CN101962806B - Preparation method of flexible cold cathode material - Google Patents
Preparation method of flexible cold cathode material Download PDFInfo
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- CN101962806B CN101962806B CN 201010298847 CN201010298847A CN101962806B CN 101962806 B CN101962806 B CN 101962806B CN 201010298847 CN201010298847 CN 201010298847 CN 201010298847 A CN201010298847 A CN 201010298847A CN 101962806 B CN101962806 B CN 101962806B
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- cathode material
- carbon cloth
- flexible
- tungsten oxide
- oxide nano
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- 239000010406 cathode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 239000004744 fabric Substances 0.000 claims abstract description 36
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 35
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 33
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- -1 and heating Chemical compound 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 abstract description 7
- 238000002207 thermal evaporation Methods 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 description 19
- 239000010937 tungsten Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 229920000307 polymer substrate Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Cold Cathode And The Manufacture (AREA)
- Carbon And Carbon Compounds (AREA)
- Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)
Abstract
The invention provides a preparation method of a flexible code cathode material. Tungsten oxide nano wires are grown on a carbon cloth through thermal evaporation to prepare a field emission cathode material which is simultaneously provided with high flexibility and high conductivity and thermal conductivity. The cathode material ban bear higher current density, and has extensive application prospects in the fields of flexible field emission flat panel displays, flexible micro-nano electronics and the like.
Description
Technical field
The present invention relates to a kind of preparation method of flexible cold negative electrode.
Background technology
Field Emission Display (FED) is compared traditional cathode ray tube (CRT), have advantages such as volume is little, in light weight, low in energy consumption, compare liquid crystal display device (LCD), at aspects such as brightness, color reproduction, response speed, visual angle, power consumption, operating voltages good performance is arranged, have broad application prospects.
Cold-cathode material is a most important part in the Field Emission Display (FED), and important utilization is arranged in X ray radiotherapy, microwave amplifier spare and vacuum microelectronic device simultaneously.Along with the development that flexible display technologies and flexible electronic are learned, the folding flexible filed emission cathode material that can curl demonstrates more and more wide utilization prospect, is the core component of flexible Field Emission Display, also is the research focus of flexible micro-nano electronics.At present, some flexible cold studies on Cathode Materials have been arranged, for example, had people's carbon nano-tube on the high molecular polymer substrate of flexibility to do the flexible cold negative electrode.But because the high molecular polymer substrate is insulating material, there is conduction in prepared flexible cold cathode material and problem such as heat conductivility is poor, current density is low.Therefore how to prepare the key issue that conductivity and thermal conductivity are good and cold-cathode material low threshold electric field is the solution flexible flat panel display device.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with flexible cold cathode material of good conductive and thermal conductive property.
A kind of preparation method of flexible cold cathode material is specially: in the vacuum plant that is filled with protective gas and oxygen, and heating, tungsten powder and oxygen generation oxidation reaction generate tungsten oxide nano at carbon cloth, obtain the flexible cold cathode material.
Described protective gas is argon gas or nitrogen.
Technique effect of the present invention is embodied in: at the uniform tungsten oxide nano of carbon cloth preparation, the carbon cloth with tungsten oxide nano that obtains keeps the superelevation flexibility, and (current density reaches 10mA/cm to an emission threshold value
2) being lower than 4.30MV/m, resistivity value is lower than 5m Ω/cm simultaneously
2, thermal conductivity coefficient is higher than 1.6W/ (mK), and thermal diffusivity is higher than 8.7x10
-7m
2/ s.This carbon cloth that proves absolutely the growth tungsten oxide nano has good field emission performance, and favorable conductive and heat conductivility are arranged simultaneously, is good flexible filed emission cathode material.
Description of drawings
Fig. 1 is the pattern schematic diagram of tungsten oxide nano, wherein Fig. 1 (a) is the optical photograph of carbon cloth after the growth aerobic tungsten nano wire, Fig. 1 (b) is the figure of the carbon cloth high power SEM before the tungsten oxide nano of not growing, Fig. 1 (c) is grown in the high power SEM figure of the tungsten oxide nano on the carbon cloth for the SEM figure of sample after the growth tungsten oxide nano, Fig. 1 (d).
Fig. 2 is the phase structure test result schematic diagram of tungsten oxide nano, wherein Fig. 2 (a) is the XPS curve of tungsten oxide nano, Fig. 2 (b) is the Raman scattering curve of tungsten oxide nano, 2 (c) are the TEM low power figure of tungsten oxide nano (illustration is EDS energy spectrogram among the figure), and 2 (d) are the high-resolution TEM picture of tungsten oxide nano.
Fig. 3 is the field emission-electric field strength curve synoptic diagram of the carbon cloth sample of growth aerobic tungsten nano wire, and illustration is its F-N curve.
Fig. 4 is the field emission stability curve synoptic diagram of the carbon cloth sample of growth aerobic tungsten nano wire.
