CN104058446A - Low-dimensional zinc oxide nano material and low-temperature plasma preparation method thereof - Google Patents
Low-dimensional zinc oxide nano material and low-temperature plasma preparation method thereof Download PDFInfo
- Publication number
- CN104058446A CN104058446A CN201410320048.0A CN201410320048A CN104058446A CN 104058446 A CN104058446 A CN 104058446A CN 201410320048 A CN201410320048 A CN 201410320048A CN 104058446 A CN104058446 A CN 104058446A
- Authority
- CN
- China
- Prior art keywords
- low
- zinc oxide
- oxide material
- preparation
- nano zinc
- 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.)
- Granted
Links
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a low-dimensional zinc oxide nano material and a low-temperature plasma preparation method thereof. The preparation method comprises the following steps: (1) depositing a layer of a zinc thin film on a silicon slice substrate by using magnetron sputtering; (2) putting a silicon slice coated with the zinc thin film into a low-temperature plasma enhanced horizontal tube furnace deposition system, performing plasma discharge treatment under the conditions of different gas atmosphere proportions after the silicon slice is put into the system, and controlling different treatment temperatures and discharge currents to obtain the zinc oxide nano material with different shapes and appearances. The zinc oxide nano material prepared by using the method disclosed by the invention is low in material growth temperature, good in quality of the grown nano material, simple in process, low in cost and stable in product performance, and has broad prospects in the photovoltaic field and the application field of gas detectors.
Description
Technical field
The present invention is specifically related to a kind of low-dimensional nano zinc oxide material and low-temperature plasma preparation thereof.
Background technology
Along with scientific and technological development, semiconductor material is being brought into play more and more vital role in social scientific-technical progress, and the particularly development of various films has in recent years promoted the fast-developing and upgrading of semiconductor nano film greatly.Zinc oxide is a kind of oxide semiconductor material of broad stopband, as a kind of direct band gap material with Wurzite structure, under room temperature, its energy gap is 3.36eV, be one of the research material of the electron device of purple light and blue light, simultaneous oxidation zinc more and more shows vital role and advantage as semi-conductor in aspect application such as gas detector, photoelectric device and photochemical catalysis.Since finding first under room temperature that zinc oxide is subject to burst of ultraviolel radiation, zinc oxide research work at home and abroad launches rapidly, preparation about zinc-oxide film at present has had reasonable technology and mode, but be also nowhere near in the preparation of low-dimensional nano zinc oxide material, in the application aspect of nano zinc oxide material, preparation and the growth mechanism of research nano zinc oxide material just seem necessary especially.Although method prepared by nano zinc oxide material is a lot, the method that using plasma technology is prepared low-dimensional nano zinc oxide material also compares vacancy at present, particularly studies plasma body even more important to the forming process of low-dimensional nano zinc oxide material.
Plasma discharge technology is exactly under the excitation of external electrical field, the accelerated energy that obtains of electronics, gas atom in these high-energy electrons and reaction chamber or molecular impact, make its dissociation, excite or ionize, thereby generation glow discharge, owing to there being a large amount of free radicals in plasma body, these free radicals have very high activity, and there is certain energy, can reduce the nano material needed temperature of growing, can improve the quality of growth material simultaneously, be conducive to reduce the generation of the situations such as thermosteresis and thermal mismatching, can better prepare the low-dimensional nano zinc oxide material of high-quality, through this technological method advantage be to realize nano zinc oxide material with lower underlayer temperature and faster the speed of growth realize growth.In reaction chamber, form on the other hand a lot of electronics, ion, active group and metastable atom and molecule etc., form these particles of plasma body, through the physical and chemical reaction process of series of complex, just more easily on substrate, form nano material.By utilizing differing temps and under different atmosphere ratio conditions, growing the low-dimensional nano zinc oxide material (comprising nano wire, nanometer sheet etc.) of various patterns on the silicon substrate of zinc-plated film.Equipment contains and is with in a large number plus-minus electric ion and neutral atom etc. in the process applying plasma discharging; Utilize argon gas atmosphere can realize better acquisition plasma body, be conducive to auxiliary oxygen molecule and obtain abundant dissociation, excite or ionize.Oxygen molecule by dissociation, excite or ionize after, have very high actively and with certain energy, more easily under proper temperature, react with zinc film; After while argon gas is ionized, also with energy, film growth is also had to certain influence, can promote Fast Growth nano zinc oxide material under low temperature.
