CN101150028A - Large area electron field emission nano structure array and its preparation method - Google Patents
Large area electron field emission nano structure array and its preparation method Download PDFInfo
- Publication number
- CN101150028A CN101150028A CNA2007100298152A CN200710029815A CN101150028A CN 101150028 A CN101150028 A CN 101150028A CN A2007100298152 A CNA2007100298152 A CN A2007100298152A CN 200710029815 A CN200710029815 A CN 200710029815A CN 101150028 A CN101150028 A CN 101150028A
- Authority
- CN
- China
- Prior art keywords
- nano
- field emission
- array
- preparation
- electron field
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
This invention discloses a new type of large area electronic field emission nano-structured array and its preparation method, in which, the structure includes: Alumina nano-conical cones of pinpoint structure are distributed uniformly on a matrix vertically and are coated with a layer of electronic field emission material and holes of the matrix are filled with conductive electrode materials. The preparation method includes: carrying out electrochemical anode oxidation process to an Al foil or Al adhered on the matrix to get a matrix with Almina film and nm holes at the surface, corroding the film with a corroding solution reacting with Almina to get the large area serial Almina nm conical array, filling the holes of the matrix with conductive electrode material and then coaring a layer of field emission material on the array to get a new type of large area electronic field emission nm-structured array.
Description
Technical field
The present invention relates to a kind of large area electron field emission nano structure array and technology of preparing thereof.
Background technology
Discover that the cutting-edge structure of field emitter can strengthen the field intensity at most advanced and sophisticated place, significantly improve the emitting performance of emitter material.As document " Lo HC; Das D; Chen KH; et al.SiC-cappednahotip arrays for field emission with ultralow turn-on field.Appl.Phys.Lett.2003; 83:14 20-1422. ", adopt plasma etching technology to prepare the Si nanometer point of orderly arrangement at silicon chip surface, its most advanced and sophisticated top has the SiC " cap " of several nanometer thickness, and the unlatching electric field of this nanostructure only is 0.35V/ μ m.As document " Tang C; Bando Y.Effect of BN coatings onoxidation resistance and field emission of SiC nanowires.Appl.Phys.Lett.2003; 83:659-661. ", SiC nano wire outer wrapping behind the BN layer of one deck 2-4nm, it is opened electric field and also reduces to 6V/ μ m by original 10V/ μ m.As document " Li YB; Bando Y; Golberg D.Z nOnanoneedles with tip surface perturbations:Excellent field emitters.Appl.Phys.Lett.2004; 84:3603-3605. ", also find to be positioned at the zinc-oxide nano needle tip, the existence of the surperficial perturbation layer of thick 1-3nm can reduce an emission electric field greatly.
The large tracts of land field emission volume array that relies on the photoetching method preparation to have the nanotip structure, its production cost is than higher.
Summary of the invention
In order to overcome above-mentioned deficiency of the prior art, the invention provides a kind of large area electron field emission nano structure array and preparation method thereof.Its preparation method controllability is good, and method is simple, is fit to preparation large tracts of land field emission array.
Large-area ordered electron field emission nano structure array of the present invention, this array structure is for being evenly distributed with aluminium oxide nano awl array vertical with matrix, that have the tip-like cutting-edge structure on the smooth matrix of large tracts of land; Be distributed with the nano-scale hole on the matrix between the aluminium oxide nano awl, in hole, be filled with electric conducting material as the emitter conductive electrode; Surface coverage at described each aluminium oxide nano awl and described electric conducting material has one deck electron field emission materials.
The length of described aluminium oxide nano awl is 5nm～5um, and the nanocone root diameter (RD) is 5nm-150nm, and the density that the aluminium oxide nano awl distributes is 10
8-10
11/ cm
2The area of nano-structure array is more than the square centimeter magnitude.
Described electron field emission materials is tungsten, molybdenum, diamond like carbon, carbon nano-tube, zinc oxide, iron oxide, tungsten oxide, molybdenum oxide, copper sulfide, zinc sulphide or cuprous sulfide, and other known broadband semiconductor with good field emission performance and narrow-band semiconductor material.
