CN1283835C - Large area tungsten Molybdenum and its oxide nano wires and array and their preparation and use - Google Patents
Large area tungsten Molybdenum and its oxide nano wires and array and their preparation and use Download PDFInfo
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- CN1283835C CN1283835C CN 03140333 CN03140333A CN1283835C CN 1283835 C CN1283835 C CN 1283835C CN 03140333 CN03140333 CN 03140333 CN 03140333 A CN03140333 A CN 03140333A CN 1283835 C CN1283835 C CN 1283835C
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
Abstract
The present invention discloses a nanometer wire made from large-area wolfram and molybdenum and oxide thereof, and an array of the nanometer wire. The present invention also discloses a preparing method for a nanometer wire made from a wolfram and molybdenum simple substance and oxide thereof, and an application of the preparing method. The preparing method of the present invention has the advantages of simplicity, directness, low requirement to equipment and low cost. Meanwhile, the nanometer wire made from large-area wolfram and molybdenum and oxide thereof of the presnet invention has excellent field electron emission properties, has wide application prospects as the electron sources of cold cathodes, particularly has wide application prospects as field electron emission flat-panel dispalys, luminous tubes of cold cathodes, cold light sources, etc.
Description
Technical field
The present invention relates to tungsten, molybdenum and oxide nano wires film thereof and nano-wire array thereof, their preparation method and application.
Background technology
Tungsten and molybdenum work function in metal is relatively low, and good mechanical property, especially high-temperature behavior are good, and rate of evaporation is little, is used as field emmision material the earliest.As field electron emission materials, they also have an advantage the most significant is exactly to export big emission, and this point is very important for using on the field-causing electron ballistic device.Tungsten oxide and molybdenum dioxide all are the oxide compounds with metallic conductivity.They also are widely used as memorizing material, catalyzer and transmitter etc.Tungstic oxide and molybdic oxide all are the wide bandgap semiconductor materials of n type, and they are used to indicating meter, transmitter, solar cell widely and are used as catalyzer etc.
Before our invention,, and utilize the report of inorganics as the synthetic tungsten nano wire film of precursor only relevant for utilizing electrochemical process to synthesize the molybdenum nano wire film.But their preparation method's cost height, low, the complex process of productive rate, and can not prepare large-area nano wire film, particularly can not prepare the nano-wire array of orderly above-mentioned materials.These have restricted their application greatly.
Summary of the invention
The object of the present invention is to provide a kind of tungsten, molybdenum and oxide nano wires film and nano-wire array thereof.
Another object of the present invention is to provide the preparation method of a kind of tungsten, molybdenum simple substance and oxide nano wires film and nano-wire array thereof.
The present invention also has a purpose to be to provide the application of a kind of tungsten, molybdenum and oxide nano wires film and nano-wire array thereof.
In our invention, we are nano wire film or nano-wire arrays of preparing large-area Tungsten oxide and molybdenum dioxide earlier, and then obtain the nano wire film or the nano-wire array of tungsten, molybdenum simple substance respectively by the reductive method, and obtain the nano wire film or the nano-wire array of tungstic oxide and molybdic oxide with the method for oxidation.
In order to prepare tungsten, molybdenum and oxide nano wires film or nano-wire array, the present invention adopts following processing step respectively:
One, the nano wire film or the nano-wire array of preparation Tungsten oxide and molybdenum dioxide:
1 cleans substrate, removes the impurity on the substrate.
2 put into the heating under vacuum device with tungsten source or molybdenum source and substrate; substrate be placed on tungsten source or molybdenum source directly over or and come same plane (distance between them is adjustable); to the forvacuum of heating under vacuum device, feed rare gas element then earlier, and keep constant current as shielding gas.
The 3 pairs of tungsten sources or molybdenum source and substrate heat up respectively.During the preparation Tungsten oxide, the tungsten source is heated to 1000～2000 ℃, and substrate is heated to 900～1400 ℃; During the preparation molybdenum dioxide, the molybdenum source is heated to 1000～2000 ℃, and substrate is heated to 800～1100 ℃.Soaking time is 1 minute to 120 minutes.