Many about preparation method of nano material such as zinc oxide nanowire and nanometer sheet, higher but control condition requires, and also preparation process is relatively complicated.In this experiment, preparation method is simple, and when prepared by zinc oxide, nano zinc oxide material is more prone to obtain simultaneously, and can be applied in electron device (comprising gas sensor, dye sensitization solar battery etc.).Therefore the method is prepared high performance nano zinc oxide material and is had important using value.
The present invention be in currently available technology, can prepare good nano zinc oxide material and cost lower, technology ratio is easier to realize.
Summary of the invention
The object of this invention is to provide a kind of low-dimensional nano zinc oxide material.
The preparation method who another object of the present invention is to provide a kind of nano zinc oxide material of low temperature, realizes the method for fast growing of nano material at a lower temperature.
Technical scheme of the present invention is as follows:
A kind of low-dimensional nano zinc oxide material, it is characterized in that comprising zinc film and nano zinc oxide material, described nano zinc oxide material comprises nano wire and nanometer sheet, spectroscopy detection Zn:O=50.1:49.9, nano wire mean diameter is 20～100nm, mean length is 600～1500nm, and nanometer sheet mean thickness is 15～80nm, and nanometer sheet average area is 200～250000nm
2.
Another technical scheme of the present invention is:
A preparation method for low-dimensional nano zinc oxide material, comprises the steps:
(1) with ethanol and acetone and deionized water ultrasonic cleaning silicon substrate, adopt magnetically controlled sputter method, power is on silicon substrate, to utilize zinc target under 30～80W and argon atmospheric pressure 3～6mtorr condition, and the sputtering sedimentation time is 10～70min, and growth zinc film thickness is 300～1000nm;
(2) the zinc film of preparation is placed in the silica tube that can realize low-temperature plasma enhancement type horizontal pipe furnace, closed quartz tube also vacuumizes, etc. the vacuum tightness of system, reach 5Pa when following, the temperature of tube furnace is risen to 380～400 ℃ of preset temperatures from room temperature, and passing into the atmosphere of certain proportion oxygen and argon gas, ratio is 3:100～1:2, first passes into argon gas, after pass into oxygen, open radio-frequency power supply and carry out plasma oxidation processing;
(3) regulate the power 100-500W of plasma rf power supply; discharging current is remained between 0.1～2A; after 30～60min Cement Composite Treated by Plasma; turn off radio-frequency power supply; keep vacuum pump to bleed; pass into argon gas as protective atmosphere simultaneously, be cooled to gradually room temperature, obtain described low-dimensional nano zinc oxide material.
Wherein, step (3) electric current is arranged between 0.5～2A; After 30～60min growth, turn off radio-frequency power supply.
Wherein, in described step (2), from room temperature, being warming up to the time that presets temperature is 20min, presets and is preferably 390 ℃.
Wherein, electric current is preferably arranged between 0.5～2A; After 30～60min growth, turn off radio-frequency power supply.
Wherein, after turning off radio-frequency power supply in described step (3), after turning off oxygen and keeping passing into 3min argon gas atmosphere, close.
Wherein, being cooled to argon gas and being cooled to room temperature under oxygen atmosphere on a small quantity in described step (3).
Main method of the present invention is that the different-shape that the ratio by controlling corresponding plasma parameter, oxygen concentration and passing into gas realizes nano zinc oxide material is grown.
Main advantage of the present invention and effect are:
1, the present invention adopts the zinc film of magnetron sputtering as the basic substance of nano material growth, is easily transplanted to other substrate surface and grows.The plasma apparatus adopting can be realized the control of gas flow precision and easily realize the nano zinc oxide material preparation of (comprising nanometer sheet, nano wire etc.), and the simultaneously further waste of saving gas effectively improves the utilization ratio of gas.
2, preparation method of the present invention adopts lower temperature plasma technology, and the Heating temperature of tube furnace is relatively low, less energy consumption; The equipment using is single, and facility investment is few, and technique is simple, with low cost, and product performance are better.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the low-dimensional nano zinc oxide material prepared of the embodiment of the present invention;
Fig. 2 is the scanning electron microscope diagram of the low-dimensional Zinc oxide nano sheet prepared of the embodiment of the present invention;
Fig. 3 is the scanning electron microscope diagram of the low-dimensional zinc oxide nanowire prepared of the embodiment of the present invention;
Fig. 4 is present device structure iron.
