CN105858715A - Preparation method of rich acceptor type ZnO microtube - Google Patents
Preparation method of rich acceptor type ZnO microtube Download PDFInfo
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- CN105858715A CN105858715A CN201610366213.5A CN201610366213A CN105858715A CN 105858715 A CN105858715 A CN 105858715A CN 201610366213 A CN201610366213 A CN 201610366213A CN 105858715 A CN105858715 A CN 105858715A
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- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
- C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The invention relates to the technical field of semiconductor materials and optics, and provides a preparation method of a rich acceptor type ZnO microtube. The method comprises the steps that ZnO powder is used as a raw material, subjected to ball milling, dried and sieved through a 200-mesh sieve; the powder is placed into a long strip-shaped rubber balloon, compacted, closed, vacuumized and pressed into a biscuit bar with uniform thickness and density under isostatic pressure; the bar is placed into a pulling rotation sintering furnace to be sintered into a ceramic bar; the ceramic bar is placed into an optical floating region furnace, the output power of a floating region furnace halogen lamp is set to be 900-1050 W/h, oxygen/air is introduced in, heat is preserved for a certain period of time, the rich acceptor type ZnO microtube is prepared through the optical gasification supersaturated precipitation growing process, the acceptor state is long-acting and stable, and a new thought is provided for preparation of a p type ZnO material; meanwhile, the microtube is large in size and complete in morphology, has the regular hexagonal section, and has the novel room temperature photoluminescence characteristic.
Description
Technical field
The present invention relates to semi-conducting material and optical technical field, particularly relate to synthesize one and prepare rich acceptor
The method of type ZnO micron tube.
Background technology
ZnO, as third generation semi-conducting material, has huge application prospect at photoelectric field, but to realize
Large-scale application, also deposits huge obstacle.Under natural conditions, ZnO presents intrinsic/n-type conduction, the most
Successfully prepare high-quality N-shaped ZnO, but the acquisition of high-quality Stable Type p ZnO is the master of this area
Want one of difficult problem.Acceptor state instability is to cause the main cause of p-type ZnO preparation difficulty.Only surely
Fixed intrinsic is rich could preferably be suppressed its self-compensation mechanism by carrying out p-type doping on principal mode ZnO, makes to mix
The recipient element entered really plays increases the effect in hole, thus realizes the p-type electric-conducting of ZnO stability and high efficiency.
Therefore, we have proposed employing optics gasification super-saturation precipitation method growth rich by principal mode ZnO monocrystalline micron tube,
Preparing the stable ZnO monocrystalline rich in acceptor is the base realizing other intrinsics/doped p type ZnO material
Plinth.In recent years, the preparation method of ZnO micron tube is concentrated mainly on Vapor Transport, hydro-thermal method, microwave
Heating etc., wherein Vapor Transport (X.Xu, C.Xu, J.Dai, J.Pan, J.Hu.J.Phys.Chem.
Solids.2012,73:858-862.) it is the most universal method, but desired reaction temperature is higher, needs
Consume a large amount of gas, relatively costly；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
Requiring higher to acid-base value, temperature, temperature retention time, grown micron tube size is less；Microwave heating method (J.
Cheng, R.Guo, Q.M.Wang..Appl.Phys.Lett.2004,85:5140-5142.) initial feed is
The block ZnO pottery of hollow structure, technique is complex.Additionally, it has been reported that intrinsic micron tube equal
For mentioning that intrinsic richness is had no report by the preparation of principal mode ZnO micron tube for rich in by principal mode ZnO material.
Summary of the invention
It is an object of the invention to critical bottleneck problem---being subject to of efficient stable for restriction ZnO development at present
Main state, it is proposed that a kind of high-quality richness of preparing, by the method for principal mode ZnO micron tube, overcomes existing micron simultaneously
The problems such as pipe technology of preparing is loaded down with trivial details, and size is less.