4 lower the temperature under inert gas atmosphere, until being cooled to room temperature.
In above-mentioned technology, adopt tungsten powder, tungsten sheet or tungsten boat as the tungsten source, molybdenum powder, molybdenum sheet or molybdenum boat are as the molybdenum source.The substrate that adopts is monocrystalline silicon piece, silicon pinpoint array, tinsel, glass, pottery and other resistant to elevated temperatures materials, and geometrical shape is not limit.
Two, the nano wire film or the nano-wire array of preparation simple substance tungsten and molybdenum:
1 puts into the heating under vacuum device with the sample of Tungsten oxide or molybdenum dioxide nano wire film or nano-wire array, earlier to the forvacuum of heating under vacuum device, feeds hydrogen then as reducing gas, and keeps constant current.
2 are warming up to 500～1000 ℃ with sample, are incubated 3 to 15 hours.
3 lower the temperature under hydrogen atmosphere, until being cooled to room temperature.
Three, the nano wire film or the nano-wire array of preparation tungstic oxide and molybdic oxide:
1 puts into the heating under vacuum device with Tungsten oxide or molybdenum dioxide nano wire film or nano-wire array, earlier to the forvacuum of heating under vacuum device, feeds the mixed gas of argon gas and oxygen then, and keeps constant current.
During 2 preparation tungstic oxides, sample is warming up to 500-1000 ℃, is incubated 2-60 minute;
During the preparation molybdic oxide, sample is warming up to 300-600 ℃, is incubated 2-60 minute.
3 lower the temperature under the mixed-gas atmosphere of argon gas and oxygen, until being cooled to room temperature.
The invention provides the method for preparing tungsten, molybdenum and oxide nano wires film and nano-wire array thereof.The preparation method is simple, direct, not high to equipment requirements, with low cost.Prove by experiment also that simultaneously they have excellent electronic emission performance, have very big application prospect as cold-cathode electron source, especially at field electron emission flat panel display, cold cathode luminotron, cold light source etc.
Description of drawings
Fig. 1 a is the XRD spectrum of molybdenum dioxide nano wire film.
Fig. 1 b is the SEM photo of molybdenum dioxide nano wire film.
Fig. 1 c is the high resolution TEM and the corresponding electron-diffraction diagram of molybdenum dioxide nano wire film.
Fig. 2 a is the XRD spectrum of simple substance molybdenum nano wire film.
Fig. 2 b is the shape appearance figure of simple substance molybdenum nano wire film.
Fig. 2 c is the high resolution TEM and the corresponding electron-diffraction diagram of simple substance molybdenum nano wire film.
Fig. 3 a is the XRD spectrum of molybdenum trioxide nano line film.
Fig. 3 b is the shape appearance figure of molybdenum trioxide nano line film.
Fig. 3 c is the high resolution TEM and the corresponding electron-diffraction diagram of molybdenum trioxide nano line film.
Fig. 4 a is the XRD spectrum of Tungsten oxide nano wire film.
Fig. 4 b is the SEM photo of Tungsten oxide nano wire film.
Fig. 4 c is the high resolution TEM and the corresponding electron-diffraction diagram of Tungsten oxide nano wire film.
Fig. 5 a is the XRD spectrum of simple substance tungsten nano wire film.
Fig. 5 b is the SEM figure of simple substance tungsten nano wire film.
Fig. 5 c is the high resolution TEM and the corresponding electron-diffraction diagram of simple substance tungsten nano wire film.
Fig. 6 a is the XRD spectrum of tungsten trioxide nano line film.
Fig. 6 b is the SEM figure of tungsten trioxide nano line film.
Fig. 6 c is the high resolution TEM and the corresponding electron-diffraction diagram of tungsten trioxide nano line film.
Fig. 7 a is the field emission picture of molybdenum dioxide nano wire film.
Fig. 8 a is the field emission picture of simple substance molybdenum nano wire film.
Fig. 9 a is the field emission picture of molybdenum trioxide nano line film.
