CN101319369A - Method of preparing type p ZnO nano-wire - Google Patents
Method of preparing type p ZnO nano-wire Download PDFInfo
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- CN101319369A CN101319369A CNA2008100110472A CN200810011047A CN101319369A CN 101319369 A CN101319369 A CN 101319369A CN A2008100110472 A CNA2008100110472 A CN A2008100110472A CN 200810011047 A CN200810011047 A CN 200810011047A CN 101319369 A CN101319369 A CN 101319369A
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Abstract
The invention relates to a method for preparing a p-type ZnO nano-wire, belonging to the semiconductor doping technical field. The invention relates to a doping technology for the p-type ZnO nano-wire, in particular to a doping technology by adoption of the chemical vapor deposition technology and utilization of arsenide as a p-type dopant of ZnO. The doping technology is characterized in that: the doping technology adopts the arsenide as a doping source of the p-type ZnO and utilizes the chemical vapor deposition technology to prepare the arsenic doped p-type ZnO nano-wire. Under the condition that the heating temperature is between 400 and 700 DEG C, the proportion of arsenic doped into the ZnO is controlled by adjusting the mol ratio of the arsenide and zinc, so as to perform growth of the p-type ZnO. The doping technology has the advantages that: the doping technology provides a simple and effective growth technology for preparing the p-tyype ZnO nano-wire with high quality and strong controllability, overcomes the defect of difficult doping of the p-type ZnO nano-wire, and further realizes a p-n junction photoelectric device of the ZnO nano-wire.
Description
Technical field
The present invention relates to the technology of preparing of p type ZnO nano wire, arsenic doping prepares the method for p type ZnO nano wire, belong to field of semiconductor materials, particularly a kind ofly adopt compound that chemical gaseous phase depositing process utilizes arsenic, carry out the preparation method of p type ZnO nano wire as doped source.
Background technology
ZnO is an another novel wide bandgap semiconductor materials after GaN, has the exciton bind energy higher than the GaN material, can realize relevant with exciton efficiently emission under the higher temperature even in room temperature.Compare with body material or thin-film material, the ZnO nano wire further increases exciton bind energy because it is limited on dimension, makes it have exciton emitting performance more efficiently.In order to realize the application of its photoelectric device, the doping of p type ZnO nano wire becomes present sixty-four dollar question, also becomes the forward position direction of ZnO investigation of materials simultaneously.
The impurity of P type ZnO is generally V group element, as nitrogen, phosphorus, arsenic etc.It is generally acknowledged that nitrogen is a shallow acceptor energy level in ZnO, but, since the ZnO nano wire the preparation method of normal employing be chemical gaseous phase depositing process, this method is a preparation ZnO nano wire under the pyritous condition, the solubleness of nitrogen is at high temperature very low, is difficult to realize mixing of nitrogen.Adopt the method for diffuse such as arsenic, phosphorus can to realize mixing of arsenic, but, also can cause ZnO nano wire degradation in the time of arsenic, phosphorous diffusion, thereby influence the later stage preparation of devices because this method is difficult to control and normally carries out after growth.
Chemical gaseous phase depositing process is to prepare the most frequently used method of ZnO nano wire, utilize this method can prepare the unadulterated n type ZnO nano wire that high quality is arranged, and the preparation of p type ZnO nano wire is the focus and the difficult point of research at present.
Summary of the invention
The objective of the invention is to overcome the problem that present p type ZnO nano wire is difficult to obtain, a kind of higher characteristic of compound vapour pressure of utilizing arsenic is provided, the compound of arsenic and zinc powder as the source material of vapour deposition, can be realized the preparation of the p type ZnO nano wire of arsenic doping at a certain temperature with the oxygen reaction.Because this method is based on and carries out under the thermal equilibrium, can obtain high-quality ZnO nano wire, this is for realizing that ZnOp-n based on this high quality p type ZnO nano wire optical diode device of binding up one's hair is very favourable.
Technical scheme of the present invention is:
The p type ZnO nano wire of arsenic doping of the present invention is based on chemical gas-phase deposition system.The step of preparation process of the p type ZnO nano wire of arsenic doping is as follows.
(1) powder of the compound of high-purity zinc powder and arsenic is carried out weighing by mass ratio 2/1～100/1 after, put into quartz crucible, together put into the silica tube of chemical gas-phase deposition system with the substrate that cleaned;
(2) with the pressure-controlling in the silica tube below 1000Pa, begin to be heated to a certain temperature spot in 400～700 ℃ of scopes.Aerating oxygen, its flow are 50-500ml/min, the growth of beginning nano wire;
(3) according to the required ZnO nanowire length control growing time, the speed of growth is 0.1～10 μ m/h;
(4) after growth is finished, close oxygen, close the substrate heater strip, slowly cool to below 100 ℃ and take out sample.
