CN106847648B - A kind of preparation method of use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material - Google Patents
A kind of preparation method of use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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
Abstract
The invention belongs to microelectronic vacuums and field of display technology, more particularly to a kind of use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material preparation method, the following steps are included: S10, using graphene oxide powder as raw material, one layer of graphene film is deposited using electrostatic spray deposition technique on a monocrystaline silicon substrate；S20, on graphene film surface using magnetron sputtering technique sputtering layer of ZnO film is penetrated frequently as seed crystal, using zinc salt and hexa as raw material, hydrothermal growth ZnO nano needle array obtains graphene on silicon substrate/ZnO nano needle array composite material；S30 deposits one layer of graphene on the surface ZnO using electrostatic spray deposition technique, graphene/zinc oxide/graphene composite cathode material with sandwich structure is made.Preparation process strong operability of the invention, equipment requirement is not high, cost is relatively low, large area can be carried out quickly to prepare, it is expected to compatible with large-scale production process, obtained use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material Flied emission Turn-on voltage is lower and emitting performance is stablized.
Description
Technical field
The invention belongs to microelectronic vacuums and field of display technology, and in particular to and a kind of use for field emission graphene/zinc oxide/
The preparation method of the composite cathode material of graphene sandwich structure.
Background technique
The plate of display unit is realized in the information age of current high speed development for " portability " for improving electronic equipment
Change and miniaturization, the more traditional hot cathode ray tube display technology of development cold-cathode field lift-off technology have a clear superiority.Cold yin
Pole Field Emission Display is beaten using the electron beam that cold cathode issues to be caused to shine on fluorescent screen to show image, is keeping excellent
Pre-heating system is avoided while image quality, and there is the features such as low Turn-on voltage, low-power consumption, small in size, structure ultrathin.
It is the cold-cathode material that exploitation is used for Flied emission that cold-cathode field, which emits most crucial technology,.In recent ten years, have more
Kind material is found to have this potentiality, for example, the GaN and AlN of early stage, subsequent carbon nanotube (CNTs), diamond/eka-gold
Hard rock or ZnO, or even the graphene occurred recently etc..Wherein, ZnO is generally considered luminescent lifetime longest, is currently the only energy
Enough cold-cathode material of the steady operation in low pressure (< 500V) within thousands of hours.In addition, ZnO can be convenient ground by doping
Change material work functions, to reduce the purpose of threshold field strength.Recent studies have shown that the unlatching field of acicular nanometer ZnO emitter
Strong and threshold field strength is minimum, and it is aligned than disordered structure with more excellent field emission performance, in a certain range, battle array
Column density is bigger, and emission current is bigger, but if density is more than a certain range, the screen effect between needle and needle will lead to field again
Enhancement factor reduces.However by the end of currently, about the preparation process of ZnO sodium rice needle array is oriented in stability and controllability side
Face is also immature, and the understanding about the affecting laws between array density and Flied emission enhancement factor is also insufficient.
Graphene (Graphene, G) also has many unique properties required for field emission cold-cathode material, such as very
High electron mobility (at room temperature 2, such as very high electron transfer, be 100 times of Si), high current density patience (2), high electricity
Current density patience is 100 times of Cu), high thermal conductivity (3-5 high thermal conductivity (patience (, suitable with CNTs) and superpower chemistry
With mechanical strength (with diamond phase when) etc., it is expected to the fields such as high-performance nano electronic device, field emmision material play it is important
Effect.
The advantages of in order to give full play to respective emissive material, nearest people attempt to carry out a variety of field emmision materials it is compound with
As novel cold cathode emitter.The Preliminary Results of ZnO/CNTs complex show that certain field emission performances obtain really
Certain improvement.Part research institution of nearest China is to the complex of ZnO nano-wire or nanometer rods and graphene in cold-cathode field
The research of transmitting aspect has also carried out preliminary trial, and proves there is lower unlatching field than single ZnO or grapheme material
By force.Proposed by the present invention is to prepare a kind of graphene/novel field emission body of ZnO nano needle array/graphene sandwich structure,
There is high current density, Low threshold field strength, and the novel cold cathode that the service life is long, stability is good to obtain one kind using process optimization
Field emission material.Preparation method strong operability of the invention, equipment requirement is not high, and cost is relatively low, and it is fast can to carry out large area
Speed preparation, emission effciency and emissive porwer with higher can provide a kind of new approaches for correlative study.
