CN104810434A - White-light light emitting diode and preparation method thereof - Google Patents
White-light light emitting diode and preparation method thereof Download PDFInfo
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- CN104810434A CN104810434A CN201510069811.1A CN201510069811A CN104810434A CN 104810434 A CN104810434 A CN 104810434A CN 201510069811 A CN201510069811 A CN 201510069811A CN 104810434 A CN104810434 A CN 104810434A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 85
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 12
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- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052738 indium Inorganic materials 0.000 claims description 9
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- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- GPYPVKIFOKLUGD-UHFFFAOYSA-N gold indium Chemical compound [In].[Au] GPYPVKIFOKLUGD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 238000004020 luminiscence type Methods 0.000 claims description 5
- 229910052594 sapphire Inorganic materials 0.000 claims description 5
- 239000010980 sapphire Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 229910052787 antimony Inorganic materials 0.000 abstract 3
- 239000004065 semiconductor Substances 0.000 description 21
- 229960001296 zinc oxide Drugs 0.000 description 21
- 239000011787 zinc oxide Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 18
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
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- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
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- 239000003708 ampul Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
- H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
- H01L33/40—Materials therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0016—Processes relating to electrodes
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Led Devices (AREA)
Abstract
The invention discloses a white-light light emitting diode. The white-light light emitting diode is characterized by comprising an n-type gallium nitride film, an antimony doped p-type zinc oxide nanowire array and a positive electrode which are sequentially stacked from the bottom up, wherein the n-type gallium nitride film is contacted with the antimony doped p-type zinc oxide nanowire array to form a heterojunction so as to act as a white-light light emitting layer, the positive electrode is contacted with the antimony doped p-type zinc oxide nanowire array so as to act as a working positive electrode, the n-type gallium nitride film is provided with a negative electrode thereon, and the negative electrode is contacted with the n-type gallium nitride film so as to act as a working negative electrode. The invention further discloses a preparation method of the white-light light emitting diode. Compared with a traditional white-light light emitting diode device, the white-light light emitting diode is simple in process, provided with low color temperature, free of ultraviolet rays, high in safety and suitable for life lighting, and plays an important role in pushing household lighting applications of the white-light light emitting diode in China.
Description
Technical field
The invention belongs to technical field of semiconductor illumination, be specifically related to a kind of white light emitting diode and preparation method thereof.
Technical background
Semiconductor lighting is one of high-tech sector most with prospects in this century, white light LEDs will become the light source forth generation electric light source of new generation of 21 century, compared to high energy consumption, the incandescent lamp that electric light transformation efficiency is low, containing toxic wastes such as mercury, life-span is shorter, stroboscopic, ultraviolet and infrared radiation and the relatively low fluorescent lamp of color rendering index, white light LEDs has low-voltage, low energy consumption, long-life, high reliability, vibration resistance and the advantage such as shock resistance and easy care, meet the energy-conservation requirement with environmental protection of Green Lighting Project, it is noticeable green light source, generally believe at present to become alternative incandescent lamp, the novel solid light source of fluorescent lamp, there is wide market and potential illumination application prospect.
The basic structure of LED is one block of electroluminescent semi-conducting material, the wafer that the core of light-emitting diode is made up of p-type semiconductor and n-type semiconductor, has a transition zone, be called p-n junction between p-type semiconductor and n-type semiconductor.In the p-n junction of some semi-conducting material, the minority carrier of injection and majority carrier compound tense can discharge unnecessary energy in the form of light, thus electric energy is directly converted to luminous energy.
At present, the technological approaches realizing white light LEDs mainly contains three kinds: the method that (1) InGaN blue chip adds YAG (yttrium-aluminium-garnet) fluorescent material makes white light LEDs.As in US Patent No. 6, in 685,852 B2, the blue-light excited YAG yellow fluorescent powder that this white light LEDs mainly uses blue-ray LED to produce produces gold-tinted, complementary and produce white light with original blue light for exciting.The making of this kind of combination is simple and easy, and in all various white light LED combination, cost is minimum and efficiency better, the white light LEDs occuping market leading position that this method makes.(2) red, green, blue three kinds of LED combination are used to make white light LEDs.As in US Patent No. 5,952, in 681, utilize three look crystal grain to be directly packaged into white light-emitting diodes, this method is the earliest for making the mode of white light, its advantage does not need the conversion through fluorescent material, can avoid obtaining preferably luminous efficiency because of the loss of fluorescent material conversion, meanwhile, separately can control the luminous intensity of Tricolor LED, reach full-color color changeable effect (variable color-temperature), and preferably color rendering can be obtained by the selection of crystal grain wavelength and intensity.(3) combination of ultraviolet LED and RGB fluorescent material.As at document " White-light emission near UV InGaN – GaN LED chip precoatedwith blue/green/red phosphors " (Sheu, J.K.et al.Photonics technology letters.15,18-20), this white light LEDs utilization has more high-octane UV photons and excites RGB fluorescent material three look to be directly made into the mode of white light.This LED mode is identical with the first LED, and cost is close, but because all white lights all come from fluorescent material itself, ultraviolet light itself has neither part nor lot in mixed light, and therefore the control of color is much easier compared with the first LED, and color uniformity is better.
Above three kinds of conventional ways being current white light and making, also have its shortcoming.Wherein, the first there will be middle blue, and the phenomenon of surrounding Huang, color rendering is on the low side, and color temperature uniformity is not good.The second is mixed light difficulty, and user can observe multiple different color everywhere easily in this light source front, and sees colored shadow at each veil rear.In addition, because use three crystal grain are all thermals source, heat dissipation problem especially other kind encapsulates 3 times of pattern, and increases its difficulty used.The third coordinates fluorescent material ultraviolet wavelength to select the difficulties such as (excitation wavelength of fluorescent material optimal conversion efficiency), the difficulty of UV-LED making and the exploitation of uv-resistant encapsulating material.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of white light emitting diode and preparation method thereof, it is based on Sb doped p-type zinc oxide/N-shaped gallium nitride heterojunction structure, realize full Interface composites, the color rendering solving current white light LEDs existence is on the low side, color temperature uniformity is not good, mixed light is difficult and fluorescent material complicated, the problems such as ratio requirement is high, poor stability.
According to one aspect of the present invention, a kind of white light emitting diode is provided, it is characterized in that, comprise the N-shaped gallium nitride film stacking gradually contact from bottom to up, Sb doped p-type zinc oxide nano-wire array and positive electrode, wherein, described N-shaped gallium nitride film contacts with described Sb doped p-type zinc oxide nano-wire array and forms heterojunction, using as white-light emitting layer, described positive electrode contacts as working positive electrode with described Sb doped p-type zinc oxide nano-wire array, described N-shaped gallium nitride film is provided with negative electrode, this negative electrode contacts using as the negative electrode that works with described N-shaped gallium nitride film.
As improvement of the present invention, described positive electrode adopts indium metal.
As improvement of the present invention, described negative electrode adopts indium gold electrode.
As improvement of the present invention, described Sb doped p-type zinc oxide nano-wire array vertical-growth is on N-shaped gallium nitride film.
As improvement of the present invention, the luminescence band of described white light emitting diode is from 400nm to 1000nm.
As improvement of the present invention, described N-shaped gallium nitride film bottom surface is provided with substrate, is preferably sapphire.
According to another aspect of the present invention, a kind of preparation method of white light emitting diode is provided, it is characterized in that, comprising:
1) preparation has the N-shaped gallium nitride film substrate of substrate;
2) on described N-shaped gallium nitride film, sputter the catalyst of gold grain as reaction;
3) on described N-shaped gallium nitride film, grow Sb doped p-type zinc oxide nano-wire array, thus form the heterojunction as white-light emitting layer with described N-shaped gallium nitride film;
4) indium metal is set at the top of described Sb doped p-type zinc oxide nano-wire array, thus contacts with described N-shaped gallium nitride film using as positive electrode;
5) indium gold electrode is set on described N-shaped gallium nitride film surface, thus with described N-shaped gallium nitride film surface contact using as negative electrode;
6) above-mentioned white light emitting diode can be formed after described positive and negative electrode being heat-treated.
As improvement of the present invention, described step 3) in, adopt chemical vapour deposition technique on N-shaped gallium nitride film, grow Sb doped p-type zinc oxide nano-wire array.
In white light emitting diode in the present invention, described heterojunction, between positive and negative electrode, to be contacted with N-shaped gallium nitride film by Sb doped p-type zinc oxide nano-wire array and is formed, as luminescent layer; Described positive electrode adopts indium metal, contacts as positive electrode with Sb doped p-type zinc oxide nano-wire array; Described negative electrode adopts indium gold electrode, contacts as negative electrode with N-shaped gallium nitride.
Described white light emitting diode of the present invention is without the need to the program of complexity, easy to use, is easy to low cost operation; The zinc oxide that use cost is cheap, reduces cost; Ultraviolet light is not had in luminous spectrum, safer; White light colour temperature is low, is applicable to lighting of home.
Preparation method of the present invention is simple, without the need to the encapsulation of complexity, without the need to fluorescent material, can realize white light emitting diode that is stable, safety.
The present invention's base material used is reliable and stable N-shaped gallium nitride semiconductor material, technology maturation, the marketization is high, use chemical vapor infiltration under high temperature, lower pressure, N-shaped gallium nitride substrates grows stable, cheap Sb doped p-type zinc oxide semi-conductor nano-wire array material and forms p-n heterojunction, as white-light emitting layer.
In the present invention, due to the zinc oxide semi-conductor of intrinsic, gallium nitride semiconductor is all n-type semiconductor, and energy gap is close to (zinc oxide 3.37eV, gallium nitride 3.39eV), and the intrinsic light-emitting zone of two concentrates on the inclined ultraviolet region of blue light.In order to realize the regulation and control of luminescence band to long-wave band visible ray, the present invention is adulterated by antimony element, in zinc oxide semi-conductor forbidden band, introduce stable Sb doped acceptor level form p-type zinc oxide, change the characteristic of semiconductor of zinc oxide, in forbidden band, introduce Sb doped deep energy level simultaneously.
The present invention not only can form stable Sb doped p-type zinc oxide semi-conductor, and makes stable white light emitting diode, and does not have ultraviolet light wave band, safer.Simultaneously, N-shaped gallium nitride is realized and stibium-doped zinc oxide p-type semiconductor forms heterojunction by full Interface composites, because Sb doped introduces stable acceptor level and abundant doped energy-band in zinc oxide forbidden band, electronics, hole in interface first with doped energy-band compound, thus make emission wavelength red shift, and wave band enriches, thus realizes white light emitting diode.In laboratory conditions, can cross more than 30 hours by steady operation, for this novel white light emitting diode, just have huge applications prospect.
The white light emitting diode prepared in the present invention, all solid state, cost is low, be applicable to lighting of home without UV environment close friend, stable performance, low color temperature white light light-emitting diode, the current white light emitting diode of better solution is difficult to the predicament entering domestic applications, has important promotional value.Particularly, compared with prior art, beneficial effect of the present invention is as follows:
1, the present invention proposes a kind of brand-new white light-emitting diodes mentality of designing.Namely chemical gaseous phase depositing process synthesis Sb doped p-type zinc oxide array is used, method is simple, convenient, not only realize reliable and stable p-type zinc oxide (difficult problem of generally acknowledging in the world at present), and utilize Energies control, make reliable and stable novel white-light light-emitting diode.
2, white light emitting diode of the present invention uses chemical vapour deposition technique to make in low temperature oven, step is simple, reproducible, the p-n heterojunction of composite demand just can be made without the need to other complex steps, without the need to the flow process that conventional method is complicated, do not need special processing, not only simplify technique, also reduce cost simultaneously.
3, the electrode fabrication of white light emitting diode of the present invention is convenient and reliable, does not have ultraviolet part in luminescent spectrum, compared to conventional light emitting diodes safety and Health.
4, white light emitting diode preparation technology of the present invention is simple and rate of finished products is high, easily promotes and industrialization, use the prices of raw and semifnished materials cheap, wide material sources, environmental friendliness.This white light-emitting diodes, as semiconductor lighting devices, has colour temperature low, is conducive to lighting of home, has potential commercial value.
5, white light emitting diode of the present invention is novel white-light luminescent device, belongs to realize first in field of semiconductor illumination, captures white-light illuminating technical protection have important function for China.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Fig. 2 is the structural characterization of stibium-doped zinc oxide nano-wire array in the present invention: the scanning electron microscope (SEM) photograph of (a) large area 30 degree of inclination angle stibium-doped zinc oxide nano-wire arrays, and illustration is more detailed stibium-doped zinc oxide nano-wire array detail view; The X-ray diffraction spectrum comparison diagram of (b) non-doping zinc-oxide and stibium-doped zinc oxide; The accurate energy-spectrum scanning of x-ray photoelectron of (c) antimony atoms 3d orbital electron; D the high resolution TEM figure of () stibium-doped zinc oxide, illustration is corresponding selected area electron diffraction figure.
Fig. 3 is the High-Resolution Map of single stibium-doped zinc oxide and corresponding elementary composition image.
Fig. 4 is the electrical performance testing of white light emitting diode in the embodiment of the present invention: (a) IV resolution chart; (b) p-type ohmic contact figure; (c) N-shaped ohmic contact figure.
Fig. 5 is (a) electroluminescent spectrum figure; (b) glow peak linear relationship chart.
Fig. 6 is the luminous pictorial diagram of white light emitting diode of (a) different voltage; The chromaticity colour temperature map analysis of (b) white light emitting diode; The colour temperature tendency chart of (c) white light emitting diode.
In all of the figs, identical Reference numeral represents same technical characteristic, and particularly, 1 is positive electrode, and 2 is Sb doped p-type zinc oxide nano-wire array, and 3 is N-shaped gallium nitride film, and 4 is negative electrode, and 5 is Sapphire Substrate.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.It should be noted that, when advantageous features performance boost, the embodiment in the application and the feature in embodiment can reasonable combination mutually, carry out Reasonable adjustment.
The white light emitting diode of the present embodiment, as shown in Figure 1, its structure is followed successively by positive electrode 1, Sb doped p-type zinc oxide nano-wire array 2, N-shaped gallium nitride film 3, negative electrode 4 and Sapphire Substrate 5.There is all solid state, easy implementation feature.
Wherein N-shaped gallium nitride film 3, Sb doped p-type zinc oxide nano-wire array 2 and positive electrode 1 stack gradually from bottom to up and contact, N-shaped gallium nitride film 3 contacts with Sb doped p-type zinc oxide nano-wire array 2 and forms heterojunction, using as white-light emitting layer, positive electrode 1 contacts as working positive electrode with Sb doped p-type zinc oxide nano-wire array 2, N-shaped gallium nitride film 3 is provided with negative electrode, and this negative electrode contacts using as the negative electrode that works with N-shaped gallium nitride film 3.
As a preferred embodiment, positive electrode adopts indium metal.
As a preferred embodiment, negative electrode adopts indium gold electrode.
As a preferred embodiment, Sb doped p-type zinc oxide nano-wire array vertical-growth is on N-shaped gallium nitride film.
As a preferred embodiment, the luminescence band of white light emitting diode is from 400nm to 1000nm.
As a preferred embodiment, N-shaped gallium nitride film 3 bottom surface is provided with substrate, is preferably sapphire.
The preparation method of white light emitting diode of the present invention, comprises the steps:
Step 1. is got N-shaped gallium nitride substrates and is cleaned, and adopts acetone, alcohol and deionized water to clean successively under ultrasonic, finally puts dry in an oven.
Step 2. on N-shaped gallium nitride film uniform sputter gold grain as reaction catalyst;
Step 3. prepares antimony oxide, zinc oxide, carbon dust biased sample as reactant;
Quartz boat put into by the biased sample that step 4. gets step 3, puts into quartz glass tube at the bottom of reactive group, and two put into low temperature oven carries out chemical vapour deposition reaction, and N-shaped gallium nitride film grows Sb doped p-type zinc oxide nano-wire array, forms heterojunction;
Step 5. uses indium metal and Sb doped p-type zinc oxide nano-wire array top contact as positive electrode;
Step 6. uses indium gold electrode and N-shaped gallium nitride film surface contact as negative electrode;
Step 7. pair positive and negative electrode heat-treats annealing, composition heterojunction white light emitting diode.
By above-mentioned preparation method, the white light emitting diode of the embodiment of the present invention can be prepared.
Below in conjunction with specific embodiment, from the aspect such as assembling and performance measured data of the preparation of white light emitting diode material of the present invention, sign, device, the present invention will be further explained.
Embodiment one:
In the present embodiment, the preparation method of white light emitting diode comprises the steps:
1) preparation of cleaning and raw material at the bottom of reactive group
N-shaped gallium nitride circular wafer is cut into the square of 5mm*5mm unified specification, put into beaker, repeatedly ultrasonic in ultrasonic cleaning 10 minutes, high purity deionized water in ultrasonic cleaning 15 minutes, room temperature ethanol solution in 50 DEG C of acetone solns successively, each 2 minutes, after substrate cleans up, put into clean baking oven to dry, obtain clean reaction substrate.
Ready reaction raw material subsequently, by Zinc oxide powder and carbon dust 1:1 in mass ratio, zinc oxide and antimony oxide powder mol ratio 1:1/20, three kinds of powder put into beaker, pour ethanolic solution into, put into magneton, use the heating of heating magnetic stirring apparatus to stir into muddy, powder mud is put into 200 DEG C of baking ovens to dry further, become uniform and delicate powder.
2) growth of stibium-doped zinc oxide nano-wire array
Select N-shaped gallium nitride substrate and 0.5 gram of mixed-powder of a slice cleaning, powder puts into quartz boat, substrate is put into single-ended closed quartz glass tube, put into the low temperature oven of two warm area together, use chemical vapour deposition technique to prepare stibium-doped zinc oxide nano-wire array.In the present embodiment, preferred powder reaction zone temperature is 930 DEG C, reaction base reservoir temperature is 880 DEG C, the warming temperature of two be all 50 DEG C per minute, the air pressure of reaction is at about 50Pa, and the reaction time is 20 minutes, current-carrying gas argon gas is 49sccm, reacting gas oxygen is 0.5sccm, after reaction terminates, length is had stibium-doped zinc oxide nano-wire array to take out.
Whole reaction is at high-cleanness quartz ampoule, ultrapure powders, hyperpure gas, high-temperature low-pressure condition next step complete.
3) electrode fabrication
As Fig. 1, at p-type stibium-doped zinc oxide nano-wire array plated metal indium as positive electrode, removed by partial oxidation zinc nano-wire array hydrochloric acid and reserve N-shaped gallium nitride film, deposited gold and indium are as negative electrode respectively.
4) the making of white light emitting diode
The electrode made is put into Muffle furnace and carries out electrode anneal, form ohmic contact, preferable temperature 300 DEG C, 5 minutes time.
Stibium-doped zinc oxide nano-wire array is the analysis of p-type semiconductor
In the present embodiment, to stibium-doped zinc oxide nano-wire array, preferably can use simple electrical testing-IV curve that the characteristic of its p-type semiconductor is described.Fig. 4 shows good diode characteristic, describes the p-type characteristic of stibium-doped zinc oxide.
The electroluminescence analysis of spectrum of white light emitting diode
As Fig. 5 a, be the electroluminescence spectrum of making alive from 4V to 16V on device, analyze and draw from luminous spectrum, when voltage 4V to 14V, luminous spectrum is luminous in visible light, and ultraviolet is inhibited, and voltage is added to 16V ultraviolet light and is just triggered.Fig. 5 b is the linear growth figure of spectral intensity with voltage of luminous spectrum.
The material object display of white light emitting diode luminescence and colour temperature analysis
If Fig. 6 a is the pictorial diagram of white light emitting diode, Fig. 6 b is white light emitting diode chromaticity diagram, and be 3500K low color warm white light, Fig. 6 c is white light emitting diode colour temperature figure under different voltage, demonstrates the stability of colour temperature.
Embodiment two
In the present embodiment, the preparation method of white light emitting diode comprises the steps:
1) preparation of cleaning and raw material at the bottom of reactive group
In the present embodiment, at the bottom of reactive group, cleaning and embodiment one difference are, Substrate treatment application HCl treatment, soaking at room temperature 48 hours, afterwards with deionized water ultrasonic cleaning repeatedly, and dries, Zinc oxide powder and antimony oxide powder stock proportioning mol ratio become 1:1/10, other parameter constants.
2) growth of stibium-doped zinc oxide nano-wire array
In the present embodiment, be with embodiment one difference, get 0.3 gram of mixed-powder, reaction temperature changes 950 DEG C into, and other conditions are constant.
Embodiment three:
In the present embodiment, the preparation method of white light emitting diode comprises the steps:
1) preparation of cleaning and raw material at the bottom of reactive group
In the present embodiment, at the bottom of reactive group, cleaning and embodiment one difference are, cleaned substrate nitrogen or compressed air are dried up.
2) growth of stibium-doped zinc oxide nano-wire array
The growth step of the stibium-doped zinc oxide nano-wire array of the present embodiment and embodiment are together.
3) electrode fabrication
The electrode fabrication step of the present embodiment and embodiment are together.
4) the making of white light emitting diode
The electrode made is put into Muffle furnace and carries out electrode anneal, form ohmic contact, temperature 500 DEG C, 3 minutes time.
It should be noted that, the parameter in each step in above-described embodiment is only that technical scheme of the present invention is not limited to above-mentioned numerical value for example to explain the preparation method of white light emitting diode of the present invention.
