CN105428183B - A kind of reflective NEA GaN nano wires array photoelectric negative electrode and preparation method - Google Patents
A kind of reflective NEA GaN nano wires array photoelectric negative electrode and preparation method Download PDFInfo
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Abstract
The present invention proposes a kind of reflective NEA GaN nano wires array photoelectric negative electrode and preparation method, the reflective NEA GaN nano wires array photoelectric negative electrode is the superficial growth p-type GaN nano wire in Si or SiC substrate, and the nano-wire array progress Cs/O activation of growth is obtained, it includes substrate layer, the nano-wire array emission layer positioned at substrate layer surface；Nano-wire array emission layer is made up of some p-type GaN nano wires, and p-type GaN nano wire surface is adsorbed with Cs/O active coatings；The substrate layer is Si or SiC.The present invention can reduce photoelectronic transport distance while material emissivity is reduced, and the diameter of control nano wire fully absorbs photon, improves GaN photocathode quantum efficiencies.
Description
Technical field
The invention belongs to photoemissive material technical field, and in particular to a kind of reflective NEA GaN nano wires array light
Electric negative electrode and preparation method.
Background technology
Photocathode is the photoemissive material that a kind of utilization external photoeffect converts light signals into electric signal.With negative
The GaN photocathodes of electron affinity, i.e. cathode surface vacuum level are less than conduction band bottom energy level, therefore photo-excited electron in vivo
Surface need to be run to, so that it may which vacuum is transmitted into by tunnelling, go to overcome the potential barrier of material surface without superfluous kinetic energy, excite light
The escape probability of electronics is greatly increased, therefore with quantum efficiency is high, dark current is small, the medium uniqueness of emitted electron energy distribution collection
Advantage.Its quantum efficiency is generally higher than 24%, is much higher than the quantum efficiency of traditional ultraviolet light photo negative electrode, also, GaN material
Response, in below 400nm, is typical " day is blind " material, with good capability of resistance to radiation.
Growth nano-wire array mainly has metal-organic chemical vapor deposition equipment method (MOCVD), dry etching method etc. at present, these
All there are some inevitable shortcomings in growing method.Metal-organic chemical vapor deposition equipment method is expensive due to its equipment, and instead
It is the shortcomings of metallorganic is not easy to maintain to answer raw material, therefore repeatability is not high；And although dry etching method equipment is simple, cost compared with
It is low, easily realize, but be due to that its reaction mechanism is to eventually form nano-wire array, therefore nanometer by corrosion resistant semiconductor material
The lattice on line surface is damaged more serious, and the surface of formation is rougher, and the diameter of nano wire does not reach nanowire photodiode the moon in addition
The order of magnitude of pole emission layer, therefore we need a kind of suitable nano wire life for preparing GaN nano wire array photoelectric negative electrode of searching
Long method.
General GaN photocathodes are made of thin-film material, and thin-film material has growth technique ripe, quality of forming film
Good the advantages of, but the emissivity of thin-film material is big, it is impossible to the energy of incident light is fully absorbed, in addition for reflective photocathode
For, the transport distance of the electronics of material is to the thickness requirement of material and material to the thickness requirement of the absorption depth of light to material
Between it is conflicting.
The content of the invention
It is an object of the invention to propose a kind of reflective NEA GaN nano wires array photoelectric negative electrode and preparation method, energy
Enough to reduce photoelectronic transport distance while material emissivity is reduced, the diameter of control nano wire fully absorbs photon, carried
High GaN photocathode quantum efficiencies.
In order to solve the above-mentioned technical problem, the present invention provides a kind of reflective NEA GaN nano wires array photoelectric negative electrode, bag
Include substrate layer, the nano-wire array emission layer positioned at substrate layer surface；Nano-wire array emission layer is by some p-type GaN nano wires
Composition, p-type GaN nano wire surface is adsorbed with Cs/O active coatings.
It is preferred that the substrate layer is Si or SiC；A diameter of 10~100nm of the p-type GaN nano wire, length is
1~100 μm, p-type doping concentration is 1 × 1019cm-3, and doped chemical is Zn.
