CN113990723B - Preparation method of arrayed vertical graphene field emission cold cathode - Google Patents
Preparation method of arrayed vertical graphene field emission cold cathode Download PDFInfo
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- CN113990723B CN113990723B CN202111126915.3A CN202111126915A CN113990723B CN 113990723 B CN113990723 B CN 113990723B CN 202111126915 A CN202111126915 A CN 202111126915A CN 113990723 B CN113990723 B CN 113990723B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
Abstract
The invention discloses a preparation method of an arrayed vertical graphene field emission cold cathode, which comprises the following steps: (1) depositing a metallic conductive layer on a silicon substrate; (2) attaching an AAO template to the metallic conductive layer; (3) Depositing on the exposed surface of the metal conducting layer to obtain a metal catalytic lattice; (4) And removing the AAO template, and growing a vertical graphene array on the metal catalytic lattice by using a CVD technology to obtain an arrayed vertical graphene field emission cold cathode. The preparation method disclosed by the invention is simple in preparation process, can be used for large-area preparation, and the obtained arrayed vertical graphene field emission cold cathode has the advantages of low starting electric field, small field shielding effect, larger current density and high emission stability.
Description
Technical Field
The invention relates to the technical field of electronic material preparation, in particular to a preparation method of an arrayed vertical graphene field emission cold cathode.
Background
The field electron emission is a process of forming electron emission by reducing the height and narrowing the width of the barrier on the surface of an object by means of a strong external electric field and enabling electrons in the object to escape by penetrating the barrier on the surface by means of tunnel effect, and is a strong and effective electron emission mode, and the main structure of the field electron emission device comprises: emitter, insulating layer, conducting layer and regulation grid. The field emission cold cathode materials are specifically classified into three main categories: new materials typified by carbon nanotubes and graphene, arrays of metal tips typified by molybdenum, and transition metal oxides. Among them, new material graphene has been attracting attention in recent years due to its excellent thermal, optical and electrical properties.
In the application of field emission of graphene, vertical graphene is considered to be an excellent field emission material because of its unique orientation and sharp edges, and the advantages of good atomicity, large thickness, good uniformity, and the like. The current vertical graphene field emission is mostly prepared based on copper foil, nickel foil or metal film. The vertical graphene directly grows on the film and is suitable for the integration of field emission devices, but short circuit, discharge non-uniformity and the like are easier to occur during discharge between large compact vertical graphene emitters, and due to a field shielding effect, the emitters are too close to cause the defects of reduced local electric field intensity, increased starting electric field and the like.
Disclosure of Invention
The invention provides a preparation method of an arrayed vertical graphene field emission cold cathode, which is simple in preparation process, capable of being prepared in a large area, and the obtained arrayed vertical graphene field emission cold cathode is low in starting electric field, small in field shielding effect, large in current density and high in emission stability.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the invention discloses a preparation method of an arrayed vertical graphene field emission cold cathode, which comprises the following steps:
(1) A metallic conductive layer is deposited on a silicon substrate.
(2) An AAO template is attached to the metal conductive layer.
(3) And depositing on the exposed surface of the metal conductive layer to obtain a metal catalytic lattice. The deposited metal selects the metal with excellent catalytic performance and high temperature resistance; the graphene array is grown by adopting a metal lattice catalysis method, so that the distance between graphene sheets is effectively increased, short circuits among the graphene sheets are prevented, the stability is improved, the field shielding effect is reduced, and the opening electric field is effectively reduced; through the AAO template, the metal layer and the metal catalytic lattice are compounded, and the two metals have different effects of catalyzing the vertical graphene growth, so that the graphene is arrayed.
(4) And removing the AAO template, and growing a vertical graphene array on the metal catalytic lattice by using a CVD technology to obtain an arrayed vertical graphene field emission cold cathode. When the vertical graphene is prepared by utilizing a CVD technology, the power and the pressure intensity should be controlled to prevent the growth rate from being too fast; relatively independent vertical graphene sheets are grown on the metal catalytic lattice, so that the field shielding effect on the surface of a cathode can be effectively reduced, the total emission current is increased, and the stability of electron emission is improved.
