CN101412534A - Method for preparing high yield tetrapod-shaped nano zinc oxide by autocatalysis - Google Patents
Method for preparing high yield tetrapod-shaped nano zinc oxide by autocatalysis Download PDFInfo
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- CN101412534A CN101412534A CNA2008102268527A CN200810226852A CN101412534A CN 101412534 A CN101412534 A CN 101412534A CN A2008102268527 A CNA2008102268527 A CN A2008102268527A CN 200810226852 A CN200810226852 A CN 200810226852A CN 101412534 A CN101412534 A CN 101412534A
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Abstract
The invention belongs to the technical field of preparation of nanophase materials, and in particular provides a method for preparing high-yield T-ZnO nanophase materials by means of autocatalysis, which realizes large-area controllable growth at low preparation temperature. The method is characterized by comprising the following three steps: 1) an n-type silicon substrate is washed to be clean in an ultrasonic cleaning machine by utilizing acetone and ethanol and is taken as a deposition substrate; 2) Zn powder with a purity of more than 99.9 percent and ZAc powder with a purity of more than 90 percent are mixed according to the atomic ratio of 10 to 1, fully and uniformly ground and placed into a porcelain boat, wherein the grinding time is between 20 and 30 minutes, and the silicon substrate is flipped on the porcelain boat; and the distance of the silicon substrate away from a reactant is kept to between 5 and 8 millimeters; and 3) a tube furnace is subjected to temperature rise to 650 DEG C first, and the porcelain boat is placed into the middle part of a quartz tube in the tube furnace; argon is introduced into the tube for 15 minutes first, wherein the flow rate is 80 cm<3>/min; oxygen is introduced into the tube for 15 minutes, wherein the flow rate is 40 cm<3>/min; and the silicon substrate is taken out and cooled to the room temperature to obtain products, namely four-pin zinc oxide which has smooth material surface and high crystallinity. The method effectively reduces the reaction temperature through the autocatalysis function of the reactant, avoids metallic pollution in the products, realizes large-area controllable preparation, and greatly improves the yield.
Description
Technical field
The invention belongs to the nano material preparation technical field, the method that particularly provides a kind of autocatalytic method to prepare high yield four-needle-like zinc oxide (T-ZnO) nano material has realized large-scale controllable growth under the low preparation temperature.
Background technology
ZnO is a kind of semiconductor material with piezoelectricity and photoelectric characteristic, energy gap is 3.37ev at normal temperatures, is typical direct band gap semiconductor material with wide forbidden band, and its exciton bind energy is up to 60meV simultaneously, high more a lot of from energy 26meV than room temperature heat, exciton is difficult for taking place hot ionization.The exciton of big bound energy is easier realizes that at room temperature high efficiency exciting penetrate owing to have, therefore compare with GaN (25meV) with ZnSe (22meV), ZnS (40meV), ZnO is a kind of under room temperature or higher temperature, have the short-wave long light-emitting material of very big application potential, have broad application prospects at aspects such as optical material, matrix material, transmitter, catalyzer.The character of material depends on size, pattern and dielectric environment, and the controlled nanostructure of therefore synthetic size and pattern is very important for its physics of control and chemical property.At present, by the preparing of people's success, different nanostructures has different potential uses to multiple structures such as zinc oxide nanowire, nano belt, four-acicular nanometer rod, nanotube, nanometer water screw, nanometer spring, nano-rings.
T-ZnO is a kind of three-dimensional four jiaos single crystal structure material that grows into, has regular three-D space structure, just because of its unique pin structure, the T-ZnO that makes is to ethanol, some oxidation-reduction quality gases such as oxygen have good air-sensitive sensitivities, are the starting material of good gas-sensitive sensor device.Simultaneously, because the T-ZnO nano structural material has unique 3-D solid structure, the needle body top is sharp-pointed, the length-to-diameter ratio height, its cut-in voltage and emission and carbon nanotube are suitable, and have stronger thermostability and chemical stability, also are the field emission body materials that has much potentiality.So, the research of T-ZnO has been caused more and more people's interest.
Since people (Y.Dai, Y.Zhang, Q.K.Li such as Zhang Yue in 2002, C.W.Nan.Chemical Physics Letters.2002,358,83～86) utilize thermal evaporation, under 850-925 ℃ of catalyst-free condition, reported first behind the four-needle-like zinc oxide, just more and more to the research of T-ZnO.Utilize the presoma of various zinc, under different condition, the T-ZnO nano material of various patterns has been prepared in the VS growth etc. that utilizes the VLS mechanism growth of catalyzer and do not add catalyzer.At present, the preparation of T-ZnO nano material presents the development of explosion type, and the nano material that comes in every shape constantly is in the news out, and some has had actual application, still also searching is more controlled constantly excavating the nano zinc oxide material with new structure for people, reliable preparation.
Four-needle-like zinc oxide is to ethanol, and some oxidation-reduction quality gases such as oxygen have good air-sensitive sensitivities, is the starting material of good gas-sensitive sensor device, so its research has more and more been caused people's interest.Up to the present, various preparation methods are found by everybody, sum up the relative merits of getting up all to have separately, and the preparation temperature that has is too high, can't mass production; What have causes in using the process of catalyzer mixing of metal in the product easily, and pollution products is unfavorable for the processing of device.
Summary of the invention
The present invention seeks in order to solve the four-needle-like zinc oxide preparation temperature too high, can't mass production or in the process of using catalyzer, cause the mixing of metal in the product, pollution products easily, the problem that is unfavorable for the processing of device, self-catalysis by reactant self, effectively reduce temperature of reaction, and avoid the pollution of metal in the product, realize the big area controllable preparation, and improve productive rate on a large scale.
A kind of method of preparing high yield tetrapod-shaped nano zinc oxide by autocatalysis, realize by following three steps:
1, n type silicon (100) substrate is cleaned up in ultrasonic cleaning machine with acetone and ethanol, as deposition substrate;
2, Zn powder (purity〉99.9%) and ZAc (zinc acetate) powder (purity〉90%) are pressed atomic ratio 10:1 and mix, fully grind evenly and be placed in the porcelain boat, milling time 20～30 minutes, afterwards with the silicon substrate back-off on porcelain boat; Silicon chip remains between the 5-8mm apart from the distance of reactant.
3, tube furnace is warming up to 650 ℃ in advance, porcelain boat is put into the silica tube middle part of tube furnace; Regulating under meter and feeding argon flow amount earlier in pipe is 80cm
3/ min kept 15 minutes; Stop logical argon gas then, change logical oxygen, the flow that keeps oxygen is at 40cm
3After/min15 minute, stop gas, take out silicon substrate.Be cooled to and utilize scanning electron microscope after the room temperature, be equipped with the transmission electron microscope of power spectrum that the sample that is deposited on silicon substrate is analyzed, confirm the products obtained therefrom four-needle-like zinc oxide.
Think that tentatively the growth of T-ZnO in this experiment is solid-liquid-gas (V-L-S) mechanism control by autocatalysis: reaction beginning, ZAc is decomposes in the atmosphere of Ar, because the ZAc that the existence of O atom own makes among the ZAc is in the process of decomposing, the oxidized ZnO small droplets that generated of Zn, just become the nucleus of ZnO growth, and be Ar owing to atmosphere this moment, and certain restriction has been played in the evaporation of Zn powder; When Ar atmosphere is changed to O
2During atmosphere, the evaporation of Zn powder, abundant and O
2In conjunction with, form solid-liquid interface, around the nucleus of ZnO, grow, grow up, finally form four horn shape nano structure of zinc oxide of different-shape, so ZAc has played the part of the effect of catalyzer in the autocatalysis at this, also make temperature of reaction reduce, pattern is variation more.
Adopt the method for reactant self autocatalysis, the mixture of thermal evaporation zinc powder and zinc acetate (ZAc) is at argon gas (Ar) and oxygen (O
2) atmosphere in, do not use the T-ZnO nano material of having prepared high-quality all kinds of patterns under catalyzer, lower temperature (650 ℃) condition, its smooth surface, crystallinity is higher, is the superior prod of making device.
The invention has the advantages that:
1. utilize the method for autocatalysis to prepare the T-ZnO nano material of bar-shaped pattern first, every bar-shaped stitch all is smooth surfaces, the single crystal structure that quality is higher.
2. we have improved the productive rate of T-ZnO nano material, and this method also will have positive reference for the productive rate that improves the ZnO monodimension nanometer material for preparing other patterns.
3. the method for forefathers preparation, preparation temperature be 700-900 ℃ all generally, relative this temperature of our result has reduced many, to the favourable saving of suitability for industrialized production cost, and more simple and easy to do than existent method.
Description of drawings
Fig. 1 is the stereoscan photograph of T-ZnO low power, demonstrates this method and is large-scale controllable growth really.
Fig. 2 is the stereoscan photograph of T-ZnO high power, and as can be seen, product is four jiaos of acicular structures on the figure, and each angle is the club shaped structure of rule, surface smoothing, and shape is regular, and one nanometer rod diameter is approximately 100nm, and being about is 2～3um.
Fig. 3 is the transmission electron microscope photo of the whole pattern of single T-ZnO among corresponding Fig. 2.
Fig. 4 is the high power transmission electron microscope photo of single T-ZnO.As can be seen from the figure, the edge of every nanometer rod has the ZnO crystal grain of nanometer shape to exist.
Fig. 5 is high-resolution-ration transmission electric-lens and corresponding diffraction spot photo.Its direction of growth is the single crystal structure of wurtzite along the growth of (0001) aufwuchsplate.
Embodiment
Tube furnace specification: long 70cm, caliber 40mm, 1300 ℃ of maximum heating temperatures.Silica tube pipe range 120cm, caliber 30mm.
The T-ZnO nano-material surface that makes under following experiment condition is level and smooth, and shape is regular, and productive rate is the highest:
At first that silicon (100) substrate is clean with acetone, alcohol ultrasonic cleaning.Zn powder (purity〉99.9%), acetic acid zinc powder (purity〉90%) are pressed atomic ratio 10:1 mix, fully grind back (more than 20 minutes) and be put in porcelain boat as raw material, silicon substrate is placed on it, and distance is about 5-8mm.Then porcelain boat is put in the silica tube middle part in the tube furnace, regulates under meter and in pipe, feed argon gas 80cm earlier
3/ min kept 15 minutes, stopped logical argon then, changed logical oxygen, and the flow that keeps oxygen is at 40cm
3After/min15 minute, stop gas, take out silicon substrate, on substrate, obtain one deck white sedimentation products.
Claims (1)
1. the method for a preparing high yield tetrapod-shaped nano zinc oxide by autocatalysis is characterized in that realizing by following three steps:
1), n type silicon substrate is cleaned up in ultrasonic cleaning machine with acetone and ethanol, as deposition substrate;
2), with purity 99.9%Zn powder and purity the 90%ZAc powder presses atomic ratio 10:1 and mixes, fully grind evenly and be placed in the porcelain boat, milling time 20～30 minutes, afterwards with the silicon substrate back-off on porcelain boat; Silicon chip remains between the 5-8mm apart from the distance of reactant;
3), tube furnace is warming up to 650 ℃ in advance, porcelain boat put into the silica tube middle part of tube furnace; Regulating under meter and feeding argon flow amount earlier in pipe is 80cm
3/ min kept 15 minutes; Stop logical argon gas then, change logical oxygen, the flow that keeps oxygen is at 40cm
3/ min after 15 minutes, stops gas, takes out silicon substrate; Be cooled to and utilize scanning electron microscope after the room temperature, be equipped with the transmission electron microscope of power spectrum that the sample that is deposited on silicon substrate is analyzed, confirm the products obtained therefrom four-needle-like zinc oxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101672810B (en) * | 2009-09-14 | 2011-06-08 | 哈尔滨飞机工业集团有限责任公司 | Method for analyzing composition uniformity of rubber material |
| CN105220229A (en) * | 2015-11-06 | 2016-01-06 | 中国科学院理化技术研究所 | A kind of preparation method of TiO2 monocrystal nano pipe array |
| CN115872438A (en) * | 2022-12-07 | 2023-03-31 | 河南城建学院 | Tetrapod-like zinc oxide gas-sensitive material with brush-like structure and preparation method and application thereof |
-
2008
- 2008-11-18 CN CNA2008102268527A patent/CN101412534A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101672810B (en) * | 2009-09-14 | 2011-06-08 | 哈尔滨飞机工业集团有限责任公司 | Method for analyzing composition uniformity of rubber material |
| CN105220229A (en) * | 2015-11-06 | 2016-01-06 | 中国科学院理化技术研究所 | A kind of preparation method of TiO2 monocrystal nano pipe array |
| CN115872438A (en) * | 2022-12-07 | 2023-03-31 | 河南城建学院 | Tetrapod-like zinc oxide gas-sensitive material with brush-like structure and preparation method and application thereof |
| CN115872438B (en) * | 2022-12-07 | 2024-03-19 | 河南城建学院 | Tetrapod-like zinc oxide gas-sensitive material with brush-like structure, and preparation method and application thereof |
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