CN101378091A - n-ZnO nanometer line/p-NiO alloplasm heterogeneous pn junction diode and preparation method thereof - Google Patents

n-ZnO nanometer line/p-NiO alloplasm heterogeneous pn junction diode and preparation method thereof Download PDF

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CN101378091A
CN101378091A CNA2008101970160A CN200810197016A CN101378091A CN 101378091 A CN101378091 A CN 101378091A CN A2008101970160 A CNA2008101970160 A CN A2008101970160A CN 200810197016 A CN200810197016 A CN 200810197016A CN 101378091 A CN101378091 A CN 101378091A
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CN100576577C (en
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方国家
黄晖辉
艾磊
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Wuhan University WHU
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Abstract

The invention discloses an n-zinc oxide nanowire/p-nickle oxide heterogeneous pn diode, which at least comprises a pn junction and an ohmic contact electrode. The pn junction consists of an n type ZnO film seed layer or an n type ZnO nanowire grown on a film seed layer doped with ZnO; and NiO material is plated on the ZnO nanowire to obtain heterogeneous pn junction. The invention first uses magnetron sputtering technology to prepare a ZnO or AZO seed layer on a glass substrate or an n type silicon chip; then adopts hydro-thermal reaction to grow the n type nanowire; and then the NiO layer is plated on the ZnO nanowire to form the heterogeneous pn junction; finally a sputtering method or thermal evaporation method is adopted to make an electrode on the pn junction; and the electrode forms ohmic contact through post annealing and alloying. The pn diode has low forward start voltage, high breakdown reverse voltage, big forward current density, good ultraviolet light sensitive characteristic, as well as simple technology of the preparation method and low cost.

Description

A kind of n-ZnO nano wire/p-NiO diode of heterogenous pn junction and preparation method thereof
Technical field
The present invention relates to a kind of nano-wire array diode of heterogenous pn junction---n-ZnO nano wire/p-NiO diode of heterogenous pn junction and preparation method thereof belongs to nano material and field of optoelectronic devices.
Background technology
ZnO is a kind of novel II-VI family direct band gap semiconductor material with wide forbidden band.The energy gap of ZnO is 3.37eV in room temperature, emission wavelength is equivalent to black light wavelength (368nm), be suitable for very much making short-wave long light-emitting and light-sensitive device, ZnO is still similar to GaN on energy gap in lattice structure, cell parameter, and have than higher fusing point of GaN and bigger exciton bind energy, have the threshold value of lower luminescence generated by light and stimulated radiation and good electromechanical coupling characteristics, thermal stability and chemical stability again.Thereby great potential is arranged in the application aspect royal purple light-emitting diode, laser and the relative photo electric device thereof.ZnO is considered to the desirable substitution material of GaN.Along with since some unique characteristics of nano material are found, the low dimensional structures of ZnO also expects to have physics and the chemical property that film and body monocrystalline are not had.
Summary of the invention
For improving the performance of traditional plane pn junction diode, the invention provides a kind of diode of heterogenous pn junction based on ZnO nano wire (bar) and preparation method thereof, the n-ZnO/p-NiO diode of heterogenous pn junction of preparation has lower forward cut-in voltage and big forward current density.With respect to traditional plane pn junction diode, its rectification characteristic and photosensitive property are improved.
Technical scheme of the present invention: the nickel oxide heterogeneous pn junction diode of a kind of n-zinc oxide nanowire/p-, at least comprise pn knot and Ohm contact electrode, described pn knot is by the n type ZnO nano wire that grows on n type ZnO film Seed Layer or the ZnO thin film doped Seed Layer; Be packed into insulating material plating NiO material on the ZnO nano wire again in the slit between nano wire earlier, or the direct heterogenous pn junction that on the ZnO nano wire, plates the NiO material and obtain.
Described insulating material is a silicon dioxide.