The present invention also proposes a kind of method that p-type GaN nano wire is grown in substrate surface, and step is as follows：
Step 101, the evaporated metal Al formation metal Al layer on substrate, grass is placed in by the substrate with metal Al layer
Electrochemical corrosion is carried out in acid solution, so that in substrate surface formation porous alumina membrane；
Step 102, the substrate that there is mesh structural porous aluminum oxide film on the surface is put into the mixed liquor of phosphoric acid and chromic acid
Immersion, removes the aluminum oxide of bottom hole portion and substrate contact on aluminum oxide film, the mesh structural porous anodic oxidation of formation rule size
Aluminium film；
Step 103, in the mesh structural porous anodic aluminum oxide film surface evaporation layer of metal Ni, then place the substrate into
Soaked in NaOH aqueous slkalis, remove the anodic aluminum oxide film of substrate surface, so as to form W metal nano particle on substrate
Dot matrix；
Step 104, substrate and reaction source be put into partition heating in the quartz boat of CVD reacting furnaces, treat substrate and reaction source
The temperature of region is reached after design temperature, and ammonia and argon gas are passed through to CVD reacting furnaces, then CVD reacting furnaces be incubated to
550 DEG C of progress deposition reactions, the p-type GaN nano wire array of Ni catalyst granules is arranged at obtained top.
It is preferred that the substrate layer is Si or SiC；It is first 1 with volume ratio on substrate before evaporated metal Al:1
Sulfuric acid and hydrogen peroxide cleaning substrate, then clean substrate with mass percent for 5% hydrofluoric acid corrosion；Electricity is used in step 1
Al layers of the evaporated metal Al formation on substrate of beamlet evaporation coating method, the Al thickness degree is 100~1000nm；Step 1 mesoxalic acid
Solution concentration is 0.5mol/L.
It is preferred that in step 102, in the phosphoric acid and chromic acid mixture, phosphoric acid quality percentage is 4%, chromic acid quality
Percentage is 2%.
It is preferred that in step 103 use Ni layer of electron beam evaporation methods evaporation metal, W metal layer thickness be 5~
100nm；The substrate, which is put into the NaOH aqueous slkalis that mass percent is 5%, to be soaked.
It is preferred that in step 104, GaCl3 is that gallium source, ZnCl2 are doped chemical Zn sources, with mole ratio 1000:1 ratio
As reaction source after example mixing, reaction source is located at close to CVD reacting furnaces air inlet and apart from substrate 10cm or so position, substrate
Positioned at the center heating location of CVD reacting furnaces；CVD reacting furnaces are first vacuumized before heating and are passed through argon purge boiler tube；Substrate institute
In position, heating-up temperature is to 850 DEG C, and reaction source position heating-up temperature is to 600 DEG C；The argon flow amount is 200ml/min,
Ammonia flow for 30ml/min；The deposition reaction time is 100~120min.
The present invention also proposes a kind of method for preparing reflective NEA GaN nano wires array photoelectric negative electrode, uses quality percentage
Number removes the Ni catalyst granules of p-type GaN nano wire array top for the mixed acid solution of 4% hydrochloric acid, phosphoric acid and hydrofluoric acid；
Heating purification is carried out in once purged feeding high-temperature vacuum system, p-type GaN nano wire array is obtained the table of Atomically clean
Face；Then Cs/O active coatings are adsorbed in p-type GaN nano wire array surface.
It is preferred that with the grease and impurity on Chemical cleaning reagent etching away p-type GaN nano wire surface, Chemical cleaning is tried
Agent is that volume ratio is 2:2:1 sulfuric acid, hydrogen peroxide and deionized water mixed liquor；Hot temperature in high-temperature vacuum system is 850 DEG C；
Using ultravacuum activation technology Cs/O active coatings are adsorbed in p-type GaN nano wire array surface.