Summary 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 knots
The preparation method of the composite cathode material of structure.
In order to solve the above technical problems, the present invention adopts the following technical scheme that:
A kind of use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material system of the invention
Preparation Method, comprising the following steps:
S10 deposits one layer using electrostatic spray deposition technique on a monocrystaline silicon substrate using graphene oxide powder as raw material
Graphene film；
S20 sputters layer of ZnO film as seed crystal, with zinc using magnetron sputtering technique is penetrated frequently on graphene film surface
Salt and hexa are raw material, and hydrothermal growth ZnO nano needle array obtains graphene on silicon substrate/ZnO nano needle array
Composite material；
S30 deposits one layer of graphene on the surface ZnO using electrostatic spray deposition technique, is made with sandwich structure
Graphene/zinc oxide/graphene composite cathode material.
Preferably, S10 is specifically included:
Graphene oxide powder is dissolved in the mixed liquor of 1,2-PD and dehydrated alcohol by S101 by 0.1~0.5mmol/l
In, ultrasonic wave obtains the suspended precursor liquid of electrostatic spray deposition (electrostatic spray deposition) after stirring 1~2h；
Monocrystalline silicon piece is fixed on substrate clamping plate by S102, and substrate temperature is then heated to 100~250 DEG C；
S103, adjusting the distance between capillary nozzle and substrate of electrostatic spray precipitation equipment is 5~7cm, added direct current
Voltage is 9~12kV；
The suspended precursor liquid for the electrostatic spray deposition that step S101 is obtained is added to electrostatic spray and deposits dress by S104
It sets, the liquid stream spray speed of setting electrostatic spray precipitation equipment is 600~800ml/h, is turned on the switch, electrostatic spray precipitation equipment starts
Electrostatic spray deposition is sprayed on substrate material with precursor liquid；
After S105, spraying 1~2h, electrostatic spray precipitation equipment is closed；It is cooled to room temperature, obtains graphene on silicon substrate
Thin-film material.
Preferably, S20 is specifically included:
S201, for graphene film as substrate, ZnO ceramics are target on the silicon substrate that step S105 is obtained, using penetrating
Frequency magnetron sputtering technique, sputters 10~30min in the argon atmosphere of 0.1~1Pa, the ZnO film of deposition with a thickness of 100~
200nm；
S202 takes 0.5~4mmol zinc salt and 0.25~2mmol hexa to be dissolved in 30ml deionized water, mechanical
It is stirred 0.1~2h；
It is anti-to be transferred to the stainless steel high pressure with polytetrafluoroethyllining lining that volume is 50ml by S203 for above-mentioned mixed solution
It answers in kettle, then the ZnO film sample deposited on the graphene substrate that step S201 is obtained is inverted in autoclave；
S204 takes out sample after sealing autoclave after 70~150 DEG C of temperature conditions are lauched thermal response 8~for 24 hours
Dry 18~36h, obtains graphene on silicon substrate/ZnO nano needle array composite material in 60 DEG C of thermostatic drying chambers.
Preferably, S30 is specifically included: the step of repeating S101-S105, and wherein substrate surface is ZnO nano needle array, is made
Graphene/zinc oxide/graphene composite cathode material with sandwich structure.
Preferably, graphene oxide powder, 1,2-PD and dehydrated alcohol are that analysis is pure, and mass percent is respectively
99%, 99.5% and 99.8%.
Preferably, the volume ratio of 1,2-PD and dehydrated alcohol is 1 in the mixed liquor of 1,2-PD and dehydrated alcohol:
2~2:1.
Preferably, monocrystalline silicon piece be N-type or p-type<100>,<111>or<001>monocrystalline silicon buffing sheet, resistivity be 3~
10。
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 to analyze pure two water zinc acetate or zinc nitrate hexahydrate, mass percent be respectively 99.99% or
99%, hexa is to analyze pure, mass percent 99.5%.