The preparation method of the nickel oxide heterogeneous pn junction diode of said n-zinc oxide nanowire/p-: at first prepare ZnO or AZO Seed Layer at glass substrate or on n type silicon chip with magnetron sputtering technique; Adopt the hydro-thermal reaction method to grow n type ZnO nano wire then; Plating NiO layer forms heterogenous pn junction on the ZnO nano wire then, or plates NiO layer formation heterogenous pn junction again with the space that the method for whirl coating is gone into filling insulating material earlier between nano wire on the ZnO nano wire; Adopt sputtering method or thermal evaporation to make electrode at last at the pn knot; Wherein, NiO surface sputtering nickel/platinum or nickel/gold electrode or ITO electrode plate indium electrode or aluminium electrode at ZnO or AZO edge; Electrode forms ohmic contact by the after annealing alloying.
Above-mentioned ZnO or AZO Seed Layer are to clean glass substrate or n type silicon chip by conventional semiconductor processing; Carry out the preparation of direct current or rf magnetron sputtering then under the following conditions: target is that ZnO ceramic target or AZO ceramic target, base vacuum degree are better than 10 -3Pa, underlayer temperature is 100～400 ℃, Ar air pressure is that 0.5～5Pa, power bracket 80～150W, sputtering time are 20 minutes～2 hours during deposition.
Being grown in the hydrothermal reaction kettle of above-mentioned nano wire finished, with etc. the hexamethylenetetramine and the zinc nitrate hexahydrate of mol ratio be dissolved in the deionized water, be configured to the equal proportion mixed solution of 0.05～0.5mol/L; 30～60mL mixed solution is put into the hydrothermal reaction kettle kettle, then the glass substrate that is shaped on ZnO or AZO Seed Layer on it or n type silicon chip Seed Layer are faced down and put on the support of solution, sealing is put into high temperature furnace and is heated to 70～130 ℃, constant temperature 5～48h naturally cools to room temperature then; Use rinsed with deionized water, oven dry gets n type ZnO nano wire.
It is the Ni metallic target of 50mm that the present invention adopts diameter, at relative partial pressure of oxygen O 2/ (O 2+ Ar)=60%, the cavity base vacuum degree before the sputter is better than 5 * 10 -4Pa, sputtering pressure are 0.5～1.5Pa, under sputtering power 100～250W condition, and plating NiO film on n type ZnO nano wire, the plated film time is 30～80min, underlayer temperature is 150～400 ℃.
The present invention utilizes ZnO nano wire (bar) array, has been compounded to form heterogenous pn junction structure with the p-NiO film.By to the control of conditions such as ZnO nano wire (bar) growth, NiO film preparation, the optimization of pn junction structure etc., improved the heterogenous pn junction performance, it is improved in the performance aspect the photosensitive detection, gives full play to the ZnO nano rod as the original advantage of monodimension nanometer material in the heterogenous pn junction application facet.
Description of drawings
Fig. 1 is that the present invention has filled SiO 2N-ZnO nano wire/p-NiO film heterogenous pn junction structure schematic diagram (embodiment one);
Fig. 2 is the I-V curve (embodiment one) that the present invention reflects the electrode ohm contact performance;
Fig. 3 is the I-V curve (embodiment one) that the present invention reflects the heterojunction rectification characteristic;
Fig. 4 is that the present invention does not fill SiO 2N-ZnO nano rod/p-NiO film heterogenous pn junction structure schematic diagram (embodiment two to four);
Fig. 5 is the I-V curve (embodiment two) that the present invention reflects the electrode ohm contact performance;
Fig. 6 is the I-V curve (embodiment two) that the present invention reflects the heterojunction rectification characteristic;
Fig. 7 is the I-V curve (embodiment three) that the present invention reflects the electrode ohm contact performance;
Fig. 8 is the I-V curve (embodiment three) that the present invention reflects the heterojunction rectification characteristic;
Fig. 9 is the I-V curve (embodiment four) that the present invention reflects the electrode ohm contact performance;
Figure 10 is the I-V curve (embodiment four) that the present invention reflects the heterojunction rectification characteristic.
