CN100371509C - ZnO nano crystal column/nano crystal filament composite structure product and its preparing process - Google Patents
ZnO nano crystal column/nano crystal filament composite structure product and its preparing process Download PDFInfo
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- CN100371509C CN100371509C CNB2005100489057A CN200510048905A CN100371509C CN 100371509 C CN100371509 C CN 100371509C CN B2005100489057 A CNB2005100489057 A CN B2005100489057A CN 200510048905 A CN200510048905 A CN 200510048905A CN 100371509 C CN100371509 C CN 100371509C
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Abstract
The present invention relates to a product of a ZnO nanometer crystal bar / nanometer crystal filament composite structure, which belongs to an oxide microstructure material made by the technology of gas phase epitaxy. The present invention is characterized in that the preparation process of the product comprises the following steps: firstly, a hexagonal structure ZnO nanometer crystal bar array is grown on the surface of a substrate with c-axis orientation in height (vertical to the surface of the substrate), high density and uniform distribution, and then, a ZnO nanometer crystal filament with high density and random orientation almost parallel to the surface of the substrate is formed on the ZnO nanometer crystal bar array. The preparation of the product is characterized in that the product is obtained by one-time growing on the surface of the substrate through a 'two-step deposition' process by using the technology of electron bundle reaction evaporation.
Description
Technical field
The invention belongs to oxide compound fine structure material and vapour phase epitaxy preparing technical field thereof, be specifically related to a kind of ZnO nano crystal column/nano crystal filament composite structure product of hexagonal structure and utilize electric beam evaporation equipment, obtain the technology of preparing of this product in the disposable growth of substrate surface by " two step deposition " technology.
Technical background
In recent years, the research to the zno-based fine structure material has been subjected to worldwide showing great attention to.At numerous zno-based fine structure materials (as nano-pillar, nano thread, nano-rings, nano belt, nanometer plate, the nanometer water screw) in, the thread zinc oxide of nano-pillar or nanometer is with accurate one dimension or four needle-likes (as the whisker) space structure and the single crystal characteristic thereof of its uniqueness, make it have high Young's modulus, extremely low coefficient of thermal expansion, good high-temperature stability and good semi-conductor and piezoelectric property, in damping, noise reduction, inhale ripple, wear-resisting, high temperature resistant, numerous areas such as antistatic and antibiotic has extensive use, for example in the damping noise reduction of high-speed railway, the wave-absorbing and camouflage of flyer, aspects such as microwave thermal conversion have important application, are called as the important brand-new material of 21st century.The zinc oxide nanocrystalline silk normally obtains (Hong Jin Fan with the method for zinc powder oxidation, Roland Scholz, Florian M.Kolb, and Margit Zacharias, Two-dimensional dendritic ZnO nanowires from oxidationof Zn microcrystals, Applied Physics Letters, 85 (2004) 4142); Or by ZnO powder via carbonaceous reducing agent, obtain (M.H.Huang, S.Mao, H.Feick, et al, Scince, 292 (2001) 1897) by thermal chemical reaction and the sedimentary method of vapor transportation.In these two kinds of methods, the interior reaction gas phase degree of supersaturation of reactor of controlling well is the key of the high-quality ZnO nano thread of preparation, if control gas phase degree of supersaturation in the reactor well, can synthesize purity height, crystalline structure is complete, yardstick is controlled zinc-oxide nano silk.But the control of high-precision gas phase degree of supersaturation is comparatively complicated, and these two kinds of methods need be introduced metal catalyst (Seu Yi Li usually, Chia Ying Lee, Tseung Yuen Tseng, Copper-catalyzed ZnO nanowires on silicon (100) grown by vapor-liquid-solidprocess, Journal of Crystal Growth 247 (2003) 357-362; Woong Lee, Min-Chang Jeong, Jae-Min Myoung, Catalyst-free growth of ZnO nanowires by metal-organic chemicalvapour deposition (MOCVD) and thermal evaporation, Acta Materiaiia 52 (2004) 3949-3957; X.Wang, Q.W.Li, Z.B.Liu, J.Zhang, Z.F.Liu, Low-temperature growthand properties of ZnO nanowires, Applied Physics Letters, 84 (2004) 4941-4943; X.H.Kong, X.M.Sun, X.L.Li, Y.D.Li, Catalytic growth of ZnO nanotubes, MaterisldChemistry and Physics, 82 (2003) 997-1001), the zinc-oxide nano silk for preparing is soft flocculence, generally need make secondary processing when doing concrete the application, and there are a series of problems such as ZnO nano thread and body material poor bonding strength inevitably in the product that secondary processing obtains.Crystal structure analysis to the ZnO nano thread product that obtained by Zn powder oxidation style shows, product often is polycrystalline structure and contains the composition (B.J.Chen of Metal Zn, X.W.Sun, C.X.Xu, B.K.Tay, Growth and Characterization of zinc oxide nano/micro-fibers by thermal chemicalreactions and vapor transport deposion in air, Physica E, 21 (2004) 103-107).If in preparation process, introduce catalyzer, for example use Au (X.Wang, Q.W.Li, Z.B.Liu, J.Zhang, Z.F.Liu, Low-temperature growth and properties of ZnO nanowires, Applied Physics Letters, 84 (2004) 494l-4943
