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CN106601884B - ZnO-based nanorod/quantum well composite ultraviolet light emitting diode and preparation method thereof - Google Patents

ZnO-based nanorod/quantum well composite ultraviolet light emitting diode and preparation method thereof Download PDF

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Publication number
CN106601884B
CN106601884B CN201610946967.8A CN201610946967A CN106601884B CN 106601884 B CN106601884 B CN 106601884B CN 201610946967 A CN201610946967 A CN 201610946967A CN 106601884 B CN106601884 B CN 106601884B
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zno
quantum well
thin film
sputtering
emitting diode
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CN106601884A (en
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龙浩
顾锦华
钟志有
王皓宁
杨春勇
侯金
李颂战
杨艳芹
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South Central Minzu University
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South Central University for Nationalities
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/811—Bodies having quantum effect structures or superlattices, e.g. tunnel junctions
    • H10H20/812—Bodies having quantum effect structures or superlattices, e.g. tunnel junctions within the light-emitting regions, e.g. having quantum confinement structures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/01—Manufacture or treatment
    • H10H20/011—Manufacture or treatment of bodies, e.g. forming semiconductor layers
    • H10H20/012—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group II-IV materials
    • H10H20/0125—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group II-IV materials with a substrate not being Group II-VI materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/815—Bodies having stress relaxation structures, e.g. buffer layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/816—Bodies having carrier transport control structures, e.g. highly-doped semiconductor layers or current-blocking structures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/822—Materials of the light-emitting regions
    • H10H20/823—Materials of the light-emitting regions comprising only Group II-VI materials, e.g. ZnO

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  • Led Devices (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)

Abstract

本发明公开了一种ZnO基纳米杆/量子阱复合紫外发光二极管及其制备方法，该发光二极管包括衬底，衬底上从下往上依次设有n型ZnO薄膜层、ZnO纳米杆阵列、ZnO/Zn1‑xMgxO量子阱有源层、p型NiO薄膜层和第一电极；第二电极与ZnO纳米杆阵列并列位于n型ZnO薄膜层上；ZnO/Zn1‑ xMgxO量子阱有源层包覆ZnO纳米杆阵列，且0.1≤x≤0.3。该发光二极管电致发光峰值波长在374nm附近，发光峰半高宽约为17nm，该发光二极管结构能充分发挥ZnO材料直接宽带隙和高激子束缚能等优势，有效减弱极化效应、提高材料与界面质量、增大有源层有效面积、提升光取出效率、提高光谱单色性，并且可实现低温制备，成本低廉，易于实现产业化。

The invention discloses a ZnO-based nanorod/quantum well composite ultraviolet light emitting diode and a preparation method thereof. The light emitting diode comprises a substrate, and the substrate is provided with an n-type ZnO thin film layer, a ZnO nanorod array, ZnO/Zn 1-x Mg x O quantum well active layer, p-type NiO thin film layer and first electrode; the second electrode and ZnO nanorod array are juxtaposed on the n-type ZnO thin film layer; ZnO/Zn 1- x Mg x The O quantum well active layer coats the ZnO nanorod array, and 0.1≤x≤0.3. The electroluminescence peak wavelength of the light-emitting diode is around 374nm, and the light-emitting peak width at half maximum is about 17nm. The light-emitting diode structure can give full play to the advantages of ZnO material such as direct wide band gap and high exciton binding energy, effectively weaken the polarization effect, improve the material The interface quality is increased, the effective area of the active layer is increased, the light extraction efficiency is improved, the spectral monochromaticity is improved, and low-temperature preparation can be realized, the cost is low, and the industrialization is easy to be realized.

Description

Zno-based nano rod/compound UV LED of Quantum Well and preparation method thereof
Technical field
The present invention relates to opto-electronic devices, in particular to a kind of zno-based nano rod/compound UV LED of Quantum Well And preparation method thereof.
Background technique
Light emitting diode (LED) is the light-emitting component made of semiconductor material, is a kind of solid-state electroluminescent cold light source. Due to light emitting diode have low energy consumption and it is environmental-friendly the features such as, large-scale application can reduce the high-carbon energy such as coal oil Source consumption, meets the theory of sustainable development requirement and low-carbon economy.Light emitting diode is low in energy consumption with its, the service life is long, light efficiency is high, Numerous advantages such as radiationless, good portability, receive great favor, and correlative study and industry have obtained great support and hair Exhibition.In LED research field, the realization and development of ultraviolet (Ultraviolet, the UV) LED of short wavelength is related fields scientific research people One of the hot spot of member and industrial circle concern, it is considered to be the another of LED applies the New World after white light, and prospect is very happy It sees.Although having some uses aluminum gallium nitride (AlGaN) and aluminium gallium nitrogen (InAlGaN) at present as active layer material prepares UV The report of LED, but generally existing fault in material density is excessive, monochromaticjty is not good enough, luminous efficiency is relatively low, service life is too short, I The problems such as state's core patented technology lacks, and UV LED is in optic communication, day-old chick detection, biological medicine, printing packaging, high density Storage etc. fields huge applications demand make related scientific issues solution and product technology research and development it is extremely urgent.