1-oxygen 2-argon gas 3-control valve 4-silica tube 5-process furnace 6-electrode 7-ground connection 8-tensimeter 9-vacuum pump 10-exhaust 11-power supply
Embodiment
By embodiment, by reference to the accompanying drawings technical scheme of the present invention is further detailed and is described below.
Embodiment 1
First by magnetron sputtering under the power of 70W on silicon substrate sputter 10min obtain the zinc film that 150nm is thick.The silicon substrate that is coated with zinc film is placed in the middle position of silica tube of tube furnace, is evacuated down to below 5Pa heated Tube-furnace, while being warmed up to 390 ℃ through 20min, open radio-frequency power supply, electric current is transferred to 1.2A, keep 30min, keep during this period plasma body glow discharge simultaneously.After deposition 30min, close radio-frequency power supply, system begins to cool down room temperature.
(1) in oxygen atmosphere and argon atmospher ratio, be that under 3sccm:44sccm condition, to prepare nanometer sheet best, as shown in Figure 2.
Embodiment 2
First by magnetron sputtering under the power of 70W on silicon substrate sputter 70min obtain the zinc film that 1000nm is thick.The silicon substrate that is coated with zinc film is placed in the middle position of silica tube of tube furnace, is evacuated down to below 5Pa heated Tube-furnace, while being warmed up to 390 ℃ through 20min, open radio-frequency power supply, electric current is transferred to 1.2A, keep 30min, keep during this period plasma body glow discharge simultaneously.After deposition 30min, close radio-frequency power supply, system begins to cool down room temperature.
(1) in oxygen atmosphere and argon atmospher ratio, be that under 12sccm:24sccm condition, to prepare nano wire best, as shown in Figure 3.
Embodiment 3
First by magnetron sputtering under the power of 30W on silicon substrate sputter 50min obtain the zinc film that 300nm is thick.The silicon substrate that is coated with zinc film is placed in the middle position of silica tube of tube furnace, is evacuated down to below 5Pa heated Tube-furnace, while being warmed up to 390 ℃ through 20min, open radio-frequency power supply, electric current is transferred to 0.5A, keep 30min, keep during this period plasma body glow discharge simultaneously.After deposition 30min, close radio-frequency power supply, system begins to cool down room temperature.
(1) in oxygen atmosphere and argon atmospher ratio, be that under 3sccm:44sccm condition, to prepare nanometer sheet best, as shown in Figure 2.
(2) at oxygen atmosphere and argon atmospher ratio, be to prepare nano wire under 5sccm:24sccm condition, as shown in Figure 3.
In addition,, when the processing parameter of aforesaid method changes in following scope, those of ordinary skills can obtain identical or close expected technique effect:
Described step passes into proportional oxygen and argon gas atmosphere in (2), and ratio, between 3:100～1:2, first passes into argon gas, after pass into oxygen.
In described step (3), from room temperature, being warming up to the time that presets temperature is 20min, and the temperature of deposition is 380～400 ℃, and this experiment is set to 390 ℃, and depositing time is 30min.
The above, be only preferred embodiment of the present invention, therefore can not limit according to this scope of the invention process, the equivalence of doing according to the scope of the claims of the present invention and description changes and modifies, and all should still belong to the scope that the present invention is contained.
Claims (7)
1. a low-dimensional nano zinc oxide material, it is characterized in that comprising zinc film and nano zinc oxide material, described nano zinc oxide material comprises nano wire and nanometer sheet, spectroscopy detection Zn:O=50.1:49.9, nano wire mean diameter is 20～100nm, mean length is 600～1500nm, and nanometer sheet mean thickness is 15～80nm, and nanometer sheet average area is 200～250000nm
2.
