CN113990724A - Full-two-dimensional vacuum tube and preparation method thereof - Google Patents
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J21/00—Vacuum tubes
- H01J21/02—Tubes with a single discharge path
- H01J21/06—Tubes with a single discharge path having electrostatic control means only
- H01J21/10—Tubes with a single discharge path having electrostatic control means only with one or more immovable internal control electrodes, e.g. triode, pentode, octode
- H01J21/105—Tubes with a single discharge path having electrostatic control means only with one or more immovable internal control electrodes, e.g. triode, pentode, octode with microengineered cathode and control electrodes, e.g. Spindt-type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- 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
-
- 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
Abstract
The invention discloses a full-two-dimensional vacuum tube and a preparation method thereof, belonging to the technical field of nano materials. The invention combines the traditional vacuum tube technology with the modern transistor technology, and takes a two-dimensional insulating material as a precursor material of a vacuum channel in the vacuum tube; taking a two-dimensional conductive material transistor as a thermal field emission source-cathode; the metal conducting material is used as an electron collecting electrode-anode, the full-two-dimensional vacuum tube is formed by vertically stacking full-two-dimensional materials, and electrons are emitted between a cathode and an anode at two ends of a nano-scale vacuum channel by a thermal field to form a basic electrical behavior similar to that of a diode one-way channel. The full-two-dimensional vacuum tube can be prepared in an array mode and is beneficial to being integrated into a modular circuit. The method is applied to product platforms such as high-precision vacuum pressure sensors, NEMS micromotor systems made of new materials, radiation-resistant thermal field emission power transistors and the like.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a full-two-dimensional vacuum tube and a preparation method thereof.
Background
The invention of the vacuum tube is mainly inspired by the research of the electron emission capability of the heating filament by Thomas Edison. Before the advent of semiconductor transistors, they were used primarily in microelectronic and high power electronic circuits such as electronic circuits, glow displays, X-ray generators, microwave oscillators, and the like. The first electron tube computer ENIAC is composed of almost twenty thousand electron vacuum tubes. However, with the advent of solid-state semiconductors, vacuum tubes have fallen behind in both miniaturization and low power consumption, which has gradually faded out the historical stage of integrated circuits in the fifties and sixties of the last century.
Although vacuum tubes do not appear to be large enough in integrated circuits, transistors are not perfect. First, with the continuous reduction of transistor size in the last 40 years, the gate dielectric layer of the present MOSFET is only a few nanometers thick, and the channel length between the source and drain is also only a few tens of nanometers wide. Nevertheless, the pursuit of faster and more energy efficient chips continues, and it is clear that typical MOSFETs have gradually failed to meet the needs of modern technological development; second, transistors are much inferior to vacuum tubes for transporting electronic media. The electrons are transmitted in vacuum without any scattering, and the transmission speed can be maximally close to the light speed of 3 multiplied by 1010cm/s, while in solid semiconductors, electrons continuously collide with atoms, lattice scattering occurs, etc., and the transmission speed is only 5X 10 at the maximum7cm/s, so the carrier transmission characteristic of the vacuum tube has great superiority. Furthermore, solid-state semiconductor devices are more susceptible to strong radiation that can destroy the atomic structure of silicon and thus prevent the correct movement of charge, compared to the excellent radiation resistance of vacuum tubes. This is a big problem for military and aerospace agencies, both requiring their own equipment to be able to function properly in highly radiant environments (e.g., outer space).