Described electric conducting material as the emitter conductive electrode of filling in hole is high conductive materials such as silver, copper, nickel or aluminium.
The preparation method of large-area ordered electron field emission body nano-structure array of the present invention is as follows: to aluminium flake or carry out electrochemical anodic oxidation attached to suprabasil aluminium foil and handle and to obtain the smooth matrix of surface for the pellumina of band nano aperture; Under 20～80 ℃ of temperature, with can with aluminium oxide reaction, to be 1%～20% etching solution carry out etch to the pellumina of gained to volumetric concentration handled 5～30 minutes, stir on etch limit, limit, and mixing speed is 5～80 rev/mins, promptly obtains large-area ordered aluminium oxide nano awl array; The method that adopts electric plating method or high-pressure smelting to fill then is filled into the electric conducting material as the emitter conductive electrode in the nano aperture; Adopt ripe physical vapor or chemical gaseous phase film plating process that the surface that electron field emission materials is covered in aluminium oxide nano awl and electric conducting material is formed continuous film or membrana granulosa again, promptly.
Described etching solution preferably sulfuric acid solution, oxalic acid solution, phosphoric acid solution, chromic acid solution or any two or more the mixed liquor in them, or NaOH, sodium acid carbonate, potassium hydroxide or any two or more the mixed liquor in them.
The volumetric concentration of described etching solution is preferably 1%～15%.
The best mixing speed that described etch is handled is 10～50 rev/mins.
Described aluminium flake or be preferably 100nm～2mm attached to the thickness of suprabasil aluminium foil.
Described substrate can be for conducting metal or non-conducting material, as semiconductor, and glass, pottery, high molecular polymer etc.
Large area electron field emission nano structure array of the present invention has the characteristics of the following aspects: what one, the nanometer of its enormous amount was regular lines up, because we know with regard to single nano-wire, may there be some defectives in itself, but regular the lining up of a large amount of nano wires formed the deficiency that array just can overcome single nano-wire; Two, the nanocone in its nano-cone array has cutting-edge structure and vertical matrix, and it has big geometry enhancer this structures shape in the field-causing electron emission; Three, its nanocone and matrix are connected as a single entity, and can guarantee that like this nano-cone array and matrix have good electrical contact performance.Four, this method for preparing nanocone has with low costly with respect to traditional micro-processing method, and process conditions are simple, are particularly suitable for advantages such as large-area preparation.Five, aluminium oxide itself is a kind of ceramic material, and is high temperature resistant, corrosion-resistant, anti-oxidant, and the good mechanical performance is arranged.So, this large tracts of land normal alumina nano-cone array is carried out finishing, can form composite array.At the surface physics gas phase and the chemical gaseous phase film plating process of aluminium oxide nano awl, cover the material that one deck has good electronics field emission performance, form the field-causing electron emitter array.Plating is adopted in hole the inside at matrix, and perhaps the method for high-pressure smelting filling prepares the filled conductive metal material, forms conductive electrode.
Description of drawings
Fig. 1 is the front plan view of the pellumina with nano aperture that makes of embodiment one.
Fig. 2 is the side sectional drawing of the pellumina with nano aperture that makes of embodiment one.
The front plan view of the ordered aluminum oxide nano-cone array that Fig. 3 makes for embodiment one.
The side sectional drawing of the ordered aluminum oxide nano-cone array that Fig. 4 makes for embodiment one.
Embodiment
Embodiment one
To thickness is that 0.2 millimeter aluminium foil (purity 99.995%) carries out mechanical polishing with abrasive pastes; temperature is 500 degrees centigrade of annealing 5 hours under the nitrogen atmosphere protection then; at ethanol: carrene: clean with ultrasonic wave in acetone (volume ratio 1: 2: the 1) mixed solution; carry out alkali cleaning with 0.24mol/L NaOH solution again and handle, the natural oxide film that lip-deep thickness is about 30～1000 is removed.At perchloric acid: carry out 3 minutes electrochemical polish in ethanol (volume ratio is 1: the 9) mixed solution, polishing voltage is selected 20V, and the temperature of polishing fluid is controlled at 5 ℃ (± 0.5 ℃).