Compared with prior art, its remarkable advantage is the present invention, and GaN nano wire array is fabricated to photocathode, can
The energy of incident light is fully absorbed by the transmitting between nano wire and refraction, and overcomes photonic absorption depth and electronics expansion
Dissipate the contradictory relation of length；When light incides nano-wire array at a proper angle, due to the unique structure of nano wire, enter
The photon entered can reflect and reflect between nano wire, finally thoroughly be absorbed by nano-wire array, form " photon capture " effect,
The loss of energy is set to be reduced to minimum, so as to greatly improve the quantum efficiency of photocathode.In addition, when photon is inside nano wire
When being absorbed, photoelectrons are excited, because the surrounding of nano wire is surface, therefore photoelectron is from the inside of nano wire to surrounding
Effusion, drastically increases the number of runaway electron, so as to increase photoelectric current, improves the quantum efficiency of photocathode.GaN
Nano-wire array is due to itself excellent photoelectric characteristic, the NEA GaN photoelectric cathode materials based on nanometer technology as a new generation,
There is positive effect to extension GaN photocathode application fields.
Brief description of the drawings
Fig. 1 is reflective NEA GaN nano wires array photoelectric negative electrode schematic diagram of the present invention.
Fig. 2 is to generate proper alignment on substrate using anodic oxidation aluminium formwork method in the present invention to have receiving for nano-wire array
The schematic flow sheet of nanowire arrays emission layer.
In Fig. 3 present invention p-type GaN nano wire array schematic diagram is grown using CVD method.
Embodiment
It is readily appreciated that, according to technical scheme, in the case where not changing the connotation of the present invention, this area
Those skilled in the art can imagine a variety of of reflective NEA GaN nano wires array photoelectric negative electrode of the invention and preparation method
Embodiment.Therefore, detailed description below and accompanying drawing are only the exemplary illustrations to technical scheme, without answering
When the whole for being considered as the present invention or it is considered as limitation or restriction to technical solution of the present invention.
Reflective NEA GaN nano wires array photoelectric negative electrode of the present invention is the superficial growth in Si or SiC substrate 1
P-type GaN nano wire 5, and the nano-wire array progress Cs/O activation of growth is obtained, it includes substrate layer, positioned at substrate layer table
The nano-wire array emission layer in face；Nano-wire array emission layer is made up of some p-type GaN nano wires 5, p-type GaN nano wire surface
It is adsorbed with Cs/O active coatings 10；The substrate layer is Si or SiC.A diameter of 10~100nm of p-type GaN nano wire, length
For 1~100 μm, p-type doping concentration is 1 × 1019cm-3, and doped chemical is Zn.
It is in the method for substrate surface growth p-type GaN nano wire：
Step 101, first use volume ratio are 1:1 sulfuric acid and hydrogen peroxide cleaning Si or SiC substrate, then uses mass percent
For 5% hydrofluoric acid corrosion cleaning substrate；
Step 102, Al layers of the evaporated metal Al formation on substrate using electron beam evaporation methods, the Al thickness degree is
100~1000nm；
Step 103, step 2 is evaporated to the substrate for having metal Al it is placed in 0.5mol/L oxalic acid solution that to carry out electrochemistry rotten
Erosion, so that in substrate surface formation porous alumina membrane；
Step 104, the substrate that there is pellumina on top layer after step 3 electrochemical corrosion is put into mass percent is 4%
Phosphoric acid, to be soaked in 2% chromic acid mixture, removes the oxygen of bottom hole portion and substrate contact on aluminum oxide film with mass percent
Change aluminium and change the size in hole, with the mesh structural porous anodic aluminum oxide film of formation rule size；
Step 105, steamed again in the mesh structural porous anodic aluminum oxide film surface that step 4 is formed using electron beam evaporation methods
Layer of metal Ni is plated, the thickness of W metal is 5~100nm；
Step 106, the substrate that step 5 is formed is put into the NaOH aqueous slkalis that mass percent is 5% and soaked, remove lining
The anodic aluminum oxide film of basal surface, so as to obtain W metal nano particle dot matrix on substrate；
Step 107, the substrate that step 6 is obtained is put into the center heating location that CVD reacting furnaces are placed in quartz boat；
Step 108, it is that gallium source, ZnCl2 are doped chemical Zn sources by GaCl3, with mole ratio 1000:1 ratio mixing
It is put into afterwards as reaction source in quartz boat, reaction source is located at close to CVD reacting furnaces air inlet apart from substrate 10cm or so position,
Substrate is located at the center heating location of reacting furnace, then vacuumizes CVD reacting furnaces and is passed through argon purge boiler tube；
Step 109, the furnace temperature for controlling each warm area of CVD reacting furnaces, first heat CVD reacting furnace central substrates position temperature
To 850 DEG C, reaction source position temperature is then reheated to 600 DEG C, and treating the temperature of above-mentioned two warm area, to rise to design temperature backward
CVD reacting furnaces are passed through ammonia and argon gas, the flow of argon gas is 200ml/min, and the flow of ammonia reacts for 30ml/min, CVD
Stove is incubated to 550 DEG C of progress deposition reactions, and sedimentation time is 100~120min, and deposition cools to room temperature with the furnace after finishing, and is made
The GaN nano wire array of the p-type doping of Ni catalyst granules is arranged at top.