[3]) or NiO (T.Y.Kim, J.Y.Kim, S.H.Lee, et al, Characterization ofZnO needle-shaped nanostructures grown on NiO catalyst-coated Si substrates, Synthetic Metals, 144 (2004) 61-68) nano particle is as catalyzer), then in ZnO nano thread finished product, can contain catalyst component equally, the quality that this has reduced the ZnO nano thread has particularly limited its application at special dimension (as microelectronics, photoelectron).
The preparation research present situation of zno-based fine structure material (as nano-pillar, nano thread, nano-rings, nano belt, nanometer plate, nanometer water screw) is: the control process complexity of gas phase degree of supersaturation in (1) reactor, if it is improper that processing condition have slightly, the product that then obtains is ZnO film often, (2) ZnO nano thread finished product is single flocculence usually on macroscopic view, when practical application, need make secondary processing, (3) in the ZnO nano thread preparation process owing to introduce catalyzer, contain the composition of Metal Zn and catalyzer in the finished product, crystalline quality is undesirable.
Summary of the invention
The present invention adopts a kind of comparatively simple electric beam evaporation method, with polycrystalline ZnO ceramic target and NH
3/ H
2Gas mixture is a raw material, under the situation of not adding metal catalyst, directly obtains the ZnO nano crystal column/nano crystal filament composite structure product of high-crystal quality in the disposable growth of substrate surface by " two step depositions " technology.This invention product can satisfy the purposes of some special aspects, for example as high performance suction ripple stealth material or microwave thermal transition material.
ZnO nano crystal column/nano crystal filament composite structure product of the present invention, its constitutional features has on ZnO ceramic substrate surface perpendicular to substrate surface, high-density and equally distributed hexagonal structure ZnO nano crystal column array, has to be parallel to substrate surface, highdensity ZnO nano crystal filament on the ZnO nano column array; Adopt the electric beam evaporation method, with polycrystalline ZnO ceramic target and NH
3/ H
2Gas mixture is a raw material, directly obtains the ZnO nano crystal column/nano crystal filament composite structure product in the disposable growth of substrate surface by " two step depositions " technology.
ZnO nano crystal column/nano crystal filament composite structure product of the present invention adopts the electric beam evaporation method to obtain, and its concrete processing step is as follows:
(1) cleans the substrate and the substrate holder of packing into, substrate holder is put into the growth room.In the crucible of ZnO ceramic target in the growth room of putting compacting and sintering, isolate target and substrate with baffle plate;
(2) take out the growth room to≤3 * 10 with vacuum pump
-3The base vacuum degree of Pa;
(3) elder generation charges into NH with the low discharge of 10sccm～20sccm
3/ H
2Gas mixture, the suitable simultaneously fine pumping valve of adjusting the growth room makes the vacuum tightness in the growth room reach 3 * 10
-2Pa also keeps constant;
(4) heated substrate is to suitable growth temperature;
(5) earlier with high-energy focusing electron beam alignment ZnO target, regulate the electron beam line, under lower line, the heating target is so that to the target degasification;
(6) degasification finishes a certain current value of back adjusting electron beam line to 30mA～40mA, makes ZnO target start vaporizer;
According to the different requirements of growth velocity speed, by regulating the parameters such as position at electron beam spot area, bundle spot center, the vapour pressure (partial pressure) of ZnO target is controlled at 2.0 * 10
-2Pa～5.0 * 10
-2Pa makes stable, the evaporation equably of ZnO target; Open baffle plate and begin the fs growth of ZnO nano crystal column/nano crystal filament composite microstructure;
(7) experience 20 minutes～after 30 minutes, mixed gas flow has been transferred the big 50sccm～60sccm of arriving when the fs growth, entered into the process of growth of subordinate phase;
(8) after the subordinate phase growth continues 30 minutes～40 minutes, close the electron beam gun high pressure, finish growth;
(9) after the end growth, at the NH that still keeps 50sccm～60sccm
3/ H
2Under the situation of mixed gas flow, reduce underlayer temperature gradually, treat underlayer temperature reduce to≤200 ℃ the time, cut off the gas mixture source of the gas;
(10) treat that underlayer temperature reduces to room temperature, open the growth room, take out sample.
The substrate of mentioning in the processing step of the present invention (1) can be single crystalline Si polished section, monocrystalline sapphire polished section or silica glass.
Processing step of the present invention is mentioned the cleaning substrate in (1), and the cleaning step of Si polished section substrate is:
Remove organism---silicon chip is put into the vitriol oil and hydrogen peroxide boiled 10 minutes～15 minutes by 1: 1 blended solution;
Deoxidation thing---silicon chip soaked for 20 second～30 seconds in 10% hydrofluoric acid solution, wash repeatedly with deionized water then;
Removing inorganics---silicon chip by 80 ℃ of water-baths in 1: 1: 6 blended solution 15 minutes～20 minutes, takes out the back deionized water rinsing at hydrogen peroxide, hydrochloric acid and deionized water;
To immerse 5～10 seconds in 10% hydrofluoric acid solution through the silicon chip that above-mentioned steps is cleaned;
In the vertical laminar flow clean bench, silicon chip is dried up at last, and put into the growth room rapidly with nitrogen.
The ZnO ceramic target material of being mentioned in the processing step of the present invention (1) is repressed and form through high temperature (1200 ℃) sintering by the ZnO powder of purity 99.99%.
The NH that mentions in the processing step of the present invention (3)
3/ H
2Gas mixture is that employing purity is 99.999% NH
3Gas and H
2Gas mixes, wherein NH
3The shared volume percent of gas is 1vol.%～50vol.%.
Processing step of the present invention mentions in (3) that " earlier the low discharge with 10sccm～20sccm charges into NH
3/ H
2Gas mixture ", flow too senior general can not guarantee that gas mixture is to arrive substrate surface with diffusion way, thereby influences the nucleation rate of ZnO nucleus.
The suitable underlayer temperature of mentioning in the processing step of the present invention (4) can be 400 ℃, 450 ℃ or 500 ℃, and temperature is too low or too high to be unfavorable for growing single crystal ZnO nano-pillar/nano wire laminated film.
The line of mentioning in the processing step of the present invention (5) lower is 5mA～10mA, and heating target 5 minutes～10 minutes is so that to the target degasification.
The vapour pressure of the ZnO target that the high-power electron beam of mentioning among the present invention evaporates is 2 * 10
-2Pa～5 * 10
-2Pa can control by regulating the electron beam gun parameter.
ZnO nano crystal column/nano crystal filament composite microstructure product of the present invention is to realize in the electric beam evaporation depositing system of a commercialization.Utilize the focused beam with higher-energy of electron beam gun emission directly to bombard the ZnO target material, the kinetic energy of electron beam becomes heat energy, make the ZnO molecule of thermal evaporation leave target material surface, scattering also deposits to the substrate surface that has heated, and the molecule or the atom that are adsorbed form nucleus by diffusion motion; Simultaneously, (10sccm～20sccm) is filled into the growth room and is diffused into the NH of substrate surface with less flow in advance
3/ H
2NH in the gas mixture
3, H
2Molecule, because the collision that is subjected to the thermal radiation of substrate surface and is subjected to the ZnO particle of thermal evaporation, part resolves into atom N and atom H.These oversaturated atom N and atom H are covered with the entire substrate surface, also surround the ZnO nucleus that had formed already, and making it be not easy to grow up apace is the ZnO crystal film of ZnO crystal grain and further formation whole piece.These oversaturated atom N and atom H interact by with the ZnO nucleus a series of molecular dynamics taking place that (wherein some N atom is to replace the lattice that 0 mode enters into the ZnO nucleus; And atom H is because its strong reducing property, meeting is to producing optionally restraining effect along non-c-axle epitaxial ZnO nucleus), the result make the ZnO nucleus optionally along with the vertical c-axle of substrate surface oriented growth, form the uniform single crystal ZnO nano-pillar of density distribution.Above process generally continues 20 minutes～30 minutes, is the first step in " two step depositions " technology, the long height to 100nm～200nm of ZnO nano crystal column this moment.