2. a preparation method for low-dimensional nano zinc oxide material, comprises the steps:
(1) with ethanol and acetone and deionized water ultrasonic cleaning silicon substrate, adopt magnetically controlled sputter method, power is on silicon substrate, to utilize zinc target under 30～80W and argon atmospheric pressure 3～6mtorr condition, and the sputtering sedimentation time is 10～70min, and growth zinc film thickness is 300～1000nm;
(2) the zinc film of preparation is placed in the silica tube that can realize low-temperature plasma enhancement type horizontal pipe furnace, closed quartz tube also vacuumizes, etc. the vacuum tightness of system, reach 5Pa when following, the temperature of tube furnace is risen to 380～400 ℃ of preset temperatures from room temperature, and passing into the atmosphere of certain proportion oxygen and argon gas, ratio is 3:100～1:2, first passes into argon gas, after pass into oxygen, open radio-frequency power supply and carry out plasma oxidation processing;
(3) regulate the power 100-500W of plasma rf power supply; discharging current is remained between 0.1～2A; after 30～60min Cement Composite Treated by Plasma; turn off radio-frequency power supply; keep vacuum pump to bleed; pass into argon gas as protective atmosphere simultaneously, be cooled to gradually room temperature, obtain described low-dimensional nano zinc oxide material.
3. the preparation method of a kind of low-dimensional nano zinc oxide material as claimed in claim 2, is characterized in that: step (3) electric current is arranged between 0.5～2A; After 30～60min growth, turn off radio-frequency power supply.
4. the preparation method of a kind of low-dimensional nano zinc oxide material as claimed in claim 2, is characterized in that: in step (2), from room temperature, being warming up to the time that presets temperature is 20min, and preset temperature is 390 ℃.
5. the preparation method of a kind of low-dimensional nano zinc oxide material as claimed in claim 2, is characterized in that: in step (3), electric current is arranged between 0.5～2A; After 30～60min growth, turn off radio-frequency power supply.
6. a kind of low-dimensional nano zinc oxide material as claimed in claim 2 and low-temperature plasma preparation thereof, is characterized in that: after turning off radio-frequency power supply in described step (3), after turning off oxygen and keeping passing into 3min argon gas atmosphere, close.
7. a kind of low-dimensional nano zinc oxide material as claimed in claim 2 and low-temperature plasma preparation thereof, is characterized in that: being cooled to argon gas and being cooled to room temperature under oxygen atmosphere on a small quantity in described step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410320048.0A CN104058446B (en) | 2014-07-08 | 2014-07-08 | Low-dimensional zinc oxide nano material and low-temperature plasma preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410320048.0A CN104058446B (en) | 2014-07-08 | 2014-07-08 | Low-dimensional zinc oxide nano material and low-temperature plasma preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104058446A true CN104058446A (en) | 2014-09-24 |
| CN104058446B CN104058446B (en) | 2015-07-08 |
Family
ID=51546426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410320048.0A Expired - Fee Related CN104058446B (en) | 2014-07-08 | 2014-07-08 | Low-dimensional zinc oxide nano material and low-temperature plasma preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104058446B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445443A (en) * | 2014-12-24 | 2015-03-25 | 哈尔滨工业大学 | Method for preparing cobaltous oxide electrode with nanosheet structure |
| CN107337229A (en) * | 2016-04-28 | 2017-11-10 | 北京大学 | A kind of method that Zinc oxide nanoparticle is prepared using atmos low-temperature plasma |
| CN107502871A (en) * | 2017-09-01 | 2017-12-22 | 泉州师范学院 | The plasma gas phase deposition preparation method of zinc sulfide nano-material under a kind of low temperature |
| CN112939060A (en) * | 2021-02-05 | 2021-06-11 | 中国人民解放军战略支援部队航天系统部装备部装备保障队 | Zinc oxide nano material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800029A (en) * | 2005-12-30 | 2006-07-12 | 北京科技大学 | Ultra-fine zinc oxide nonometer line and its preparation method |
| CN101580267A (en) * | 2009-02-23 | 2009-11-18 | 中山大学 | Method for growing nanometer zinc oxide structure through low-temperature heating of zinc and catalyst and application thereof |
| CN102050481A (en) * | 2009-11-04 | 2011-05-11 | 中国科学院半导体研究所 | Method for preparing zinc oxide nano material |