The above-mentioned p-type GaN nano wire array being grown on substrate is further fabricated to as nano-wire array emission layer
The method of reflective NEA GaN nano wires array photoelectric negative electrode is：
Step 201, the mixed acid solution of the hydrochloric acid, phosphoric acid and hydrofluoric acid that are 4% with mass percent remove p-type GaN and received
Ni particles at the top of rice noodles；
Step 11, grease and impurity with Chemical cleaning reagent etching away p-type GaN nano wire surface, Chemical cleaning examination
Agent is that volume ratio is 2:2:1 sulfuric acid, hydrogen peroxide and deionized water mixed liquor；Then p-type GaN nano wire array is sent into high temperature
Heating purification is carried out in vacuum system, heating-up temperature is 850 DEG C, p-type GaN nano wire array is obtained the table of Atomically clean
Face；
Step 12, using ultravacuum activation technology p-type GaN nano wire array surface adsorb Cs/O active coatings, now send out
Penetrate layer surface and reach negative electron affinity (NEA), reflective NEA GaN nano wires array photoelectric negative electrode is finally made.
Reflection type GaN nano-wire array photocathode of the present invention solves photonic absorption and electron transport pair in thin-film material
The problem of material emission layer thickness requirement is conflicting, so as to while material emissivity is reduced, reduce photoelectronic
Transport distance, the diameter of control nano wire fully absorbs photon, realizes the imagination for improving GaN photocathode quantum efficiencies；This
Invention prepares nanoscale Ni catalyst granules as CVD growth using anodic oxidation aluminium formwork method, simple with preparation method, can
Reproducible, cost is low, and catalyst particle size is controllable, the advantages of marshalling；The present invention is preparing p using CVD method
During type GaN nano wire, compared with MOCVD methods, the reaction source used is GaCl3, ZnCl2, ammonia and argon gas, with raw material
The cheap and controllable advantage of growth course；The present invention prepares p-type GaN nano wire array using CVD method, is carved with existing dry method
Erosion technology is compared, less with GaN nano wire surface defect, the more small advantage of size, and length and diameter ratio are bigger,
The quantum efficiency of nanowire photodiode negative electrode can preferably be lifted；The present invention is born using GaN nano wire material activation into reflective
Electron affinity GaN nano wire photocathode, can adsorb one layer of Cs/O active coating around nano wire after activating successfully, produce negative electricity
Sub- affinity, so as to form high in the middle of one in nano wire, the low band structure of surrounding, this band structure is very beneficial for
The photoelectron excited in nano wire is transported and is transmitted into vacuum toward surface.
Embodiment
The method for adsorbing proper alignment nanoscale Ni catalyst granules in substrate surface：
First, it is 1 with volume ratio:1 sulfuric acid and hydrogen peroxide cleaning Si or SiC substrate 1, be then with mass percent
5% hydrofluoric acid corrosion cleaning cleaning Si or SiC substrate, the method for electron beam evaporation plating is utilized in substrate in the substrate surface of cleaning
Evaporated metal Al layers forms in Al films 2, such as Fig. 2 shown in (a) on layer, and the thickness of Al films 2 is 100~1000nm；Will evaporation
The substrate for having Al films 2, which is placed in 0.5mol/L oxalic acid solution, carries out electrochemical corrosion, in substrate surface formation porous oxidation
Aluminium film；The substrate that there is pellumina on top layer after electrochemical corrosion is put into the phosphoric acid and quality hundred that mass percent is 4%
Fraction is soaks in 2% chromic acid mixture, the aluminum oxide of removal aperture bottom and substrate contact and the size for changing hole, with shape
Into the mesh structural porous anodic aluminum oxide film 3 of regular size, in such as Fig. 2 shown in (b)；In the mesh structural porous anodised aluminium of formation
Layer of metal Ni layers 4 are deposited using the method for electron beam evaporation plating in the surface of film 3 again, in such as Fig. 2 shown in (c), the thickness of category Ni layers 4
For 5~100nm；Then the backing material of formation is put into the NaOH aqueous slkalis that mass concentration is 5% and soaked, remove substrate table
The anodised aluminium in face, is obtained in W metal nano particle dot matrix, such as Fig. 2 on substrate shown in (d).
