CN109801819A - A kind of the composite Nano cold cathode structure and preparation method of high stable electron emission - Google Patents
A kind of the composite Nano cold cathode structure and preparation method of high stable electron emission Download PDFInfo
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Abstract
本发明公开了一种高稳定电子发射的复合纳米冷阴极结构及制备方法。该复合纳米冷阴极结构包括衬底；直立制备在衬底上的低维纳米冷阴极；覆盖在低维纳米冷阴极尖端上的二维薄膜材料；用于调控二维薄膜材料尖端几何曲率的支撑结构。该结构的优点是利用了二维薄膜材料的表面无悬挂键结构，来获得干净的发射表面。另外，通过调控二维薄膜材料尖端的几何曲率，能够控制发射电子的输运过程，使其成为能量较高的热电子，从而有更低的开启电场。更干净的表面以及表面势垒的降低使得该复合低维纳米冷阴极能够实现高稳定的电子发射。
The invention discloses a composite nanometer cold cathode structure with high stable electron emission and a preparation method. The composite nano-cold cathode structure includes a substrate; a low-dimensional nano-cold cathode prepared upright on the substrate; a two-dimensional thin film material covered on the tip of the low-dimensional nano cold cathode; a support for regulating the geometric curvature of the tip of the two-dimensional thin film material structure. The advantage of this structure is that the surface of the two-dimensional thin film material has no dangling bond structure to obtain a clean emission surface. In addition, by adjusting the geometric curvature of the tip of the two-dimensional thin film material, the transport process of the emitted electrons can be controlled, making them become hot electrons with higher energy, thus having a lower turn-on electric field. The cleaner surface and reduced surface potential barrier enable the composite low-dimensional nanocold cathode to achieve highly stable electron emission.
Description
Technical field
The present invention relates to vacuum microelectronics technique fields.More particularly to a kind of cold yin of composite Nano of high stable electron emission
Pole structure further relates to a kind of composite Nano cold cathode preparation method of high stable electron emission.
Background technique
Cold-cathode electron source has brightness high, and coherence is good, is convenient for the advantages that integrated, therefore micro- in high-precision electronic
Mirror, X-ray plane source, FPD, parallel electron beam etching etc. have important application.However, the transmitting that cold cathode is intrinsic
Current instability limits its development.
In general, the unstability of cold cathode is mainly related with two aspects.One is adsorption desorption process, should
Process is mainly related with surface dangling bonds and surface charge.Currently, mainly by being heated at high temperature the method for cold cathode come as far as possible
Ground removes binding molecule (such as Field emission microscopy of carbon nanotube caps).However, high temperature
The method of heating has larger limitation to the fusing point of material therefor in electronic source construction, and when temperature drops to normal working temperature
When, residual gas can be still adsorbed on cold cathode.
Another factor is that surface texture will form atom level protrusion under strong electric field, so as to cause the change of internal field
Change.According to field emission theory, the surface potential barrier of cold cathode is higher, and emission current is more sensitive to electric field change, and therefore, electric field is disturbed
It is dynamic to cause bigger current fluctuation.
Summary of the invention
The present invention in order to overcome at least one of the drawbacks of the prior art described above, provides a kind of answering for high stable electron emission
Close nanometer cold cathode structure.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
Composite Nano cold cathode structure of the invention includes substrate, prepares low-dimensional nanometer cold cathode on substrate, is covered on low
Two-dimensional film material on wiener rice cold cathode tip, and the support knot for adjusting two-dimensional film material tip geometric buckling
The geometric buckling of structure, two-dimensional film material tip is less than the geometric buckling at low-dimensional nano structure tip.
Substrate can be the planar structures such as silicon wafer or glass, be also possible to the sharp tapered structure such as tungsten needle.Support construction can be with
It is low-dimensional nanometer cold cathode array, is also possible to the cavernous structures such as integrated insulating layer or isolated ceramics.
According to geometry, when the geometric buckling at two-dimensional film material tip is less than the geometric buckling at low-dimensional nano structure tip
When, tip can be in close contact, and otherwise will form hanging structure at tip, be unfavorable for the stabilization of thermionic generation and electronics
Transmitting.