The current vacuum tube device generally still faces the problems of large mass and volume, high power consumption, difficult integration and the like. One scheme for solving the problems is to carry out micro-nano treatment on the vacuum tube to prepare the on-chip vacuum electronic device. NASA research group of the American space agency (NASA) shows an integratable micro-nano vacuum tube by using a Si circuit (Nature Electronics,2,405,2019)](ii) a China Beijing university group general graphiteThe alkene and the carbon nano tube are suspended, the electron probe of a scanning electron microscope is adopted to research the thermal field emission effect in vacuum, and the current density can reach 1.33A/cm at most2[Nature Communications,7,11513,2015；Advanced Functional Materials,30,1907814,2020]。
However, up to now, a full two-dimensional van der waals vacuum tube study has been left blank. The full-two-dimensional vacuum tube can further improve the integration level, measurable measurement and other performances of the device, and has great application potential in the aspects of power devices, lab-on-a-chips (lab-on-a-chips) and the like; secondly, the following characteristics are provided: the radiation immune characteristic is excellent, so that the radiation immune characteristic is directly applied to extreme environments such as aerospace, nuclear radiation and the like; (II) extremely fast response speed, making it a candidate for so-called high frequency technology; and (III) the small-sized X-ray tube is used for detecting the fingerprint of certain fixed-frequency molecules.
Disclosure of Invention
The invention provides a full-two-dimensional vacuum tube and a preparation method thereof, aiming at the problems of large mass and volume, high power consumption and difficult integration of the existing vacuum tube device.
The invention discloses a method for realizing a novel full-two-dimensional vacuum tube with a vacuum channel and compatible with a MOSFET (metal-oxide-semiconductor field effect transistor) framework. The invention adopts the two-dimensional layered material as the joule heat emission material and the vacuum channel, overcomes the mass and size limitation of the traditional vacuum tube, greatly reduces the size and the mass of the device, and provides a precursor nano structure for a lab-on-a-chip, a power device, a nano performance system, a micro-nano X-ray tube and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a kind of whole two-dimentional vacuum tube, the said whole two-dimentional vacuum tube is the precursor material of the vacuum channel in the vacuum tube with two-dimentional insulating material; taking a two-dimensional conductive material transistor as a thermal field emission source-cathode; the metal conductive material is used as an electron collecting electrode-anode.
Further, the two-dimensional insulating material is a two-dimensional layered material with good dielectric property; the metal conductive material is any one of graphite, Au, Pd, Ti and Ni; the two-dimensional conductive material is a material with good joule heat emission performance. The two-dimensional insulating material prevents the dielectric breakdown phenomenon from occurring and influencing the performance of the vacuum tube; a metal conductive material for ensuring stability of an anode voltage; two-dimensional conductive material for providing stable thermal field emission current.
Further, the two-dimensional insulating material is hexagonal boron nitride and MnPSe with the thickness of 200-400 nm3。
Further, the two-dimensional conductive material is any one of graphene, few-layer graphene, thin-layer graphite, molybdenum disulfide and tungsten diselenide. At present, experiments prove that the materials have good joule heat emission performance and can bear ultrahigh current density.
A preparation method of a full-two-dimensional vacuum tube comprises the following steps:
step 1, etching holes in a two-dimensional insulating material by adopting an electron beam exposure and etching technology to prepare a vacuum channel in a vacuum tube to obtain a hole insulator;
step 3, transferring the single-layer or multi-layer two-dimensional conductive material to the surface of the double-layer structure in the step 2 by using an adhesive polymer, and slowly heating to 160 ℃ for melting and remaining to obtain a four-layer stacking heterostructure;
and 5, carrying out graphical processing through electron beam exposure and reactive ion etching to obtain an electron emission electrode-cathode in the vacuum tube, and completing the preparation of the full-two-dimensional vacuum tube.
Further, the insulating material is hexagonal boron nitride and MnPSe with the thickness of 200-400 nm3。
Further, the viscous polymer is an arc PDMS/PPC double-layer structure material. The PDMS is an arc-shaped substrate naturally dried in a liquid drop mode, and the viscous polymer can completely transfer the two-dimensional material.
Further, the two-dimensional conductive material is any one of graphene, few-layer graphene, thin-layer graphite, molybdenum disulfide and tungsten diselenide.
Further, the surface residual polymer is completely volatilized by annealing treatment. Compared with methods such as acetone cleaning, the method does not damage the sample and pollute the surface, and the surface is cleaner after treatment.