Fig. 7 b is the field emission J-E and the F-N performance diagram of molybdenum dioxide nano wire film.
Fig. 8 b is the field emission J-E and the F-N performance diagram of simple substance molybdenum nano wire film.
Fig. 9 b is the field emission J-E and the F-N performance diagram of molybdenum trioxide nano line film.
Fig. 7 c is the field emission stability curve of molybdenum dioxide nano wire film.
Fig. 8 c is the field emission stability curve of simple substance molybdenum nano wire film.
Fig. 9 c is the field emission stability curve of molybdenum trioxide nano line film.
Figure 10 is the field emission J-E and the F-N performance diagram of Tungsten oxide nano wire film.
Figure 11 a is the field emission picture of Tungsten oxide nano wire film.
Figure 11 b is the field emission J-E and the F-N performance diagram of simple substance tungsten nano wire film.
Figure 11 c is the field emission stability graphic representation of Tungsten oxide nano wire film.
Figure 12 a is the field emission picture of tungsten trioxide nano line film.
Figure 12 b is the field emission J-E and the F-N performance diagram of tungsten trioxide nano line film.
Figure 12 c is the field emission stability graphic representation of tungsten trioxide nano line film.
Figure 13 a is that the molybdenum oxide nano wire film is applied in the cold cathode luminotron situation that luminotron is being worked.
Figure 13 b be anode voltage when being 7 kilovolts the molybdenum oxide nano wire film be applied in the cold cathode luminotron I-V rational curve when anode voltage is 7 kilovolts.
Embodiment
One, the nano wire film of preparation molybdenum dioxide.
1 monocrystalline silicon piece of selecting (100) face for use is as substrate, ultrasonic cleaning 5 minutes in acetone earlier, ultrasonic cleaning 5 minutes in dehydrated alcohol then.
2 select for use molybdenum boat as the molybdenum source, molybdenum boat are placed in the heating under vacuum device (φ 350 * 400mm), and directly over the source of molybdenum boat, the distance between them is 1mm with silicon slice placed.Earlier to heating under vacuum device forvacuum to 1.0 * 10
-2Torr feeds argon gas then as shielding gas, and airshed is 200 standard cubic centimeter per seconds, and keeps constant current.
3 heat up molybdenum boat, and heat-up rate is 100 a ℃/per minute, are warming up to 1200 ℃ and be incubated 30 minutes at last.
4 lower the temperature under argon gas atmosphere, until being cooled to room temperature.
Two, the nano wire film of preparation simple substance molybdenum.
1 is placed on molybdenum dioxide nano wire film sample that (φ 350 * 400mm) in the heating under vacuum device.With heating under vacuum device forvacuum to 1.0 * 10
-2Torr feeds high-purity hydrogen then, and the hydrogen gas stream amount is 200 standard cubic centimeter per seconds.
2 heat up to sample, and heat-up rate is 100 a ℃/per minute, are warming up to 800 ℃ and be incubated 10 hours at last.
3 lower the temperature under hydrogen atmosphere, until being cooled to room temperature.
Three, the nano wire film of preparation molybdic oxide.
1 is placed on molybdenum dioxide nano wire film sample that (φ 350 * 400mm) in the heating under vacuum device.With heating under vacuum device forvacuum to 1.0 * 10
-2Torr feeds the mixed gas of argon gas and oxygen then, and airshed is respectively 100 standard cubic centimeter per seconds.
2 heat up sample, and heat-up rate is 100 a ℃/per minute, are warming up to 400 ℃ and be incubated 30 minutes at last.
3 lower the temperature under the mixed-gas atmosphere of argon gas and oxygen, until being cooled to room temperature.
Four, the nano wire film of preparation Tungsten oxide.
1 monocrystalline silicon piece of selecting (100) face for use is as substrate, ultrasonic cleaning 5 minutes in acetone earlier, ultrasonic cleaning 5 minutes in dehydrated alcohol then.