The know-why of optics proposed by the invention gasification super-saturation precipitation method is: ZnO is more than 1500 DEG C
Can be decomposed into zinc fume and oxygen steam, in very short time, high temperature zinc steam and oxygen expand with near adiabatic
Mode spread rapidly, in uniform temperature field, zinc fume pressure is gradually increased to saturated.When zinc fume divides
When pressure increases further, due to dissolubility supersaturation, environment there will be a large amount of zinc atom surplus and divide with oxygen
Son reacts, and in nucleation district deposition and progressively grows.Using photon as energy carrier, under oxygen enriched environment,
Separate out based on uniform temperature gas phase supersaturation, effectively lower Zinc vacancies and combine energy, it is achieved ZnO richness acceptor is steady
Stationary state；Required condition is supersaturation zinc fume pressure；Oxygen enriched environment；Uniform temperature field and temperature control accurately
System.In conjunction with the feature of optics floating region stove grower, the rich acceptor's ZnO monocrystalline micron tube of preparation.
The present invention is achieved by the following scheme
A kind of richness is by the preparation method of principal mode ZnO micron tube, it is characterised in that comprise the following steps:
(1) 200 mesh sieves are crossed after being dried by ZnO powder ball milling；
(2) cross the powder after 200 mesh sieves load in strip rubber balloon be compacted, close, evacuation,
The biscuit rod of thickness, dense uniform is made under 70MPa isostatic pressed；
(3) biscuit rod 700 DEG C of insulation 10h sintering in lifting whirl-sintering furnace are obtained ceramic rod；Pottery
The porcelain a diameter of 0.8-1cm of rod；
(4) wearing into coniform by ceramic rod top, cone height is 0.5-1cm, is then tied up by ceramic rod
Under the stove of optics floating region at swingle bracket, installing quartz ampoule, regulation swingle makes ceramic rod be in halogen
Light focusing region, arranging the ceramic rod speed of rotation is 10rpm, and floating region stove Halogen light output is
900-1050W/h, the heating-up time is 0.5h, is passed through the oxygen/air that speed is 2L/min, during insulation
Between be 0.1-2.5h, increasingly generate ZnO micron tube at ceramic rod top；
(5) arranging temperature fall time is 0.3h, and the micron tube of growth is cooled to room temperature.
Being clearly advantageous that of present invention process compared with the prior art
(1) provide and a kind of grow the rich new method by principal mode ZnO micron tube.Utilize optics gasification satiety
And deposition method, prepare the intrinsic ZnO monocrystalline micron tube rich in acceptor first, by alternating temperature photoluminescence spectrum
(accompanying drawing 2) and x-ray photoelectron power spectrum (accompanying drawing 3) have abundant acceptor in confirming this micron tube,
Preparation for p-type ZnO provides new thinking.Additionally, this micron tube has the room temperature photoluminescence of novelty
Characteristic, i.e. occurs stronger glow peak (accompanying drawing 4) at 392nm.
(2) directly utilizing ZnO ceramic rod is raw material, it is not necessary to substrate and catalyst, simple and quick pollution-free.
(3) grown ZnO micron tube size is relatively big, length up to 1cm, diameter up to 100 μm, and
Pattern is complete, inside and outside wall smooth surface, has regular hexagonal cross section, and crystalline quality is high.
Accompanying drawing explanation
Fig. 1 is the growth pictorial diagram of ZnO micron tube of the present invention.
The alternating temperature luminescence generated by light spectrogram of Fig. 2 ZnO of the present invention micron tube
X-ray photoelectron power spectrum (XPS) figure of Fig. 3 ZnO of the present invention micron tube
Fig. 4 is Photoluminescence (PL) figure of ZnO micron tube of the present invention.
Fig. 5 is X-ray diffraction (XRD) figure of the ZnO micron tube of embodiment 1 preparation.