Using the present invention have it is following the utility model has the advantages that
1, preparation process strong operability of the invention, 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 compatible with large-scale production process, obtained use for field emission graphene/zinc oxide/graphene sandwich structure is answered
Conjunction cathode material Flied emission Turn-on voltage is lower and emitting performance is stablized；
2, ZnO nano needle array structure is controllable, by adjusting hydrothermal temperature, reactant concentration, pH value and reaction time
Controllable nanoneedle draw ratio, array density etc.；
3, use for field emission graphene/compound yin of zinc oxide/graphene sandwich structure is made by means of the present invention
Pole material field transmitting property is excellent, and transmitting Turn-on voltage is lower and emitting performance is stablized.
Detailed description of the invention
Fig. 1 is that the present invention is reasonable use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material
The preparation technology flow chart of material；
Fig. 2 is use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material of the embodiment of the present invention
The SEM of material schemes；
Fig. 3 is use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material of the embodiment of the present invention
The Flied emission I-V curve of material.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.Based on this hair
Embodiment in bright, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
Embodiment 1:
As shown in Figure 1, measuring the pure 1,2-PD 33.33ml of analysis and the quality hundred that mass percent is 99.5% respectively
It is point dehydrated alcohol 66.67ml purer than the analysis for 99.8%, after the two is sufficiently mixed, obtain 1,2-PD and dehydrated alcohol
Volume ratio is the mixed liquor 100ml of 1:2, and the analysis pure zirconia graphene powder that 0.05mmol mass percent is 99% is dissolved in
In the mixed liquor, after ultrasonic wave stirs 1h, the suspended precursor liquid of electrostatic spray deposition (ESD) is obtained；Then by N-type<001>
Monocrystalline silicon buffing sheet (resistivity 3) is fixed on substrate clamping plate, and substrate temperature is heated to 100 DEG C, it is heavy to adjust electrostatic spray
The distance between the capillary nozzle of product device and substrate are 5cm, and adding DC voltage is 12kV, and prepared electrostatic spray is deposited
It is 600ml/h that precursor liquid, which is added and sets the liquid stream spray speed of electrostatic spray precipitation equipment to electrostatic spray precipitation equipment, and opening is opened
It closes, electrostatic spray precipitation equipment starts for electrostatic spray deposition precursor liquid to be sprayed on substrate material, after spraying 2h, closes electrostatic
Sprayed deposit device, is cooled to room temperature, obtains graphene film material on silicon substrate；Graphene on the silicon substrate of acquisition is thin
For film as substrate, the ZnO ceramics that mass percent is 99.99% are target, using radiofrequency magnetron sputtering technology, in the argon of 1Pa
10min is sputtered in gas (mass percent 99.995%) atmosphere, the ZnO film of deposition is with a thickness of 100nm；0.5mmol is taken again
Pure six methylene of analysis that the pure two water zinc acetate of analysis and 2mmol mass percent that mass percent is 99.99% are 99.5%
Urotropine is dissolved in 30ml deionized water, and after mechanical stirring mixes 0.5h, being transferred to volume is 50ml with polytetrafluoroethylene (PTFE)
In the stainless steel autoclave of liner, then the graphene substrate obtained above for being deposited with ZnO film seed crystal is inverted in height
It presses in reaction kettle, after autoclave is sealed after 70 DEG C of temperature conditions are lauched thermal response for 24 hours, takes out sample in 60 DEG C of constant temperature
Dry 18h, obtains graphene on silicon substrate/ZnO nano needle array composite material in drying box；Finally the composite material is consolidated again
It is scheduled on substrate clamping plate, uses identical electrostatic spray depositing operation using the suspended precursor liquid of above-mentioned electrostatic spray deposition, i.e.,
100 DEG C of substrate temperature, distance is 5cm between capillary nozzle and substrate, and added DC voltage is 9kV, and liquid stream spray speed is 600ml/h,
After spraying 1h, final sample is obtained -- with graphene/ZnO nano needle array/graphene of sandwich structure on silicon substrate
Composite material.
