liquid using above-mentioned ESD
Sprayed deposit technique, i.e. 180 DEG C of substrate temperature, distance is 5.5cm between capillary nozzle and substrate, and added DC voltage is 10kV,
Liquid stream spray speed is 750ml/h, after spraying 1h, obtains final sample -- the Graphene/ZnO with sandwich structure receives on silicon substrate
The composite of rice pin array/Graphene.
Final composite sample is made into negative electrode, copper sheet does anode, is placed in high voltage direct current pressure, test its field emission performance,
Obtain I-V curve.The sample surfaces ZnO nano pin draw ratio 8:1, Graphene is distributed in that array is more uniform, and Turn-on voltage is
11.6V/μm。
Embodiment 5
As shown in figure 1, measuring the pure 1,2-PD 33.33ml of analysis and quality hundred that mass percent is 99.5% respectively
Divide than the pure absolute ethyl alcohol 66.67ml of analysis for 99.8%, after both are sufficiently mixed, obtain 1,2-PD and absolute ethyl alcohol
Volume ratio is 1：2 mixed liquor 100ml, the analysis pure zirconia graphene powder that 0.02mmol mass percents are 99% is dissolved in
In the mixed liquor, after ultrasonic wave stirring 1h, the suspended precursor liquid of electrostatic spray deposition (ESD) is obtained；Then by p-type<111>
(resistivity is fixed on substrate clamping plate monocrystalline silicon buffing sheet for 7.9 mating plates (), and substrate temperature is heated into 220 DEG C, adjusts ESD
The distance between capillary nozzle and substrate of device are 6cm, plus DC voltage is 10kV, and the ESD precursor liquids that will be prepared are added
To ESD devices, the liquid stream spray speed for setting ESD devices is 700ml/h, opens switch, and ESD devices start to spray ESD precursor liquids
To backing material, after spraying 1.2h, ESD devices are closed, be cooled to normal temperature, obtain graphene film material on silicon substrate；
Graphene film is used as substrate on the silicon substrate that will be obtained, mass percent be 99.99% ZnO ceramics for target, using penetrating
Frequency magnetron sputtering technique, 20min is sputtered in argon gas (mass percent is 99.995%) atmosphere of 0.6Pa, and the ZnO of deposition is thin
Film thickness is 150nm；The pure two water zinc acetate of analysis and 2mmol mass percentages that 2.5mmol mass percents are 99.99% are taken again
It is dissolved in 30ml deionized waters than the pure hexa of analysis for 99.5%, after mechanical agitation mixing 2h, is transferred to volume
In for the stainless steel autoclave with polytetrafluoroethyllining lining of 50ml, then deposition obtained above there is ZnO film seed
Brilliant graphene substrate is inverted in autoclave, after autoclave is sealed under 100 DEG C of temperature conditionss hydro-thermal reaction
After 16h, take out sample and dry 24h in 60 DEG C of thermostatic drying chambers, obtain Graphene on silicon substrate/ZnO nano pin array and be combined
Material；The composite is fixed on substrate clamping plate again finally, identical electrostatic is used with suspended precursor liquid using above-mentioned ESD
Sprayed deposit technique, i.e. 220 DEG C of substrate temperature, distance is 6cm between capillary nozzle and substrate, and added DC voltage is 10kV, liquid
Stream spray speed is 700ml/h, after spraying 1.2h, obtains final sample -- the Graphene/ZnO with sandwich structure receives on silicon substrate
The composite of rice pin array/Graphene.