Further, the annealing treatment is any one of vacuum annealing or inert atmosphere annealing; the vacuum degree of the vacuum annealing is not less than 10-3mbar; the inert atmosphere in the inert atmosphere annealing is argon and argon-hydrogen mixed gas; the vacuum degree is not lower than 10 mbar. The sample is prevented from being degraded or surface-modified at high temperature. The annealing temperature of the annealing treatment is not lower than 100 ℃. Ensuring that the polymer on the surface of the sample can be completely volatilized.
Compared with the prior art, the invention has the following advantages:
1. compatible with the current solid-state electronic device process of mainstream semiconductors (silicon and the like);
2. the novel full-two-dimensional vacuum tube with a vacuum channel and a compatible MOSFET structure can be realized on the basis of being compatible with the process of the solid electronic device of the current mainstream semiconductor (silicon and the like), and the vertical dimension is reduced to 200 nm;
3. the full-two-dimensional vacuum tube can be prepared in an array mode and is beneficial to being integrated into a modular circuit. The method is applied to product platforms such as high-precision vacuum pressure sensors, NEMS micromotor systems made of new materials, radiation-resistant thermal field emission power transistors and the like.
Drawings
FIG. 1 is a schematic diagram of a fully two-dimensional vacuum tube structure according to the present invention;
FIG. 2 is a schematic diagram of a process for preparing a two-dimensional vacuum tube according to the present invention;
FIG. 3 is a schematic diagram of a fully two-dimensional vacuum tube device in example 1;
FIG. 4 is a schematic diagram of a fully two-dimensional vacuum tube device in example 2.
Detailed Description
Example 1
A full-two-dimensional vacuum tube device with 300nm hole boron nitride as a vacuum channel, 13.5nm graphite as a vacuum tube cathode and an Au/Ti (30/5nm) electrode as a vacuum tube anode is shown in figure 3.
As shown in the flow chart of FIG. 2, hexagonal boron nitride with the thickness of about 300nm is subjected to hole etching treatment by using a reactive ion etching technology, and the size of the holes is 1 multiplied by 4 mu m2Then transferring the boron nitride/Ti (30/5nm) electrode to the surface of an Au/Ti (30/5nm) electrode by using a viscous polymer to form a boron nitride/Au electrode double-layer structure, and carrying out vacuum annealing treatment; transferring the boron nitride/graphite double-layer structure transferred to the surface of the viscous polymer to the surface of the hole boron nitride, and removing the residual polymer on the surface of the boron nitride by high-vacuum annealing to form a four-layer stacking heterostructure; and then, carrying out evaporation plating of the electrode and graphical processing of a thermal emission area to prepare a novel full-two-dimensional vacuum tube device with a vacuum channel and compatibility with the MOSFET framework.
Where fig. 3a is an optical photograph of the device, the black dashed area is the anode Au electrode area, and the scale is 10 μm.
Fig. 3b is a SEM scanning image of the device with a scale of 1 μm, and it can be seen from the SEM scanning that the cathode electrode in the device is not collapsed or damaged, and is suspended perfectly above the hole.
FIG. 3c is a schematic view of the measured thermal field emission curve, as found by thermal field emission measurements, when anode V is usedcWhen the voltage is 45V, the emission current can reach 10nA, and the on-state voltage V ison1V, see FIG. 3c, inset is a partial magnified view.
Example 2
The device is a full-two-dimensional vacuum tube device which takes boron nitride with 200nm holes as a vacuum channel, single-layer graphene as a vacuum tube cathode and an Au/Ti (30/5nm) electrode as a vacuum tube anode;
etching holes in hexagonal boron nitride with the thickness of about 200nm by adopting a reactive ion etching technology, wherein the size of the holes is 3 multiplied by 3 mu m2Then transferring the hole boron nitride to the surface of the metal graphite by using a viscous polymer to form a boron nitride/graphite double-layer structure, and removing surface residues by vacuum annealing treatmentThe polymer obtains a clean surface; transferring the boron nitride/single-layer graphene double-layer structure transferred to the surface of the viscous polymer to the surface of the hole boron nitride, and removing the residual polymer on the surface of the boron nitride by high-vacuum annealing to form a four-layer stacking heterostructure; and then, carrying out evaporation plating of the electrode and graphical processing of a thermal emission area to prepare a novel full-two-dimensional vacuum tube device with a vacuum channel and compatibility with the MOSFET framework.