Final composite sample is made into cathode, copper sheet does anode, and it is placed in high voltage direct current pressure, tests its field emission performance,
Obtain I-V curve.Sample surfaces ZnO nano needle draw ratio 8:1, graphene are 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
It is dehydrated alcohol 50ml purer than the analysis for 99.8%, after the two is sufficiently mixed, obtain 1,2-PD and dehydrated alcohol volume
Than the mixed liquor 100ml for 1:1, the analysis pure zirconia graphene powder that 0.03mmol mass percent is 99% is dissolved in this and is mixed
It closes in liquid, after ultrasonic wave stirs 1.5h, obtains the suspended precursor liquid of electrostatic spray deposition (electrostatic spray deposition)；Then by N
Type<111>monocrystalline silicon buffing sheet (resistivity 8.1) is fixed on substrate clamping plate, and substrate temperature is heated to 150 DEG C, is adjusted quiet
The distance between the capillary nozzle of electrospray deposition device and substrate are 6cm, and adding DC voltage is 11kV, by prepared electrostatic
It is 650ml/h that sprayed deposit precursor liquid, which is added and sets the liquid stream spray speed of electrostatic spray precipitation equipment to electrostatic spray precipitation equipment,
It turning on the switch, electrostatic spray precipitation equipment starts for electrostatic spray deposition precursor liquid to be sprayed on substrate material, after spraying 1.5h,
Electrostatic spray precipitation equipment is closed, room temperature is cooled to, obtains graphene film material on silicon substrate；It will be on the silicon substrate of acquisition
For graphene film as substrate, the ZnO ceramics that mass percent is 99.99% are target, using radiofrequency magnetron sputtering technology,
15min is sputtered in argon gas (mass percent 99.995%) atmosphere of 0.5Pa, the ZnO film of deposition is with a thickness of 120nm；Again
Take the pure two water zinc acetate of analysis that 2mmol mass percent is 99.99% and the analysis that 0.5mmol mass percent is 99.5%
Pure hexa is dissolved in 30ml deionized water, and after mechanical stirring mixes 0.1h, being transferred to volume is that having for 50ml is poly-
In the stainless steel autoclave of tetrafluoroethene liner, then the graphene substrate obtained above for being deposited with ZnO film seed crystal
It is inverted in autoclave, after autoclave is sealed after 120 DEG C of temperature conditions are lauched thermal response 16h, takes out sample
Dry 30h, obtains graphene on silicon substrate/ZnO nano needle array composite material in 60 DEG C of thermostatic drying chambers.
Finally the composite material is fixed on substrate clamping plate again, is deposited using above-mentioned electrostatic spray and is adopted with suspended precursor liquid
With identical electrostatic spray depositing operation, i.e. 150 DEG C of substrate temperature, distance is 6cm, added direct current between capillary nozzle and substrate
Pressure is 11kV, and liquid stream spray speed is 650ml/h, after spraying 1.5h, obtains final sample -- with sandwich structure on silicon substrate
Graphene/ZnO nano needle array/graphene composite material；Final composite sample is made into cathode, copper sheet does anode, is placed in height
The pressure of straightening galvanic electricity, tests its field emission performance, obtains I-V curve.Sample surfaces ZnO nano needle draw ratio 10:1, graphite
It is more uniform that alkene is distributed in array, and 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 the quality hundred that mass percent is 99.5% respectively
It is point dehydrated alcohol 66.67ml purer than the analysis for 99.8%, after the two is sufficiently mixed, obtain 1,2-PD and dehydrated alcohol
Volume ratio is the mixed liquor 100ml of 1:2, and the analysis pure zirconia graphene powder that 0.02mmol mass percent is 99% is dissolved in
In the mixed liquor, after ultrasonic wave stirs 1h, the suspended precursor liquid of electrostatic spray deposition (electrostatic spray deposition) is obtained；Then will
N-type<100>monocrystalline silicon buffing sheet (resistivity 5.8) is fixed on substrate clamping plate, and substrate temperature is heated to 200 DEG C, is adjusted
The distance between the capillary nozzle of electrostatic spray precipitation equipment and substrate are 6cm, and adding DC voltage is 10kV, will be prepared quiet
It is 700ml/ that electrospray deposition precursor liquid, which is added and sets the liquid stream spray speed of electrostatic spray precipitation equipment to electrostatic spray precipitation equipment,
H is turned on the switch, and electrostatic spray precipitation equipment starts for electrostatic spray deposition precursor liquid to be sprayed on substrate material, after spraying 1h,
