CN107316927A - A kind of core shell structure turns white optical device and preparation method thereof - Google Patents
A kind of core shell structure turns white optical device and preparation method thereof Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/08—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a plurality of light emitting regions, e.g. laterally discontinuous light emitting layer or photoluminescent region integrated within the semiconductor body
Abstract
The present invention relates to optoelectronic integrated technology field, specifically a kind of core shell structure turns white optical device and preparation method thereof, it is characterized in that this described turns white, the base substrate of optical device is GaN substrate layer, the top of GaN substrate layer is provided with ZnO film Seed Layer, it is provided with above ZnO film Seed Layer around ZnO nanorod, described ZnO nanorod and coats ZnS:Mn film shells, ZnO nanorod and ZnS:Mn films shell constitutes ZnO/ZnS:Mn core-shell nanometer rod arrays, ZnS:Mn films shell, ZnO nanorod, ZnO film Seed Layer, GaN substrate layer constitute ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices, ZnS:Mn/ZnO/GaN core-shell nanometer rods array device is under the ultraviolet excitation of 325nm wavelength, and the blue light that sends of GaN substrate layer can pass through overlying material, and with the green-yellow light and ZnS of ZnO nanorod:The orange light of Mn film shells is superimposed, and obtains white light, have the advantages that it is simple in construction, do not need that fluorescent material, pollution-free, cost is low, luminous efficiency is high and stable.
Description
Technical field
The present invention relates to optoelectronic integrated technology field, specifically it is a kind of it is simple in construction, do not need fluorescent material, without dirt
Dye, cost is low, luminous efficiency is high and stable core shell structure turns white optical device and preparation method thereof.
Background technology
It is well known that due in high brightness blue light-emitting diode（LED）The great achievement made in terms of research, 2014
Annual Nobel Prize in physics is granted by the red rugged brave of Japan Nagoya university, and wild great and California, USA university the middle village in day is repaiied
Two, what the breakthrough of blue-ray LED made solid-state white illuminating device is implemented as possibility, and this also causes white light LEDs to be shone as the mankind
Leaping again after incandescent lamp, fluorescent lamp in Ming History, white light LEDs are a kind of electric energy to be directly converted into the new of white light
Type semiconductor cooling light source, has the advantages that efficiency high, pollution-free, long lifespan, responds fast, small volume, easy care, be referred to as the 4th
For lighting source（Or green illumination light source）, had broad application prospects in illumination, display and military field.
At present, realizing the scheme of white light LEDs mainly has three kinds, and one is to excite yellow fluorescent powder, two using blue-ray LED
It is to excite red-green-blue fluorescent material using ultraviolet leds.Both schemes being used current commercialized white light LEDs more,
But both approach all include secondary excitation process, this causes the luminous efficiency of device to be lowered, restricted to a certain extent
The further development of device；The third scheme is that three kinds of LED of red, green, blue are packaged together to directly obtain white light, but due to
Three kinds of LED driving voltage is different, and this not only makes, and the control circuit of device is more complicated, and energy consumption will also be greatly improved.
Presence in view of the above problems, people want to realize always the monolithic semiconductor white light emitting device of unstressed configuration powder, special
It is not in actual production process, typically all to make and the qualified of product is carried out after complete luminescent device i.e. electrode is installed
Rate is checked, underproof product is destroyed, work difficulty is so increased, and is also increased during particularly increasing electrode
Production cost.
The content of the invention
Present invention aim to address above-mentioned the deficiencies in the prior art there is provided one kind it is simple in construction, do not need fluorescent material, nothing
Pollution, cost is low, luminous efficiency is high and stable core shell structure turns white optical device and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of core shell structure turns white optical device, it is characterised in that the base substrate of the described optical device that turns white is GaN substrate layer,
The top of GaN substrate layer, which is provided with above ZnO film Seed Layer, ZnO film Seed Layer, is provided with ZnO nanorod, described ZnO nano
ZnS is coated around rod:Mn film shells, ZnO nanorod and ZnS:Mn films shell constitutes ZnO/ZnS:Mn core-shell nanometer rods battle array
Row, ZnS:Mn films shell, ZnO nanorod, ZnO film Seed Layer, GaN substrate layer constitute ZnS:Mn/ZnO/GaN core-shell nanos
Rod array device, ZnS:Mn/ZnO/GaN core-shell nanometer rods array device is under the ultraviolet excitation of 325nm wavelength, GaN substrate
The blue light that sends of layer can pass through overlying material, and with the green-yellow light and ZnS of ZnO nanorod:The orange light of Mn film shells is folded
It is added together, obtains white light.
ZnO/ZnS of the present invention:The array gap of Mn core-shell nanometer rod arrays and top filling are provided with electrically conducting transparent
Film, transparent conductive film is by ZnO/ZnS:Gap filling between Mn core-shell nanometer rod arrays, makes ZnO/ZnS:Mn nucleocapsids are received
It is connected with each other between rice rod array by transparent conductive film, described GaN substrate layer surface is provided with Pt/Ni（50nm/30nm）
Electrode, the ZnS with transparent conductive film:Mn/ZnO nucleocapsids layer surface is provided with Pt/Ti（50nm/30nm）Electrode, in positive electricity
Under pressure excitation, white light emission is presented in the device.