ZnO is a kind of II-VI group direct band gap semiconductor material with wide forbidden band, and the forbidden bandwidth of ZnO is 3.37eV at room temperature, Corresponding emission wavelength is near 370nm, in ultraviolet wavelength range.Lattice structure, cell parameter and the forbidden bandwidth of ZnO It is similar to conventional photo functional material gallium nitride (GaN), but ZnO has fusing point more higher than GaN and bigger exciton confinement Can, and have lower luminescence generated by light and stimulated radiation threshold and good electromechanical coupling characteristics, thermal stability and chemistry steady Qualitative, material is easy to get, preparation cost is cheap, environmental-friendly.Thus, ZnO is considered as the ideal alternative materials of GaN, in shortwave Application in terms of long light emitting diode, laser and related photoelectric device has huge potentiality.In addition, by carrying out magnesium to ZnO (Mg) it adulterates, its forbidden bandwidth is adjusted, realize energy band engineering；And the lattice of low-doped magnesium zinc (ZnMgO) and ZnO lose It is small with spending, it can be applied to ZnO/ZnMgO quantum well structure, expanded the application field of ZnO material.
At present there are also about using ZnO as the report of ultraviolet light emitting device material, such as: Chinese patent application 200810120346.X disclosing a kind of ZnO based LED of multiple quantum wells, the Zn provided1-xMgxO/Zn1-yCdyO volume Sub- trap active layer is conventional planar structure, has compared with strong polarity effect, and active layer limited area, influences its luminous efficiency.It should The Zinc oxide single crystal substrate that scheme provides is with high costs, and monocrystalline substrate then will lead to strong lattice mismatch, influence active Layer material quality, the good high quality p-type ZnO of this external stability are still that current industry makes great efforts the important problem solved, and there is also move The problems such as shifting rate, carrier concentration are relatively low and stability is poor.In addition, Liu Weizhen (ZnO nano-wire heterojunction ultraviolet light emitting The device research Changchun [D]: Northeast Normal University, 2013.) use pulse laser deposition and hydro-thermal method to be prepared for MgZnO/ZnO core Shell heterogeneous structural nano linear array, and luminescent device is constituted with p-type GaN.The ZnO nano-wire that the program prepares hydro-thermal method as Light-emitting active layer, more defect and impurity will seriously affect luminous efficiency.
Generally speaking, the existing generally existing following problems of zno-based ultraviolet light emitting device: 1) lattice mismatch and polarity effect It is lower that caused quantu m_confined Stark effect results in light emitting diode internal quantum efficiency；2) poor interface quality and material Deep energy level caused by defect shines, and causes LED ultraviolet monochromatic poor；3) light extraction efficiency caused by traditional planar structure is inclined It is low；4) preparation process is complicated, condition control is stringent, needs preparation cost caused by the factors such as high temperature preparation high.It is aforementioned these Problem limits the application of zno-based ultra-violet light-emitting device.
Summary of the invention
Present invention aim to provide a kind of zno-based nano rod/compound UV LED of Quantum Well and its system Preparation Method, the UV LED good luminous performance realize the pure ultraviolet electroluminescent hair that luminous peak position is located near 374nm Light.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of zno-based nano rod/Quantum Well is compound ultraviolet Light emitting diode, including substrate are successively arranged N-shaped ZnO film layer, ZnO nano bar array, ZnO/ on the substrate from the bottom up Zn1-xMgxO mqw active layer, p-type NiO film layer and first electrode；Second electrode and the ZnO nano bar array position arranged side by side In on the N-shaped ZnO film layer；The ZnO/Zn1-xMgxO mqw active layer coats the ZnO nano bar array, and 0.1 ≤x≤0.3。
Further, the ZnO/Zn1-xMgxO mqw active layer by 2~10 periods ZnO film and Zn1-xMgxO Film alternating deposit forms.
Further, the first electrode is Au, Pt, Pt/Ni or Au/Ni.
Further, the second electrode is In, Al, Ga or Ag.
Further, the substrate is Sapphire Substrate.
A kind of preparation method of zno-based nano rod/compound UV LED of Quantum Well, comprising the following steps:
1) substrate is cleaned；
2) N-shaped ZnO film layer is sputtered using rf magnetron sputtering technique on substrate；
3) ZnO nano bar array is grown on N-shaped ZnO film layer using hydro-thermal method；
4) replace ZnO Thin Films Sputtered and Zn on the ZnO nano bar array using rf magnetron sputtering technique1-xMgxO Film forms the ZnO/Zn being coated on the ZnO nano bar array1-xMgxO mqw active layer；
5) in the ZnO/Zn1-xMgxReactive sputtering p-type NiO film layer on O mqw active layer；
6) first electrode is plated in the p-type NiO thin-film surface using rf magnetron sputtering technique, and in the N-shaped ZnO film layer edge plates second electrode.
Further, in the step 2), sputtering target material is ZnO:Al ceramic target, background air pressure≤10 when sputtering-3Pa, lining Bottom temperature is 200~400 DEG C, and air pressure is 0.5~8Pa when deposition, and sputter gas Ar, sputtering power is 20~150W, sputtering Time is 5~20min.