2 select for use the tungsten boat as the tungsten source, the tungsten boat is placed in the heating under vacuum device (φ 350 * 400mm), with silicon slice placed on the tungsten boat.Earlier to heating under vacuum device forvacuum to 1.0 * 10
-2Torr feeds argon gas then as shielding gas, and airshed is 200 standard cubic centimeter per seconds, and keeps constant current.
3 heat up the tungsten boat, and heat-up rate is 100 a ℃/per minute, are warming up to 1200 ℃ and be incubated 30 minutes at last.
4 lower the temperature under argon gas atmosphere, until being cooled to room temperature.
Five, the nano wire film of preparation simple substance tungsten.
1 is placed on Tungsten oxide nano wire film sample that (φ 350 * 400mm) in the heating under vacuum device.With heating under vacuum device forvacuum to 1.0 * 10
-2Torr feeds high-purity hydrogen then, and the hydrogen gas stream amount is 200 standard cubic centimeter per seconds.
2 heat up to sample, and heat-up rate is 100 a ℃/per minute, are warming up to 800 ℃ and be incubated 10 hours at last.
3 lower the temperature under hydrogen atmosphere, until being cooled to room temperature.
Six, the nano wire film of preparation tungstic oxide.
1 is placed on Tungsten oxide nano wire film sample that (φ 350 * 400mm) in the heating under vacuum device.With heating under vacuum device forvacuum to 1.0 * 10
-2Torr feeds the mixed gas of argon gas and oxygen then, and airshed is respectively 100 standard cubic centimeter per seconds.
2 heat up sample, and heat-up rate is 100 a ℃/per minute, are warming up to 800 ℃ and be incubated 30 minutes at last.
3 lower the temperature under the mixed-gas atmosphere of argon gas and oxygen, until being cooled to room temperature.
For tungsten prepared among the top embodiment, molybdenum and oxide nano wires film thereof, we observe and analyze with X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), power spectrum (EDS) and Raman spectrum (RAMAN) etc.Also studied their field-causing electron emission characteristic, and be applied in the cold cathode luminotron.The invention will be further described below in conjunction with accompanying drawing and subordinate list.
Fig. 1 (a) is the XRD spectrum of molybdenum dioxide nano wire film, and by this spectrum is analyzed, we can know that this nano wire film is to have monocline molybdenum dioxide nano wire.Can see that from the SEM photo (Fig. 1 (b)) of typical sample nano wire is perpendicular to substrate growth, the diameter of nano wire is about 150 nanometers, and being about is 3 microns.Analyze by high resolution TEM (Fig. 1 (c)) and corresponding electron diffraction (Fig. 1 (c) upper right corner illustration), we can also know that this nano wire has crystalline structure.Fig. 2 (a) is the XRD spectrum of simple substance molybdenum nano wire film, and by this spectrum is analyzed, we can know that this nano wire film is the very pure molybdenum nano wire with body-centered cubic structure.The pattern of molybdenum nano wire is similar to the molybdenum dioxide nano wire, and the diameter of nano wire is a little bit smaller a little, is about 100nm[Fig. 2 (b)].By high resolution TEM[Fig. 2 (c)] and corresponding electron diffraction (Fig. 2 (c) upper right corner illustration) analysis, we can know that the molybdenum nano wire also has crystalline structure.Fig. 3 (a) is the XRD spectrum of molybdenum trioxide nano line film, and by analyzing, we can know that this nano wire film is the very pure molybdenum trioxide nano line with orthohormbic structure.The molybdenum trioxide nano line also is the vertical substrates growth, and pattern is similar substantially to the molybdenum dioxide nano wire, and diameter is about 200nm[Fig. 3 (b)].By high resolution TEM[Fig. 3 (c)] and corresponding electron diffraction (Fig. 3 (c) upper right corner illustration) analysis, we can know that this nano wire has crystalline structure.Fig. 4 (a) is the XRD spectrum of Tungsten oxide nano wire film, and by this spectrum is analyzed, we can know that this nano wire film is to have monocline Tungsten oxide nano wire.Can see that the diameter of nano wire is about 100 nanometers from the SEM photo (Fig. 4 (b)) of typical sample, being about is 2 microns.Analyze by high resolution TEM (Fig. 4 (c)) and corresponding electron diffraction (Fig. 1 (c) upper right corner illustration), we can also know that this nano wire has crystalline structure, but a lot of defectives are arranged.Fig. 5 (a) is the XRD spectrum of simple substance tungsten nano wire film, and by this spectrum is analyzed, we can know that this nano wire film is the very pure tungsten nano wire with body-centered cubic structure.Fig. 5 (b) is the SEM figure of tungsten nano wire.By high resolution TEM[Fig. 5 (c)] and corresponding electron diffraction (Fig. 2 (c) upper right corner illustration) analysis, we can know that the tungsten nano wire also has crystalline structure.Fig. 6 (a) is the XRD spectrum of tungsten trioxide nano line film, and by analyzing, we can know that this nano wire film is the very pure tungsten trioxide nano line with monocline.Fig. 6 (b) is the SEM figure of tungsten trioxide nano line film.By high resolution TEM[Fig. 6 (c)] and corresponding electron diffraction (Fig. 6 (c) upper right corner illustration) analysis, we can know that this nano wire has single crystal structure.