Preferably, substrate is planar substrate or pointed cone type substrate.Substrate can be the planar substrates such as glass, ceramics, silicon,
Or the pointed cones type substrate such as tungsten tip, nickel needle point, acupuncture needle point.Wherein, planar substrate is suitable for the system of cold-cathode electron source array
Make, and pointed cone type substrate is suitable for the production of cold cathode point-like electron source device.
Preferably, support construction can be low-dimensional nanometer cold cathode array itself, further, be also possible to additionally make
Standby cavernous structure integrally or separately.Wherein, it is constituted using low-dimensional nanometer cold cathode array sum aggregate itself at cavernous structure
Support construction be suitable for the production of electron source array, and an electricity is then suitable for as support construction using isolated cavernous structure
The production of component device.Have structure simple using the support construction of low-dimensional nanometer cold cathode array itself, it is excellent to be easy production etc.
Point, but it there are certain requirements the draw ratio of low-dimensional nanometer cold cathode, and if draw ratio is too big, two-dimensional film material is easy to overwhelm
Low-dimensional nanometer cold cathode, and integrated cavernous structure can then reduce that low-dimensional nanometer cold cathode born from two-dimensional film material
Pressure in the gravity of itself and its transfer process.
Preferably, integrated cavernous structure can be by the insulation films such as silica, silicon nitride or aluminium oxide or chromium, tungsten, copper etc.
Metallic film is constituted.
Preferably, separation cavernous structure can be made of ceramics or copper, aluminium, the metals such as iron.Since electronics mainly passes through
Low-dimensional nanometer cold cathode is injected into two-dimensional film material, so support construction can be conductor and be also possible to insulator.
The present invention also provides a kind of preparation methods of the composite nanostructure of high stable electron emission, including clean substrate,
It makes contour or is transferred to low-dimensional nanometer cold close to contour low-dimensional nanometer cold cathode and support construction, then two-dimensional film material
On cathode and support construction.
Preferably, low-dimensional nanometer cold cathode can be the quasi-one dimensional nanostructures such as nano wire, nanometer rods, nanocone, upright stone
The two-dimensional nanostructures such as black alkene, nm wall and spindt cold cathode etc., and its material can for zinc oxide, tungsten oxide, copper oxide,
Silicon, carbon, molybdenum, nickel, tungsten etc..
Preferably, two-dimensional film material can by graphene, molybdenum disulfide, two selenizing molybdenums, tungsten disulfide, two tungsten selenides and
Other transient metal sulfides, one or more material compositions such as hexagonal boron nitride.
The principle that the present invention improves electron emission stability is the clean surface for utilizing two-dimensional film material, two-dimensional film material
Expect no surface dangling bonds, reduces the adsorption/desorption process on surface, and thermoelectron energy caused by its Electronic Transport Processes
Surface potential barrier is reduced, to improve the stability of electron emission.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention has a wide range of application, the support constituted using low-dimensional nanometer cold cathode array sum aggregate itself at cavernous structure
Structure is suitable for the production of electron source array, and is then suitable for point-like electron source device as support construction using isolated cavernous structure
The production of part.The composite Nano cold cathode structure of the electron emission is suitable on vacuum point-like electron source and plate electron source array
Application.
(2) composite Nano cold cathode structure of the invention has structure simple, the high advantage of operability.
(3) present invention utilizes the surfaces of two-dimensional film material without suspension bond structure, to obtain clean emitting surface.Separately
Outside, by regulating and controlling the geometric buckling at two-dimensional film material tip, the transport process of launching electronics can be controlled, energy is become
Higher thermoelectron, to there is lower threshold electric field.The reduction on cleaner surface and surface potential barrier is so that this is compound low
Wiener rice cold cathode can be realized the electron emission of high stable.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of compound low-dimensional nanometer cold cathode on the basis of various substrates；
Fig. 2 is the production process schematic diagram of composite Nano cold cathode structure shown in Fig. 1 a in embodiment 1；
Fig. 3 is the production process schematic diagram of composite Nano cold cathode structure shown in Fig. 1 b in embodiment 1；
Fig. 4 is the production process schematic diagram of composite Nano cold cathode structure shown in Fig. 1 c in embodiment 1；
Fig. 5 is the compound low-dimensional nanometer cold yin that two-dimensional film material tip curvature is greater than/is less than low-dimensional nano structure tip curvature
The structural schematic diagram of pole；
Fig. 6 is surface energy band curved mould of the two selenizing W film of single layer of different-thickness under the extra electric field of 2.5 V/nm
Quasi- result；
Fig. 7 is the electron scanning micrograph and stability test result of the composite Nano cold cathode structure of actual fabrication.