Fig. 6 a is single complete scan ultramicroscope (SEM) figure of the ZnO micron tube of embodiment 1 preparation
Fig. 6 b is port cross-sectional scanning electron microscope (SEM) figure of the ZnO micron tube of embodiment 1 preparation
Fig. 6 c is port cross-sectional scanning electron microscope (SEM) figure of the ZnO micron tube of embodiment 1 preparation
Fig. 6 d is port cross-sectional scanning electron microscope (SEM) figure of the ZnO micron tube of embodiment 1 preparation
Fig. 6 e is tube wall scanning electron microscope (SEM) figure of the ZnO micron tube of embodiment 1 preparation
Detailed description of the invention
Embodiment 1:
(1) dried by ZnO powder ball milling, 200 mesh sieve；
(2) powder prepared in (1) is loaded in strip rubber balloon be compacted, close, evacuation,
The biscuit rod of thickness, dense uniform is made under isostatic pressed (70MPa)；
(3) biscuit rod prepared in (2) 700 DEG C of insulation 10h in lifting whirl-sintering furnace are sintered
Ceramic rod to dense uniform；The a diameter of 0.8cm of ceramic rod；
(4) wearing into coniform by the ceramic rod top prepared in (3), cone height is 0.7cm, then
Being tied to by ceramic rod under the stove of optics floating region at swingle bracket, install quartz ampoule, regulation swingle makes pottery
Rod is in halogen light focal zone, and arranging the ceramic rod speed of rotation is 10rpm, and floating region stove Halogen light exports
Power is 975W/h, and the heating-up time is 0.5h, is passed through the oxygen that speed is 2L/min, and temperature retention time is
1.5h。
(5) arranging temperature fall time is 0.3h, and the micron tube of growth is cooled to room temperature.
ZnO micron tube obtained by this example has carried out structured testing and morphology observation by the good SEM of XRD,
Seeing accompanying drawing 5-6e, as seen from the figure, more a height of pure phase ZnO of this micron tube crystalline quality, its pattern is complete, interior
Outer wall surface is smooth, has regular hexagonal cross section, a diameter of 50-100 μm, a length of 3-10mm, wall
Thickness is 1-2 μm.
Embodiment 2:
Being tied to by ceramic rod under the stove of optics floating region at swingle bracket, install quartz ampoule, regulation swingle makes
Ceramic rod is in halogen light focal zone, and arranging the ceramic rod speed of rotation is 10rpm, floating region stove Halogen light
Output is 900W/h, and the heating-up time is 0.5h, is passed through the oxygen that speed is 2L/min, during insulation
Between be 1.5h, other are with embodiment 1.Lower the grown micron tube pattern of this parameter and crystal structure and enforcement
Example 1 is similar to, as shown in Fig. 5-6e.
Embodiment 3:
Being tied to by ceramic rod under the stove of optics floating region at swingle bracket, install quartz ampoule, regulation swingle makes
Ceramic rod is in halogen light focal zone, and arranging the ceramic rod speed of rotation is 10rpm, floating region stove Halogen light
Output is 1050W/h, and the heating-up time is 0.5h, is passed through the oxygen that speed is 2L/min, during insulation
Between be 1.5h, other are with embodiment 1.Lower the grown micron tube pattern of this parameter and crystal structure and enforcement
Example 1 is similar to, as shown in Fig. 5-6e.
Embodiment 4:
Being tied to by ceramic rod under the stove of optics floating region at swingle bracket, install quartz ampoule, regulation swingle makes
Ceramic rod is in halogen light focal zone, and arranging the ceramic rod speed of rotation is 10rpm, floating region stove Halogen light
Output is 975W/h, and the heating-up time is 0.5h, is passed through the air that speed is 2L/min, during insulation
Between be 2.5h, other are with embodiment 1.Lower the grown micron tube pattern of this parameter and crystal structure and enforcement
Example 1 is similar to, as shown in Fig. 5-6e.
Embodiment 5:
Being tied to by ceramic rod under the stove of optics floating region at swingle bracket, install quartz ampoule, regulation swingle makes
Ceramic rod is in halogen light focal zone, and arranging the ceramic rod speed of rotation is 10rpm, floating region stove Halogen light
Output is 900W/h, and the heating-up time is 0.5h, is passed through the oxygen that speed is 2L/min, during insulation
Between be 0.5h, other are with embodiment 1.Lower the grown micron tube pattern of this parameter and crystal structure and enforcement
Example 1 is similar to, as shown in Fig. 5-6e.