Further, in the step 3), hydro-thermal method prepare the presoma that the ZnO nano bar array uses for 0.01~ The zinc nitrate hexahydrate and hexa mixed solution of 0.1mol/L, hydrothermal temperature are 80~120 DEG C, the reaction time For 1~3h.
Further, in the step 4), the sputtering target material of the ZnO film is ZnO ceramic target, the Zn1-xMgxO is thin The sputtering target material of film is Mg and ZnO hybrid target, and the area ratio of Mg metallic target and ZnO ceramic target is 1:0.5~1.5；When sputtering Background air pressure≤10-3Pa, underlayer temperature are 200~400 DEG C, and air pressure is 0.5~8Pa, relative partial pressure of oxygen O when deposition2/(O2+ It Ar) is 15~40%, sputtering power is 20~150W, the ZnO film and the Zn1-xMgxEvery layer of sputtering time of O film is 1 ~3min.
Further, in the step 5), sputtering target material is Ni metallic target, relative partial pressure of oxygen O2/(O2+ Ar) be 50~ 70%, cavity background air pressure≤10 before sputtering-3Pa, underlayer temperature are 150~250 DEG C, and sputtering pressure is 0.5~8Pa, sputtering 20~150W of power, sputtering time are 20~60min.
The present invention is acted on using quantum confinement possessed by ZnO quantum well structure, while it is exclusive to introduce ZnO nano material Small-size effect and skin effect combine the quantum well structure (ZnO/ZnMgO) based on ZnO with ZnO 1-dimention nano bar, shape At ZnO nano bar/Quantum Well core-shell structure as light-emitting active layer, the ZnO base LED based on the structure is constructed, it is real Existing luminous peak position is located at the pure UV electroluminescence near 374nm and shows following advantage compared with prior art:
First, weakening polarity effect: the characteristics of utilizing ZnO nano bar material, in ZnO nano bar outgrowth Quantum Well knot Structure, the isoepitaxial growth film on its lateral non-polar m face, can substantially weaken polarity effect；Nano material is big simultaneously Specific surface area can preferably discharge inter-laminar stress, so that lattice mismatch big at heterogeneous interface is eased, further The effect is reduced, to obtain device performance boost.
Second, improving material and interface quality: when ZnO is having certain lattice mismatched substrate surface heterogeneous medium nucleating growth When, there is highest energy to cause its strong tendency in forming three-dimensional column structure in (0001) face, be formed in film a large amount of Crystal boundary simultaneously accumulates a large amount of defect and impurity, it is difficult to and even curface is obtained, the application of quantum well structure is unfavorable for, and it is of the invention It can get the ZnO film of low defect density and high-crystal quality and the high quality heterogeneous structure material that surface is smooth, interface is precipitous, Improve radiative recombination rate.
Third, increasing active layer effective area: quantum well structure is prepared on the basis of One-Dimensional ZnO nano material substantially to be increased Add the effective area of quantum well layer, it may be assumed that the region of light-emitting active layer is significantly increased, it is achieved that the exciton of higher efficiency radiates Recombination luminescence.
Fourth, promoting light extraction efficiency: in view of the reflection of ZnO nano bar hexagonal column structure and upper and lower surface, passing through Reasonable optical design can be such that its light extraction efficiency is improved to promote the luminescent properties of device entirety.
Fifth, being conducive to improve spectrum monochromaticjty: the optical waveguide effect of ZnO nano bar/Quantum Well core-shell structure The lasing of Whispering-gallery-mode or Fabry-Perot modes can be caused to shine.Optical resonator is formed in material internal, and light is having Lattice scattering occurs in active layer and forms optical circuit, population inversion can be achieved after reaching threshold value, compared to two pole of Conventional luminescent Pipe, the design for not needing specific resonant cavity can substantially reduce luminous peak width, improve spectrum monochromaticjty.
Sixth, low temperature preparation can be realized: zno-based nano rod of the present invention/Quantum Well compound UV LED whole The temperature of preparation link is can be controlled within 400 DEG C, substantially lower than 1000 DEG C of mainstream GaN base light emitting semiconductor device or more Preparation temperature smoothly realizes low temperature preparation, is conducive to cost control and the application of associated materials.
Seventh, the N-shaped ZnO film using growth on a sapphire substrate, is both the good seed of ZnO nano bar growth Layer and ZnO/Zn1-xMgxThe electron injecting layer of O mqw active layer, double action are beneficial to simplify preparation process, reduce life Produce cost.
Eighth, forbidden bandwidth is bigger with respect to ZnO at room temperature using p-type NiO as hole injection layer, give full play to The super injection advantage of hetero-junctions；Meanwhile there are Ni in NiO film2+Vacancy, so that natural hole is presented at room temperature and leads for film Electricity, the influence so as to avoid excessive doping to crystal quality.
Ninth, the present invention prepares mqw active layer using rf magnetron sputtering system, organise relative to common metal Object chemical gas-phase deposition system is closed, cost is greatly reduced, and is advantageously implemented industrialization production.