Electrostatic spray precipitation equipment is closed, room temperature is cooled to, obtains graphene film material on silicon substrate；It will be on the silicon substrate of acquisition
For graphene film as substrate, the ZnO ceramics that mass percent is 99.99% are target, using radiofrequency magnetron sputtering technology,
20min is sputtered in argon gas (mass percent 99.995%) atmosphere of 0.3Pa, the ZnO film of deposition is with a thickness of 150nm；Again
Take the pure two water zinc acetate of analysis that 1mmol mass percent is 99.99% and the analysis that 1mmol mass percent is 99.5% pure
Hexa is dissolved in 30ml deionized water, and after mechanical stirring mixes 1h, being transferred to volume is 50ml with polytetrafluoro
In the stainless steel autoclave of ethylene liner, then the graphene substrate inversion obtained above for being deposited with ZnO film seed crystal
In autoclave, after autoclave is sealed after 90 DEG C of temperature conditions are lauched thermal response 12h, sample is taken out at 60 DEG C
Dry 36h, obtains graphene on silicon substrate/ZnO nano needle array composite material in thermostatic drying chamber；Finally again by the composite wood
Material is fixed on substrate clamping plate, deposits work using identical electrostatic spray with suspended precursor liquid using above-mentioned electrostatic spray deposition
Skill, i.e. 200 DEG C of substrate temperature, distance is 6cm between capillary nozzle and substrate, and added DC voltage is 10kV, and liquid stream spray speed is
After 700ml/h, spraying 1h, final sample is obtained -- graphene/ZnO nano needle array on silicon substrate with sandwich structure/
The composite material of graphene.
Final composite sample is made into cathode, copper sheet does anode, and it is placed in high voltage direct current pressure, tests its field emission performance,
Obtain I-V curve.Sample surfaces ZnO nano needle draw ratio 15:1, it is uniform that graphene is distributed in array, as shown in attached drawing 2.It is multiple
The minimum Turn-on voltage for closing object is 2.8V/ μm, sees attached 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
It is dehydrated alcohol 60ml purer than the analysis for 99.8%, after the two is sufficiently mixed, obtain 1,2-PD and dehydrated alcohol volume
Than the mixed liquor 100ml for 1:1.5, the analysis pure zirconia graphene powder that 0.04mmol mass percent is 99% is dissolved in this
In mixed liquor, after ultrasonic wave stirs 2h, the suspended precursor liquid of electrostatic spray deposition (electrostatic spray deposition) is obtained；Then by P
Type<100>monocrystalline silicon buffing sheet (resistivity 6.9) is fixed on substrate clamping plate, and substrate temperature is heated to 180 DEG C, is adjusted quiet
The distance between the capillary nozzle of electrospray deposition device and substrate are 5.5cm, and adding DC voltage is 10kV, will be prepared quiet
It is 750ml/ that electrospray deposition precursor liquid, which is added and sets the liquid stream spray speed of electrostatic spray precipitation equipment to electrostatic spray precipitation equipment,
H is turned on the switch, and electrostatic spray precipitation equipment starts for electrostatic spray deposition precursor liquid to be sprayed on substrate material, after spraying 1h,
Electrostatic spray precipitation equipment is closed, room temperature is cooled to, obtains graphene film material on silicon substrate；It will be on the silicon substrate of acquisition
For graphene film as substrate, the ZnO ceramics that mass percent is 99.99% are target, using radiofrequency magnetron sputtering technology,
25min is sputtered in argon gas (mass percent 99.995%) atmosphere of 0.8Pa, the ZnO film of deposition is with a thickness of 180nm；Again
Take the pure two water zinc acetate of analysis that 3mmol mass percent is 99.99% and the analysis that 1.5mmol mass percent is 99.5%
Pure hexa is dissolved in 30ml deionized water, and after mechanical stirring mixes 1.5h, being transferred to volume is that having for 50ml is poly-
In the stainless steel autoclave of tetrafluoroethene liner, then the graphene substrate obtained above for being deposited with ZnO film seed crystal
It is inverted in autoclave, after autoclave is sealed after 110 DEG C of temperature conditions are lauched thermal response 20h, takes out sample
Drying for 24 hours, obtains graphene on silicon substrate/ZnO nano needle array composite material in 60 DEG C of thermostatic drying chambers；Finally again should
Composite material is fixed on substrate clamping plate, heavy using identical electrostatic spray with suspended precursor liquid using above-mentioned electrostatic spray deposition
Product 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 -- with graphene/ZnO nano needle battle array of sandwich structure on silicon substrate
Column/graphene composite material.