Aluminium foil carries out an anodic oxidation through after the above-mentioned preliminary treatment in the 0.3M/L oxalic acid solution, the voltage during oxidation is selected 40V, 5 ℃ of temperature (± 0.5 ℃), 2 hours once oxidation time; Use mixed acid solution (6wt% phosphoric acid+1.8wt% chromic acid) to erode the oxide-film of anodic oxidation growth then; The last two-step anodization, 4 hours secondary oxidation time of under the condition identical, carrying out with once oxidation.The pellumina with nano aperture for preparing is keeping the matrix of hole, and is combined as a whole fully with unoxidized aluminium foil.As shown in Figure 1, 2.
With volume ratio be 1% phosphoric acid solution as etching solution, the pellumina that the two-step anodization method is prepared carries out etch, the temperature of etching solution is 20 degrees centigrade, stir speed (S.S.) is 10 rev/mins, the etch time is 30 minutes.
Through said process, prepare ordered aluminum oxide nano-cone array as shown in Figure 3, Figure 4.On alumina substrate, be evenly distributed with taper alumina nanowires vertical with matrix, that have the tip-like cutting-edge structure.Matrix thickness is 2000nm, and the length of taper nanocone and nanocone root diameter (RD) are than 2200nm: 80nm=27.5 in the nano-cone array.
Use electrochemical method, use CuSO
4Solution is as electroplate liquid, and electro-deposition Cu is as conductive electrode in the hole of alumina substrate.
With pulse Vacuum arc source deposition technique, having applied a layer thickness on the above-mentioned aluminium oxide nano awl array for preparing is diamond like carbon (DLC) film of 5nm, promptly obtains large area electron field emitter nano-structure array.
Embodiment two
On monocrystalline silicon piece, plate the thick silver of one deck 500nm with magnetically controlled sputter method, on silver, plate the aluminium of one deck 5 micron thickness with the method for evaporation then, obtain attached to the suprabasil aluminium of silver.
Being placed on attached to the suprabasil aluminium of silver of obtaining carried out an anodic oxidation in the 0.3M/L oxalic acid solution, the voltage during oxidation is selected 40V, 5 ℃ of temperature (± 0.5 ℃), and oxidization time is 30 minutes.The pellumina with nano aperture for preparing is keeping the matrix of hole, and and money base at the bottom of be combined as a whole fully.
With volume ratio be 5% oxalic acid solution as etching solution, the pellumina that the antianode method for oxidation prepares carries out etch, the temperature of etching solution is 40 degrees centigrade, stir speed (S.S.) is 30 rev/mins, the etch time is 5 minutes.
Through said process, make large-area ordered aluminium oxide nano awl array.
The length of nanocone and nanocone root diameter (RD) are than 200nm: 75nm=2.67 in the nano-cone array.
Use electrochemical method, use NiCl
2Solution is as electroplate liquid, and deposit N i is as conductive electrode in the hole of alumina substrate.
Use hot evaporation coating technique, having applied a layer thickness on the above-mentioned aluminium oxide nano awl array for preparing is the W film of 5nm, obtains large tracts of land tungsten electron field emission body nano-structure array.
Embodiment three
Carry out one described operating procedure earlier, obtain and the pellumina that is combined as a whole fully of alumina foil not with nano aperture as embodiment.Then, remove not alumina foil, obtain having the pellumina of nano aperture with saturated HgCl solution.To plate thickness on the pellumina of nano aperture be that 20 microns copper is as substrate having with magnetically controlled sputter method.With volume ratio be 10% sulfuric acid solution as etching solution, carry out etch to resulting attached to the suprabasil pellumina of copper, the temperature of etching solution is 60 degrees centigrade, stir speed (S.S.) is 50 rev/mins, the etch time is 50 minutes.
Through said process, prepare large-area ordered aluminum oxide nano-wire array.
The length of nano wire and nano wire root diameter (RD) are than 3500nm: 62nm=56.45 in the nano-wire array.
Use electrochemical method, use NiCl
2Solution is as electroplate liquid, and deposit N i is as conductive electrode in the hole of alumina substrate.