Final composite sample is made into negative electrode, copper sheet does anode, is placed in high voltage direct current pressure, test its field emission performance,
Obtain I-V curve.The sample surfaces ZnO nano pin draw ratio 6:1, Graphene is distributed in that array is more uniform, and Turn-on voltage is
18.1V/μm。
Embodiment 6
As shown in figure 1, measuring the pure 1,2-PD 66.67ml of analysis and quality hundred that mass percent is 99.5% respectively
Divide than the pure absolute ethyl alcohol 33.33ml of analysis for 99.8%, after both are sufficiently mixed, obtain 1,2-PD and absolute ethyl alcohol
Volume ratio is 2:1 mixed liquor 100ml, the analysis pure zirconia graphene powder that 0.01mmol mass percents are 99% is dissolved in
In the mixed liquor, after ultrasonic wave stirring 2h, the suspended precursor liquid of electrostatic spray deposition (ESD) is obtained；Then by p-type<001>
Monocrystalline silicon buffing sheet (resistivity is 10 silicon polishings) is fixed on substrate clamping plate, and substrate temperature is heated into 250 DEG C, adjusts ESD
The distance between capillary nozzle of device and substrate are 7cm, plus DC voltage is 9kV, the ESD precursor liquids that will be prepared add to
ESD devices, the liquid stream spray speed for setting ESD devices is 800ml/h, opens switch, and ESD devices start to be sprayed to ESD precursor liquids
On backing material, after spraying 1h, ESD devices are closed, be cooled to normal temperature, obtain graphene film material on silicon substrate；To obtain
Silicon substrate on graphene film as substrate, mass percent be 99.99% ZnO ceramics for target, using radio-frequency magnetic
Control sputtering technology, sputters 30min in argon gas (mass percent is 99.995%) atmosphere of 0.1Pa, and the ZnO film of deposition is thick
It is 200nm to spend；The pure two water zinc acetate of analysis and 0.25mmol mass percents that 4mmol mass percents are 99.99% are taken again
The pure hexa of analysis for 99.5% is dissolved in 30ml deionized waters, after mechanical agitation mixing 0.5h, is transferred to volume
In for the stainless steel autoclave with polytetrafluoroethyllining lining of 50ml, then deposition obtained above there is ZnO film seed
Brilliant graphene substrate is inverted in autoclave, after autoclave is sealed under 150 DEG C of temperature conditionss hydro-thermal reaction
After 8h, take out sample and dry 24h in 60 DEG C of thermostatic drying chambers, obtain Graphene on silicon substrate/ZnO nano pin array composite wood
Material；The composite is fixed on substrate clamping plate again finally, identical electrostatic is used with suspended precursor liquid using above-mentioned ESD
Mist depositing operation, i.e. 250 DEG C of substrate temperature, distance is 7cm between capillary nozzle and substrate, and added DC voltage is 9kV, the spray of liquid stream
Speed is 800ml/h, after spraying 2h, obtains final sample -- the Graphene with sandwich structure/ZnO nano pin battle array on silicon substrate
The composite of row/Graphene.
Final composite sample is made into negative electrode, copper sheet does anode, is placed in high voltage direct current pressure, test its field emission performance,
Obtain I-V curve.The sample surfaces ZnO nano pin draw ratio 7:1, Graphene is distributed in that array is more uniform, and Turn-on voltage is
12.3V/μm。
It should be appreciated that exemplary embodiment as herein described is illustrative and be not restrictive.Although being retouched with reference to accompanying drawing
One or more embodiments of the invention is stated, it should be understood by one skilled in the art that without departing from appended right
It is required that in the case of the spirit and scope of the present invention for being limited, the change of various forms and details can be made.
Claims (10)
1. a kind of preparation method of the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure, it is special
Levy and be, comprise the following steps：
S10, with graphene oxide powder as raw material, on a monocrystaline silicon substrate using one layer of graphite of electrostatic spray techniques of deposition
Alkene film；
S20, penetrates magnetron sputtering technique and sputters layer of ZnO film as seed crystal on graphene film surface by the use of frequency, with zinc salt and
Hexa is raw material, and hydrothermal growth ZnO nano pin array obtains Graphene on silicon substrate/ZnO nano pin array and is combined
Material；
S30, a layer graphene is deposited using electrostatic spray deposition technique on ZnO surfaces, and the graphite with sandwich structure is obtained
Alkene/zinc oxide/Graphene composite cathode material.
2. the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure according to claim 1
Preparation method, it is characterised in that S10 is specifically included：
S101, graphene oxide powder is dissolved in mixed liquor of the 1,2-PD with absolute ethyl alcohol by 0.1~0.5mmol/l,
Ultrasonic wave obtains the suspended precursor liquid that electrostatic spray deposits (ESD) after stirring 1~2h；
S102, monocrystalline silicon piece is fixed on substrate clamping plate, and substrate temperature then is heated into 100~250 DEG C；
S103, it is 5~7cm to adjust the distance between capillary nozzle and substrate of ESD devices, and added DC voltage is 9~12kV；
The suspended precursor liquid of S104, the ESD that step S101 is obtained adds the liquid stream spray speed that ESD devices are set to ESD devices
It is the liquid of 600~800 μ 00, opens switch, ESD devices starts to be sprayed to ESD precursor liquids on backing material；
S105, after 1~2h of spraying, closes ESD devices；Normal temperature is cooled to, graphene film material on silicon substrate is obtained.