| CN102476787A (en) * | 2010-11-26 | 2012-05-30 | 海洋王照明科技股份有限公司 | Preparation method of ZnO nanowire array |
-
2014
- 2014-07-08 CN CN201410320048.0A patent/CN104058446B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800029A (en) * | 2005-12-30 | 2006-07-12 | 北京科技大学 | Ultra-fine zinc oxide nonometer line and its preparation method |
| CN101580267A (en) * | 2009-02-23 | 2009-11-18 | 中山大学 | Method for growing nanometer zinc oxide structure through low-temperature heating of zinc and catalyst and application thereof |
| CN102050481A (en) * | 2009-11-04 | 2011-05-11 | 中国科学院半导体研究所 | Method for preparing zinc oxide nano material |
| CN102476787A (en) * | 2010-11-26 | 2012-05-30 | 海洋王照明科技股份有限公司 | Preparation method of ZnO nanowire array |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445443A (en) * | 2014-12-24 | 2015-03-25 | 哈尔滨工业大学 | Method for preparing cobaltous oxide electrode with nanosheet structure |
| CN104445443B (en) * | 2014-12-24 | 2016-02-03 | 哈尔滨工业大学 | A kind of method preparing nanometer sheet structure cobalt oxide electrode |
| CN107337229A (en) * | 2016-04-28 | 2017-11-10 | 北京大学 | A kind of method that Zinc oxide nanoparticle is prepared using atmos low-temperature plasma |
| CN107502871A (en) * | 2017-09-01 | 2017-12-22 | 泉州师范学院 | The plasma gas phase deposition preparation method of zinc sulfide nano-material under a kind of low temperature |
| CN112939060A (en) * | 2021-02-05 | 2021-06-11 | 中国人民解放军战略支援部队航天系统部装备部装备保障队 | Zinc oxide nano material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104058446B (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103489967B (en) | The preparation method of a kind of gallium oxide epitaxial film and gallium oxide epitaxial film | |
| CN102912308B (en) | Process for manufacturing vanadium dioxide thin film with low phase-transition temperature | |
| CN104058446B (en) | Low-dimensional zinc oxide nano material and low-temperature plasma preparation method thereof | |
| CN105648414B (en) | A method of nitrogenous titanium deoxid film is prepared using magnetron sputtering method | |
| CN105826362A (en) | Gallium-oxide nanowire array and preparation method thereof | |
| CN105821391B (en) | A kind of controllable fast preparation method of vertical substrate grown tungsten selenide nano sheet film materials | |
| CN106684184B (en) | A kind of copper-indium-galliun-selenium film solar cell Window layer and preparation method thereof | |
| CN101325227A (en) | Method for preparing ZnO/nanometer diamond coplane grid ultraviolet light detector | |
| Lee et al. | Effects of annealing and plasma treatment on the electrical and optical properties of spin-coated ITZO films | |
| CN113073300A (en) | Method for plating high-purity zinc sulfide film on surface of non-metallic material in penetrating manner | |
| CN105568229B (en) | A kind of preparation method of nitrogen doped titanium dioxide film | |
| CN105463396A (en) | Method for preparing photocatalytic water splitting bismuth vanadate thin film through DC magnetron sputtering | |
| CN103757594A (en) | Method for preparing high-performance AZO transparent electro-conductive film on flexible substrate at room temperature | |
| CN103572232A (en) | Preparation method of CuO/CoTiO3 composite air-sensitive film | |
| CN108085651A (en) | A kind of secondary laminated film of resistance to beam bombardment and preparation method thereof | |
| CN104195523A (en) | Method for preparing aluminum-doped zinc oxide thin film through plasma-enhanced atomic layer deposition | |
| WO2020143101A1 (en) | Magnetron sputtering preparation method for gradient self-doped pure-phase multi-element metal oxide thin film | |
| CN110318035A (en) | The more hot filament deposit method and devices of the discrete of alloy cpd film | |
| CN105154841B (en) | The preparation method of bismuth doped stannum oxide film | |
| CN105132875B (en) | A kind of method that diffusion method prepares high concentration gradient AZO monocrystalline conductive films | |
| CN109599470B (en) | Method for reducing resistivity of magnesium-doped zinc oxide film | |
| CN113564522A (en) | Vanadium dioxide thin film and preparation method and application thereof | |
| CN111826610A (en) | Method for preparing graphene at low temperature by using amorphous carbon | |
| CN105161288B (en) | A kind of method for strengthening zno-based diluted semi-conductor thin-film room-temperature ferromagnetic | |
| CN104810249B (en) | The method of CdS film or CdS nanostructureds is grown in CdTe thin film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150708 Termination date: 20180708 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |