CN1270327C - Method for producing high yield zinc oxide nano cable - Google Patents
Method for producing high yield zinc oxide nano cable Download PDFInfo
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- CN1270327C CN1270327C CN 200410080423 CN200410080423A CN1270327C CN 1270327 C CN1270327 C CN 1270327C CN 200410080423 CN200410080423 CN 200410080423 CN 200410080423 A CN200410080423 A CN 200410080423A CN 1270327 C CN1270327 C CN 1270327C
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Abstract
The present invention provides a method for manufacturing a ZnO nanometer cable with high yield, which comprises that the ultrasonic cleanness of a silicon (100) substrate is carried out in a solution of HNO3 and HF, the silicon (100) substrate is cleanly washed by respectively using deionized water and alcohol, and then, a layer of gold film of which the thickness is from 15 to 25 nanometer is splashed on the washed silicon (100) substrate; pure zinc powder and pure stannum powder are fully and uniformly ground in the mass ratio of 1 to 1 to be put in a porcelain boat, the porcelain boat is put in the middle part of a quartz tube in a tubular furnace, and a flow meter is regulated to charge mixed gas of 98% of argon and 2% of oxygen at the speed of 300 standard cubic centimeters / minute; the tubular furnace is heated to reach 530 to 570 DEG C under the condition of the atmosphere to carry out heat insulation for 20 to 25 minutes, and the tubular furnace is cooled to room temperature to obtain a product of the nanometer cable with a structure of core (ZnO)/coating SiOx. The present invention has the advantages that large-scale controllable growth is realized, and manufacturing temperature is greatly reduced.
Description
Technical field
The invention belongs to the nano material preparation technical field, a kind of method for preparing high yield ZnO nano-cable particularly is provided, realized large-scale controllable growth, and greatly reduced preparation temperature.
Background technology
The ZnO material has excellent electrically conducting transparent performance, and its room temperature band gap is 337eV, and exciton binding energy is a kind of ultraviolet photoelectric semiconductor material with very big potential using value up to 60meV, and in addition, it also has good piezoelectric effect, biological safety.The chemical compatibility of nano wire and one dimension characteristic (small-size effect, interfacial effect, quantum effect and quantum tunneling effect) more make the ZnO material have the performance of the excellence that more conventional materials do not possess at aspects such as magnetic, light, electricity, sensitivities.The preparation of One-Dimensional ZnO nano material and application worldwide have been subjected to people at present and have paid close attention to greatly.By the preparing of people's success, different nanostructures has potential different purposes to multiple structures such as zinc oxide nanowire, nano belt, four-acicular nanometer rod, nanotube, nanometer screw, nanometer spring, nano-rings; At present, constructed multiple nano-device as meteorological sensing, field effect transistor, nanometer cantilever beam etc. based on ZnO monodimension nanometer material people.The ZnO nano-cable is expected to: (1) as important nano-electron element application in the nano functional device; (2) based on the piezoelectric effect of zinc oxide, can be made into mechanics, the coupling of optical signalling and switching device; (3) directional transmissions of realization optical signalling.
At present, the people such as L.Dai of Inst. of Physics, CAS adopt " two-step method " successfully to prepare the ZnO/SiO of diameter between 50to 100nm in 850 ℃
xNano-cable (L.Dai, X.L.Chen, X.Zhang, T.Zhouand B.Hu, Coaxial ZnO/SiO
2Nanoeables fabricated by thermalevaporation/oxidation, Applied Physics A 78,557-559 (2004))
Should " two-step method " be 850 ℃ and under pure argon atmosphere, evaporate zinc powder, in reactor, feed 5% oxygen generation oxidation reaction then, make the ZnO nano-cable after the cooling.
The preparation of one-dimensional zinc oxide nanometer material at present presents the development of explosion type, the nano material that comes in every shape constantly is in the news out, some has had actual application, and still also searching is more controlled constantly excavating the nano zinc oxide material with new structure for people, reliable preparation.In general, aspect preparation, there are several important problem assistant officers to be solved at present, two aspects wherein are: reduce preparation temperature and the large-scale growth of real realization, a lot of in recent years researchs all are being devoted to solve this problem aspect two, and the problem of this two aspect is actually and links together and condition each other.Reducing preparation temperature is to consider for the angle of energy efficient and reduction preparation requirement, but assembling or the self assembly (this step can't realize under the high temperature) in order to realize nano-device especially.The method that prepare at present nano zinc oxide material is the most reliable with Wang Zhonglin group evaporation pure zinc oxide method, and the temperature of its requirement is more than 1300 ℃, also needs temperature more than 900 ℃ with ZnO+C as the carbothermic method of raw material.Low temperature preparation method (below 200 ℃) comprises that preparation methods such as liquid phase method, template are easier to the device assembling, but can't compare with solid phase method on the prepared quality of materials.
With pure zinc is that the preparation method of raw material is temperature required lower, between 500 ℃-900 ℃.Yet because the evaporation and the oxidation rate of zinc powder should not be controlled in the reactor, so this method is Comparatively speaking repeatable poor, productive rate is lower.The ZnO/SiO that comprises people such as L.Dai above-mentioned preparation
xNano-cable, simple zinc powder evaporation reliability is relatively poor, and productive rate is not high.
Summary of the invention
The objective of the invention is to a kind of method for preparing high yield ZnO nano-cable, solved the problem of the not high and controllable growth of productive rate, realized large-scale controllable growth, and greatly reduced preparation temperature.
Concrete technology of the present invention realizes by following three steps:
1, with silicon (100) substrate at HNO
3Ultrasonic cleaning is also rinsed well respectively with deionized water and alcohol in+the HF solution.The golden film of sputter one deck 15～25 nanometer thickness thereon afterwards.Require HNO
3+ HF solution mol ratio was at 2: 1, and golden film is to adopt magnetic control sputtering device to be plated on the silicon chip, and its thickness is controlled with the quartz crystal oscillator that carries.Monocrystalline silicon is preparation one dimension oxide-based nanomaterial deposition substrate commonly used, and deposition one deck gold film is to make ZnO/SiO as catalyst
xNano-cable is realized epitaxial growth.
2, pure zinc powder and pure tin powder (mass ratio 1: 1) are fully ground evenly and be placed in the porcelain boat, milling time 20～30 minutes, the silicon chip back-off that will be coated with golden film afterwards is on porcelain boat;
3, porcelain boat is put into the quartz ampoule middle part of tube furnace, regulated flowmeter and in pipe, feed argon (98%)/oxygen (2%) mist (300 standard cubic centimeters per minute).Under this atmosphere, tube furnace is warming up to 530～570 ℃ and be incubated 20～25 minutes.Be cooled to and utilize ESEM after the room temperature, be equipped with the transmission electron microscope of power spectrum that the sample that is deposited on silicon chip is analyzed, confirm that products obtained therefrom is for having core (ZnO)/coating (SiO
x) nano-cable of structure.
Although the fusing point of gold and silicon is respectively 1064 ℃ and 1410 ℃, the temperature of gold silicon eutectic reaction only is 370 ℃.When temperature of reactor begins to reach 370 ℃, golden film and silicon chip the gold silicon eutectic reaction at first takes place at the interface, the local au-si alloy that forms; After temperature further raise, zinc fume discharged gradually, and au-si alloy begins to absorb zinc fume in reactor, absorbed silicon atom to keep balance in substrate.This process makes the liquid alloy system reach the supersaturation attitude rapidly, so ZnO/SiO
xNano-cable comes out from the superficial growth of liquid alloy, and by the oxidation reaction continued growth.The silicon chip that is coated with golden film makes SiO in reaction
xOuter at a lower temperature be grown to serve as possibility.
Though 50% glass putty is arranged, in the raw material to the ZnO/SiO that makes
xThe analysis showed that of nano-cable do not contained tin element in its composition.Yet for this method, it is necessary adding glass putty in the raw material, otherwise will can not obtain required material.Glass putty has low melting point: 232 ℃, and higher boiling point: 2270 ℃.It is first for melting than zinc powder, but because boiling point is very high, vapour pressure is very low in 200-300 ℃ temperature, its drop is directly oxidized in porcelain boat, oxide will also not have the zinc powder of fusing tightly to coat, make it difficultly under suitable evaporating temperature discharge zinc fume, thus better controlled the dividing potential drop of zinc fume in the reactor, and this point is particularly important for the preparation of one-D nano zinc oxide.
The invention has the advantages that;
1. prepared the ZnO nano-cable of diameter between 30-60nm, 50-100nm greatly reduces than existing methods.
2. greatly improved ZnO/SiO
xThe productive rate of nano-cable, and this method also will have positive reference for the productive rate that improves other One-Dimensional ZnO nano materials of preparation.
3. the existing methods preparation temperature is 850 ℃, and result of the present invention this temperature has relatively reduced by 300 ℃.
Description of drawings
Fig. 1 (a) and Fig. 1 (b) are the stereoscan photograph of the made ZnO nano-cable of the present invention, and as can be seen, the material productive rate that makes is very high, draw ratio considerable (greater than 50) from the figure.Figure (a) is a macrograph, demonstrates the method and is large-scale controllable growth really.
Fig. 1 (c) is a high-resolution-ration transmission electric-lens photo of the present invention.As can be seen from the figure, the well-regulated striped of core space can be affirmed this zone for having the zinc oxide of hexagonal wurtzite structure according to electron diffraction pattern, and it is along the growth of [20 21] direction.Coating layer has lower contrast, does not have the feature streak line of crystal to occur, and can affirm that it is an amorphous layer.By energy spectrum analysis, its chemical composition is silicon and oxygen, and ratio is about 1: 1, and amorphous silica as passivation layer and insulating barrier, is widely used aspect the circuit assembling.
Embodiment
Tube furnace specification: long 75cm, caliber 45mm, 1000 ℃ of maximum heating temperatures.Quartz ampoule pipe range 100cm, caliber 32mm.
The ZnO/SiO that under following experiment condition, makes
xIts draw ratio of nano-cable is best, and productive rate is the highest:
At first with silicon (100) substrate at HNO
3(mol ratio 2: 1) ultrasonic cleaning is also rinsed well with deionized water, alcohol respectively in the+HF solution.Use the golden film of magnetic control sputtering device sputter one deck 20 nanometer thickness thereon.Pure zinc powder and pure tin powder (mass ratio 1: 1) fully are put in porcelain boat as raw material in grinding back (20 minutes), and the silicon chip that is coated with golden film is placed on it.Then porcelain boat is put in the quartz ampoule middle part in the tube furnace, regulates flowmeter and in pipe, feed argon (98%)/oxygen (2%) mist (300 standard cubic centimeters per minute).Under this atmosphere, tube furnace is warming up to 550 ℃ and be incubated 20 minutes with the speed of 20 ℃ of per minutes.Continue the ventilation body and be cooled to room temperature until tube furnace, take off silicon chip, white velvet-like thing of deposition is required product on it.
Claims (1)
1, a kind of method for preparing high yield ZnO nano-cable is characterized in that: concrete technology is:
A, with silicon (100) substrate at HNO
3Ultrasonic cleaning and rinsing well respectively in+the HF solution with deionized water and alcohol, the golden film of sputter one deck 15～25 nanometer thickness thereon afterwards, HNO
3HNO in the+HF solution
3: the HF mol ratio was at 2: 1, the gold film is to adopt magnetic control sputtering device to be plated on the silicon chip, its thickness is preparation One-Dimensional ZnO nano material deposition substrate commonly used with the quartz crystal oscillator control that carries, silicon (100), and deposition one deck gold film is to make ZnO/SiO as catalyst
xNano-cable is realized epitaxial growth;
B, with pure zinc powder and pure tin powder mass ratio 1: 1, fully grind evenly and be placed in the porcelain boat, milling time 20～30 minutes, the silicon chip back-off that will be coated with golden film afterwards is on porcelain boat;
C, porcelain boat put into the quartz ampoule middle part of tube furnace, regulate flowmeter and in pipe, feed argon 98%/oxygen 2% mist 300 standard cubic centimeters per minute, under this atmosphere, tube furnace is warming up to 530～570 ℃ and be incubated 20～25 minutes, be cooled to room temperature, products obtained therefrom is for having core ZnO/ coating SiO
xThe nano-cable of structure.
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| CN 200410080423 CN1270327C (en) | 2004-10-09 | 2004-10-09 | Method for producing high yield zinc oxide nano cable |
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| CN 200410080423 CN1270327C (en) | 2004-10-09 | 2004-10-09 | Method for producing high yield zinc oxide nano cable |
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| CN1270327C true CN1270327C (en) | 2006-08-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100437950C (en) * | 2006-12-22 | 2008-11-26 | 中国科学院上海硅酸盐研究所 | Height tropism zinc oxide nano column array ultrasonic auxiliary water solution preparation method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100377295C (en) * | 2005-07-04 | 2008-03-26 | 同济大学 | Method for preparing silicon carbide/silicon dioxide co-axial nano cable |
| CN100411063C (en) * | 2006-05-24 | 2008-08-13 | 中山大学 | SnO2/Sn coaxial nano cable and preparation method and application thereof |
| CN101328609B (en) * | 2008-04-11 | 2010-12-08 | 北京科技大学 | Method for preparing tin doping zinc oxide nanowire by vapor deposition |
| CN106601592B (en) * | 2016-12-22 | 2019-05-07 | 中国科学院理化技术研究所 | A kind of saturating semiconductor material of light and preparation method thereof |
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2004
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100437950C (en) * | 2006-12-22 | 2008-11-26 | 中国科学院上海硅酸盐研究所 | Height tropism zinc oxide nano column array ultrasonic auxiliary water solution preparation method |
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