Fig. 7 (a), Fig. 8 (a) and Fig. 9 (a) are respectively the field emission pictures of molybdenum dioxide, simple substance molybdenum and molybdenum trioxide nano line film, we can find that these nano wire film field emissions are very even, the pattern of light-emitting zone and film morphology (upper left corner illustration of Fig. 7 (a), Fig. 8 (a) and Fig. 9 (a)) basically identical.Fig. 7 (b), Fig. 8 (b) and Fig. 9 (b) and upper left corner illustration are respectively the field emission J-E and the F-N performance diagrams of molybdenum dioxide, simple substance molybdenum and molybdenum trioxide nano line film, and we can find that (opening electric field and threshold field is defined as respectively and produces 10 μ A/cm for the unlatching electric field of molybdenum dioxide, simple substance molybdenum and molybdenum trioxide nano line film and threshold field from their J-E performance chart
2And 10mA/cm
2The electric field that current density is required) is respectively 2MV/m, 2.2MV/m, 3.5MV/m and 4.75MV/m, 6.24MV/m and 7.65MV/m.Their threshold field can be suitable with the threshold field of carbon nanotube.Their F-N curve is linear, illustrates that their the satisfied classical field emission of field emission is theoretical.Fig. 7 (c), Fig. 8 (c) and Fig. 9 (c) they are respectively the field emission stability curves of molybdenum dioxide, simple substance molybdenum and molybdenum trioxide nano line film, their fluctuation has only respectively ± 2.5%, ± 5% and ± 10%.Figure 11 (a) and Figure 12 (a) are respectively the field emission pictures of Tungsten oxide and tungsten trioxide nano line film, and we can find that these nano wire film field emissions are very even, the pattern of light-emitting zone and film morphology (Figure 11 (a) and Figure 12 (a)) basically identical.Figure 10, Figure 11 (b) and Figure 12 (b) and upper left corner illustration are respectively the field emission J-E and the F-N performance diagrams of Tungsten oxide, simple substance tungsten and tungsten trioxide nano line film, and we can find unlatching electric field 5.2MV/m, 8MV/m and the 2.45MV/m of Tungsten oxide, simple substance tungsten and tungsten trioxide nano line film from their J-E performance chart.Figure 11 (c) and Figure 12 (c) they are respectively the field emission stability curves of Tungsten oxide and tungsten trioxide nano line film, their fluctuation has only respectively ± and 4% and ± 2%.This illustrates that they have excellent field emission stability, and this to them in actual applications highly significant.Table 1 has provided the field emission characteristic of various nano wire films: (seeing Table one)
Table 1
| Title material | Open electric field (MV/m) | Threshold field (MV/m) | Stability (fluctuation per-cent) |
| The W | 8 | ||
| WO 2Nano wire film | 5.2 | 13.5 | ±4％ |
| WO 3Nano wire film | 2.45 | 6.5 | ±2％ |
| The Mo nano wire film | 2.2 | 6.24 | ±5％ |
| MoO
2 | 2 | 4.75 | ±2.5％ |
| MoO 3Nano wire film | 3.5 | 7.65 | ±10％ |
| The C nanotube | ＜0.75 | 1.6 |
| The SiC nano wire film | 0.9 | 2.5～3.5 | |
| Cu 2The S nano wire film | 6.0 | 12 | |
| MoO 3Nano belt | 8.7 | 12.9 | |
| The ZnO nano wire film | 6.6 | ＞11 |
Can see that from table the unlatching electric field of the nano wire film that we are prepared and threshold field are higher than the best carbon nanotube and the silicon carbide nanometer line film of report, can be quite or better but compare with other material.Figure 13 has provided the molybdenum dioxide nano wire film and has been applied to situation in the cold cathode luminotron.Figure 13 (a) is the situation that luminotron is being worked, and can see that luminotron is luminous very even; 13 (b) have provided the I-V rational curve when anode voltage is 7 kilovolts, can see from curve, and luminotron just begins that transmitter current has been arranged being lower than 500 volts.