Fig. 5 is the field emission-electric field strength curve synoptic diagram of the carbon cloth of the tungsten oxide nano of not growing.
Fig. 6 is the electrical testing schematic diagram of flexible cold cathode material, wherein Fig. 6 (a) growth has the current-voltage curve of carbon cloth sample under different condition of tungsten oxide nano, 6 (b) are carbon cloth-tungsten oxide nano and copper piece clip laminar electrical testing curve (upper left corner illustration is instrumentation plan, and the lower right corner is pictorial diagram).
Fig. 7 is the thermal diffusivity test schematic diagram of the conduction carbon cloth of growth aerobic tungsten nano wire.
Embodiment
Below in conjunction with drawings and Examples the present invention is elaborated.
1. clip carbon cloth 3cm * 1.5cm size is cleaned and drying for standby.
2. select for use potsherd as pad, ultrasonic cleaning 5 minutes in acetone earlier, ultrasonic cleaning 5 minutes in absolute ethyl alcohol then.
3. (100 * 20 * 0.3mm) as heating source, takes by weighing 2 gram purity 99.8% tungsten powders and places in the tungsten boat, drips a small amount of absolute ethyl alcohol, and tungsten powder is dispersed in the tungsten boat, places then in the vacuum drying chamber to absolute ethyl alcohol to volatilize fully for the tungsten boat.
4. the tungsten boat is placed in the heating in vacuum device (350 * 400mm), the potsherd pad is placed on the tungsten boat, place carbon cloth at pad again, carbon cloth and tungsten boat are apart from 1mm.Earlier with the forvacuum of heating in vacuum device to 0.1Pa; feeding purity then is that 99.999% argon gas is as protective gas; throughput is 100 standard cubic centimeter per seconds (SCCM), feeds purity simultaneously and be 99.999% oxygen as reacting gas, and throughput is 1SCCM.This moment, vacuum pressure was 100Pa.
5. heat up for the tungsten boat by regulating electric current, be warming up to 1100 ℃ at last, kept 15 minutes.
6. cooling (dropping to below 400 ℃ in 5 minutes) under the maintenance aeration status is until being cooled to room temperature.
7. taking-up carbon cloth has the blue region of even growth on the carbon cloth.
1. clip carbon cloth 2cm * 1cm size is cleaned and drying for standby.
2. select for use silicon chip as pad, ultrasonic cleaning 5 minutes in acetone earlier, ultrasonic cleaning 5 minutes in absolute ethyl alcohol then.
3. (120 * 10 * 0.3mm) as heating source, takes by weighing 1 gram purity, 99.8% tungsten powder and places in the tungsten boat, and tungsten powder is dispersed in the tungsten boat for the tungsten boat.
4. the tungsten boat is placed in the heating in vacuum device (350 * 400mm), the silicon chip pad is placed on the tungsten boat, place carbon cloth at pad again, carbon cloth and tungsten boat are apart from 1.2mm.Earlier with the forvacuum of heating in vacuum device to 0.1Pa; feeding purity then is that 99.999% nitrogen is as protective gas; throughput is 50 standard cubic centimeter per seconds (SCCM), feeds purity simultaneously and be 99.999% oxygen as reacting gas, and throughput is 0.5SCCM.This moment, vacuum pressure was 66Pa.
5. heat up for the tungsten boat by regulating electric current, be warming up to 1120 ℃ at last, kept 15 minutes.
6. cooling (dropping to below 400 ℃ in 5 minutes) under the maintenance aeration status is until being cooled to room temperature.
7. taking-up carbon cloth has the blue region of even growth on the carbon cloth.
To the sample of preparation, analyze with x-ray photoelectron power spectrum (XPS), Raman spectrum (Raman), ESEM (SEM) and transmission electron microscope (TEM), determine pattern, the structure of matter and composition of the material of growing on the carbon cloth etc.Last test the electronic emission performance of sample, conduction and heat conductivility.Describe below in conjunction with accompanying drawing.
Fig. 1 (a) is the growth tungsten oxide nano optical photograph of carbon cloth afterwards, the frame of broken lines zone is the growth tungsten oxide nano, what illustration (1) and (2) showed respectively is sample optical photograph under slight bending and wide-angle bending, tungsten oxide nano evenly growth on carbon cloth as can be seen, and can keep well flexible, bendable angle is up to 180 °.Fig. 1 (b) and (c) be respectively before the growth tungsten oxide nano and afterwards carbon cloth SEM photo, the upper right corner illustration of Fig. 1 (b) is low power SEM figure, photo shows that carbon cloth is formed by the about 10 microns carbon fiber knit of diameter, tungsten oxide nano evenly coats growth on carbon fiber, Fig. 1 (d) is the high power SEM photo of tungsten oxide nano, show that tungsten oxide nano is about the 10-20 micron, have the very tip of taper, be very beneficial for the field-causing electron emission.Fig. 2 is respectively XPS, Raman, TEM and the EDS test of tungsten oxide nano, can learn that by the test result analysis-by-synthesis institute's grown nano wire is W
20O
58, the direction of growth is (010) crystal orientation, spacing of lattice is 0.38nm.