Preferably, in step (1), a metal conductive film is deposited using a vacuum physical deposition technique.
Preferably, the vacuum physical deposition technique is an electron beam evaporation technique, a magnetron sputtering technique or a pulsed laser deposition technique.
Preferably, in the step (1), the thickness of the metal conductive film is 200 to 300nm.
Preferably, in step (1), the metal of the metal conductive film is molybdenum. The metal of the metal conductive film is molybdenum, the molybdenum has good conductivity, and under the same growth condition, the capability of catalyzing the growth of graphene is extremely weak, so that the vertical graphene only grows on a metal catalysis lattice.
Preferably, in the step (2), the specific step of attaching the AAO template is: and sucking a proper amount of ethanol on the silicon substrate by using a dropper, and attaching the AAO template to the silicon substrate when the ethanol is not completely volatilized.
Preferably, in the step (3), a metal catalytic lattice is obtained by deposition using a vacuum physical deposition technique.
Preferably, the vacuum physical deposition technique is an electron beam evaporation technique, a magnetron sputtering technique or a pulsed laser deposition technique.
Preferably, in the step (3), the thickness of the metal catalytic lattice is 100-200 nm. The thickness of the metal catalytic lattice is 100-200 nm, so that preparation is made for the growth of graphene.
Preferably, the metal of the metal catalytic lattice is nickel or copper.
Therefore, the invention has the following beneficial effects: the preparation process is simple, the starting electric field is low, the current density is large, the stability is high, the large-area preparation can be realized, and the problems of low current density of the current graphene field emission cold cathode emission, complex preparation process and the like are solved.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
FIG. 2 is a SEM image of the metal catalyst lattice obtained in example 1.
FIG. 3 is a metal catalyzed lattice EDS diagram obtained in example 1.
Fig. 4 is a SEM image of vertical graphene generated on a nickel catalytic lattice.
Fig. 5 is a vertical graphene SEM image generated on the nickel film.
Detailed Description
The invention is further described below with reference to the drawings and detailed description.
Example 1
The specific process flow diagram of example 1 is shown in fig. 1, and the specific steps are:
(1) The method comprises the steps of adopting a silicon wafer with the length of 1.5cm and the width of 1cm, using absolute ethyl alcohol to carry out ultrasonic cleaning for 15min, taking out, drying by nitrogen, placing the silicon wafer on a sample stage of electron beam evaporation equipment, placing a molybdenum target, shielding the sample stage by a baffle, opening a mechanical pump, opening an angle valve, closing the angle valve after the vacuum degree is less than 10Pa, opening an electromagnetic valve and a molecular pump, and pumping air until the pressure drop is 10 -4 KPa or lower; opening an electron beam evaporation source power supply, adjusting 'presetting' to enable the current of a gun filament to be 0.2-0.3A, preheating for 3min, and adjusting to be 0.5A; the high-voltage selection switch is adjusted to 6KV, then a high-voltage knob is pressed, a light spot is adjusted to the center of a target material, then the beam current is slowly adjusted to 100-150 mA, after the deposition rate is stable, a baffle is opened, the parameters of a film thickness monitor are set, the film thickness is recorded by a film thickness recorder, and 200nm of deposition is carried out.
(2) Taking out the silicon wafer deposited with the molybdenum conductive layer, sucking a proper amount of absolute ethyl alcohol by using a dropper, dripping the absolute ethyl alcohol at the center of the silicon wafer deposited with the molybdenum conductive layer, transferring the AAO template onto the molybdenum conductive layer when the ethyl alcohol is not completely volatilized, and airing.