Where fig. 4a is an optical photograph of the device, the black dashed area is the anodic graphite area and the scale is 10 μm.
FIG. 4b is a schematic diagram of the measured thermal field emission curve, which is found by the thermal field emission measurement when the anode V is atcAt 40V, the emission current can reach 160pA, with the inset being a close-up view.
As not specifically stated, the present invention employs a viscous polymer of PDMS/PPC bilayer structure.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (10)
1. A full two-dimensional vacuum tube is characterized in that: the full-two-dimensional vacuum tube takes a two-dimensional insulating material as a precursor material of a vacuum channel in the vacuum tube; taking a two-dimensional conductive material transistor as a thermal field emission source-cathode; the metal conductive material is used as an electron collecting electrode-anode.
2. A fully two-dimensional vacuum tube according to claim 1, characterized in that: the two-dimensional insulating material is a two-dimensional layered material with good dielectric property; the metal conductive material is any one of graphite, Au, Pd, Ti and Ni; the two-dimensional conductive material is a material with good joule heat emission performance.
3. A fully two-dimensional vacuum tube according to claim 2, characterized in that: the two-dimensional insulating material is hexagonal boron nitride and MnPSe with the thickness of 200-400 nm3。
4. A fully two-dimensional vacuum tube according to claim 3, characterized in that: the two-dimensional conductive material is any one of graphene, few-layer graphene, thin-layer graphite, molybdenum disulfide and tungsten diselenide.
5. A preparation method of a full-two-dimensional vacuum tube is characterized by comprising the following steps: the method comprises the following steps:
step 1, etching holes in a two-dimensional insulating material by adopting an electron beam exposure and etching technology to prepare a vacuum channel in a vacuum tube to obtain a hole insulator;
step 2, transferring the hole insulator of the vacuum channel in the step 1 to the surface of a metal conductive material by using a viscous polymer to form a double-layer structure, and completely volatilizing the residual polymer on the surface to obtain a clean surface;
step 3, transferring the single-layer or multi-layer two-dimensional conductive material to the surface of the double-layer structure in the step 2 by using an adhesive polymer, and slowly heating to 160 ℃ for melting and remaining to obtain a four-layer stacking heterostructure;
step 4, volatilizing all the residual polymers on the surface in the step 3, and evaporating and plating metal electrodes through electron beam exposure and electron beam evaporation;
and 5, carrying out graphical processing through electron beam exposure and reactive ion etching to obtain an electron emission electrode-cathode in the vacuum tube, and completing the preparation of the full-two-dimensional vacuum tube.
6. The method for preparing a full-two-dimensional vacuum tube as claimed in claim 5, wherein: the two-dimensional insulating material is hexagonal boron nitride and MnPSe with the thickness of 200-400 nm3。
7. The method for preparing a full-two-dimensional vacuum tube as claimed in claim 6, wherein: the viscous polymer is an arc PDMS/PPC double-layer structure material.
8. The method for preparing a full-two-dimensional vacuum tube as claimed in claim 7, wherein: the two-dimensional conductive material is any one of graphene, few-layer graphene, thin-layer graphite, molybdenum disulfide and tungsten diselenide.
9. The method of claim 8 wherein the vacuum tube is prepared by: and (4) completely volatilizing the residual polymer on the surface by annealing treatment.
10. The method of claim 9 wherein the method comprises the steps of: the annealing treatment is any one of vacuum annealing and inert atmosphere annealing; the vacuum degree of the vacuum annealing is not less than 10-3mbar; the inert atmosphere in the inert atmosphere annealing is argon and argon-hydrogen mixed gas; the vacuum degree is not lower than 10 mbar. The annealing temperature of the annealing treatment is not lower than 100 ℃.
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