Use physical gas phase deposition technology, having applied a layer thickness on the above-mentioned aluminium oxide nano awl array for preparing is the ZnO film of 5nm, obtains large tracts of land ZnO electron field emission body nano-structure array.
Claims (10)
1. large-area ordered electron field emission nano structure array, this array structure is for being evenly distributed with aluminium oxide nano awl array vertical with matrix, that have the tip-like cutting-edge structure on the smooth matrix of large tracts of land; Be distributed with the nano-scale hole on the matrix between the aluminium oxide nano awl, in hole, be filled with electric conducting material as the emitter conductive electrode; Surface coverage at described each aluminium oxide nano awl and described electric conducting material has one deck electron field emission materials.
2. large-area ordered electron field emission nano structure array according to claim 1 is characterized in that: the length of described aluminium oxide nano awl is 5nm～5 μ m, and the nanocone root diameter (RD) is 5nm-150nm, and the density that the aluminium oxide nano awl distributes is 10
8-10
11/ cm
2The area of nano-structure array is more than the square centimeter magnitude.
3. large-area ordered electron field emission nano structure array according to claim 1 is characterized in that: described electron field emission materials is tungsten, molybdenum, diamond like carbon, carbon nano-tube, zinc oxide, iron oxide, tungsten oxide, molybdenum oxide, copper sulfide, zinc sulphide or cuprous sulfide.
4. large-area ordered electron field emission nano structure array according to claim 1 is characterized in that: described electric conducting material as the emitter conductive electrode of filling in hole is silver, copper, nickel or aluminium.
5. the preparation method of a large-area ordered electron field emission nano structure array as claimed in claim 1, to aluminium flake or carry out electrochemical anodic oxidation attached to suprabasil aluminium foil and handle and to obtain the smooth matrix of surface for the pellumina of band nano aperture, it is characterized in that: under 20～80 ℃ of temperature, with can with aluminium oxide reaction, to be 1%～20% etching solution carry out etch to the pellumina of gained to volumetric concentration handled 5～30 minutes, stir on etch limit, limit, mixing speed is 5～80 rev/mins, promptly obtains large-area ordered aluminium oxide nano awl array; The method that adopts electric plating method or high-pressure smelting to fill then is filled into the electric conducting material as the emitter conductive electrode in the nano aperture; Adopt ripe physical vapor or chemical gaseous phase film plating process that the surface that electron field emission materials is covered in aluminium oxide nano awl and electric conducting material is formed continuous film or membrana granulosa again, promptly.
6. preparation method according to claim 5, it is characterized in that: described etching solution is sulfuric acid solution, oxalic acid solution, phosphoric acid solution, chromic acid solution or any two or more the mixed liquor in them, or NaOH, sodium acid carbonate, potassium hydroxide or any two or more the mixed liquor in them.
7. preparation method according to claim 5 is characterized in that: the volumetric concentration of described etching solution is 1%～15%.
8. preparation method according to claim 5 is characterized in that: the mixing speed that described etch is handled is 10～50 rev/mins.
9. preparation method according to claim 5 is characterized in that: described aluminium flake or be 100nm～2mm attached to the thickness of suprabasil aluminium foil.
