CN105858715B - A kind of method for preparing rich acceptor type ZnO micron tubes - Google Patents
A kind of method for preparing rich acceptor type ZnO micron tubes Download PDFInfo
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- CN105858715B CN105858715B CN201610366213.5A CN201610366213A CN105858715B CN 105858715 B CN105858715 B CN 105858715B CN 201610366213 A CN201610366213 A CN 201610366213A CN 105858715 B CN105858715 B CN 105858715B
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Abstract
It is a kind of method for preparing rich acceptor type ZnO micron tubes the present invention relates to semi-conducting material and optical technical field.It is using ZnO powder as raw material；Ball milling drying, the sieving of 200 mesh；Load strip rubber balloon, compacting is closed, vacuumized, and thickness, the biscuit rod of even density are made under isostatic pressed；The rod is put into lifting whirl-sintering furnace and is sintered to ceramic rod；Ceramic rod is put into the stove of optics floating region, setting floating region stove Halogen lamp LED power output is 900 1050W/h, is passed through speed oxygen/air, held for some time, the growth course separated out by optics gasification supersaturation, rich acceptor type ZnO micron tubes are prepared, the long-acting stabilization of acceptor state provides new thinking for the preparation of p-type ZnO material, this micron of pipe size is larger simultaneously, pattern is complete, with regular hexagonal section, and with novel room temperature photoluminescence characteristic.
Description
Technical field
The present invention relates to semi-conducting material and optical technical field, more particularly to synthesize one kind and prepare rich acceptor type ZnO
The method of micron tube.
Background technology
ZnO has huge application prospect in photoelectric field, but to realize extensive answer as third generation semi-conducting material
With also depositing huge obstacle.Under natural conditions, intrinsic/n-type conduction is presented in ZnO, has successfully prepared high-quality n-type ZnO at present,
But high-quality Stable Type p ZnO acquisition is one of main bugbear of this area.Unstable acceptor state is to cause p-type ZnO to prepare to be stranded
Difficult main cause.P-type doping is only carried out on stable intrinsic rich acceptor type ZnO could preferably suppress its self compensation effect
Should, make the recipient element of incorporation really play a part of increasing hole, so as to realize the p-type electric-conducting of ZnO stability and high efficiencies.Therefore,
We have proposed using the rich acceptor type ZnO monocrystalline micron tubes of optics gasification super-saturation precipitation method growth, stable be rich in is prepared
The ZnO monocrystalline of acceptor is the basis for realizing other intrinsic/doped p type ZnO materials.In recent years, the preparation method master of ZnO micron tubes
Concentrate on Vapor Transport, hydro-thermal method, microwave heating method etc., wherein Vapor Transport (X.Xu, C.Xu, J.Dai, J.Pan,
J.Hu.J.Phys.Chem.Solids.2012,73:858-862.) it is more universal method, but required reaction temperature at present
It is higher, it is necessary to consume a large amount of gases, cost is higher；Hydro-thermal method (A.Wei, X.W.Sun, C.X.Xu, Z.L.Dong, Y.Yang,
S.T.Tan,W.Huang.Nanotechnology 2006,17:1740-1744.) complex steps are to acid-base value, temperature, insulation
Time requirement is higher, grows micron pipe size smaller；Microwave heating method (J.Cheng, R.Guo,
Q.M.Wang..Appl.Phys.Lett.2004,85:5140-5142.) initial feed is ceramic for the block ZnO of hollow structure,
Technique is complex.In addition, it has been reported that intrinsic micron tube be to refer to as rich in acceptor type ZnO material, intrinsic rich acceptor
The preparation of type ZnO micron tubes has no report.
The content of the invention
The purpose of the present invention is critical bottleneck problem --- the acceptor state of efficient stable for restriction ZnO development at present, is carried
Gone out it is a kind of prepare the method for high-quality rich acceptor type ZnO micron tubes, while overcome existing micron tube technology of preparing cumbersome, size
Smaller the problems such as.
The technical principle of optics proposed by the invention gasification super-saturation precipitation method is：ZnO can be decomposed into more than 1500 DEG C
Zinc fume and oxygen steam, in very short time, high temperature zinc fume and oxygen spread rapidly in the way of near adiabatic expands, equal
In even temperature field, zinc fume pressure is gradually increased to saturation.When zinc fume partial pressure further increases, due to solubility satiety
With occur that a large amount of zinc atoms are superfluous and reacted with oxygen molecule in environment, deposit and progressively grow in nucleation area.With photon
As energy carrier, under oxygen-enriched environment, based on the supersaturated precipitation of uniform temperature gas phase, effectively lower Zinc vacancies and combine energy, in fact
The existing rich acceptor's stable states of ZnO；Required condition is supersaturated zinc fume pressure；Oxygen-enriched environment；Uniform temperature field and accurate temperature
Control.With reference to the characteristics of the stove grower of optics floating region, rich acceptor's ZnO monocrystalline micron tubes are prepared.