Fig. 3 is the field transmission test result that growth has tungsten oxide nano on the carbon cloth.Therefrom emission reaches 10mA/cm as can be seen
2The time, electric field strength is 4.30MV/m, the carbon cloth of the tungsten oxide nano of not growing among Fig. 5 in contrast then needs the electric field strength of about 8.7MV/m just can reach 10mA/cm
2Emission.This explanation tungsten oxide nano has effectively strengthened field emission performance, has reduced a required threshold field intensity of emission.Fig. 4 is the time dependent curve of carbon cloth field emission current that growth has tungsten oxide nano, and the field emission stability of its interpret sample is very good, and the current density fluctuation range is less than 5%.
Fig. 6 is the electrical testing that growth has the tungsten oxide nano carbon cloth, and wherein (a) figure shows sample under straightened condition and case of bending, and the resistance change at its two ends is very little, and current-voltage curve shows the pure resistance characteristic, and resistance value is 3.32 Ω.(b) figure result shows that tungsten oxide nano also has good electric conductivity, and the resistance value between carbon cloth-tungsten oxide nano-copper sheet is 3.22 Ω.Excellent conducting performance has determined sample to have to bear the ability of big emission, a transmission test digital proof sample can bear 12mA/cm
2Even higher current density, this is the peak of the flexible filed emission cathode material reported of present document, compares than the cathode material of the high molecular polymer substrate carbon nano-tube of having reported to exceed 100 times.
Fig. 7 grows to have the heat conductivility of the carbon cloth material of tungsten oxide nano to measure, and the result shows that its thermal diffusivity is 8.7x10
-7m
2/ s, thermal conductivity coefficient is 1.6W/ (mK), this heat conductivility than common high molecular polymer substrate exceeds 10 times, compare the flexible filed emission cathode material that adopts the high molecular polymer substrate, oxidate nano wire material based on carbon cloth has better thermal stability, and this also is that it can bear high field emission and keeps the stable and reason that can not be burnt of an emission current for a long time.
Can reach a conclusion from above-mentioned analysis result, the present invention is by utilizing thermal evaporation growth tungsten oxide nano at the conduction carbon cloth, can prepare the high electricity that has good flexibility simultaneously and lead filed emission cathode material with thermal conductivity, it can bear higher current density, and (corresponding current density is 10mA/cm to threshold field
2) being about 4.30MV/m, this cold-cathode material has a broad prospect of the use in fields such as flexible Field Emission Display and flexible micro-nano electronics.
Claims (2)
1. the preparation method of a flexible cold cathode material is specially: in being filled with the heating in vacuum device of protective gas and oxygen, and heating, tungsten powder and oxygen generation oxidation reaction generate tungsten oxide nano at carbon cloth, obtain the flexible cold cathode material.
2. the preparation method of flexible cold cathode material according to claim 1 is characterized in that, described protective gas is argon gas or nitrogen.
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| CN 201010298847 CN101962806B (en) | 2010-09-30 | 2010-09-30 | Preparation method of flexible cold cathode material |
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| CN105810532A (en) * | 2016-05-16 | 2016-07-27 | 中国科学院兰州化学物理研究所 | Preparation method of flexible field emission cold cathode employing pencil writing |
| CN109872931B (en) * | 2018-11-27 | 2020-12-04 | 西北大学 | Field emission cathode material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353816A (en) * | 2008-07-08 | 2009-01-28 | 中山大学 | Growth method of tungsten oxide pencil-shaped nanostructured array |
| CN101553895A (en) * | 2006-09-08 | 2009-10-07 | 通用汽车环球科技运作公司 | One-dimensional metal and metal oxide nanostructures |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101553895A (en) * | 2006-09-08 | 2009-10-07 | 通用汽车环球科技运作公司 | One-dimensional metal and metal oxide nanostructures |
| CN101353816A (en) * | 2008-07-08 | 2009-01-28 | 中山大学 | Growth method of tungsten oxide pencil-shaped nanostructured array |
Non-Patent Citations (3)
| Title |
|---|
| D. Y. Lu et al.Raman spectroscopic study of oxidation and phase transition in W18O49 nanowires.《JOURNAL OF RAMAN SPECTROSCOPY》.2006,第38卷全文. * |
| Lingfei Chi et al.An approach for synthesizing various types of tungsten oxide nanostructure.《Nanotechnology》.2006,第17卷全文. * |
| 卢东昱等.氧化钨纳米线结构相变的拉曼光谱研究.《光散射学报》.2006,第18卷(第2期),全文. * |
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