The compound of above-mentioned arsenic can adopt one or more compounds in the compound of arsenic of gallium arsenide or indium arsenide or the contour vapour pressure of arsenic zinc.
Substrate adopts sapphire, Si, GaAs, InP, CaF
2, quartzy, glass and metal substrate etc. all can.
The present invention can prepare the arsenic doping p type ZnO nano wire of different levels of doping by the molar content of the compound of adjusting zinc and arsenic.
Effect of the present invention and benefit provide a kind of preparation method of p type ZnO nano wire of simple arsenic doping, overcome the problem of p type ZnO nano wire preparation difficulty, and then can prepare p-n junction type ZnO nano wire photoelectric device.
Description of drawings
Fig. 1 is the synoptic diagram of inside deposition system in the chemical gas-phase deposition system that adopts of the present invention, and silica tube indirect heating cavity does not provide.
Among the figure: 1 is inlet mouth; 2 is silica tube; 3 is quartz crucible; 4 is evaporation source; 5 is substrate; 6 is bleeding point;
Fig. 2 is the X-ray diffraction pattern (XRD) of the p type ZnO nano wire of acquisition.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Growth diameter is about the p type ZnO nano-wire array of 100nm
(1) powder of high-purity zinc powder and gallium arsenide is carried out weighing by mass ratio 6/1 after, put into quartz crucible, together put into the silica tube of chemical gas-phase deposition system with the silicon substrate that cleaned.
(2) silica tube is evacuated to below the 1000Pa, when temperature was heated to 650 ℃, aerating oxygen, its flow were 100ml/min, the growth of beginning nano wire, and growth time is 30 minutes.
(3) after growth is finished, close oxygen, close heating power supply, slowly cool to below 100 ℃ and take out sample.
Utilize the present invention, prepared the p type ZnO nano wire that diameter is about 100nm.X-ray diffraction spectrum shows, have only ZnO (002) diffraction peak to occur, show that the As doped p type ZnO nano wire that the inventive method makes has good crystalline quality, vertical and the substrate growth of the ZnO nano wire that scanning electronic microscope prepares as can be seen, and density, diameter and length are even, its length is 1.5-2 μ m, and diameter is about 100nm.
Growth diameter is about the p type ZnO nano-wire array of 50nm
(1) powder of high-purity zinc powder and gallium arsenide is carried out weighing by mass ratio 6/1 after, put into quartz crucible, together put into the silica tube of chemical gas-phase deposition system with the substrate that cleaned.
(3) silica tube is evacuated to below the 1000Pa, when temperature was heated to 700 ℃, aerating oxygen, its flow were 300ml/min, the growth of beginning nano wire, and growth time is 30 minutes.
(3) after growth is finished, close oxygen, close heating power supply, slowly cool to below 100 ℃ and take out sample.
Utilize the present invention, prepared the p type ZnO nano wire that diameter is about 50nm.X-ray diffraction spectrum shows that the As doped p type ZnO nano wire that the inventive method makes has good crystalline quality, and ZnO nanowire density, diameter and length that scanning electronic microscope prepares as can be seen are even, and its length is 2-3 μ m, and diameter is about 50nm.
Present embodiment is identical substantially with the step of embodiment 2 with embodiment 1, and institute's difference is that process of growth adopts arsenic zinc and high-purity zinc powder as evaporation source, and other growth conditions is almost consistent.
Present embodiment is identical substantially with the step of embodiment 2 with embodiment 1, and institute's difference is that process of growth adopts indium arsenide and high-purity zinc powder as evaporation source, and other growth conditions is almost consistent.
Claims (3)
1. the preparation method of a p type ZnO nano wire is characterized in that step is as follows:
(1) powder of the compound of high-purity zinc powder and arsenic is carried out weighing by mass ratio 2/1～100/1 after, put into quartz crucible, together put into the silica tube of chemical gas-phase deposition system with the substrate that cleaned;
(2) with the pressure-controlling in the silica tube below 1000Pa, begin to be heated to a certain temperature spot in 400～700 ℃ of scopes.Aerating oxygen, its flow are 50-500ml/min, the growth of beginning nano wire;
(3) according to the required ZnO nanowire length control growing time, the speed of growth is 0.1～10 μ m/h;
(4) after growth is finished, close oxygen, close the substrate heater strip, slowly cool to below 100 ℃ and take out sample.
2. the preparation method of a kind of p type ZnO nano wire according to claim 1, it is characterized in that utilizing chemical vapour deposition technique, adopting the high-vapor-pressure compound of arsenic is doped source, and the compound of arsenic can be that one or more mixtures such as indium arsenide, gallium arsenide and arsenic zinc prepare arsenic doping p type ZnO nano wire.
