CN102185049B - Preparation method of ZnO-based light-emitting device - Google Patents
Preparation method of ZnO-based light-emitting device Download PDFInfo
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- CN102185049B CN102185049B CN2011101016018A CN201110101601A CN102185049B CN 102185049 B CN102185049 B CN 102185049B CN 2011101016018 A CN2011101016018 A CN 2011101016018A CN 201110101601 A CN201110101601 A CN 201110101601A CN 102185049 B CN102185049 B CN 102185049B
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Abstract
The invention discloses a preparation method of a ZnO-based light-emitting device. The light-emitting device is provided with a substrate, an n-type ZnO layer, a ZnO-based light-emitting layer and a p-type ZnO layer in sequence from bottom to top, wherein the n-type ZnO layer and the ZnO-based light-emitting layer are prepared by adopting a plasma enhanced molecular beam epitaxial method, and the p-type ZnO layer is prepared by adopting a laser enhanced molecular beam epitaxial method. Since the material of the whole ZnO-based light-emitting device grows in situ in same equipment, the possible contamination is reduced. Except the p-type ZnO layer, the structures of all the layers are prepared by adopting the plasma enhanced molecular beam epitaxial method, therefore the crystal quality and the interface smoothness are effectively guaranteed, the defect density is reduced, and the light emitting efficiency of the ZnO-based light-emitting device can be improved. The p-type ZnO layer is prepared by adopting the laser enhanced molecular beam epitaxial method, the unbalanced process effectively improves the p-type doping efficiency, and is beneficial to the obtainment of a stable and reliable p-type ZnO layer with high cavity concentration.
Description
Technical field
The present invention relates to a kind of method for preparing the zno-based luminescent device, belong to technical field of semiconductor luminescence.
Background technology
As a kind of novel direct wide bandgap semiconductor materials, ZnO has huge application potential in transparency conductive electrode, indigo plant/UV LED (LED) and fields such as laser (LD), ultraviolet detector, spin electric device and transducer.Common zno-based luminescent device has substrate, n type ZnO layer, zno-based luminescent layer and p type ZnO layer from bottom to top successively.The preparation method who adopts has magnetron sputtering, pulsed laser deposition, metal organic chemical vapor deposition and molecular beam epitaxy.Wherein, the zno-based luminescent device of magnetron sputtering and pulsed laser deposition preparation, because the crystal mass of each layer film is relatively poor relatively, evenness is not enough, has seriously restricted the luminous efficiency of device; Metal organic chemical vapor deposition needs to adopt high-purity organic source, and because of lacking the organic source of business-like high-purity N a at present, its application is restricted; Though molecular beam epitaxy is realized the ZnO film of high-crystal quality, high surface smoothness easily, carrying out there is deficiency aspect the doping of the efficient p type of ZnO.Therefore, press for a kind of new zno-based luminescent device preparation method of development.
Summary of the invention
The objective of the invention is deficiency, a kind of method for preparing the zno-based luminescent device is provided to prior art.
The preparation method of zno-based luminescent device of the present invention, this luminescent device has substrate, n type ZnO layer, zno-based luminescent layer and p type ZnO layer from bottom to top successively, and its preparation method may further comprise the steps:
1) cleaned substrate is put into molecular beam epitaxial device, underlayer temperature is heated to 300～800 ℃, and regulating growth room's pressure is 1 * 10
-5～6 * 10
-5Torr is with the pure O through rf active
2Be the O source, the Metal Zn source is a reaction source, and metal Ga source is a n type doped source, growing n type ZnO layer on substrate;
2) have on the substrate of n type ZnO layer in growth, with pure O through rf active
2Be the O source, Metal Zn source and metal M g source are reaction source, and under 300～800 ℃ of temperature, the ZnMgO/ZnO multiple quantum well layer in 4-10 cycle of growth is as the zno-based luminescent layer;
3) adopting frequency is that 1～5Hz, energy are the ZnO ceramic target that Na is mixed in the laser bombardment of 200～400mJ, and wherein the Na molar content is 0.5～1%, growing P-type ZnO layer under 400～700 ℃ of temperature.