Final composite sample is made into cathode, copper sheet does anode, and it is placed in high voltage direct current pressure, tests its field emission performance,
Obtain I-V curve.Sample surfaces ZnO nano needle draw ratio 8:1, graphene are 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 the quality hundred that mass percent is 99.5% respectively
It is point dehydrated alcohol 66.67ml purer than the analysis for 99.8%, after the two is sufficiently mixed, obtain 1,2-PD and dehydrated alcohol
Volume ratio is the mixed liquor 100ml of 1:2, and the analysis pure zirconia graphene powder that 0.02mmol mass percent is 99% is dissolved in
In the mixed liquor, after ultrasonic wave stirs 1h, the suspended precursor liquid of electrostatic spray deposition (electrostatic spray deposition) is obtained；Then will
P-type<111>monocrystalline silicon buffing sheet (resistivity 7.9) is fixed on substrate clamping plate, and substrate temperature is heated to 220 DEG C, is adjusted
The distance between the capillary nozzle of electrostatic spray precipitation equipment and substrate are 6cm, and adding DC voltage is 10kV, will be prepared quiet
It is 700ml/ that electrospray deposition precursor liquid, which is added and sets the liquid stream spray speed of electrostatic spray precipitation equipment to electrostatic spray precipitation equipment,
H is turned on the switch, and electrostatic spray precipitation equipment starts for electrostatic spray deposition precursor liquid to be sprayed on substrate material, spraying 1.2h
Afterwards, electrostatic spray precipitation equipment is closed, room temperature is cooled to, obtains graphene film material on silicon substrate；The silicon of acquisition is served as a contrast
For graphene film as substrate, the ZnO ceramics that mass percent is 99.99% are target on bottom, utilize rf magnetron sputtering skill
Art, sputters 20min in argon gas (mass percent 99.995%) atmosphere of 0.6Pa, the ZnO film of deposition with a thickness of
150nm；The pure two water zinc acetate of the analysis for taking 2.5mmol mass percent to be 99.99% again and 2mmol mass percent are
The pure hexa of 99.5% analysis is dissolved in 30ml deionized water, and after mechanical stirring mixes 2h, being transferred to volume is
In the stainless steel autoclave with polytetrafluoroethyllining lining of 50ml, then obtained above it is deposited with ZnO film seed crystal
Graphene substrate be inverted in autoclave, be lauched thermal response 16h in 100 DEG C of temperature conditions after autoclave is sealed
Afterwards, it takes out sample drying in 60 DEG C of thermostatic drying chambers and for 24 hours, obtains graphene on silicon substrate/ZnO nano needle array composite wood
Material；Finally the composite material is fixed on substrate clamping plate again, uses phase using the suspended precursor liquid of above-mentioned electrostatic spray deposition
Same electrostatic spray depositing operation, 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 -- with the graphite of sandwich structure on silicon substrate
Alkene/ZnO nano needle array/graphene composite material.