Embodiment
The nickel oxide heterogeneous pn junction diode of n-zinc oxide nanowire/p-of the present invention comprises pn knot and Ohm contact electrode at least, and described pn knot is by the n type ZnO nano wire that grows on n type ZnO film Seed Layer or the ZnO thin film doped Seed Layer; Be packed into insulating material plating NiO material on the ZnO nano wire again in the slit between nano wire earlier, or the direct heterogenous pn junction that on the ZnO nano wire, plates the NiO material and obtain.
Its concrete preparation process is as follows:
(1) adopt the cleaning method in the semiconductor technology to clean glass substrate and silicon chip and oven dry;
(2) growth ZnO or AZO Seed Layer: used conditional parameter is when carrying out rf magnetron sputtering: target is that the good AZO ceramic target of ZnO ceramic target or conductivity, base vacuum degree are less than 10 -3Pa, underlayer temperature is 100～400 ℃, Ar air pressure is 0.5～5Pa during deposition, sputtering power scope 80～150W, sputtering time be 20 minutes～120 minutes (as document Guojia Fang, et al., Influence of post-deposition annealingon the properties of transparent conductive nanocrystalline AZO (ZnO:Al) thin filmsprepared by RF magnetron sputtering with highly conductive ceramic target, ThinSolid Films, 2002,418 (2): 156-162);
(3) growth of nano wire (bar): adopt the hydro-thermal reaction synthesis technique (as document Shuang Ma, Guojia Fang, Chun Li, Su Sheng, Linggang Fang, Qiang Fu, Xing-Zhong Zhao, ControllableSynthesis of Vertically Aligned ZnO Nanorod Arrays in Aqueous Solution, Journal ofNanoscience ﹠amp; Nanotechnology, 2006,6 (7), 2062-2066.), being grown in the hydrothermal reaction kettle of nano rod finished, and the main material of reactor is the 1Cr18Ni9Ti stainless steel, and the lining material is a polytetrafluoroethylene, and the volume of still is 100mL.It is pure that predecessor that uses in this experiment and catalyst are commercially available analysis, the hexamethylenetetramine ((CH of mol ratio such as disposes in the experimentation 2) 6N 4, HMT) and zinc nitrate hexahydrate (Zn (NO 3) 26H 2O), it is dissolved in the deionized water, is configured to the equal proportion mixed solution of 0.05～0.5mol/L.Stir 30min under the room temperature.Evenly 20～70mL mixed solution is put into kettle, substrate coating is faced down vertically put on the support of solution then, sealing is put into high temperature furnace and is heated to temperature requiredly, keeps constant temperature to required time, naturally cools to room temperature then.This experiment employing condition is 70～130 ℃ of temperature, time 5～48h.Use rinsed with deionized water, oven dry gets n type ZnO nano wire (bar) array;
(4) preparation of p-NiO: adopting diameter is the Ni metallic target of 50mm.Report (I.Hotovy, J.Huran, J. according to people such as I.Hotovy Et al., Deposition and properties of nickel oxide filmsproduced by DC reactive magnetron sputtering, Vacuum, 1998,51 (2): 157.), the NiO film of reactive magnetron sputtering preparation, the O in mixed atmosphere 2When ratio raise, the resistivity of film can rise thereupon, and light transmittance then can descend thereupon, to make the NiO film and had higher electric conductivity and light transmission simultaneously, the relative partial pressure of oxygen O that we adopt in order to make 2/ (O 2+ Ar)=30%～40% this is traded off and measures.Cavity base vacuum degree before the sputter is better than 5 * 10 -4Pa, sputtering pressure are 0.5～1.5Pa, sputtering power 100～250W.Before plated film, pre-sputter 10min is to remove the impurity of target material surface.Growing plating NiO film on the substrate of having got well ZnO nano wire (bar).The plated film time is 30～80min, and underlayer temperature is 150～400 ℃.
(5) preparation of electrode: adopt surface and ZnO or the AZO edge making electrode of methods such as sputtering method or thermal evaporation (as: Tang Weizhong work, thin-film material preparation principle, technology and application, metallurgical industry publishing house 1998 front pages) at NiO.NiO surface sputtering platinum or nickel/platinum or nickel/gold electrode or ito transparent electrode, ZnO edge plate indium electrode or aluminium electrode.Electrode forms ohmic contact by the after annealing alloying.