3. the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure according to claim 1
Preparation method, it is characterised in that S20 is specifically included：
S201, using graphene film as substrate, ZnO ceramics are target, using radiofrequency magnetron sputtering technology, 0.1~1Pa's
10~30min is sputtered in argon gas atmosphere, the ZnO film thickness of deposition is 100~200nm；
S202, takes 0.5~4mmol zinc salts and 0.25~2mmol hexas are dissolved in 30ml deionized waters, mechanical agitation
0.1~2h of mixing；
S203, above-mentioned mixed solution is transferred in the stainless steel autoclave with polytetrafluoroethyllining lining, then step
The ZnO film sample deposited on the graphene substrate that S201 is obtained is inverted in autoclave；
S204, after autoclave is sealed after 8~24h of hydro-thermal reaction under 70~150 DEG C of temperature conditionss, takes out sample 60
18~36h is dried in DEG C thermostatic drying chamber, Graphene on silicon substrate/ZnO nano pin array composite material is obtained.
4. the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure according to claim 2
Preparation method, it is characterised in that S30 is specifically included：The step of repeating S101-S105, wherein substrate surface are ZnO nano pin battle array
Row, are obtained the Graphene/zinc oxide/Graphene composite cathode material with sandwich structure.
5. the composite cathode of the use for field emission Graphene/zinc oxide/Graphene sandwich structure according to claim 2 or 4
The preparation method of material, it is characterised in that the graphene oxide powder, 1,2-PD and absolute ethyl alcohol are analyzes pure,
Mass percent is respectively 99%, 99.5% and 99.8%.
6. the composite cathode of the use for field emission Graphene/zinc oxide/Graphene sandwich structure according to claim 2 or 4
The preparation method of material, it is characterised in that the 1,2-PD and 1,2-PD in the mixed liquor of absolute ethyl alcohol with it is anhydrous
The volume ratio of ethanol is 1：2~2：1.
7. according to compound the moon of any described use for field emission Graphene/zinc oxide/Graphene sandwich structures of claim 1-4
The preparation method of pole material, it is characterised in that the monocrystalline silicon piece is N-type or p-type<100>、<111>Or<001>Monocrystalline silicon is thrown
Mating plate, resistivity is 3~10 silicon polishings.
8. the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure according to claim 3
Preparation method, it is characterised in that the mass percent of described ZnO target material is 99.99%, and the mass percent of argon gas is
99.995%.
9. the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure according to claim 3
Preparation method, it is characterised in that the zinc salt is the pure two water zinc acetate of analysis or zinc nitrate hexahydrate, and mass percent is respectively
99.99% or 99%.