Can reach a conclusion from above-mentioned analytical results, we are prepared to have gone out tungsten, molybdenum and oxide nano wires film thereof.Above-mentioned nano wire film has good field emission characteristic simultaneously, their unlatching electric field and threshold field are all lower, stability is than more excellent, they can satisfy the requirement of launching display material as field-causing electron fully this explanation, can be applied to field-emission plane display, cold cathode luminotron, cold light source etc.
Claims (9)
1, a kind of tungsten, molybdenum and oxide nano thread film and nano-wire array is characterized in that: tungsten, molybdenum and oxide nano wires thereof are grown in and form film and array on the substrate.
2, a kind of tungsten according to claim 1, molybdenum and oxide nano thread film and nano-wire array, it is characterized in that: described substrate is monocrystalline silicon piece, tinsel, glass or pottery, geometrical shape is not limit, and nanowire growth forms nano wire film and nano-wire array on above-mentioned substrate.
3, a kind of tungsten according to claim 1, molybdenum and oxide nano thread film and nano-wire array is characterized in that: described substrate is the silicon pinpoint array, and tungsten, molybdenum and oxide nano wires thereof are grown on the silicon needle point and form nano-wire array.
4, the Tungsten oxide in claim 1, the described oxide compound of 2 or 3 arbitrary claims and the preparation method of molybdenum dioxide nano wire film and nano-wire array thereof, carry out according to the following steps:
A) clean substrate, remove the impurity on the substrate;
B) tungsten or molybdenum source and substrate are placed on the heating under vacuum device, will install forvacuum earlier, feed rare gas element then, and keep constant current as shielding gas;
C) heated up respectively in tungsten or molybdenum source and substrate, during the preparation Tungsten oxide, the tungsten source is heated to 1000～2000 ℃, and substrate is heated to 900～1400 ℃; During the preparation molybdenum dioxide, the molybdenum source is heated to 1000～2000 ℃, and substrate is heated to 800～1100 ℃, and soaking time is 1 minute to 120 minutes;
D) under inert gas atmosphere, lower the temperature, until being cooled to room temperature.
5, the preparation method of the nano wire film of Tungsten oxide according to claim 4 and molybdenum dioxide and nano-wire array thereof is characterized in that: described tungsten source is tungsten powder, tungsten sheet or tungsten boat, and the molybdenum source is molybdenum powder, molybdenum sheet or molybdenum boat.
6, the nano wire film of the tungsten of claim 1,2 or 3 described simple substance, molybdenum and the preparation method of nano-wire array thereof, carry out according to the following steps:
A) will there be the sample of Tungsten oxide or molybdenum dioxide nano wire film or nano-wire array to be placed in the heating under vacuum device according to the length of claim 4 or 5 described method preparations, earlier to the forvacuum of heating under vacuum device, feed hydrogen then as reducing gas, and keep constant current;
B) sample is warming up to 500～1000 ℃, is incubated 3 to 15 hours;
C) under hydrogen atmosphere, lower the temperature, until being cooled to room temperature.