(6) can increase the filling step of insulating barrier between step (3) and (4), promptly with the whirl coating method filling insulating material be gone into space, bottom between the ZnO nano wire, drying forms a layer insulating.The insulating barrier the selection of material is: silicon dioxide.
(7) test
With the ohmic contact characteristic of Keithley 2400 detecting electrodes and the I of diode of heterogenous pn junction-V characteristic (rectification characteristic).
Above-mentioned substrate is glass or silicon chip.
Embodiment one:
1. substrate cleans: adopt normal silicate glass as substrate, be cut into 25mm * 30mm size, adopt alcohol, acetone, deionized water ultrasonic cleaning 30min respectively, dry up with nitrogen gun at last.
2. the growth of Seed Layer: use the method for radio frequency frequency magnetron sputtering to go up deposition AZO film (2) (as the Seed Layer of subsequent growth nano wire) at substrate (1).Target is selected the good AZO ceramic target of conductivity for use, and base vacuum is less than 10 -3Pa, deposition substrate temperature: 300 ℃; Ar air pressure: 1.0Pa during deposition; Sputtering power 140W; Sputtering time: 20min.
3. the growth of nano wire: it is reaction vessel that employing has the teflon-lined high-pressure hydrothermal reaction kettle, and its volume is 100mL.The hexamethylenetetramine ((CH of configuration 0.05mol/L 2) 6N 4, HMT) and zinc nitrate hexahydrate (Zn (NO 3) 26H 2O) mixed solution is put into 20mL in kettle, substrate coating is faced down vertically put on the support of solution, and 90 ℃ kept 7 hours, and promptly obtained ZnO nano rod (3).
4. the filling of insulating barrier adopts the whirl coating method that the colloidal sol of silicon dioxide is packed into space, bottom between the ZnO nano wire, and drying forms a layer insulating (7), and (preparation technology of silicon dioxide gel sees document: side country, Liu Zuli, Yao Kailun, nanometer micropore SiO 2The Sol-Gel preparation of film and porosity control, functional material, 1999,30 (2): 190).
5.p-NiO preparation: the method for using reactive sputtering is deposition NiO film (4) on the long sheet glass that the ZnO nano rod arranged.Target is selected highly purified metal Ni target for use, and base vacuum is less than 10 -3Pa, deposition substrate temperature: 300 ℃; Deposition pressure: 1.0Pa, wherein Ar:O 2=6:4; Power: 80W, sputtering time: 80min.
6. the preparation of electrode: adopt the method for rf magnetron sputtering to prepare Ni/Pt electrode (6) under NiO film surface normal temperature, wherein the sedimentation time of metal Ni is 30s, and the sedimentation time of metal Pt is 200s.The AZO film of substrate surface uses In as electrode (5).The structure chart that obtains at last as shown in Figure 1.
7. test: be ohmic contact with Keithley 2400 detecting electrodes, the contact performance curve as shown in Figure 2.Record this diode of heterogenous pn junction I-the V characteristic curve as shown in Figure 3.
Embodiment two:
1. substrate cleans: adopt normal silicate glass as substrate, be cut into 25mm * 30mm size, adopt alcohol, acetone, deionized water ultrasonic cleaning 30min respectively, dry up with nitrogen gun at last.
2. the growth of Seed Layer: use the method for radio frequency frequency magnetron sputtering to go up deposition AZO film (2) (as the Seed Layer of subsequent growth nano wire) at substrate (1).Target is selected the good AZO ceramic target of conductivity for use, and base vacuum is less than 10 -3Pa, deposition substrate temperature: 100 ℃; Ar air pressure: 2.0Pa during deposition; Power 120W; Sputtering time: 50min.