Final composite sample is made into cathode, copper sheet does anode, and it is placed in high voltage direct current pressure, tests its field emission performance,
Obtain I-V curve.Sample surfaces ZnO nano needle draw ratio 6:1, graphene are 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 the quality hundred that mass percent is 99.5% respectively
It is point dehydrated alcohol 33.33ml purer than the analysis for 99.8%, after the two is sufficiently mixed, obtain 1,2-PD and dehydrated alcohol
Volume ratio is the mixed liquor 100ml of 2:1, and the analysis pure zirconia graphene powder that 0.01mmol mass percent is 99% is dissolved in
In the mixed liquor, after ultrasonic wave stirs 2h, the suspended precursor liquid of electrostatic spray deposition (electrostatic spray deposition) is obtained；Then will
P-type<001>monocrystalline silicon buffing sheet (resistivity 10) is fixed on substrate clamping plate, and substrate temperature is heated to 250 DEG C, is adjusted quiet
The distance between the capillary nozzle of electrospray deposition device and substrate are 7cm, and adding DC voltage is 9kV, by prepared electrostatic
It is 800ml/h that sprayed deposit precursor liquid, which is added and sets the liquid stream spray speed of electrostatic spray precipitation equipment to electrostatic spray precipitation equipment,
It turns on the switch, electrostatic spray precipitation equipment starts for electrostatic spray deposition precursor liquid to be sprayed on substrate material, after spraying 1h, closes
Electrostatic spray precipitation equipment is closed, room temperature is cooled to, obtains graphene film material on silicon substrate；By stone on the silicon substrate of acquisition
For black alkene film as substrate, the ZnO ceramics that mass percent is 99.99% are target, using radiofrequency magnetron sputtering technology,
30min is sputtered in argon gas (mass percent 99.995%) atmosphere of 0.1Pa, the ZnO film of deposition is with a thickness of 200nm；Again
Take the pure two water zinc acetate of analysis that 4mmol mass percent is 99.99% and point that 0.25mmol mass percent is 99.5%
It analyses pure hexa to be dissolved in 30ml deionized water, after mechanical stirring mixes 0.5h, being transferred to volume is having for 50ml
In the stainless steel autoclave of polytetrafluoroethyllining lining, then the graphene lining obtained above for being deposited with ZnO film seed crystal
Bottom is inverted in autoclave, after autoclave is sealed after 150 DEG C of temperature conditions are lauched thermal response 8h, takes out sample
Drying for 24 hours, obtains graphene on silicon substrate/ZnO nano needle array composite material in 60 DEG C of thermostatic drying chambers；Finally again should
Composite material is fixed on substrate clamping plate, heavy using identical electrostatic spray with suspended precursor liquid using above-mentioned electrostatic spray deposition
Product technique, i.e. 250 DEG C of substrate temperature, distance is 7cm between capillary nozzle and substrate, and added DC voltage is 9kV, and liquid stream spray speed is
After 800ml/h, spraying 2h, final sample is obtained -- graphene/ZnO nano needle array on silicon substrate with sandwich structure/
The composite material of graphene.
Final composite sample is made into cathode, copper sheet does anode, and it is placed in high voltage direct current pressure, tests its field emission performance,
Obtain I-V curve.Sample surfaces ZnO nano needle draw ratio 7:1, graphene are distributed in that array is more uniform, and Turn-on voltage is
12.3V/μm。
It should be appreciated that exemplary embodiment as described herein is illustrative and be not restrictive.Although being retouched in conjunction with attached drawing
One or more embodiments of the invention is stated, it should be understood by one skilled in the art that not departing from through appended right
In the case where the spirit and scope of the present invention defined by it is required that, the change of various forms and details can be made.
Claims (10)
1. a kind of use for field emission graphene/zinc oxide/graphene sandwich structure composite cathode material preparation method, special
Sign is, comprising the following steps:
S10 deposits one layer of graphite using electrostatic spray deposition technique on a monocrystaline silicon substrate using graphene oxide powder as raw material
Alkene film；
S20, on graphene film surface using penetrating magnetron sputtering technique sputtering layer of ZnO film frequently as seed crystal, with zinc salt with
Hexa is raw material, and it is compound to obtain graphene on silicon substrate/ZnO nano needle array for hydrothermal growth ZnO nano needle array
Material；
S30 deposits one layer of graphene on the surface ZnO using electrostatic spray deposition technique, the graphite with sandwich structure is made
Alkene/zinc oxide/graphene composite cathode material.