After process of growth continues 20 minutes～30 minutes, enter into second step of " two step depositions " technology, increase NH this moment
3/ H
2The flow of gas mixture (as increasing to 60sccm, the also corresponding increase of its flow velocity this moment) allows the gas mixture be that mode with conduction (be convection current, rather than diffusion) arrives substrate surface basically.At this moment, the ZnO nano crystal column of c-axle orientation is interfered along the condition of further growing tall with the vertical direction of substrate, and it just grows up to the nano thread shape of mixed and disorderly orientation gradually subsequently, though along c-axle oriented growth, but this moment, the c-axle was no longer vertical with substrate, but random orientation.Just finally obtained the ZnO nano crystal column/nano crystal filament composite structure product like this in lasting 30 minutes～40 minutes later on.Because this is (to be NH with two step method
3/ H
2Mixed gas flow is earlier little, the back is big) the technology growth obtains, therefore control the parameters such as airshed size in time length and two stages of forward and backward two processes well, just can effectively modulate the characteristics such as pattern of ZnO nano crystal column/nano crystal filament composite structure product.
The ZnO fine structure material sample of being grown is carried out the analysis of surface topography, crystalline structure and component content respectively with field emission scanning electron microscope (FESEM), X-ray diffraction (XRD) and energy dispersion X-ray diffraction (EDX) technology, the result shows, the sample of growing is the pattern that is the ZnO nano crystal column/nano crystal filament composite structure, and does not detect the elemental composition of N and H in sample.
Major technique advantage of the present invention is:
ZnO nano crystal column/nano crystal filament composite microstructure is the electric beam evaporation system that adopts commercialization, with the polycrystalline ZnO ceramic target and the NH that are easy to obtain
3/ H
2Gas mixture is a source material, obtains in the disposable growth of substrate surface by " two step depositions " technology, and preparation technology is easy to control, is applicable to the preparation of big area laminated film, and preparation cost is low, helps industrialization production.
Finished product advantage of the present invention is:
The brilliant silk of ZnO that obtain with the methods such as carbon reduction of zinc powder oxidation and ZnO powder, a byssaceous product is compared, the present invention obtains be a kind of surface topography controlled, combine firm, highly purified novel ZnO nano crystal column/nano crystal filament composite structure product with substrate.It is characterized in that earlier the substrate surface growth distribution evenly, be height c-axle orientation and with the vertical ZnO nano crystal column of substrate surface array, and then the nanocrystalline line of staggered ground ZnO of above array, along almost parallel direction even compact ground, growing with substrate.Just because of its unique surface topography characteristic, it is particularly suitable for the application as aspects such as wave-absorbing and camouflage, microwave thermal conversions.
Description of drawings
Field emission scanning electron microscope (FESEM) the surface topography photo of ZnO nano crystal column/nano crystal filament composite structure sample under 50000 times of magnifications that Fig. 1 is according to a preferred embodiment of the present invention to be grown.
Field emission scanning electron microscope (FESEM) the surface topography photo of ZnO nano crystal column/nano crystal filament composite structure sample under 5000 times of magnifications that Fig. 2 is according to a preferred embodiment of the present invention to be grown
Electron energy chromatic dispersion X-ray diffraction (EDX) spectrogram of the ZnO nano crystal column/nano crystal filament composite structure sample that Fig. 3 is according to a preferred embodiment of the present invention to be grown.
X-ray diffraction (XRD) spectrogram of the ZnO nano crystal column/nano crystal filament composite structure sample that Fig. 4 is according to a preferred embodiment of the present invention to be grown.