Detailed description of the invention
Fig. 1 is a kind of zno-based nano rod/Quantum Well compound UV LED structural schematic diagram.
Fig. 2 is zno-based nano rod/Quantum Well compound UV LED room temperature electroluminescent made from embodiment 1 Spectrogram.
Fig. 3 is zno-based nano rod/Quantum Well compound UV LED room temperature electroluminescent made from embodiment 2 Spectrogram.
Fig. 4 is zno-based nano rod/Quantum Well compound UV LED room temperature electroluminescent made from embodiment 3 Spectrogram.
Specific embodiment
The following further describes the present invention in detail with reference to the accompanying drawings and specific embodiments, convenient for more clearly understanding this Invention, but they limiting the invention.
The zno-based nano rod as shown in Figure 1/compound UV LED of Quantum Well, including substrate 1, substrate 1 are blue precious Stone lining bottom is successively arranged N-shaped ZnO film layer 2, ZnO nano bar array 3, ZnO/Zn on substrate 1 from the bottom up1-xMgxO Quantum Well Active layer 4, p-type NiO film layer 5 and first electrode 6；Second electrode 7 and ZnO nano bar array 3 are located at N-shaped ZnO film side by side On layer 2；ZnO/Zn1-xMgx4 clading ZnO nano bar array 3 of O mqw active layer, and 0.1≤x≤0.3, ZnO/Zn1-xMgxO amount Sub- trap active layer 4 by 2~10 periods ZnO film and Zn1-xMgxO film alternating deposit forms.First electrode 6 be Au, Pt, Pt/Ni or Au/Ni, second electrode 7 are In, Al, Ga or Ag.Zno-based nano rod/Quantum Well compound UV LED system Standby process sees below Examples 1 to 3.
Embodiment 1
1) substrate cleans: using sapphire as substrate, be cut into 15mm × 15mm size, using acetone, alcohol and Deionized water is cleaned by ultrasonic 3min respectively, finally uses N2Drying.
2) Sapphire Substrate after surface clean the preparation of N-shaped ZnO film layer: is put into the life of rf magnetron sputtering system In long room, growth room is evacuated to background air pressure 5 × 10-4Pa, heating substrate to temperature are 200 DEG C.Select AZO ceramic target The target of (ZnO:Al ceramic target) as depositing n-type ZnO film layer.Before plated film, pre-sputtering 10min is to remove target material surface Impurity, then using radio frequency magnetron sputtering method depositing n-type ZnO film layer on a sapphire substrate.Deposition substrate temperature 200 DEG C, gas is argon gas, air pressure 0.5Pa, sputtering power 60W, sputtering time 20min when deposition.
3) preparation of ZnO nano bar array: the sample of N-shaped ZnO film layer is placed in Zn (NO sputtering3)2·6H2O and six Methenamine concentration is that hydro-thermal reaction is carried out in the precursor solution of 0.01mol/L, and hydro-thermal reaction occurs closed anti- It answers in kettle, reaction temperature is 100 DEG C, reaction time 2h, after reaction, sample is taken out and ultrasound 5s is residual to remove reaction It stays, is then cleaned with a large amount of deionized waters, finally use N2Drying is placed in heating furnace, is annealed under the conditions of 400 DEG C in air 30min。
4)ZnO/Zn1-xMgxThe growth of O mqw active layer: the sample that grown ZnO nano bar array is put into In the growth room of rf magnetron sputtering system, growth room is evacuated to background air pressure 5 × 10-4Pa, heating substrate to temperature are 200 DEG C, it selects ZnO ceramic target as the target of deposition ZnO potential well layer, selects the mixing target conduct of Mg metallic target and ZnO ceramic target Deposit Zn1-xMgxThe target of O barrier layer, wherein the area ratio of Mg metallic target and ZnO ceramic target is 2:3, the preparation of this condition Zn1-xMgxX=0.1 in O layers；Before plated film, then pre-sputtering 10min uses radio-frequency magnetic to remove the impurity of target material surface Control the method sputtered alternating deposit ZnO film layer on the sample that successively growth has N-shaped ZnO film layer and ZnO nano bar array And Zn0.9Mg0.1O film layer forms the ZnO/Zn in 10 periods0.9Mg0.1O mqw active layer, 200 DEG C of deposition substrate temperature, Air pressure 0.5Pa when deposition, relative partial pressure of oxygen O2/(O2+ Ar) be 40%, sputtering power 60W, 1min/ layers of sputtering time.
5) preparation of p-type NiO: using the method for reactive sputtering in ZnO/Zn0.9Mg0.1Continue to sink on O mqw active layer Product p-type NiO film, before plated film, for pre-sputtering 5min to remove the impurity of target material surface, target selects the W metal of high-purity Target, background air pressure 5 × 10-4Pa, 150 DEG C of deposition substrate temperature, deposition pressure 0.5Pa, relative partial pressure of oxygen O2/(O2+ Ar) be 50%, sputtering power 120W, sputtering time 30min.