Above-mentioned substrate can be ZnO body monocrystalline or sapphire or SiC.
In the preparation process, the thickness of n type ZnO layer, zno-based luminescent layer and p type ZnO layer is determined by growth time.
Beneficial effect of the present invention is:
Whole zno-based luminescent device material growth in situ in same equipment reduces possible contamination.Each layer structure except that p type ZnO layer adopts plasma to strengthen the molecular beam epitaxial method preparation, effectively guaranteed crystal mass and interface planarization, reduces defect concentration, helps improving the luminous efficiency of zno-based luminescent device.P type ZnO layer adopts the preparation of laser-enhanced molecular beam epitaxial method, and this nonequilibrium process will effectively improve p type doping efficiency, help obtaining the reliable p type of high hole steady concentration ZnO layer.
Description of drawings
Fig. 1 is a zno-based luminescent device structural representation.
Among the figure: 1 is that substrate, 2 is that n type ZnO layer, 3 is that zno-based luminescent layer, 4 is p type ZnO layer.
Embodiment
Embodiment 1
1) ZnO body single crystalline substrate is carried out putting into molecular beam epitaxial device after the clean, underlayer temperature is heated to 800 ℃, and regulating growth room's pressure is 1 * 10
-5Torr is with the pure O through rf active
2(purity 99.9999%) is the O source, activation O
2Radio-frequency power be 400W, the Metal Zn source is a reaction source, metal Ga source is a n type doped source, growth thickness is the n type ZnO layer of 350 nanometers on ZnO body monocrystalline;
2) have on the zno-based sheet of n type ZnO layer in growth, with pure O through rf active
2(purity 99.9999%) is the O source, activation O
2Radio-frequency power be 400W, Metal Zn source and metal M g source are reaction source, under 600 ℃ of temperature, the ZnMgO/ZnO multiple quantum well layer that grow 10 cycles, thickness are 200 nanometers is as the zno-based luminescent layer;
3) use frequency to mix the ZnO ceramic target of Na as 5Hz, energy as the laser bombardment of 200mJ, wherein the Na molar content is 0.5%, at 600 ℃ of following growth thickness p type ZnO layer that is 500 nanometers.
Embodiment 2
1) Sapphire Substrate is carried out putting into molecular beam epitaxial device after the clean, underlayer temperature is heated to 500 ℃, and regulating growth room's pressure is 3 * 10
-5Torr is with the pure O through rf active
2(purity 99.9999%) is the O source, activation O
2Radio-frequency power be 350W, the Metal Zn source is a reaction source, metal Ga source is a n type doped source, growth thickness is the n type ZnO layer of 500 nanometers on sapphire;
2) have on the sapphire substrate of n type ZnO layer in growth, with pure O through rf active
2(purity 99.9999%) is the O source, activation O
2Radio-frequency power be 350W, Metal Zn source and metal M g source are reaction source, under 800 ℃ of temperature, the ZnMgO/ZnO multiple quantum well layer that grow 6 cycles, thickness are 120 nanometers is as the zno-based luminescent layer;
3) use frequency to mix the ZnO ceramic target of Na as 3Hz, energy as the laser bombardment of 300mJ, wherein the Na molar content is 0.8%, at 700 ℃ of following growth thickness p type ZnO layer that is 350 nanometers.
Embodiment 3
1) the SiC substrate is carried out putting into molecular beam epitaxial device after the clean, underlayer temperature is heated to 300 ℃, and regulating growth room's pressure is 6 * 10
-5Torr is with the pure O through rf active
2(purity 99.9999%) is the O source, activation O
2Radio-frequency power be 250W, the Metal Zn source is a reaction source, metal Ga source is a n type doped source, growth thickness is the n type ZnO layer of 200 nanometers on ZnO body monocrystalline;
2) have on the SiC substrate of n type ZnO layer in growth, with pure O through rf active
2(purity 99.9999%) is the O source, activation O
2Radio-frequency power be 250W, Metal Zn source and metal M g source are reaction source, under 300 ℃ of temperature, the ZnMgO/ZnO multiple quantum well layer that grow 4 cycles, thickness are 80 nanometers is as the zno-based luminescent layer;
3) use frequency to mix the ZnO ceramic target of Na as 1Hz, energy as the laser bombardment of 400mJ, wherein the Na molar content is 1%, at 400 ℃ of following growth thickness p type ZnO layer that is 200 nanometers.