The present invention is achieved by the following scheme
A kind of preparation method of rich acceptor type ZnO micron tubes, it is characterised in that comprise the following steps：
(1) 200 mesh sieves are crossed after ZnO powders ball milling is dried；
(2) powder crossed after 200 mesh sieves, which is fitted into strip rubber balloon, is compacted, closes, vacuumizing, in 70MPa isostatic presseds
Under thickness, the biscuit rod of dense uniform is made；
(3) by biscuit rod, 700 DEG C of insulation 10h sintering obtain ceramic rod in lifting whirl-sintering furnace；Ceramic rod is a diameter of
0.8-1cm；
It (4) will wear at the top of ceramic rod coniform, cone height is 0.5-1cm, and ceramic rod then is tied into optics floating region
Under stove at swingle bracket, quartz ampoule is installed, regulation swingle makes ceramic rod be in halogen light focal zone, sets ceramics
The rod speed of rotation is 10rpm, and floating region stove Halogen lamp LED power output is 900-1050W/h, and the heating-up time is 0.5h, is passed through speed and is
2L/min oxygen/air, soaking time is 0.1-2.5h, and ZnO micron tubes are increasingly generated at the top of ceramic rod；
(5) set temperature fall time to be 0.3h, the micron tube of growth is cooled to room temperature.
Present invention process is clearly advantageous that compared with the prior art
(1) a kind of new method for growing rich acceptor type ZnO micron tubes is provided.Using optics gasification super-saturation precipitation method,
The intrinsic ZnO monocrystalline micron tube rich in acceptor is prepared first, passes through alternating temperature photoluminescence spectrum (accompanying drawing 2) and x-ray photoelectron
Power spectrum (accompanying drawing 3) confirms there is abundant acceptor in the micron tube, and new thinking is provided for p-type ZnO preparation.In addition, should
Micron tube has novel room temperature photoluminescence characteristic, i.e., occur stronger glow peak (accompanying drawing 4) at 392nm.
(2) it is raw material directly using ZnO ceramic rods, it is simple and quick pollution-free without substrate and catalyst.
(3) ZnO microns of pipe sizes are grown larger, length is up to 1cm, and diameter is up to 100 μm, and pattern is complete, interior
Outer wall surface is smooth, and with regular hexagonal section, crystalline quality is high.
Brief description of the drawings
Fig. 1 is the growth pictorial diagram of ZnO micron tubes of the present invention.
The alternating temperature luminescence generated by light spectrogram of Fig. 2 ZnO micron tubes of the present invention
X-ray photoelectron power spectrum (XPS) figure of Fig. 3 ZnO micron tubes of the present invention
Fig. 4 is Photoluminescence (PL) figure of ZnO micron tubes of the present invention.
Fig. 5 is X-ray diffraction (XRD) figure of ZnO micron tubes prepared by embodiment 1.
Fig. 6 a are single complete scan electron microscope (SEM) figure of ZnO micron tubes prepared by embodiment 1
Fig. 6 b are port cross-sectional SEM (SEM) figure of ZnO micron tubes prepared by embodiment 1
Fig. 6 c are port cross-sectional SEM (SEM) figure of ZnO micron tubes prepared by embodiment 1
Fig. 6 d are port cross-sectional SEM (SEM) figure of ZnO micron tubes prepared by embodiment 1
Fig. 6 e are tube wall SEM (SEM) figure of ZnO micron tubes prepared by embodiment 1
Embodiment
Embodiment 1：
(1) drying of ZnO powders ball milling, 200 mesh are sieved；
(2) obtained powder in (1) is fitted into strip rubber balloon and is compacted, closes, vacuumizing, in isostatic pressed
Thickness, the biscuit rod of dense uniform are made under (70MPa)；
(3) by obtained biscuit rod in (2), 700 DEG C of insulation 10h sintering obtain dense uniform in lifting whirl-sintering furnace
Ceramic rod；The a diameter of 0.8cm of ceramic rod；
It (4) will wear into coniform in (3) at the top of obtained ceramic rod, cone height is 0.7cm, is then tied to ceramic rod
Under the stove of optics floating region at swingle bracket, quartz ampoule is installed, regulation swingle makes ceramic rod be in halogen light focal zone,
It is 10rpm to set the ceramic rod speed of rotation, and floating region stove Halogen lamp LED power output is 975W/h, and the heating-up time is 0.5h, is passed through speed
Rate is 2L/min oxygen, and soaking time is 1.5h.
(5) set temperature fall time to be 0.3h, the micron tube of growth is cooled to room temperature.
ZnO micron tubes obtained by this example have carried out structured testing and morphology observation by the good SEM of XRD, see accompanying drawing 5-
6e, as seen from the figure, the more a height of pure phase ZnO of the micron tube crystalline quality, its pattern are complete, and inside and outside wall surface is smooth, with rule
Hexagonal cross-section, a diameter of 50-100 μm, length is 3-10mm, and wall thickness is 1-2 μm.