Embodiment
Embodiment
1. the Si substrate is put into the vitriol oil and hydrogen peroxide and boiled 10 minutes, remove surface organic matter by 1: 1 blended solution; Afterwards the Si substrate was soaked for 30 seconds in 10% hydrofluoric acid solution, take out the back and wash repeatedly with deionized water; Again with the Si substrate at HCl: H
2O
2: deionized water boiled in the blended solution 15 minutes by 1: 1: 6, removed the surface inorganic thing; The taking-up back is washed repeatedly with deionized water and is soaked several seconds in HF solution, uses N
2Put into the growth room rapidly after drying up substrate.
2. that will suppress and be that 99.99% ZnO ceramic target material places crucible through the purity that 1200 ℃ of high temperature sinterings are crossed, with baffle plate target source and substrate are separated.With vacuum pump the background air pressure of reaction chamber is evacuated to about 3 * 10
-3Pa.
3. the flow with 10sccm charges into NH
3Content is the NH of 2.7vol.%
3/ H
2Gas mixture (NH
3With H
2Purity be 99.999%), adjust simultaneously suitably the fine pumping valve of growth room, make the vacuum tightness in the reaction chamber reach 3 * 10
-2Pa also keeps constant; Heated substrate then;
4. treat that substrate is heated to 450 ℃, with acceleration voltage is the high energy electron beam heating ZnO target of 6KV, to target degasification 5 minutes: promptly regulate the electron beam gun line to the 5mA, regulate the bundle spot area of electron beam and the position at bundle spot center, make bundle spot area cover the surface of monoblock target just and kept 5 minutes.
5. regulate the electron beam gun line to 35mA, and regulate the bundle spot area of electron beam and the position at bundle spot center, when the partial pressure of ZnO target reaches 3 * 10
-2During Pa, open baffle plate, the fs growth growth of beginning laminated film.Keep 450 ℃ of underlayer temperatures constant in the process of growth, make air pressure keep constant by fine setting line, bundle spot size and position thereof simultaneously, so that guarantee the constant growth velocity.
6. after the fs, growth continued 20 minutes, under the situation of not cutting off electron beam source, with NH
3/ H
2The flow of gas mixture is transferred greatly to 50sccm, enters into the process of growth of the subordinate phase of laminated film.
7. after the subordinate phase growth continues 30 minutes, close electron beam gun line and high pressure, finish growth.
8. after finishing growth, at the NH that still keeps the 50sccm flow
3/ H
2Under the situation that gas mixture charges into, reduce underlayer temperature gradually, when treating that underlayer temperature is reduced to 200 ℃, cut off the gas mixture source of the gas.
Treat that underlayer temperature reduces to room temperature, open the growth room, take out sample, obtain ZnO nano crystal column/nano thread composite structure product.
The ZnO nano crystal column/nano crystal filament composite structure sample of present embodiment growth is at field emission scanning electron microscope (FESEM) surface topography photo, see Fig. 1, Fig. 2, its constitutional features has on ZnO ceramic substrate surface perpendicular to substrate surface, high-density and equally distributed hexagonal structure ZnO nano crystal column array, has to be parallel to substrate surface, highdensity ZnO nano crystal filament on the ZnO nano column array; The diameter of nano-pillar and nano thread is about 140nm, and nano thread length is about 4400nm.
Electron energy chromatic dispersion X-ray diffraction (EDX) spectrogram of the ZnO nano crystal column/nano crystal filament composite structure sample of present embodiment growth is seen Fig. 3.Do not detect the existence of N, H element in the sample.
X-ray diffraction (XRD) spectrogram of the ZnO nano crystal column/nano crystal filament composite structure sample of present embodiment growth is seen Fig. 4.ZnO nano crystal column in the sample and nano crystal filament are the c-axle orientation characteristic of height.
Claims (7)
1. ZnO nano crystal column/nano crystal filament composite structure product, its constitutional features is: have perpendicular to substrate surface, high-density and equally distributed hexagonal structure ZnO nano crystal column array at substrate surface, be parallel to substrate surface, highdensity ZnO nano crystal filament on the ZnO nano column array; Adopt the electric beam evaporation method, with ZnO ceramic target and NH
3/ H
2Gas mixture is a raw material, directly obtains the ZnO nano crystal column/nano crystal filament composite structure product in the disposable growth of substrate surface by " two step depositions " technology.