The method of further growth p-type GaN nano wire array is：
With reference to Fig. 3, the substrate that obtained surface there are proper alignment nanometer Ni catalyst particles is put into juxtaposition in quartz boat
In the center heating location of CVD reacting furnaces；Using GaCl3 as gallium source, ZnCl2 is doped chemical Zn sources, with mole ratio 1000:1
Ratio mixing after be put into as reaction source 8 in quartz boat, be placed with reaction source quartz boat be located at close to air outlet apart from substrate
10~15cm position, substrate is located at the center heating location of reacting furnace, vacuumizes and is passed through the cleaning boiler tube of argon gas 7；Control is each
The furnace temperature of warm area, first heating reaction furnace central substrate position rises to 850 DEG C, reheats reaction source position and rises to 600 DEG C, treats
The temperature of above-mentioned two warm area, which is risen to after design temperature, is passed through ammonia 6 and argon gas 7, and the flow of argon gas is 200ml/min, ammonia
Flow for 30ml/min, insulation is to 550 DEG C of progress deposition reactions, and sedimentation time is 100~120min, and deposition stops after finishing
Carrier gas is passed through, substrate cools to room temperature with the furnace, the top is made on substrate the GaN of p-type doping of Ni catalyst granules
In nano-wire array, such as Fig. 2 shown in (e)；Mixed acid solution with mass percent for 3% hydrochloric acid, phosphoric acid and hydrofluoric acid is removed
The Ni particles gone at the top of nano wire, are obtained in the p-type GaN nano wire array of proper alignment, such as Fig. 2 shown in (f).
The method for further preparing reflective NEA GaN nano wires array photoelectric negative electrode is：
Remove the grease and impurity of nanowire surface by chemical attack, the reagent volume ratio of Chemical cleaning is 2:2:1
Sulfuric acid, hydrogen peroxide and deionized water.Progress heating purification in high-temperature vacuum system is re-fed into, heating-up temperature is 850 DEG C, makes p-type
GaN nano wire emission layer obtain atomically clean surfaces；P-type GaN nano wire emission layer is made by ultravacuum activation technology again
Adsorption Cs/O active coatings 10, Cs, the process of O activation continues for Cs, and discontinuously, transmitting layer surface reaches that negatron is affine in O sources
Gesture, it is final that reflective NEA GaN nano wires array photoelectric negative electrode as shown in Figure 1 is made.Reflective NEA GaN nano wires array
The photocathode a diameter of 10~100nm of its nano wire 5, length is 1~100 μm, and p-type doping concentration is 1 × 1019cm-3, doping
Element is Zn.
Claims (8)
1. a kind of reflective NEA GaN nano wires array photoelectric negative electrode, it is characterised in that including substrate layer, positioned at substrate layer table
The nano-wire array emission layer in face；Nano-wire array emission layer is made up of some p-type GaN nano wires, p-type GaN nano wire surface
It is adsorbed with Cs/O active coatings；The substrate layer is Si or SiC；The method of the p-type GaN nano wire is grown in substrate surface
For：
Step 101, the evaporated metal Al formation metal Al layer on substrate, are placed in oxalic acid molten by the substrate with metal Al layer
Electrochemical corrosion is carried out in liquid, so as to form mesh structural porous aluminum oxide film in substrate surface；
Step 102, by the substrate that there is mesh structural porous aluminum oxide film on the surface be put into the mixed liquor of phosphoric acid and chromic acid soak,
The aluminum oxide of bottom hole portion and substrate contact on aluminum oxide film is removed, the mesh structural porous anodised aluminium of formation rule size is thin
Film；
Step 103, in the mesh structural porous anodic aluminum oxide film surface evaporation layer of metal Ni, then place the substrate into NaOH
Soaked in aqueous slkali, remove the anodic aluminum oxide film of substrate surface, so as to form W metal nano particle dot matrix on substrate；
Step 104, substrate and reaction source be put into partition heating in the quartz boat of CVD reacting furnaces, where treating substrate and reaction source
The temperature in region is reached after design temperature, and ammonia and argon gas are passed through to CVD reacting furnaces, and then CVD reacting furnaces are incubated to 550 DEG C
Deposition reaction is carried out, the p-type GaN nano wire array of Ni catalyst granules is arranged at obtained top；Formed with hydrochloric acid, phosphoric acid and hydrofluoric acid
Mixed acid solution remove the Ni catalyst granules of p-type GaN nano wire array top, hydrochloric acid, phosphoric acid and hydrofluoric acid are described mixed
It is 4% to close total mass percent shared in acid solution.