Embodiment 2：
Ceramic rod is tied under the stove of optics floating region at swingle bracket, quartz ampoule is installed, regulation swingle makes ceramic rod
In halogen light focal zone, it is 10rpm to set the ceramic rod speed of rotation, and floating region stove Halogen lamp LED power output is 900W/h,
Heating-up time is 0.5h, is passed through the oxygen that speed is 2L/min, soaking time is 1.5h, other be the same as Examples 1.Institute under the parameter
Grow micron tube pattern and crystal structure is similar to Example 1, as shown in Fig. 5-6e.
Embodiment 3：
Ceramic rod is tied under the stove of optics floating region at swingle bracket, quartz ampoule is installed, regulation swingle makes ceramic rod
In halogen light focal zone, it is 10rpm to set the ceramic rod speed of rotation, and floating region stove Halogen lamp LED power output is 1050W/h,
Heating-up time is 0.5h, is passed through the oxygen that speed is 2L/min, soaking time is 1.5h, other be the same as Examples 1.Institute under the parameter
Grow micron tube pattern and crystal structure is similar to Example 1, as shown in Fig. 5-6e.
Embodiment 4：
Ceramic rod is tied under the stove of optics floating region at swingle bracket, quartz ampoule is installed, regulation swingle makes ceramic rod
In halogen light focal zone, it is 10rpm to set the ceramic rod speed of rotation, and floating region stove Halogen lamp LED power output is 975W/h,
Heating-up time is 0.5h, is passed through the air that speed is 2L/min, soaking time is 2.5h, other be the same as Examples 1.Institute under the parameter
Grow micron tube pattern and crystal structure is similar to Example 1, as shown in Fig. 5-6e.
Embodiment 5：
Ceramic rod is tied under the stove of optics floating region at swingle bracket, quartz ampoule is installed, regulation swingle makes ceramic rod
In halogen light focal zone, it is 10rpm to set the ceramic rod speed of rotation, and floating region stove Halogen lamp LED power output is 900W/h,
Heating-up time is 0.5h, is passed through the oxygen that speed is 2L/min, soaking time is 0.5h, other be the same as Examples 1.Institute under the parameter
Grow micron tube pattern and crystal structure is similar to Example 1, as shown in Fig. 5-6e.
Embodiment 6：
Ceramic rod is tied under the stove of optics floating region at swingle bracket, quartz ampoule is installed, regulation swingle makes ceramic rod
In halogen light focal zone, it is 10rpm to set the ceramic rod speed of rotation, and floating region stove Halogen lamp LED power output is 1050W/h,
Heating-up time is 0.5h, is passed through the air that speed is 2L/min, soaking time is 1h, other be the same as Examples 1.The parameter is lower to give birth to
Long micron tube pattern and crystal structure are similar to Example 1, as shown in Fig. 5-6e.
Claims (1)
1. a kind of method for preparing rich acceptor type ZnO micron tubes, it is characterised in that comprise the following steps：
(1) 200 mesh sieves are crossed after ZnO powders ball milling is dried；
(2) powder crossed after 200 mesh sieves, which is fitted into strip rubber balloon, is compacted, closes, vacuumizing, and is made under 70MPa isostatic presseds
Into thickness, the biscuit rod of dense uniform；
(3) by biscuit rod, 700 DEG C of insulation 10h sintering obtain ceramic rod in lifting whirl-sintering furnace；The a diameter of 0.8- of ceramic rod
1cm；
It (4) will wear at the top of ceramic rod coniform, cone height is 0.5-1cm, and then ceramic rod is tied under the stove of optics floating region
At swingle bracket, quartz ampoule is installed, regulation swingle makes ceramic rod be in halogen light focal zone, sets ceramic rod to revolve
Rotational speed rate is 10rpm, and floating region stove Halogen lamp LED power output is 900-1050W/h, and the heating-up time is 0.5h, is passed through speed for 2L/
Min oxygen or air, soaking time is 0.1-2.5h, and ZnO micron tubes are increasingly generated at the top of ceramic rod；
(5) set temperature fall time to be 0.3h, the micron tube of growth is cooled to room temperature.
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| CN108286073A (en) * | 2018-01-17 | 2018-07-17 | 北京工业大学 | A kind of method of original position optics gas phase super-saturation precipitation method fast-growth ultra-thin-wall Zinc oxide single crystal micron tube |
| CN109626413B (en) * | 2019-01-15 | 2021-07-30 | 北京工业大学 | Method for preparing micro-nano structure by laser irradiation of ZnO micron tube and obtained material |
| CN111938236B (en) * | 2020-08-26 | 2022-09-06 | 北京石油化工学院 | Sterilizing mask and preparation method thereof |
| CN115321584B (en) * | 2022-07-21 | 2023-06-23 | 北京工业大学 | Preparation of beta-Ga 2 O 3 Method of micro-banding |
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