3. the growth of nano rod: it is reaction vessel that employing has the teflon-lined high-pressure hydrothermal reaction kettle, and its volume is 100mL.The hexamethylenetetramine ((CH of configuration 0.2mol/L 2) 6N 4, HMT) and zinc nitrate hexahydrate (Zn (NO 3) 26H 2O) mixed solution is put into 30mL in kettle, substrate coating is faced down vertically put on the support of solution, and 70 ℃ kept 5 hours, and promptly obtained ZnO nano rod (3).
4.p-NiO preparation: the method for using reactive sputtering is deposition NiO film (4) on the long sheet glass that the ZnO nano rod arranged.Target is selected highly purified metal Ni target for use, and base vacuum is less than 10 -3Pa, deposition substrate temperature: 150 ℃; Deposition pressure: 0.5Pa, wherein Ar:O 2=7:3; Power: 250W, sputtering time: 30min.
5. the preparation of electrode: adopt the method normal temperature of rf magnetron sputtering to prepare Pt electrode (6) down, its sedimentation time is 200s.The AZO film of substrate surface uses In as electrode (5).The structure chart that obtains at last as shown in Figure 4.
6. test: be ohmic contact with Keithley 2400 detecting electrodes, the contact performance curve as shown in Figure 5.Record this diode of heterogenous pn junction I-the V characteristic curve as shown in Figure 6.
Embodiment three:
1. substrate cleans: adopt normal silicate glass as substrate, be cut into 25mm * 30mm size, adopt alcohol, acetone, deionized water ultrasonic cleaning 30min respectively, dry up with nitrogen gun at last.
2. the growth of Seed Layer: use radio frequency method (1) deposition AZO film (2) (as the Seed Layer of subsequent growth nano wire) on substrate of magnetron sputtering frequently.Target is selected the good AZO ceramic target of conductivity for use, and base vacuum is less than 10 -3Pa, deposition substrate temperature: 200 ℃; Ar air pressure: 0.5Pa during deposition; Power 150W; Sputtering time: 20min.
3. the growth of nano rod: it is reaction vessel that employing has the teflon-lined high-pressure hydrothermal reaction kettle, and its volume is 100mL.The hexamethylenetetramine ((CH of configuration 0.5mol/L 2) 6N 4, HMT) and zinc nitrate hexahydrate (Zn (NO 3) 26H 2O) mixed solution is put into 30mL in kettle, substrate coating is faced down vertically put on the support of solution, and 130 ℃ kept 48 hours, and promptly obtained ZnO nano rod (3).
4.p-NiO preparation: the method for using reactive sputtering is deposition NiO film (4) on the long sheet glass that the ZnO nano rod arranged.Target is selected highly purified metal Ni target for use, and base vacuum is less than 10 -3Pa, deposition substrate temperature: 300 ℃; Deposition pressure: 1.5Pa, wherein Ar:O 2=7:3; Power: 250W, sputtering time: 50min.
5. the preparation of electrode: the method that adopts the radio frequency magnetron reactive sputtering is at NiO surface preparation transparent ITO electrode (6).Sputtering target material adopts In/Ga metallic target (wherein In content is 90%), and base vacuum is less than 10 -3Pa, deposition substrate temperature: 300 ℃; Deposition pressure: 1.0Pa, wherein Ar:O 2=7:3; Power: 160W, sputtering time: 20min.The AZO film of substrate surface uses In as electrode (5).The structure chart that obtains at last as shown in Figure 4.
6. test: be ohmic contact with Keithley 2400 detecting electrodes, the contact performance curve as shown in Figure 7.Record this diode of heterogenous pn junction I-the V characteristic curve as shown in Figure 8.
Embodiment four:
1. substrate cleans: adopt n type (100) orientation silicon chip as substrate.Adopt No. 1 liquid commonly used in the semiconductor technology and the method for No. 2 liquid to come cleaning silicon chip.The prescription of No. 1 liquid is: concentrated ammonia liquor: 30% hydrogen peroxide: deionized water=1:2:7 (volume ratio); The prescription of No. 2 liquid is: concentrated hydrochloric acid: 30% hydrogen peroxide: deionized water=1:2:7 (volume ratio).Earlier boil silicon chip, make it boiling for a moment, treat that its cooling cleans up with deionized water again with No. 1 liquid.Put into No. 2 liquid then and boil silicon chip, make it boiling for a moment, treat the last taking-up of its cooling, clean up with deionized water again, at last oven dry.