By ESEM morphology analysis known stibium-doped zinc oxide nano-wire array vertical-growth on gallium nitride film; The known stibium-doped zinc oxide nano wire of TEM (transmission electron microscope) analysis remains the wurtzite structure of monocrystalline and preferentially maintains the c-axis direction of growth; X-ray diffraction spectrum shows that stibium-doped zinc oxide makes the spacing between atom change, and antimony atoms adulterates successfully; X-ray photoelectron spectroscopic analysis result shows that antimony atoms replaces zinc atom, realizes successfully adulterating; Electroluminescence spectrum analysis shows, under certain voltage, ultraviolet light successfully realizes suppressing; The chromaticity diagram analysis of 1931 Commission Internationale De L'Eclairage shows, the light that white light emitting diode sends is the low color temperature white light being easy to domestic applications; White light emitting diode pictorial diagram under different voltage shows that white light emitting diode successfully realizes.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a white light emitting diode, it is characterized in that, comprise the N-shaped gallium nitride film (3) stacking gradually contact from bottom to up, Sb doped p-type zinc oxide nano-wire array (2) and positive electrode (1), wherein, described N-shaped gallium nitride film (3) contacts with described Sb doped p-type zinc oxide nano-wire array (2) and forms heterojunction, using as white-light emitting layer, described positive electrode (1) contacts as working positive electrode with described Sb doped p-type zinc oxide nano-wire array (2), described N-shaped gallium nitride film (3) is provided with negative electrode (4), this negative electrode contacts using as the negative electrode that works with described N-shaped gallium nitride film (3).
2. a kind of white light emitting diode according to claim 1, is characterized in that, described positive electrode adopts indium metal.
3. a kind of white light emitting diode according to claim 1 and 2, is characterized in that, described negative electrode adopts indium gold electrode.
4. a kind of white light emitting diode according to any one of claim 1-3, is characterized in that, described Sb doped p-type zinc oxide nano-wire array vertical-growth is on N-shaped gallium nitride film.
5. a kind of white light emitting diode according to any one of claim 1-4, is characterized in that, the luminescence band of described white light emitting diode is from 400nm to 1000nm.
6. a kind of white light emitting diode according to any one of claim 1-5, is characterized in that, described N-shaped gallium nitride film (3) bottom surface is provided with substrate (5), is preferably sapphire.
7. a preparation method for white light emitting diode, is characterized in that, comprising:
1) preparation has the N-shaped gallium nitride film substrate of substrate;
2) on described N-shaped gallium nitride film, sputter the catalyst of gold grain as reaction;
3) on described N-shaped gallium nitride film, grow Sb doped p-type zinc oxide nano-wire array, thus form the heterojunction as white-light emitting layer with described N-shaped gallium nitride film;
4) indium metal is set at the top of described Sb doped p-type zinc oxide nano-wire array, thus contacts with described N-shaped gallium nitride film using as positive electrode;
5) indium gold electrode is set on described N-shaped gallium nitride film surface, thus with described N-shaped gallium nitride film surface contact using as negative electrode;
6) above-mentioned white light emitting diode can be formed after described positive and negative electrode being heat-treated.
8. the preparation method of a kind of white light emitting diode according to claim 7, is characterized in that, described step 3) in, adopt chemical vapour deposition technique on N-shaped gallium nitride film, grow Sb doped p-type zinc oxide nano-wire array.
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| CN102280535A (en) * | 2011-07-08 | 2011-12-14 | 东北师范大学 | Method for preparing top electrode of nanowire array LED (light-emitting diode) based on graphite oxide |
| CN103715325A (en) * | 2013-12-26 | 2014-04-09 | 辽宁师范大学 | Manufacturing method for single ZnO micron wire homojunction light emitting diode |
| CN103746056A (en) * | 2013-12-28 | 2014-04-23 | 华中科技大学 | Wave length-adjustable light-emitting diode based on gallium-doped zinc oxide nanowire array and manufacturing method thereof |
| CN103956416A (en) * | 2014-05-15 | 2014-07-30 | 深圳大学 | ZnO-based white light LED and preparing method thereof |
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| CN102280535A (en) * | 2011-07-08 | 2011-12-14 | 东北师范大学 | Method for preparing top electrode of nanowire array LED (light-emitting diode) based on graphite oxide |
| CN103715325A (en) * | 2013-12-26 | 2014-04-09 | 辽宁师范大学 | Manufacturing method for single ZnO micron wire homojunction light emitting diode |
| CN103746056A (en) * | 2013-12-28 | 2014-04-23 | 华中科技大学 | Wave length-adjustable light-emitting diode based on gallium-doped zinc oxide nanowire array and manufacturing method thereof |
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