(3) And (3) placing the silicon wafer in the step (2) into electron beam evaporation equipment, changing a target material into a nickel target, and carrying out metal catalytic lattice deposition on the exposed surface of the molybdenum conductive layer by using the method of the step (1), wherein the deposition thickness is 100nm, and the obtained nickel catalytic lattice SEM image are respectively shown in figures 2 and 3.
(4) Using an adhesive tape to adhere an AAO template, wherein in the process, care should be taken not to damage a molybdenum conducting layer, and growing a vertical graphene array on a nickel catalytic lattice by using a CVD technology, wherein an SEM (scanning electron microscope) diagram of the generated vertical graphene array is shown as a figure 4, so as to obtain an arrayed vertical graphene field emission cold cathode; the specific steps of growing the vertical graphene array on the nickel catalytic lattice by using the CVD technology are as follows: placing the sample in a quartz boat, vacuumizing the device, reducing the pressure to 6Pa, heating the device to 750 ℃, and introducing H 2 200sccm，Ar 400sccm，Preserving heat for 10min, introducing methane 80sccm, and collecting H 2 And the flow is reduced to 15sccm, and the temperature is kept for 15min, so that the growth of the graphene is completed.
Comparative example 1
Comparative example 1 is different from example 1 in that step (2) and step (3) are omitted, a nickel film is deposited on the molybdenum conductive layer, vertical graphene is grown on the surface of the nickel film by CVD technique, and the rest is exactly the same as example 1. An SEM image of the vertical graphene on the nickel film is shown in fig. 5.
As can be seen by comparing fig. 4 with fig. 5, the vertical graphene grown on the nickel film in fig. 4 can be seen with large graphene sheets connected; in fig. 5, the array vertical graphene grown on the nickel catalytic lattice has a large pitch, and the emitter pitch is effectively increased.
The above-described embodiment is only a preferred embodiment of the present invention, and is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (4)
1. The preparation method of the arrayed vertical graphene field emission cold cathode is characterized by comprising the following steps of:
(1) Depositing a metal conductive layer on a silicon substrate;
(2) Attaching an AAO template on the metal conductive layer;
(3) Depositing on the exposed surface of the metal conducting layer to obtain a metal catalytic lattice; the metal of the metal catalytic lattice is nickel;
(4) Removing the AAO template, and growing a vertical graphene array on the metal catalytic lattice by using a CVD technology to obtain an arrayed vertical graphene field emission cold cathode;
in the step (1), a metal conductive film is deposited by adopting a vacuum physical deposition technology, and the specific process comprises the following steps:
placing molybdenum target on sample stage of electron beam evaporation equipment, shielding sample stage with baffle plate, opening mechanical pump, opening angle valve, closing angle valve after vacuum degree is less than 10Pa, opening electromagnetic valve and molecular pump, and pumping air until pressure drop is 10 -4 KPa or lower; turning on the power supply of the electron beam evaporation source to regulatePresetting to enable the current of the gun filament to be 0.2-0.3A, preheating for 3min and adjusting to be 0.5A; the high-voltage selection switch is adjusted to 6KV, then a high-voltage knob is pressed, a light spot is adjusted to the center of a target, the beam current is slowly adjusted to 100-150 mA, and after the deposition rate is stable, a baffle is opened to deposit 200nm.
2. The method for preparing an arrayed vertical graphene field emission cold cathode according to claim 1, wherein in the step (2), the specific step of attaching an AAO template is as follows: and sucking a proper amount of ethanol on the silicon substrate by using a dropper, and attaching the AAO template to the silicon substrate when the ethanol is not completely volatilized.
3. The method for preparing an arrayed vertical graphene field emission cold cathode according to claim 1, wherein in the step (3), a metal catalytic lattice is obtained by deposition using a vacuum physical deposition technique.
4. The method for preparing an arrayed vertical graphene field emission cold cathode according to claim 1, wherein in the step (3), the thickness of the metal catalytic lattice is 100-200 nm.
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