2. reflective NEA GaN nano wires array photoelectric negative electrode as claimed in claim 1, it is characterised in that the p-type GaN receives
A diameter of 10~100nm of rice noodles, length is 1~100 μm, and p-type doping concentration is 1 × 1019cm-3, doped chemical is Zn.
3. reflective NEA GaN nano wires array photoelectric negative electrode as claimed in claim 1, it is characterised in that the substrate layer is
Si or SiC；It is first 1 with volume ratio on substrate before evaporated metal Al:1 sulfuric acid and hydrogen peroxide cleaning substrate, Ran Houyong
Mass percent cleans substrate for 5% hydrofluoric acid corrosion；Electron beam evaporation methods evaporated gold on substrate is used in step 101
Belong to Al layers of Al formation, the Al thickness degree is 100~1000nm；Step 101 medium-height grass acid solutions are 0.5mol/L.
4. reflective NEA GaN nano wires array photoelectric negative electrode as claimed in claim 1, it is characterised in that in step 102, institute
State phosphoric acid and in chromic acid mixture, phosphoric acid quality percentage is 4%, chromic acid mass percent is 2%.
5. reflective NEA GaN nano wires array photoelectric negative electrode as claimed in claim 1, it is characterised in that used in step 103
Ni layers of electron beam evaporation methods evaporation metal, the thickness of W metal layer is 5~100nm；The substrate is put into mass percent
Soaked in 5% NaOH aqueous slkalis.
6. reflective NEA GaN nano wires array photoelectric negative electrode as claimed in claim 1, it is characterised in that in step 104,
GaCl3For gallium source, ZnCl2For doped chemical Zn sources, with mole ratio 1000:Reaction source, reaction source are used as after 1 ratio mixing
Positioned at close to CVD reacting furnaces air inlet and apart from substrate 10cm or so position, substrate is located at the center heating position of CVD reacting furnaces
Put；CVD reacting furnaces are first vacuumized before heating and are passed through argon purge boiler tube；Substrate position heating-up temperature is to 850 DEG C, reaction
Source position heating-up temperature is to 600 DEG C；The argon flow amount is 200ml/min, ammonia flow for 30ml/min；Deposition is anti-
It is 100~120min between seasonable.
7. a kind of method for preparing reflective NEA GaN nano wires array photoelectric negative electrode, it is characterised in that in substrate surface growth
Heating purification is carried out in p-type GaN nano wire array, once purged feeding high-temperature vacuum system, p-type GaN nano wire array is obtained
Obtain the surface of Atomically clean；Then Cs/O active coatings are adsorbed in p-type GaN nano wire array surface；Institute is grown in substrate surface
The method for stating p-type GaN nano wire is：
Step 201, the evaporated metal Al formation metal Al layer on substrate, are placed in oxalic acid molten by the substrate with metal Al layer
Electrochemical corrosion is carried out in liquid, so as to form mesh structural porous aluminum oxide film in substrate surface；
Step 202, by the substrate that there is mesh structural porous aluminum oxide film on the surface be put into the mixed liquor of phosphoric acid and chromic acid soak,
The aluminum oxide of bottom hole portion and substrate contact on aluminum oxide film is removed, the mesh structural porous anodised aluminium of formation rule size is thin
Film；
Step 203, in the mesh structural porous anodic aluminum oxide film surface evaporation layer of metal Ni, then place the substrate into NaOH
Soaked in aqueous slkali, remove the anodic aluminum oxide film of substrate surface, so as to form W metal nano particle dot matrix on substrate；
Step 204, substrate and reaction source be put into partition heating in the quartz boat of CVD reacting furnaces, where treating substrate and reaction source
The temperature in region is reached after design temperature, and ammonia and argon gas are passed through to CVD reacting furnaces, and then CVD reacting furnaces are incubated to 550 DEG C
Deposition reaction is carried out, the p-type GaN nano wire array of Ni catalyst granules is arranged at obtained top；Formed with hydrochloric acid, phosphoric acid and hydrofluoric acid
Mixed acid solution remove the Ni catalyst granules of p-type GaN nano wire array top, hydrochloric acid, phosphoric acid and hydrofluoric acid are described mixed
It is 4% to close total mass percent shared in acid solution.