Claims (2)
1.ZnO the preparation method of base luminescent device, this luminescent device has substrate, n type ZnO layer, zno-based luminescent layer and p type ZnO layer from bottom to top successively, and its preparation method may further comprise the steps:
1) cleaned substrate is put into molecular beam epitaxial device, underlayer temperature is heated to 300～800 ℃, and regulating growth room's pressure is 1 * 10
-5～6 * 10
-5Torr is with the pure O through rf active
2Be the O source, the Metal Zn source is a reaction source, and metal Ga source is a n type doped source, growing n type ZnO layer on substrate;
2) have on the substrate of n type ZnO layer in growth, with pure O through rf active
2Be the O source, Metal Zn source and metal M g source are reaction source, and under 300～800 ℃ of temperature, the ZnMgO/ZnO multiple quantum well layer in 4-10 cycle of growth is as the zno-based luminescent layer;
3) adopting frequency is that 1～5Hz, energy are the ZnO ceramic target that Na is mixed in the laser bombardment of 200～400mJ, and wherein the Na molar content is 0.5～1%, growing P-type ZnO layer under 400～700 ℃ of temperature.
2. the preparation method of zno-based luminescent device according to claim 1 is characterized in that said substrate is ZnO body monocrystalline or sapphire or SiC.
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| CN2011101016018A CN102185049B (en) | 2011-04-22 | 2011-04-22 | Preparation method of ZnO-based light-emitting device |
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| CN102185049B true CN102185049B (en) | 2012-11-07 |
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| CN102373425B (en) * | 2011-11-03 | 2013-04-24 | 浙江大学 | Method for preparing Na-doped p-type NnO film |
| CN102534767B (en) * | 2011-12-29 | 2014-06-18 | 浙江大学 | Na-mixing method for growing p-type ZnO single crystal film |
| CN105742190A (en) * | 2016-05-09 | 2016-07-06 | 常州工学院 | Preparation method of ZnO-based asymmetric quantum well tunneling homogeneous p-n diode |
| CN110444644B (en) * | 2019-07-26 | 2022-10-14 | 浙江大学 | Device for enhancing silicon-based erbium-doped ZnO thin film electroluminescence and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6525345B1 (en) * | 1998-08-17 | 2003-02-25 | Murata Manufacturing Co., Ltd. | Semiconductor photonic device |
| CN1945867A (en) * | 2006-11-02 | 2007-04-11 | 浙江大学 | ZnO base LED and its preparing method |
| CN1953284A (en) * | 2006-11-14 | 2007-04-25 | 浙江大学 | A ZnO-based quantum dot laser diode and its manufacture method |
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| JP2004022625A (en) * | 2002-06-13 | 2004-01-22 | Murata Mfg Co Ltd | Manufacturing method of semiconductor device and its manufacturing method |
| TW200409378A (en) * | 2002-11-25 | 2004-06-01 | Super Nova Optoelectronics Corp | GaN-based light-emitting diode and the manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6525345B1 (en) * | 1998-08-17 | 2003-02-25 | Murata Manufacturing Co., Ltd. | Semiconductor photonic device |
| CN1945867A (en) * | 2006-11-02 | 2007-04-11 | 浙江大学 | ZnO base LED and its preparing method |
| CN1953284A (en) * | 2006-11-14 | 2007-04-25 | 浙江大学 | A ZnO-based quantum dot laser diode and its manufacture method |
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Application publication date: 20110914 Assignee: HANGZHOU SILAN AZURE Co.,Ltd. Assignor: Zhejiang University Contract record no.: 2016330000058 Denomination of invention: Preparation method of ZnO-based light-emitting device Granted publication date: 20121107 License type: Common License Record date: 20160330 |
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