10. the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure according to claim 3
The preparation method of material, it is characterised in that hexa is pure for analysis, and mass percent is 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710116167.8A CN106847648B (en) | 2017-03-01 | 2017-03-01 | A kind of preparation method of use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710116167.8A CN106847648B (en) | 2017-03-01 | 2017-03-01 | A kind of preparation method of use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106847648A true CN106847648A (en) | 2017-06-13 |
| CN106847648B CN106847648B (en) | 2019-01-08 |
Family
ID=59137673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710116167.8A Active CN106847648B (en) | 2017-03-01 | 2017-03-01 | A kind of preparation method of use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106847648B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188163A (en) * | 2017-06-28 | 2017-09-22 | 华南农业大学 | A kind of self assembly graphene growth in situ nanometer stick array composite membrane and preparation method thereof |
| CN107731638A (en) * | 2017-09-20 | 2018-02-23 | 西安石油大学 | Cold cathode structure based on the miniature emitting area of graphene oxide/graphene and preparation method thereof |
| CN107731637A (en) * | 2017-09-20 | 2018-02-23 | 西安石油大学 | A kind of Flied emission based on graphene oxide/graphene ZnO micro-structurals is adjusted and controlled and method |
| CN113921826A (en) * | 2021-10-09 | 2022-01-11 | 深圳石墨烯创新中心有限公司 | Vertical graphene/nano-silver composite material and preparation method and application thereof |
| CN115020528A (en) * | 2022-05-06 | 2022-09-06 | 北京科技大学 | Graphene-zinc oxide-graphene vertical photoelectric detector and construction method |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157315A (en) * | 2011-03-21 | 2011-08-17 | 福州大学 | Emitting cathode based on composite material of graphene/zinc oxide nanowire and preparation of same |
| CN102222572A (en) * | 2011-03-21 | 2011-10-19 | 中国科学院半导体研究所 | Preparation method of light anode with a composite nano-wire array/ nano-crystalline porous membrane structure |
| CN102280259A (en) * | 2011-03-21 | 2011-12-14 | 中国科学院半导体研究所 | Method for preparing nanometer polychromatic-light anode of dye-sensitized solar cell |
| CN102290248A (en) * | 2011-06-10 | 2011-12-21 | 浙江东晶电子股份有限公司 | Method for preparing efficient compound light anode of dye sensitized solar cell |
| CN102557728A (en) * | 2012-02-17 | 2012-07-11 | 上海大学 | Method for preparing graphene film and graphene composite carbon film |
| CN102903541A (en) * | 2012-10-16 | 2013-01-30 | 湖南大学 | Method for preparing graphene-based electrode material for super-capacitor |
| CN103252227A (en) * | 2013-04-27 | 2013-08-21 | 北京交通大学 | Tetrapod-like zinc oxide/graphene composite material and preparation method thereof |
| CN104167537A (en) * | 2014-09-12 | 2014-11-26 | 杭州电子科技大学 | Graphene/zinc oxide negative electrode material for lithium ion battery, and preparation method thereof |
| CN105244249A (en) * | 2015-10-20 | 2016-01-13 | 天津师范大学 | Graphene sheet-carbon nanotube film flexible composite material, preparation method and application thereof |
| CN105271362A (en) * | 2015-10-31 | 2016-01-27 | 合肥师范学院 | Preparation method of ZnO nano-structure with petal effect |
| CN105390676A (en) * | 2015-11-02 | 2016-03-09 | 北京师范大学 | Quick preparation method for graphene base metal or metal oxide with sandwich structure |
-
2017
- 2017-03-01 CN CN201710116167.8A patent/CN106847648B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157315A (en) * | 2011-03-21 | 2011-08-17 | 福州大学 | Emitting cathode based on composite material of graphene/zinc oxide nanowire and preparation of same |
| CN102222572A (en) * | 2011-03-21 | 2011-10-19 | 中国科学院半导体研究所 | Preparation method of light anode with a composite nano-wire array/ nano-crystalline porous membrane structure |
| CN102280259A (en) * | 2011-03-21 | 2011-12-14 | 中国科学院半导体研究所 | Method for preparing nanometer polychromatic-light anode of dye-sensitized solar cell |
| CN102290248A (en) * | 2011-06-10 | 2011-12-21 | 浙江东晶电子股份有限公司 | Method for preparing efficient compound light anode of dye sensitized solar cell |
| CN102557728A (en) * | 2012-02-17 | 2012-07-11 | 上海大学 | Method for preparing graphene film and graphene composite carbon film |
| CN102903541A (en) * | 2012-10-16 | 2013-01-30 | 湖南大学 | Method for preparing graphene-based electrode material for super-capacitor |
| CN103252227A (en) * | 2013-04-27 | 2013-08-21 | 北京交通大学 | Tetrapod-like zinc oxide/graphene composite material and preparation method thereof |
| CN104167537A (en) * | 2014-09-12 | 2014-11-26 | 杭州电子科技大学 | Graphene/zinc oxide negative electrode material for lithium ion battery, and preparation method thereof |