6) N-shaped ZnO film layer, ZnO nano bar array, ZnO/Zn will the preparation of electrode: be sequentially prepared0.9Mg0.1O quantum The sample covering metal mask version of trap active layer, p-type NiO film, is put into the growth room of rf magnetron sputtering, growth room takes out true Sky is to background air pressure 5 × 10-4Pa, heating substrate to temperature are 100 DEG C.Select Au metallic target as deposition first electrode (Au electricity Pole) target.Before plated film, pre-sputtering 10s is to remove the impurity of target material surface.Then existed using radio frequency magnetron sputtering method It is covered with deposition first electrode (Au electrode) on the p-type NiO film of metal mask version.100 DEG C of deposition substrate temperature；Gas when deposition Body is Ar gas, air pressure 0.5Pa；Sputtering power 20W；Sputtering time 40s.Continue to plate In on the N-shaped ZnO of substrate surface as the Two electrodes.
The electroluminescent hair of the nano rod of zno-based made from the present embodiment 1/compound UV LED of Quantum Well is measured at room temperature Light spectrogram is as shown in Figure 2.
Embodiment 2
1) substrate cleans: using sapphire as substrate, being cut into 15mm × 15mm size, using acetone, alcohol is gone Ionized water is cleaned by ultrasonic 3min respectively, finally uses N2Drying.
2) Sapphire Substrate after surface clean the preparation of N-shaped ZnO film layer: is put into the life of rf magnetron sputtering system In long room, growth room is evacuated to background air pressure 1 × 10-4Pa, heating substrate to temperature are 400 DEG C.Select the conduct of AZO ceramic target The target of depositing n-type ZnO film layer.Before plated film, pre-sputtering 10min is to remove the impurity of target material surface, then using penetrating Frequency magnetically controlled sputter method depositing n-type ZnO film layer on a sapphire substrate；400 DEG C of deposition substrate temperature, gas is Ar when deposition Gas, air pressure 5.0Pa, sputtering power 150W, sputtering time 5min.
3) sample that sputtering has N-shaped ZnO film the preparation of ZnO nano bar array: is placed in Zn (NO3)2·6H2O and six is sub- Tetramine concentration is in the precursor solution of 0.1mol/L.The reaction temperature in closed reaction kettle occurs for hydro-thermal reaction It is 80 DEG C, reaction time 3h.After, sample is taken out and ultrasound 5s is to remove reaction residual, then with a large amount of deionizations Water cleaning, finally uses N2Drying is placed in heating furnace, and anneal under the conditions of 400 DEG C 30min in air.
4)ZnO/Zn1-xMgxThe growth of O mqw active layer: the sample that grown ZnO nano bar array is put into In the growth room of rf magnetron sputtering system, growth room is evacuated to background air pressure 1 × 10-4Pa, heating substrate to temperature are 400 ℃.It selects ZnO ceramic target as the target of deposition ZnO potential well layer, selects the mixing target conduct of Mg metallic target and ZnO ceramic target Deposit Zn1-xMgxThe target of O barrier layer, wherein the area ratio of Mg metallic target and ZnO ceramic target is 1:1, the preparation of this condition Zn1-xMgxX=0.18 in O layers.Before plated film, pre-sputtering 10min is to remove the impurity of target material surface.Then radio-frequency magnetic is used Control the method sputtered alternating deposit ZnO film layer on the sample that successively growth has N-shaped ZnO film layer and ZnO nano bar array And Zn0.82Mg0.18O film layer forms the ZnO/Zn in 2 periods0.82Mg0.18O mqw active layer.Deposition substrate temperature 400 ℃；Air pressure 5.0Pa when deposition；Relative partial pressure of oxygen O2/(O2+ Ar) it is 15%；Sputtering power 150W；2min/ layers of sputtering time.
5) preparation of p-type NiO: using the method for reactive sputtering in ZnO/Zn0.82Mg0.18Continue to sink on O mqw active layer Product p-type NiO film.Before plated film, pre-sputtering 5min is to remove the impurity of target material surface.The W metal of target selection high-purity Target, background air pressure 1 × 10-4Pa, 200 DEG C of deposition substrate temperature；Deposition pressure 8.0Pa；Relative partial pressure of oxygen O2/(O2+ Ar) be 60%；Sputtering power 150W, sputtering time 20min.
6) N-shaped ZnO, ZnO nano bar array, ZnO/Zn will the preparation of electrode: be sequentially prepared0.82Mg0.18O Quantum Well has Active layer, the sample covering metal mask version of p-type NiO film, are put into the growth room of rf magnetron sputtering, growth room is evacuated to Background air pressure 1 × 10-4Pa, heating substrate to temperature are 100 DEG C.Select Pt metallic target as deposition first electrode (Pt electrode) Target.Before plated film, pre-sputtering 10s is to remove the impurity of target material surface.Then it is being covered using radio frequency magnetron sputtering method There is deposition first electrode (Pt electrode) on the p-type NiO film of metal mask version.100 DEG C of deposition substrate temperature；Gas is when deposition Ar gas, air pressure 0.8Pa；Sputtering power 30W；Sputtering time 30s.Continue to plate Ga on the N-shaped ZnO of substrate surface as the second electricity Pole.