2. the described ZnO nano crystal column/nano crystal filament composite structure product of claim 1 preparation technology, processing step is as follows:
A) clean the substrate and the substrate holder of packing into, substrate holder is put into the growth room, put in the crucible of polycrystalline ZnO ceramic target in the growth room of suppressing and sintering, isolate target and substrate with baffle plate;
B) take out the growth room to≤3 * 10 with vacuum pump
-3The base vacuum degree of Pa;
C) elder generation charges into NH with the low discharge of 10～20sccm
3/ H
2Gas mixture, the suitable simultaneously fine pumping valve of adjusting the growth room makes the vacuum tightness in the growth room reach 3 * 10
-2Pa also keeps constant;
D) heated substrate is to suitable growth temperature;
E) earlier with high-energy focusing electron beam alignment ZnO target, regulate the electron beam line, under lower line, the heating target is so that to the target degasification;
F) after degasification finishes line is adjusted to a certain current value of 30～40mA, makes ZnO target start vaporizer; According to the different requirements of growth velocity speed, by regulating the parameters such as position at electron beam spot area, bundle spot center, the vapour pressure partial pressure of ZnO target is controlled at 2.0 * 10
-2～5.0 * 10
-2Pa makes stable, the evaporation equably of ZnO target; Open baffle plate and begin the fs growth of ZnO nano crystal column/nano crystal filament composite structure;
G) after the fs, growth was experienced 20～30 minutes, mixed gas flow is transferred greatly to 50～60sccm, entered into the subordinate phase process of growth;
H) continue 30～40 minutes when the subordinate phase process of growth, close the electron beam gun high pressure, finish growth;
I) after the end growth, at the NH that still keeps 50～60sccm
3/ H
2Under the situation of mixed gas flow, reduce underlayer temperature gradually, treat underlayer temperature reduce to≤200 ℃ the time, cut off the gas mixture source of the gas;
J) treat that underlayer temperature reduces to room temperature, open the growth room, take out product.
3. Zn0 nano crystal column/nano crystal filament composite structure product preparation technology according to claim 2 is characterized in that: described substrate material is single crystalline Si polished section, silica glass or monocrystalline sapphire polished section.
4. Zn0 nano crystal column/nano crystal filament composite structure product preparation technology according to claim 2 is characterized in that: described ZnO ceramic target material is repressed and form through 1200 ℃ of high temperature sinterings by the ZnO powder of purity 99.99%.
5. Zn0 nano crystal column/nano crystal filament composite structure product preparation technology according to claim 2, it is levied the spy and is: described NH
3/ H
2NH in the gas mixture
3Volumn concentration be 1vol.%～50vol.%.
6. according to the described Zn0 nano crystal column/nano crystal filament composite structure product of claim 2 preparation technology, it is levied the spy and is: described suitable growth temperature is 400 ℃, 450 ℃ or 500 ℃.
7. according to the described ZnO nano crystal column/nano crystal filament composite structure product of claim 2 preparation technology, it is levied the spy and is: described lower line is 5～10mA, heating target 5～10 minutes.
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| CN101244895B (en) * | 2007-02-16 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Method for controlling ZnO nano-pole array density |
| CN101275073B (en) * | 2007-09-26 | 2010-07-21 | 浙江大学 | Preparation for ZnO quantum dot |
| CN101538062B (en) * | 2009-04-14 | 2010-12-08 | 北京科技大学 | Nano ZnO semiconductor junction array and preparation method thereof |
| CN102191540B (en) * | 2011-05-10 | 2012-11-21 | 中国科学院半导体研究所 | Method for growing horizontally arranged zinc oxide nanowires on non-polar sapphire substrate |
| CN104402039B (en) * | 2014-12-01 | 2016-01-20 | 中国科学院重庆绿色智能技术研究院 | A kind of method preparing three-dimensional ZnO nano gauze |
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| CN1099816A (en) * | 1994-07-08 | 1995-03-08 | 清华大学 | Zinc oxide crystal whisker preparing method and device |
| CN1396300A (en) * | 2002-07-17 | 2003-02-12 | 清华大学 | Process for preparing large-area zinc oxide film with nano lines by physical gas-phase deposition |
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