2. the growth of Seed Layer: method (1) deposition ZnO film (2) (as the Seed Layer of subsequent growth nano wire) on substrate that uses rf magnetron sputtering.Target is selected the ZnO ceramic target for use, and base vacuum is less than 10 -3Pa, deposition substrate temperature: 400 ℃; Ar air pressure: 5.0Pa during deposition; Power 80W; Sputtering time: 120min.
3. the growth of nano rod: it is reaction vessel that employing has the teflon-lined high-pressure hydrothermal reaction kettle, and its volume is 100mL.The hexamethylenetetramine ((CH of configuration 0.1mol/L 2) 6N 4, HMT) and zinc nitrate hexahydrate (Zn (NO 3) 26H 2O) mixed solution is put into 70mL in kettle, substrate coating is faced down vertically put on the support of solution, and 80 ℃ kept 7 hours, and promptly obtained ZnO nano rod (3).
4.p-NiO preparation: the method for using reactive sputtering is deposition NiO film (4) on the long sheet glass that the ZnO nano rod arranged.Target is selected highly purified metal Ni target for use, and base vacuum is less than 10 -3Pa, deposition substrate temperature: 300 ℃; Deposition pressure: 1.0Pa, wherein Ar:O 2=6:4; Power: 100W, sputtering time: 80min.
5. the preparation of electrode: at NiO surface preparation Ni/Au electrode (6), its sedimentation time is 200s under the method normal temperature of employing magnetron sputtering.The ZnO film evaporating Al of substrate surface is as electrode (5).The structure chart that obtains at last as shown in Figure 4.
6. test: be ohmic contact with Keithley 2400 detecting electrodes, the contact performance curve as shown in Figure 9.Record this diode of heterogenous pn junction I-the V characteristic curve as shown in figure 10.

Claims (6)

1、一种n-氧化锌纳米线/p-氧化镍异质pn结二极管，至少包括pn结和欧姆接触电极，其特征在于：所述pn结是由n型ZnO薄膜种子层或者掺杂ZnO薄膜种子层上生长出的n型ZnO纳米线；纳米线间的缝隙中先填充入绝缘材料再在ZnO纳米线上镀NiO材料，或直接在ZnO纳米线上镀NiO材料而得到的异质pn结。1. An n-zinc oxide nanowire/p-nickel oxide heterogeneous pn junction diode, comprising at least a pn junction and an ohmic contact electrode, characterized in that: the pn junction is made of an n-type ZnO thin film seed layer or doped ZnO The n-type ZnO nanowires grown on the film seed layer; the gaps between the nanowires are first filled with insulating materials and then coated with NiO materials on the ZnO nanowires, or directly coated with NiO materials on the ZnO nanowires to obtain heterogeneous pn Knot. 2、根据权利要求1所述的n-氧化锌纳米线/p-氧化镍异质pn结二极管，其特征在于：所述绝缘材料为二氧化硅。2. The n-zinc oxide nanowire/p-nickel oxide heterogeneous pn junction diode according to claim 1, characterized in that: the insulating material is silicon dioxide. 3、权利要求1或2所述n-氧化锌纳米线/p-氧化镍异质pn结二极管的制备方法，其特征在于：首先用磁控溅射工艺在玻璃基片或在n型硅片上制备ZnO或AZO种子层；然后采用水热反应法生长出n型ZnO纳米线；然后在ZnO纳米线上镀NiO层形成异质pn结，或用甩胶的方法先将绝缘材料填充入纳米线间的空隙再在ZnO纳米线上镀NiO层形成异质pn结；最后采用溅射法或热蒸发法在pn结制作电极；其中，NiO表面溅射镍/铂或镍/金电极或ITO电极，在ZnO或AZO边缘镀上铟电极或铝电极；电极通过后退火合金化形成欧姆接触。