| CN105244249A (en) * | 2015-10-20 | 2016-01-13 | 天津师范大学 | Graphene sheet-carbon nanotube film flexible composite material, preparation method and application thereof |
| CN105271362A (en) * | 2015-10-31 | 2016-01-27 | 合肥师范学院 | Preparation method of ZnO nano-structure with petal effect |
| CN105390676A (en) * | 2015-11-02 | 2016-03-09 | 北京师范大学 | Quick preparation method for graphene base metal or metal oxide with sandwich structure |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188163A (en) * | 2017-06-28 | 2017-09-22 | 华南农业大学 | A kind of self assembly graphene growth in situ nanometer stick array composite membrane and preparation method thereof |
| CN107731638A (en) * | 2017-09-20 | 2018-02-23 | 西安石油大学 | Cold cathode structure based on the miniature emitting area of graphene oxide/graphene and preparation method thereof |
| CN107731637A (en) * | 2017-09-20 | 2018-02-23 | 西安石油大学 | A kind of Flied emission based on graphene oxide/graphene ZnO micro-structurals is adjusted and controlled and method |
| CN113921826A (en) * | 2021-10-09 | 2022-01-11 | 深圳石墨烯创新中心有限公司 | Vertical graphene/nano-silver composite material and preparation method and application thereof |
| CN113921826B (en) * | 2021-10-09 | 2023-08-04 | 深圳石墨烯创新中心有限公司 | Upright graphene/nano silver composite material and preparation method and application thereof |
| CN115020528A (en) * | 2022-05-06 | 2022-09-06 | 北京科技大学 | Graphene-zinc oxide-graphene vertical photoelectric detector and construction method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106847648B (en) | 2019-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106847648A (en) | A kind of preparation method of the composite cathode material of use for field emission Graphene/zinc oxide/Graphene sandwich structure | |
| CN100593015C (en) | Surface nano tip array and its preparing method | |
| CN105244249B (en) | A kind of graphene film carbon nano-tube film flexible composite and preparation method and application | |
| US6342755B1 (en) | Field emission cathodes having an emitting layer comprised of electron emitting particles and insulating particles | |
| CN102103953B (en) | Cold cathode field emission material epitaxially growing on silicon carbide substrate and method | |
| Lee et al. | Field-emission triode of low-temperature synthesized ZnO nanowires | |
| CN104882346B (en) | Method for preparing field emission cathode of carbon nanotube array coated with carbon nanoparticles | |
| CN105970184A (en) | Metal nanoparticle/diamond composite film with excellent field emission performance and preparation method | |
| CN100442438C (en) | Manufacturing method of amorphous carbon-film semiconductor | |
| CN104882347B (en) | A kind of preparation method of nanometer of carbon plate silicon nanowires composite construction field-transmitting cathode | |
| CN108987214A (en) | A method of promoting carbon nano pipe array field emission performance | |
| CN103663437A (en) | Graphene quantum dot prepared by virtue of magnetron sputtering technology | |
| CN108987215A (en) | A method of promoting graphene film-carbon nano-tube array composite material field emission performance | |
| CN104952674A (en) | Method for manufacturing nano carbon sheet-carbon nano tube composite-structure field-emission cathode | |
| CN201359984Y (en) | Combined type field emission cathode structure | |
| CN111180293A (en) | Flexible ZnO @ TiN core-shell structure array cathode and preparation method thereof | |
| CN102398892A (en) | Preparation method and application of zinc oxide nanowires | |
| TWI309843B (en) | Electron emission source and field emission display device | |
| CN108987218A (en) | A method of promoting graphene film-silicon nanowire array composite material field emission performance | |
| CN202473819U (en) | Zinc oxide nano wire emitter on orientation carbon nanotube array die plate | |
| CN101488431A (en) | Composite field emission cathode construction and manufacturing method thereof | |
| CN101587805B (en) | Method for preparing composite nano diamond thin film electron emitting cathode | |
| CN103021762A (en) | Method for processing field emission cathode | |
| CN102280331B (en) | Field emission cathode with electron emission-enhanced mixed phase nitride film and preparation method of field emission cathode | |
| CN108987217A (en) | A method of promoting graphene sheet-carbon nanotube film flexible composite field emission performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200410 Address after: 518054 Room 301, building 4, Wanke Qianhai enterprise mansion, No. 63, Qianwan 1st Road, Nanshan street, Qianhai Shenzhen Hong Kong cooperation zone, Shenzhen City, Guangdong Province Patentee after: Shenzhen Qianhai graphene Industry Co., Ltd Address before: Hangzhou City, Zhejiang province 310018 Xiasha Higher Education Park No. 2 street Patentee before: HANGZHOU DIANZI University |
|
| TR01 | Transfer of patent right |