7, tungstic oxide and the nano wire film of molybdic oxide and the preparation method of nano-wire array thereof in claim 1, the 2 or 3 described oxide compounds, carry out according to the following steps:
A) will there be the nano wire film of Tungsten oxide or molybdenum dioxide or the sample of nano-wire array to be placed in the heating under vacuum device according to the length of claim 4 or 5 described method preparations, earlier to the forvacuum of heating under vacuum device, feed the mixed gas of argon gas and oxygen then, and keep constant current;
When b) preparing tungstic oxide sample is warming up to 500-1000 ℃, is incubated 2-60 minute; The preparation molybdic oxide is warming up to 300-600 ℃ to sample, is incubated 2-60 minute;
C) under the mixed-gas atmosphere of argon gas and oxygen, lower the temperature, until being cooled to room temperature.
8, claim 1,2 or 3 described tungsten, molybdenum and oxide nano wires film thereof and nano-wire array thereof are as the application of field-causing electron emission cold-cathode material.
9, application according to claim 8 comprises the application of cold cathode luminotron.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03140333 CN1283835C (en) | 2003-08-29 | 2003-08-29 | Large area tungsten Molybdenum and its oxide nano wires and array and their preparation and use |
| PCT/CN2004/000992 WO2005040455A1 (en) | 2003-08-29 | 2004-08-27 | Nanowire and nanoarray composed of tusnsten, molybdenum and the oxide thereof which have a large area and the preparation and the application |
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| CN 03140333 CN1283835C (en) | 2003-08-29 | 2003-08-29 | Large area tungsten Molybdenum and its oxide nano wires and array and their preparation and use |
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| CN1283835C true CN1283835C (en) | 2006-11-08 |
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| KR101046976B1 (en) * | 2004-10-19 | 2011-07-07 | 삼성에스디아이 주식회사 | Composition for forming electron emission source, method for manufacturing electron emission source using same and electron emission source |
| CN100402695C (en) * | 2005-03-22 | 2008-07-16 | 中山大学 | Physical vapor deposition method for direct developing Nano metal wire in single component |
| WO2006099776A1 (en) * | 2005-03-25 | 2006-09-28 | Zhongshan University | Preparing a single component metal nanowire directly by physical vapor phase method |
| CN102358938B (en) * | 2011-07-14 | 2014-04-09 | 中山大学 | Method for controllably synthesizing single-crystal WO2 and WO3 nanowire arrays with good field emission characteristics in low temperature and large area |
| CN103117199A (en) * | 2011-11-17 | 2013-05-22 | 浙江海洋学院 | Pine-shaped nanometer array field emitting negative pole manufacturing method |
| CN103515180B (en) * | 2013-05-16 | 2016-08-03 | 中山大学 | A kind of in-situ plasma glow processing method improving tungsten oxide nanometer material film field emission characteristic |
| CN104928642B (en) * | 2015-07-14 | 2018-02-16 | 合肥工业大学 | A kind of preparation method of molybdenum dioxide nano-wire array |
| CN105543972B (en) * | 2016-02-24 | 2018-03-27 | 中国地质大学（北京） | High-purity high-density MoO2The preparation method of lamellar nanostructured |
| CN105859151B (en) * | 2016-03-31 | 2018-10-02 | 东华大学 | A kind of method that spray coating method prepares the porous electrochomeric films of large area |
| CN107626300B (en) * | 2017-09-30 | 2021-01-26 | 五邑大学 | Thermally driven catalyst and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6190634B1 (en) * | 1995-06-07 | 2001-02-20 | President And Fellows Of Harvard College | Carbide nanomaterials |
| CH690720A5 (en) * | 1996-12-18 | 2000-12-29 | Eidgenoess Tech Hochschule | Nanotubes, use of such nanotubes as well as methods for their preparation. |
| JP2001052652A (en) * | 1999-06-18 | 2001-02-23 | Cheol Jin Lee | White light source and its manufacture |
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| WO2005040455A1 (en) | 2005-05-06 |
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