The electroluminescent hair of the nano rod of zno-based made from the present embodiment 2/compound UV LED of Quantum Well is measured at room temperature Light spectrogram is as shown in Figure 3.
Embodiment 3
1) substrate cleans: using sapphire as substrate, being cut into 15mm × 15mm size, using acetone, alcohol is gone Ionized water is cleaned by ultrasonic 3min respectively, finally uses N2Drying.
2) Sapphire Substrate after surface clean the preparation of N-shaped ZnO film layer: is put into the life of rf magnetron sputtering system In long room, growth room is evacuated to background air pressure 1 × 10-3Pa, heating substrate to temperature are 300 DEG C.Select the conduct of AZO ceramic target The target of depositing n-type ZnO film layer.Before plated film, pre-sputtering 10min is to remove the impurity of target material surface.Then using penetrating Frequency magnetically controlled sputter method depositing n-type ZnO film layer on a sapphire substrate.300 DEG C of deposition substrate temperature, gas is Ar when deposition Gas, air pressure 8.0Pa, sputtering power 20W, sputtering time 15min.
3) sample that sputtering has N-shaped ZnO film the preparation of ZnO nano bar array: is placed in Zn (NO3)2·6H2O and six is sub- Tetramine concentration is in the precursor solution of 0.05mol/L.The reaction temperature in closed reaction kettle occurs for hydro-thermal reaction It is 120 DEG C, reaction time 1h.After, sample is taken out and ultrasound 5s is to remove reaction residual, then with a large amount of deionizations Water cleaning, finally uses N2Drying is placed in heating furnace, and anneal under the conditions of 400 DEG C 30min in air.
4)ZnO/Zn1-xMgxThe growth of O mqw active layer: the sample that grown ZnO nano bar array is put into In the growth room of rf magnetron sputtering system, growth room is evacuated to background air pressure 1 × 10-3Pa, heating substrate to temperature are 300 ℃.It selects ZnO ceramic target as the target of deposition ZnO potential well layer, selects the mixing target conduct of Mg metallic target and ZnO ceramic target Deposit Zn1-xMgxThe target of O barrier layer, wherein the area ratio of Mg metallic target and ZnO ceramic target is 2:1, the preparation of this condition Zn1-xMgxX=0.3 in O layers.Before plated film, pre-sputtering 10min is to remove the impurity of target material surface.Then radio-frequency magnetic is used Control the method sputtered alternating deposit ZnO film layer on the sample that successively growth has N-shaped ZnO film layer and ZnO nano bar array And Zn0.7Mg0.3O film layer forms the ZnO/Zn in 8 periods0.7Mg0.3O mqw active layer.300 DEG C of deposition substrate temperature；It is heavy Air pressure 8.0Pa when product；Relative partial pressure of oxygen O2/(O2+ Ar) it is 70%；Sputtering power 20W；3min/ layers of sputtering time.
5) preparation of p-type NiO: using the method for reactive sputtering in ZnO/Zn0.7Mg0.3Continue to sink on O mqw active layer Product p-type NiO film.Before plated film, pre-sputtering 5min is to remove the impurity of target material surface.The W metal of target selection high-purity Target, background air pressure 1 × 10-3Pa, 250 DEG C of deposition substrate temperature；Deposition pressure 5.0Pa；Relative partial pressure of oxygen O2/(O2+ Ar) be 60%；Sputtering power 20W, sputtering time 60min.
6) N-shaped ZnO, ZnO nano bar array, ZnO/Zn will the preparation of electrode: be sequentially prepared0.7Mg0.3O Quantum Well is active The sample covering metal mask version of layer, p-type NiO film, is put into the growth room of rf magnetron sputtering, growth room is evacuated to this Spirit pressure 1 × 10-3Pa, heating substrate to temperature are 100 DEG C.Select Ni metallic target and Pt metallic target as the first electricity of deposition respectively The target of pole (Pt/Ni electrode).Before plated film, pre-sputtering 10s is to remove the impurity of target material surface.Then radio frequency magnetron is used Sputtering method is sequentially depositing Ni film and Pt film as first electrode on the p-type NiO film for being covered with metal mask version (Pt/Ni electrode).100 DEG C of deposition substrate temperature；Gas is Ar gas, air pressure 0.5Pa when deposition；Sputtering power 20W；Ni film and The sputtering time of Pt film is respectively 20s and 40s.Continue to plate Ag on the N-shaped ZnO of substrate surface as second electrode.
The electroluminescent hair of the nano rod of zno-based made from the present embodiment 3/compound UV LED of Quantum Well is measured at room temperature Light spectrogram is as shown in Figure 4.
From the embodiment of the present invention as can be seen that nano rod/Quantum Well composite construction ZnO UV LED of preparation With preferable luminescent properties, the light emitting diode issue peak position be located at wavelength 374 (± 2) nm, the peak width that shines for 17 (± 8) UV electroluminescence of nm.