Description of symbols
Substrate 1；Low-dimensional nanometer cold cathode 2；Two-dimensional film material 3；Support construction 4.
Specific embodiment
The present invention is further illustrated With reference to embodiment.
The same or similar label correspond to the same or similar components in the attached drawing of the embodiment of the present invention；It is retouched in of the invention
In stating, it is to be understood that if there is the orientation of the instructions such as term " on ", "lower", "left", "right", "top", "bottom", "inner", "outside"
Or positional relationship is to be based on the orientation or positional relationship shown in the drawings, and is merely for convenience of description of the present invention and simplification of the description, and
It is not that the device of indication or suggestion meaning or element must have a particular orientation, be constructed and operated in a specific orientation, therefore
The terms describing the positional relationship in the drawings are only for illustration, should not be understood as the limitation to this patent.
In addition, if there is the terms such as " first ", " second " to be used for description purposes only, be mainly used for distinguishing different devices,
Element or component (specific type and construction may identical may also be different), is not intended to show or implies indicated fill
It sets, the relative importance and quantity of element or component, and should not be understood as indicating or implying relative importance.
Embodiment 1
As shown in Figure 1, giving on the basis of various substrates, three kinds using nano wire as low-dimensional cold-cathode material are compound low
The structural schematic diagram of wiener rice cold cathode.
The basic structure of the cold cathode includes substrate 1, low-dimensional nanometer cold cathode 2, two-dimensional film material 3 and support construction 4.
Substrate 1 is planar structure in Fig. 1 a, and support construction is low-dimensional nanometer cold cathode array itself；Substrate 1 is in Fig. 1 b
Planar structure, support construction are integrated insulating layer aperture；Substrate 1 is sharp tapered structure in Fig. 1 c, and support construction is separation
Ceramic network/copper mesh.
Embodiment 2
The production process schematic diagram of composite Nano cold cathode structure based on Fig. 1.
As shown in Fig. 2, Fig. 2 gives the production flow diagram of the composite Nano cold cathode structure in embodiment 1 in Fig. 1 a.It is first
First prepare planar substrate 1(Fig. 2 a)；Then upright contour low-dimensional nanometer cold cathode 2, multiple low-dimensional nanometers are prepared on it
Cold cathode 2 constitutes low-dimensional nanometer cold cathode array (Fig. 2 b)；Two-dimensional film material 3 is finally transferred to low-dimensional nanometer cold cathode 2
Upper (Fig. 2 c).Contour low-dimensional nanometer cold cathode ensure that the geometric buckling at two-dimensional film material tip is less than nanowire tip
Geometric buckling.
As shown in figure 3, Fig. 3 gives the production flow diagram of the composite Nano cold cathode structure in embodiment 1 in Fig. 1 b.It is first
First prepare planar substrate 1(Fig. 3 a)；Then layer insulating film 4(Fig. 3 b is deposited on it)；Then in insulating layer of thin-film 4
In etch an aperture (Fig. 3 c)；Preparation and contour low-dimensional nanometer cold cathode 2(Fig. 3 d of insulating layer of thin-film) in aperture again；Most
Two-dimensional film material 3 is transferred in aperture afterwards, and rides on nano wire (Fig. 3 e).It is kept between nano wire and insulating layer of thin-film
Identical height ensure that the geometric buckling at two-dimensional film material tip is less than the geometric buckling of nanowire tip.