Embodiment 6:
Being tied to by ceramic rod under the stove of optics floating region at swingle bracket, install quartz ampoule, regulation swingle makes
Ceramic rod is in halogen light focal zone, and arranging the ceramic rod speed of rotation is 10rpm, floating region stove Halogen light
Output is 1050W/h, and the heating-up time is 0.5h, is passed through the air that speed is 2L/min, during insulation
Between be 1h, other are with embodiment 1.Lower the grown micron tube pattern of this parameter and crystal structure and embodiment
1 is similar to, as shown in Fig. 5-6e.
Claims (1)
1. prepare the rich method by principal mode ZnO micron tube for one kind, it is characterised in that comprise the following steps:
(1) 200 mesh sieves are crossed after being dried by ZnO powder ball milling；
(2) cross the powder after 200 mesh sieves load in strip rubber balloon be compacted, close, evacuation,
The biscuit rod of thickness, dense uniform is made under 70MPa isostatic pressed；
(3) biscuit rod 700 DEG C of insulation 10h sintering in lifting whirl-sintering furnace are obtained ceramic rod；
The a diameter of 0.8-1cm of ceramic rod；
(4) wearing into coniform by ceramic rod top, cone height is 0.5-1cm, then by ceramic rod
Being tied under the stove of optics floating region at swingle bracket, install quartz ampoule, regulation swingle makes at ceramic rod
In halogen light focal zone, arranging the ceramic rod speed of rotation is 10rpm, and floating region stove Halogen light exports
Power is 900-1050W/h, and the heating-up time is 0.5h, is passed through the oxygen/air that speed is 2L/min,
Temperature retention time is 0.1-2.5h, increasingly generates ZnO micron tube at ceramic rod top；
(5) arranging temperature fall time is 0.3h, and the micron tube of growth is cooled to room temperature.
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| CN201610366213.5A CN105858715B (en) | 2016-05-28 | 2016-05-28 | A kind of method for preparing rich acceptor type ZnO micron tubes |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109626413A (en) * | 2019-01-15 | 2019-04-16 | 北京工业大学 | Laser irradiation ZnO micron tube prepares the method and resulting materials of micro-nano structure |
| CN111938236A (en) * | 2020-08-26 | 2020-11-17 | 北京石油化工学院 | Sterilizing mask and preparation method thereof |
| CN115321584A (en) * | 2022-07-21 | 2022-11-11 | 北京工业大学 | Preparation of beta-Ga 2 O 3 Method of making micro-tape |
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| CN101654806A (en) * | 2009-09-11 | 2010-02-24 | 云南冶金集团总公司技术中心 | Method for preparing crystal whisker of zinc oxide in large size |
| CN104313690A (en) * | 2014-10-10 | 2015-01-28 | 北京工业大学 | Method for growing GZO(ZnO: Ga) crystals |
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2016
- 2016-05-28 CN CN201610366213.5A patent/CN105858715B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654806A (en) * | 2009-09-11 | 2010-02-24 | 云南冶金集团总公司技术中心 | Method for preparing crystal whisker of zinc oxide in large size |
| CN104313690A (en) * | 2014-10-10 | 2015-01-28 | 北京工业大学 | Method for growing GZO(ZnO: Ga) crystals |
Non-Patent Citations (1)
| Title |
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| 郭星原: ""ZnO晶须和TiO2单晶的浮区法生长及其光谱研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109626413A (en) * | 2019-01-15 | 2019-04-16 | 北京工业大学 | Laser irradiation ZnO micron tube prepares the method and resulting materials of micro-nano structure |
| CN111938236A (en) * | 2020-08-26 | 2020-11-17 | 北京石油化工学院 | Sterilizing mask and preparation method thereof |
| CN111938236B (en) * | 2020-08-26 | 2022-09-06 | 北京石油化工学院 | Sterilizing mask and preparation method thereof |
| CN115321584A (en) * | 2022-07-21 | 2022-11-11 | 北京工业大学 | Preparation of beta-Ga 2 O 3 Method of making micro-tape |
| 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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