3. the preparation method of a kind of p type ZnO nano wire according to claim 1 is characterized in that said substrate is Al
2O
3Or Si or GaAs or InP or CaF
2Or SiO
2Or glass or metal substrate.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985774A (en) * | 2010-11-09 | 2011-03-16 | 北京大学 | Method for synthesizing single crystal nano wire array |
| CN102212792A (en) * | 2011-06-15 | 2011-10-12 | 蚌埠玻璃工业设计研究院 | Method for preparing nitrogen-doped P-type zinc oxide film in one step by using nitrogen as doping source |
| CN102275978A (en) * | 2011-05-26 | 2011-12-14 | 长春理工大学 | Vapor phase deposition for autocatalytic growth of ZnO nano structure |
| CN102345110A (en) * | 2011-09-28 | 2012-02-08 | 长春理工大学 | Method for self-assembling growth of GaAs nano structure in MOCVD (Metal-Organic Chemical Vapor Deposition) manner |
| CN104986792A (en) * | 2015-06-13 | 2015-10-21 | 温州生物材料与工程研究所 | Method for preparing na-doped p-type zinc oxide nanowire with assistance of graphene |
| CN105551937A (en) * | 2015-12-18 | 2016-05-04 | 厦门大学 | Method for controlled growth of zinc oxide nano-structure on zinc oxide aluminum-doped conductive glass |
| CN106809869A (en) * | 2017-01-16 | 2017-06-09 | 华南师范大学 | A kind of preparation method of ZnO micro wires |
| CN107827144A (en) * | 2017-11-14 | 2018-03-23 | 大连智讯科技有限公司 | P-type doping zinc oxide nanometer rod preparation method |
| CN108251798A (en) * | 2018-01-15 | 2018-07-06 | 济南大学 | A kind of preparation method of overlength zinc oxide micrometer line |
| CN111348936A (en) * | 2018-12-21 | 2020-06-30 | 汉能新材料科技有限公司 | Crucible oxidation device and oxidation method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19907704A1 (en) * | 1999-02-23 | 2000-08-24 | Bayer Ag | Nano-scale precipitating zinc oxide used e.g. for protecting UV-sensitive organic polymers consists of particles having an average specified primary particle diameter |
| CN1239395C (en) * | 2002-01-22 | 2006-02-01 | 大连三科科技发展有限公司 | Process for preparing nano zinc oxide material |
| DE10212121A1 (en) * | 2002-03-15 | 2003-09-25 | Bayer Ag | Process for the preparation of nano-zinc oxide dispersions stabilized by hydroxyl-containing inorganic polymers |
| CN101045553A (en) * | 2007-04-06 | 2007-10-03 | 北京科技大学 | Preparation method of tin mixed with zinc oxide nanowire |
| CN101070614A (en) * | 2007-05-30 | 2007-11-14 | 北京科技大学 | Single-crystal zinc-oxide nano column array and preparing method |
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2008
- 2008-04-15 CN CN2008100110472A patent/CN101319369B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985774A (en) * | 2010-11-09 | 2011-03-16 | 北京大学 | Method for synthesizing single crystal nano wire array |
| CN102275978A (en) * | 2011-05-26 | 2011-12-14 | 长春理工大学 | Vapor phase deposition for autocatalytic growth of ZnO nano structure |
| CN102212792A (en) * | 2011-06-15 | 2011-10-12 | 蚌埠玻璃工业设计研究院 | Method for preparing nitrogen-doped P-type zinc oxide film in one step by using nitrogen as doping source |
| CN102345110A (en) * | 2011-09-28 | 2012-02-08 | 长春理工大学 | Method for self-assembling growth of GaAs nano structure in MOCVD (Metal-Organic Chemical Vapor Deposition) manner |
| CN104986792A (en) * | 2015-06-13 | 2015-10-21 | 温州生物材料与工程研究所 | Method for preparing na-doped p-type zinc oxide nanowire with assistance of graphene |
| CN105551937A (en) * | 2015-12-18 | 2016-05-04 | 厦门大学 | Method for controlled growth of zinc oxide nano-structure on zinc oxide aluminum-doped conductive glass |
| CN105551937B (en) * | 2015-12-18 | 2018-07-31 | 厦门大学 | The method of controllable growth nano structure of zinc oxide on doped zinc oxide aluminium electro-conductive glass |
| CN106809869A (en) * | 2017-01-16 | 2017-06-09 | 华南师范大学 | A kind of preparation method of ZnO micro wires |
| CN107827144A (en) * | 2017-11-14 | 2018-03-23 | 大连智讯科技有限公司 | P-type doping zinc oxide nanometer rod preparation method |
| CN108251798A (en) * | 2018-01-15 | 2018-07-06 | 济南大学 | A kind of preparation method of overlength zinc oxide micrometer line |
| CN111348936A (en) * | 2018-12-21 | 2020-06-30 | 汉能新材料科技有限公司 | Crucible oxidation device and oxidation method |
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| CN101319369B (en) | 2011-06-22 |
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