As shown in figure 4, Fig. 4 gives the production flow diagram of the composite Nano cold cathode structure in embodiment 1 in Fig. 1 c.It is first
First prepare pointed cone type substrate 1(Fig. 4 a)；Then low-dimensional nanometer cold cathode 2(Fig. 4 b is prepared on it)；One is then ready for have
The ceramic network of aperture/copper mesh 4(Fig. 4 c)；Two-dimensional film material 3 is transferred in aperture (Fig. 4 d) again；Finally ceramic network/copper
Net 4 is placed in the top of low-dimensional nanometer cold cathode 2, and is moved to the two contact (Fig. 4 e).It needs to ensure two-dimensional film material in movement
The geometric buckling at tip is less than the geometric buckling of nanowire tip.
The production of composite Nano cold cathode structure based on other low-dimensional nanometer cold cathodes in the present invention can be according to the above example
The basic step of son carries out.It is important to note that composite Nano cold cathode structure in Fig. 1 a, Fig. 1 b and Fig. 1 c and not only
It is limited only to single emitter shown in figure, is also applied in the emitter array structure of large area.
Embodiment 3
Fig. 5 is the compound low-dimensional nanometer cold yin that two-dimensional film material tip curvature is greater than/is less than low-dimensional nano structure tip curvature
The analog result of pole surface band curvature.
As shown in figure 5 a and 5b, the geometric buckling at two-dimensional film material tip is listed respectively larger and smaller than nano wire
The structural schematic diagram of tip geometric buckling.According to geometry, two-dimensional film material in Fig. 5 b is at tip and nanowire tip
It is in close contact, and the two-dimensional film material in Fig. 5 a then forms a hanging structure at tip.
Fig. 6 is that surface energy band of the two selenizing W film of single layer of different-thickness under the extra electric field of 2.5 V/nm is curved
Analog result；For using two tungsten selenides as two-dimensional film material, it is curved that numerical value calculates its energy band under 2.5 V/nm electric fields
Bent situation.Wherein, Fig. 6 a is the analog result of the two selenizing W film of single layer with a thickness of 0.7 nm.Fig. 6 b is with a thickness of 700
The analog result of two tungsten selenide of block of nm, from result as it can be seen that for single thin film, surface potential can be only about 0.13
EV, and for bulk shape, surface potential can be about 1.4 eV.
In conjunction with Fig. 5 and Fig. 6, in the structure of Fig. 5 a, two-dimensional film material tip be it is hanging, therefore, launching electronics only two
Tie up the acceleration on the c-axis direction of thin-film material by infiltration electrical field.So the energy of its infiltration electrical field is single thin film
Surface potential energy, such as Fig. 6 a, i.e. 0.13 eV.And in the structure of Fig. 5 b, two-dimensional material tip and nano wire are to be in close contact
, therefore, launching electronics can be injected into two-dimensional material under infiltration electrical field by nano wire acceleration.So its infiltration electrical field
Energy can be approximately the surface potential energy of bulk shape, such as Fig. 6 b, i.e. 1.4 eV.It can be seen that the structure in Fig. 5 b can obtain
The launching electronics for obtaining higher energy, to there is lower surface potential barrier.
Embodiment 4
This gives using zinc oxide nanowire, as quasi- one-dimensional low-dimensional nanometer cold cathode, two selenizing W film of single layer is made
For the manufacturing process and electron-microscope scanning and stability test result of the compound low-dimensional nanometer cold cathode of two-dimensional film material.
Specific making step is referring to attached drawing 2.Silicon chip substrate is used respectively first acetone, ethyl alcohol and deionized water ultrasound clear
It washes 30 minutes.After being dried with nitrogen, the zinc film with a thickness of 1 micron is prepared using electron beam evaporation technique in silicon chip substrate.
Then silicon wafer is put into the tube furnace under atmospheric environment and carries out thermal oxide.The temperature of tube furnace first rises to 470 DEG C from room temperature,
Then 3 hours are kept the temperature at 470 DEG C.After silicon wafer natural cooling, zinc film can grow zinc oxide low-dimensional nanometer cold cathode battle array
Column.And then two selenizing W film of single layer is transferred on low-dimensional nanometer cold cathode array using the method for organosol auxiliary.