Claims (9)

1.一种ZnO基纳米杆/量子阱复合紫外发光二极管，包括衬底(1)，其特征在于：所述衬底(1)上从下往上依次设有n型ZnO薄膜层(2)、ZnO纳米杆阵列(3)、ZnO/Zn1-xMgxO量子阱有源层(4)、p型NiO薄膜层(5)和第一电极(6)；第二电极(7)与所述ZnO纳米杆阵列(3)并列位于所述n型ZnO薄膜层(2)上；所述ZnO/Zn1-xMgxO量子阱有源层(4)包覆所述ZnO纳米杆阵列(3)，且0.1≤x≤0.3；1. a ZnO-based nanorod/quantum well composite ultraviolet light-emitting diode, comprising a substrate (1), characterized in that: the substrate (1) is sequentially provided with an n-type ZnO thin film layer (2) from bottom to top , ZnO nanorod array (3), ZnO/Zn 1-x Mg x O quantum well active layer (4), p-type NiO thin film layer (5) and first electrode (6); second electrode (7) and The ZnO nanorod array (3) is juxtaposed on the n -type ZnO thin film layer (2); the ZnO/Zn1 - xMgxO quantum well active layer (4) covers the ZnO nanorod array (3), and 0.1≤x≤0.3; 所述ZnO基纳米杆/量子阱复合紫外发光二极管的制备方法，包括以下步骤：The preparation method of the ZnO-based nanorod/quantum well composite ultraviolet light emitting diode comprises the following steps: 1)清洗衬底；1) cleaning the substrate; 2)采用射频磁控溅射工艺在衬底上溅射n型ZnO薄膜层；2) using radio frequency magnetron sputtering process to sputter n-type ZnO thin film layer on the substrate; 3)采用水热法在n型ZnO薄膜层上生长ZnO纳米杆阵列；3) The ZnO nanorod array is grown on the n-type ZnO thin film layer by hydrothermal method; 4)采用射频磁控溅射工艺在所述ZnO纳米杆阵列上交替溅射ZnO薄膜和Zn1-xMgxO薄膜形成包覆于所述ZnO纳米杆阵列上的ZnO/Zn1-xMgxO量子阱有源层；4) Using a radio frequency magnetron sputtering process to alternately sputter a ZnO thin film and a Zn 1-x Mg x O thin film on the ZnO nanorod array to form ZnO/Zn 1-x Mg coated on the ZnO nanorod array x O quantum well active layer; 5)在所述ZnO/Zn1-xMgxO量子阱有源层上反应溅射p型NiO薄膜层；5) reactively sputtering a p-type NiO thin film layer on the ZnO/Zn 1-x Mg x O quantum well active layer; 6)采用射频磁控溅射工艺在所述p型NiO薄膜层表面镀上第一电极，并在所述n型ZnO薄膜层边缘镀上第二电极；6) adopting the radio frequency magnetron sputtering process to plate the first electrode on the surface of the p-type NiO thin film layer, and plate the second electrode on the edge of the n-type ZnO thin film layer; 所述ZnO/Zn1-xMgxO量子阱有源层(4)由2～10个周期的ZnO薄膜和Zn1-xMgxO薄膜交替沉积而成。The ZnO/Zn 1-x Mg x O quantum well active layer (4) is formed by alternately depositing 2-10 periods of ZnO thin films and Zn 1-x Mg x O thin films. 2.根据权利要求1所述ZnO基纳米杆/量子阱复合紫外发光二极管，其特征在于：所述第一电极(6)为Au、Pt、Pt/Ni或Au/Ni。2. The ZnO-based nanorod/quantum well composite ultraviolet light emitting diode according to claim 1, wherein the first electrode (6) is Au, Pt, Pt/Ni or Au/Ni. 3.根据权利要求1所述ZnO基纳米杆/量子阱复合紫外发光二极管，其特征在于：所述第二电极(7)为In、Al、Ga或Ag。3. The ZnO-based nanorod/quantum well composite ultraviolet light emitting diode according to claim 1, wherein the second electrode (7) is In, Al, Ga or Ag. 4.根据权利要求1所述ZnO基纳米杆/量子阱复合紫外发光二极管，其特征在于：所述衬底(1)为蓝宝石衬底。4. The ZnO-based nanorod/quantum well composite ultraviolet light emitting diode according to claim 1, wherein the substrate (1) is a sapphire substrate. 5.一种ZnO基纳米杆/量子阱复合紫外发光二极管的制备方法，包括以下步骤：5. A preparation method of a ZnO-based nanorod/quantum well composite ultraviolet light-emitting diode, comprising the following steps: 1)清洗衬底；1) cleaning the substrate; 2)采用射频磁控溅射工艺在衬底上溅射n型ZnO薄膜层；2) using radio frequency magnetron sputtering process to sputter n-type ZnO thin film layer on the substrate; 3)采用水热法在n型ZnO薄膜层上生长ZnO纳米杆阵列；3) The ZnO nanorod array is grown on the n-type ZnO thin film layer by hydrothermal method; 4)采用射频磁控溅射工艺在所述ZnO纳米杆阵列上交替溅射ZnO薄膜和Zn1-xMgxO薄膜形成包覆于所述ZnO纳米杆阵列上的ZnO/Zn1-xMgxO量子阱有源层；4) Using a radio frequency magnetron sputtering process to alternately sputter a ZnO thin film and a Zn 1-x Mg x O thin film on the ZnO nanorod array to form ZnO/Zn 1-x Mg coated on the ZnO nanorod array x O quantum well active layer; 5)在所述ZnO/Zn1-xMgxO量子阱有源层上反应溅射p型NiO薄膜层；5) reactively sputtering a p-type NiO thin film layer on the ZnO/Zn 1-x Mg x O quantum well active layer; 6)采用射频磁控溅射工艺在所述p型NiO薄膜层表面镀上第一电极，并在所述n型ZnO薄膜层边缘镀上第二电极。