8. the method for reflective NEA GaN nano wires array photoelectric negative electrode is prepared as claimed in claim 7, it is characterised in that used
The grease and impurity on Chemical cleaning reagent etching away p-type GaN nano wire surface, Chemical cleaning reagent is that volume ratio is 2:2:1
Sulfuric acid, hydrogen peroxide and deionized water mixed liquor；Heating-up temperature in high-temperature vacuum system is 850 DEG C；Activated using ultravacuum
Technique adsorbs Cs/O active coatings in p-type GaN nano wire array surface.
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| CN108630510A (en) * | 2018-05-21 | 2018-10-09 | 南京理工大学 | Varying doping GaN nano wire array photoelectric cathode and preparation method thereof |
| CN109103059A (en) * | 2018-07-25 | 2018-12-28 | 南京理工大学 | Become the reflective NEA Al of componentxGa1-xN nano-wire array photocathode and preparation method |
| CN111370276A (en) * | 2018-12-26 | 2020-07-03 | 中国电子科技集团公司第十二研究所 | Vacuum channel type photoelectric cathode and preparation method thereof |
| CN110223897B (en) * | 2019-05-13 | 2021-07-09 | 南京理工大学 | GaN nanowire array photocathode based on field-assisted index doping structure |
| CN110491751A (en) * | 2019-05-27 | 2019-11-22 | 南京理工大学 | Vertical Launch GaAs nano-wire array photocathode and preparation method |
| CN110610838B (en) * | 2019-09-12 | 2021-08-03 | 南京理工大学 | Additional electric field assisted GaN nanowire array photocathode and preparation method thereof |
| CN112880823B (en) * | 2019-11-29 | 2022-05-13 | 中国科学技术大学 | Solar blind ultraviolet electrochemical photodetector and product thereof |
| CN112880821B (en) * | 2019-11-29 | 2022-05-13 | 中国科学技术大学 | Solar blind ultraviolet electrochemical photodetector and preparation method thereof |
| CN113964003A (en) * | 2021-10-09 | 2022-01-21 | 电子科技大学长三角研究院(湖州) | GaN photocathode with nanotube structure and preparation method thereof |
| CN114927394A (en) * | 2022-04-26 | 2022-08-19 | 电子科技大学 | GaN photocathode with modified nanometer pyramid structure and preparation method thereof |
| CN116519175B (en) * | 2023-07-03 | 2023-11-10 | 南京邮电大学 | Flexible device for growing GaN-based nanowires based on Si substrate and preparation method |
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| JPH1196896A (en) * | 1997-09-24 | 1999-04-09 | Hamamatsu Photonics Kk | Semiconductor photoelectric surface |
| CN101229912B (en) * | 2007-12-26 | 2010-06-16 | 中国科学院上海微系统与信息技术研究所 | Method for preparing gallium nitride nano-wire array by using dry etching |
| US20100025796A1 (en) * | 2008-08-04 | 2010-02-04 | Amir Massoud Dabiran | Microchannel plate photocathode |
| CN100595858C (en) * | 2008-12-11 | 2010-03-24 | 重庆大学 | Reflexion type GaN ultraviolet photocathode material structure and making method therof |
| CN103594302B (en) * | 2013-11-19 | 2016-03-23 | 东华理工大学 | A kind of GaAs nano-wire array photocathode and preparation method thereof |
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