Finally silicon chip sample is put into vacuum tube furnace and is rapidly heated to 450 DEG C, and is kept for 2 hours to remove organosol.
We have carried out scanning electron microscope observation to the composite Nano cold cathode structure of preparation.Fig. 7 is actual fabrication
Composite Nano cold cathode structure electron scanning micrograph and stability test result.
As shown in fig. 7, Fig. 7 a is the picture for the composite Nano cold cathode structure that scanning electron microscope is observed.Wherein,
White arrow meaning is the tip location that two tungsten selenides are contacted with zinc oxide nanowire.It can be seen that two tungsten selenides are relatively flatly
It is covered on nano wire, and the geometric buckling of two tungsten selenides is less than the geometric buckling of nanowire tip.Fig. 7 b is the structure
Field emission stability test result.It can be seen that the field emission stability of cold cathode is very good within 300 seconds testing times,
Fluctuation is down to 0.79%.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of composite Nano cold cathode structure of high stable electron emission characterized by comprising
Substrate；
Prepare the low-dimensional nanometer cold cathode on above-mentioned substrate；
The two-dimensional film material being covered on the tip of above-mentioned low-dimensional nanometer cold cathode；
For adjusting the support construction of the tip geometric buckling of above-mentioned two-dimensional film material；
The tip geometric buckling of the two-dimensional film material is less than the tip geometric buckling of low-dimensional nanometer cold cathode.
2. the composite Nano cold cathode structure of high stable electron emission according to claim 1, which is characterized in that the substrate
For planar substrate or pointed cone type substrate.
3. the composite Nano cold cathode structure of high stable electron emission according to claim 1, which is characterized in that the low-dimensional
Nanometer cold cathode is upright quasi- one-dimensional low-dimensional nanometer cold cathode or upright two-dimentional low-dimensional nanometer cold cathode.
4. high stable electron emission composite Nano cold cathode structure according to claim 1, which is characterized in that the support
Structure includes the low-dimensional nanometer cold cathode array being made of multiple low-dimensional nanometer cold cathodes.
5. high stable electron emission composite Nano cold cathode structure according to claim 1, which is characterized in that the support
Structure includes integrated cavernous structure or separation cavernous structure.
6. high stable electron emission composite Nano cold cathode structure according to claim 7, which is characterized in that described integrated
The material of cavernous structure includes insulation film or metallic film.
7. high stable electron emission composite Nano cold cathode structure according to claim 7, which is characterized in that the separation
The material of cavernous structure includes ceramics or metal.
8. a kind of preparation method of high stable electron emission composite Nano cold cathode structure according to claim 1, special
Sign is, comprising the following steps:
Clean substrate；
It prepares contour or close to contour low-dimensional nanometer cold cathode and support construction；
Two-dimensional film material is transferred on above-mentioned low-dimensional nanometer cold cathode.
9. the preparation method of the composite Nano cold cathode structure of high stable electron emission, feature exist according to claim 8
In the low-dimensional nanometer cold cathode includes zinc oxide, tungsten oxide, copper oxide, molybdenum oxide, silicon, silicon carbide, boron, carbon, molybdenum, nickel, tungsten
Etc. one or more materials.
10. the preparation method of high stable electron emission composite Nano cold cathode structure according to claim 8, feature exist
In the two-dimensional film material includes graphene, molybdenum disulfide, two selenizing molybdenums, tungsten disulfide, two tungsten selenides and other transition gold
Belong to sulfide, one of hexagonal boron nitride or multiple material.
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| CN113555461A (en) * | 2021-06-09 | 2021-10-26 | 浙江芯国半导体有限公司 | A photodiode based on SiC and tungsten diselenide heterojunction and its preparation method |
| CN120236951A (en) * | 2023-12-29 | 2025-07-01 | 北京大学 | Electron source and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113555461A (en) * | 2021-06-09 | 2021-10-26 | 浙江芯国半导体有限公司 | A photodiode based on SiC and tungsten diselenide heterojunction and its preparation method |
| CN120236951A (en) * | 2023-12-29 | 2025-07-01 | 北京大学 | Electron source and its preparation method and application |
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