6) A first electrode is plated on the surface of the p-type NiO thin film layer by a radio frequency magnetron sputtering process, and a second electrode is plated on the edge of the n-type ZnO thin film layer. 6.根据权利要求5所述ZnO基纳米杆/量子阱复合紫外发光二极管的制备方法，其特征在于：所述步骤2)中，溅射靶材为ZnO：Al陶瓷靶，溅射时本底气压≤10-3Pa，衬底温度为200～400℃，沉积时气压为0.5～8Pa，溅射气体为Ar，溅射功率为20～150W，溅射时间为5～20min。6. The method for preparing a ZnO-based nanorod/quantum well composite ultraviolet light-emitting diode according to claim 5, wherein in the step 2), the sputtering target is a ZnO:Al ceramic target, and the background during sputtering The gas pressure is less than or equal to 10 -3 Pa, the substrate temperature is 200-400°C, the gas pressure during deposition is 0.5-8Pa, the sputtering gas is Ar, the sputtering power is 20-150W, and the sputtering time is 5-20min. 7.根据权利要求5或6所述ZnO基纳米杆/量子阱复合紫外发光二极管的制备方法，其特征在于：所述步骤3)中，水热法制备所述ZnO纳米杆阵列采用的前驱体为0.01～0.1mol/L的六水合硝酸锌和六亚甲基四胺混合溶液，水热反应温度为80～120℃，反应时间为1～3h。7. The method for preparing a ZnO-based nanorod/quantum well composite ultraviolet light emitting diode according to claim 5 or 6, wherein in the step 3), a precursor used for preparing the ZnO nanorod array by hydrothermal method It is a mixed solution of 0.01-0.1 mol/L zinc nitrate hexahydrate and hexamethylenetetramine, the hydrothermal reaction temperature is 80-120 DEG C, and the reaction time is 1-3h. 8.根据权利要求5或6所述ZnO基纳米杆/量子阱复合紫外发光二极管的制备方法，其特征在于：所述步骤4)中，所述ZnO薄膜的溅射靶材为ZnO陶瓷靶，所述Zn1-xMgxO薄膜的溅射靶材为Mg与ZnO混合靶，且Mg金属靶和ZnO陶瓷靶的面积比为1：0.5～1.5；溅射时本底气压≤10-3Pa，衬底温度为200～400℃，沉积时气压为0.5～8Pa，相对氧分压O2/(O2+Ar)为15～40％，溅射功率为20～150W，所述ZnO薄膜和所述Zn1-xMgxO薄膜每层溅射时间为1～3min。8. The preparation method of the ZnO-based nanorod/quantum well composite ultraviolet light emitting diode according to claim 5 or 6, characterized in that: in the step 4), the sputtering target of the ZnO film is a ZnO ceramic target, The sputtering target of the Zn 1-x Mg x O thin film is a mixed target of Mg and ZnO, and the area ratio of the Mg metal target and the ZnO ceramic target is 1:0.5-1.5; the background pressure during sputtering is ≤10 -3 Pa, the substrate temperature is 200～400℃, the gas pressure during deposition is 0.5～8Pa, the relative oxygen partial pressure O 2 /(O 2 +Ar) is 15～40%, the sputtering power is 20～150W, the ZnO thin film And the sputtering time of each layer of the Zn 1-x Mg x O thin film is 1-3 min. 9.根据权利要求5或6所述ZnO基纳米杆/量子阱复合紫外发光二极管的制备方法，其特征在于：所述步骤5)中，溅射靶材为Ni金属靶，相对氧分压O2/(O2+Ar)为50～70％，溅射前的腔体本底气压≤10-3Pa，衬底温度为150～250℃，溅射气压为0.5～8Pa，溅射功率20～150W，溅射时间为20～60min。9. The preparation method of the ZnO-based nanorod/quantum well composite ultraviolet light-emitting diode according to claim 5 or 6, characterized in that: in the step 5), the sputtering target is a Ni metal target, and the relative oxygen partial pressure is 0 2 /(O 2 +Ar) is 50～70%, the cavity background pressure before sputtering is ≤10 -3 Pa, the substrate temperature is 150～250℃, the sputtering pressure is 0.5～8Pa, the sputtering power is 20 ~150W, sputtering time is 20 ~ 60min.
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