3. The method for preparing the n-zinc oxide nanowire/p-nickel oxide heterogeneous pn junction diode according to claim 1 or 2, characterized in that: firstly, the magnetron sputtering process is used on the glass substrate or on the n-type silicon wafer Prepare ZnO or AZO seed layer; then use hydrothermal reaction method to grow n-type ZnO nanowires; then plate NiO layer on ZnO nanowires to form a heterogeneous pn junction, or use the method of spinning glue to fill the insulating material into the nanometer The gap between the wires is then plated with NiO layer on the ZnO nanowires to form a heterogeneous pn junction; finally, sputtering or thermal evaporation is used to make electrodes at the pn junction; among them, nickel/platinum or nickel/gold electrodes or ITO are sputtered on the surface of NiO Electrodes, indium electrodes or aluminum electrodes are plated on the edge of ZnO or AZO; the electrodes are alloyed by post-annealing to form ohmic contacts. 4、根据权利要求3所述的制备方法，其特征在于：ZnO或AZO种子层是通过传统半导体工艺清洗玻璃基片或n型硅片；然后在下述条件下进行直流或射频磁控溅射制备：靶材是ZnO陶瓷靶或AZO陶瓷靶、本底真空度优于10-3Pa，衬底温度为100～400℃，沉积时Ar气压为0.5～5Pa、功率范围80～150W、溅射时间为20分钟～2小时。4. The preparation method according to claim 3, characterized in that: the ZnO or AZO seed layer is prepared by cleaning the glass substrate or n-type silicon wafer by traditional semiconductor technology; and then performing DC or RF magnetron sputtering under the following conditions : The target material is ZnO ceramic target or AZO ceramic target, the background vacuum is better than 10 -3 Pa, the substrate temperature is 100-400°C, the Ar pressure is 0.5-5Pa during deposition, the power range is 80-150W, and the sputtering time is 20 minutes to 2 hours. 5、根据权利要求3所述的制备方法，其特征在于：上述纳米线的生长在水热反应釜内完成，将等摩尔比的六次甲基四胺和六水合硝酸锌溶解于去离子水中，配置成0.05～0.5mol/L的等比例混合溶液；将30～60mL混合溶液放入水热反应釜釜体，然后把其上制有ZnO或AZO种子层的玻璃基片或n型硅片种子层面朝下放入溶液中的支架上，密封放入高温炉内加热升温到70～130℃，恒温5～48h，然后自然冷却到室温；用去离子水漂洗，烘干，得n型ZnO纳米线。5. The preparation method according to claim 3, characterized in that: the growth of the nanowires is completed in a hydrothermal reactor, and hexamethylenetetramine and zinc nitrate hexahydrate in equimolar ratio are dissolved in deionized water , configured as a mixed solution in equal proportions of 0.05-0.5mol/L; put 30-60mL of the mixed solution into the body of the hydrothermal reactor, and then put the glass substrate or n-type silicon wafer with ZnO or AZO seed layer on it Put the seed layer face down on the support in the solution, seal it and put it in a high-temperature furnace, heat up to 70-130°C, keep the temperature for 5-48h, and then naturally cool to room temperature; rinse with deionized water and dry to obtain n-type ZnO Nanowires. 6、根据权利要求3或4或5所述的制备方法，其特征在于：采用直径为50mm的Ni金属靶，在相对氧分压O2/(O2+Ar)＝60％、溅射前的腔体本底真空度优于5×10-4Pa、溅射气压为0.5～1.5Pa，溅射功率100～250W条件下，在n型ZnO纳米线上镀NiO膜，镀膜时间为30～80min，衬底温度为150～400℃。6. The preparation method according to claim 3, 4 or 5, characterized in that: a Ni metal target with a diameter of 50mm is used, before the relative oxygen partial pressure O 2 /(O 2 +Ar) = 60%, sputtering The background vacuum of the cavity is better than 5×10 -4 Pa, the sputtering pressure is 0.5~1.5Pa, and the sputtering power is 100~250W, the NiO film is coated on the n-type ZnO nanowire, and the coating time is 30~ 80min, the substrate temperature is 150-400°C.
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