2. use for field emission graphene according to claim 1/zinc oxide/graphene sandwich structure composite cathode material
Preparation method, which is characterized in that S10 is specifically included:
Graphene oxide powder is dissolved in the mixed liquor of 1,2-PD and dehydrated alcohol by S101 by 0.1~0.5mmol/l,
Ultrasonic wave obtains the suspended precursor liquid of electrostatic spray deposition (ESD) after stirring 1~2h；
Monocrystalline silicon piece is fixed on substrate clamping plate by S102, and substrate temperature is then heated to 100~250 DEG C；
S103, adjusting the distance between capillary nozzle and substrate of electrostatic spray precipitation equipment is 5~7cm, added DC voltage
For 9~12kV；
The suspended precursor liquid for the electrostatic spray deposition that step S101 is obtained is added to electrostatic spray precipitation equipment S104, if
The liquid stream spray speed for determining electrostatic spray precipitation equipment is 600~800ml/h, is turned on the switch, electrostatic spray precipitation equipment starts will be quiet
Electrospray deposition is sprayed on substrate material with precursor liquid；
After S105, spraying 1~2h, electrostatic spray precipitation equipment is closed；It is cooled to room temperature, obtains graphene film on silicon substrate
Material.
3. use for field emission graphene according to claim 1/zinc oxide/graphene sandwich structure composite cathode material
Preparation method, which is characterized 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 atmosphere, the ZnO film of deposition is with a thickness of 100~200nm；
S202 takes 0.5~4mmol zinc salt and 0.25~2mmol hexa to be dissolved in 30ml deionized water, mechanical stirring
Mix 0.1~2h；
Above-mentioned mixed solution is transferred in the stainless steel autoclave with polytetrafluoroethyllining lining by S203, then step
The ZnO film sample deposited on the graphene substrate that S201 is obtained is inverted in autoclave；
S204 takes out sample 60 after sealing autoclave after 70~150 DEG C of temperature conditions are lauched thermal response 8~for 24 hours
Dry 18~36h, obtains graphene on silicon substrate/ZnO nano needle array composite material in DEG C thermostatic drying chamber.
4. use for field emission graphene according to claim 2/zinc oxide/graphene sandwich structure composite cathode material
Preparation method, which is characterized in that S30 is specifically included: repeat S101-S105 the step of, wherein substrate surface be ZnO nano needle battle array
Graphene/zinc oxide/graphene composite cathode material with sandwich structure is made in column.
5. use for field emission graphene according to claim 2 or 4/zinc oxide/graphene sandwich structure composite cathode
The preparation method of material, which is characterized in that the graphene oxide powder, 1,2-PD and dehydrated alcohol are that analysis is pure,
Mass percent is respectively 99%, 99.5% and 99.8%.
6. use for field emission graphene according to claim 2 or 4/zinc oxide/graphene sandwich structure composite cathode
The preparation method of material, which is characterized in that in the mixed liquor of the 1,2-PD and dehydrated alcohol 1,2-PD with it is anhydrous
The volume ratio of ethyl alcohol is 1:2~2:1.
7. use for field emission graphene according to claim 2/zinc oxide/graphene sandwich structure composite cathode material
Preparation method, which is characterized in that monocrystalline silicon piece be N-type or p-type<100>,<111>or<001>monocrystalline silicon buffing sheet, resistivity
It is 3~10.
8. use for field emission graphene according to claim 3/zinc oxide/graphene sandwich structure composite cathode material
Preparation method, which is characterized in that the mass percent of the ZnO ceramics is 99.99%, and the mass percent of argon gas is
99.995%.
9. use for field emission graphene according to claim 3/zinc oxide/graphene sandwich structure composite cathode material
Preparation method, which is characterized in that the zinc salt is to analyze pure two water zinc acetate or zinc nitrate hexahydrate, mass percent are respectively
99.99% or 99%.
10. use for field emission graphene according to claim 3/zinc oxide/graphene sandwich structure composite cathode material
The preparation method of material, which is characterized in that hexa is to analyze pure, mass percent 99.5%.
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| 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 |
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