10. preparation method according to claim 5 is characterized in that: described substrate is conducting metal or non-conducting material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100298152A CN101150028A (en) | 2007-08-21 | 2007-08-21 | Large area electron field emission nano structure array and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100298152A CN101150028A (en) | 2007-08-21 | 2007-08-21 | Large area electron field emission nano structure array and its preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101150028A true CN101150028A (en) | 2008-03-26 |
Family
ID=39250479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100298152A Pending CN101150028A (en) | 2007-08-21 | 2007-08-21 | Large area electron field emission nano structure array and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101150028A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101887828A (en) * | 2010-06-03 | 2010-11-17 | 重庆启越涌阳微电子科技发展有限公司 | Carbon-based nano novel field electron emission material in areatus layered structure and preparation method thereof |
| CN103117199A (en) * | 2011-11-17 | 2013-05-22 | 浙江海洋学院 | Pine-shaped nanometer array field emitting negative pole manufacturing method |
| CN106756897A (en) * | 2016-11-15 | 2017-05-31 | 重庆科技学院 | Ag doped ferric oxide nano-tube array structure films and preparation method thereof |
| CN112126964A (en) * | 2020-09-16 | 2020-12-25 | 太原理工大学 | Preparation method of field emission diamond-like carbon-titanium dioxide nanotube composite film |
-
2007
- 2007-08-21 CN CNA2007100298152A patent/CN101150028A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101887828A (en) * | 2010-06-03 | 2010-11-17 | 重庆启越涌阳微电子科技发展有限公司 | Carbon-based nano novel field electron emission material in areatus layered structure and preparation method thereof |
| CN101887828B (en) * | 2010-06-03 | 2013-04-24 | 重庆启越涌阳微电子科技发展有限公司 | Carbon-based nano novel field electron emission material in areatus layered structure and preparation method thereof |
| CN103117199A (en) * | 2011-11-17 | 2013-05-22 | 浙江海洋学院 | Pine-shaped nanometer array field emitting negative pole manufacturing method |
| CN106756897A (en) * | 2016-11-15 | 2017-05-31 | 重庆科技学院 | Ag doped ferric oxide nano-tube array structure films and preparation method thereof |
| CN112126964A (en) * | 2020-09-16 | 2020-12-25 | 太原理工大学 | Preparation method of field emission diamond-like carbon-titanium dioxide nanotube composite film |
| CN112126964B (en) * | 2020-09-16 | 2021-08-10 | 太原理工大学 | Preparation method of field emission diamond-like carbon-titanium dioxide nanotube composite film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20060270229A1 (en) | Anodized aluminum oxide nanoporous template and associated method of fabrication | |
| US20040072494A1 (en) | Field emission type cold cathode device, manufacturing method thereof and vacuum micro device | |
| CN101638781B (en) | Method for directly heating metal membrane to grow oxide nanowires in array-type arranged microcavity structure, and application thereof | |
| US20170271080A1 (en) | Method for forming a boron-containing thin film and multilayer structure | |
| US8070929B2 (en) | Catalyst particles on a tip | |
| EP1102298A1 (en) | Field emission display device using vertically-aligned carbon nanotubes and manufacturing method thereof | |
| CN101150028A (en) | Large area electron field emission nano structure array and its preparation method | |
| CN101494144B (en) | Structure of nanometer line cold-cathode electron source array with grid and method for producing the same | |
| JP2007504607A (en) | Field emission device | |
| US7554255B2 (en) | Electric field emission device having a triode structure fabricated by using an anodic oxidation process and method for fabricating same | |
| JP2001291465A (en) | Cold cathode and manufacturing method thereof | |
| CN101236872A (en) | Making method for transmission array of field radiation cathode carbon nano pipe | |
| CN101369504B (en) | Preparation method of compound film used for field emission display equipment | |
| CN101093771A (en) | Field emission body of Nano carbon tube, and preparation method | |
| Geng-Min et al. | Field emission from an array of free-standing metallic nanowires | |
| Ye et al. | Application of ZnO nanopillars and nanoflowers to field-emission luminescent tubes | |
| CN113594873B (en) | Electrode with metal micro-column array on surface and preparation method thereof | |
| CN101819913A (en) | Front gate type field emission cathode structure with edge enhancement effect and preparation method thereof | |
| US10858746B2 (en) | Method of manufacturing graphene by DC switching | |
| RU205789U1 (en) | AUTO EMISSION CELL BASED ON NANOSIZED CARBON MATERIAL | |
| KR101388839B1 (en) | Metal nanowire with carbon nanotube and method for manufacturing the same | |
| CN100427379C (en) | Nano monocrystalline antimony wire/alumina ordered mesoporous complex and preparation method thereof | |
| WO2015079706A1 (en) | Anisotropic conductive film, method for producing same, device, electron emission element, field emission lamp, and field emission display | |
| JP3583387B2 (en) | Electron-emitting device, method of manufacturing the same, and image display device provided with electron-emitting device | |
| TWI510142B (en) | Micro plasma device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20080326 |