A kind of core shell structure turns white the preparation method of optical device, it is characterised in that described making step is as follows：
Step one：Clean GaN substrate, the p-GaN epitaxial wafers that Mg is adulterated（With sapphire（0001）For substrate, undoped with
The Mg doping p-GaN films of about 1 μ m-thick are grown on GaN cushions）, successively it is put into ultrasonic wave in acetone and ethanol solution and shakes
Cleaning 10-30min is swung, is then rinsed well, is dried up with nitrogen with deionized water, the luminous peak position of GaN substrate layer is 430-
450nm；
Step 2：ZnO film Seed Layer is deposited on GaN substrate layer, the method for deposition ZnO film Seed Layer has：Pulse laser
Sedimentation, magnetron sputtering method, electron-beam vapor deposition method, the ZnO of deposition thickness is 30-50nm；
Step 3：ZnO nanorod is prepared in ZnO film Seed Layer, preparing the method for ZnO nanorod has：Hydrothermal synthesis method, change
Water-bath sedimentation, electrodeposition process are learned, the luminous peak position of ZnO nanorod is 375-387nm and 560-580nm；
Step 4：ZnS is coated on ZnO nanorod:Mn film shells, deposit ZnS:The method of Mn film shells has：Pulse swashs
Photodeposition, magnetron sputtering method, electron-beam vapor deposition method, ZnS:The luminous peak position of Mn film shells is 580-610nm, ZnO nano
Rod and ZnS:Mn films shell constitutes ZnO/ZnS:Mn core-shell nanometer rod arrays, ZnS:Mn films shell, ZnO nanorod, ZnO are thin
Film Seed Layer, GaN substrate layer constitute ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices, ZnS:Mn/ZnO/GaN core-shell nanos
Rod array device is under the ultraviolet excitation of 325nm wavelength, and the blue light that sends of GaN substrate layer can pass through overlying material, and with
The green-yellow light and ZnS of ZnO nanorod:The orange light of Mn film shells is superimposed, and obtains white light, and chromaticity coordinates is（0.31~
0.35,0.30 ~ 0.34）Increase electrode is carried out again carries out production practicality；
Step 5：In ZnO/ZnS:The top deposition transparent conductive film of Mn core-shell nanometer rod arrays, thickness is 100-120nm,
Transparent conductive film is filled in ZnO/ZnS:In Mn core-shell nanometer rod arrays gap, and overlay on ZnO/ZnS:Mn core-shell nanometer rods battle array
The top of row makes ZnO/ZnS:Mn core-shell nanometer rods array is connected with each other；
Step 6：Respectively Pt/Ni is prepared in GaN substrate layer（50nm/30nm）Electrode, in cladding ZnO/ZnS:Mn core-shell nanometer rods
Pt/Ti is prepared on the transparent conductive film of array surface（50nm/30nm）Electrode；
Step 7：ZnS is excited with forward voltage:Mn/ZnO/GaN core-shell nanometer rod arrays, obtain the stronger white light of visible region
Transmitting, obtained white light emission spectral wavelength ranges are 350-800nm, and chromaticity coordinates is（0.335 ~ 0.3393,0.3334 ~
0.3366）.
Transparent conductive film of the present invention is transparent conductive film, and the transparent conductive film of the superiors is neither
Influence luminous efficiency, and the easy making of device.
ZnS of the present invention:The doping concentration of Mn2+ in Mn film shells is 1% ~ 3%, under the doping concentration
ZnS:Can occur the orange light transmitting of Mn2+ 580-610nm or so appropriate intensity in Mn film shells, such nucleocapsid is received
Rice rod array device will produce preferably luminous chromaticity coordinates.
ZnS of the present invention:The optimization doping concentration of Mn2+ in Mn film shells is 1%, under the doping concentration
ZnS:Can occur the orange light transmitting of Mn2+ 580-610nm or so appropriate intensity in Mn film shells, such nucleocapsid is received
Rice rod array device will produce the luminous chromaticity coordinates of optimization.
The present invention due to use said structure and preparation method, with it is simple in construction, do not need fluorescent material, it is pollution-free, into
The advantages of this low, luminous efficiency is high and stable.
Brief description of the drawings
Fig. 1 is the structural representation of the present invention.
Fig. 2 is the structural representation with electrode.
Fig. 3 is the structural representation of transparent conductive film.
Fig. 4 is the chromatic diagram of the present invention.
Embodiment
The present invention is further described below in conjunction with the accompanying drawings：
As shown in drawings, a kind of core shell structure turns white optical device, it is characterised in that the base substrate of the described optical device that turns white
For GaN substrate layer 1, the top of GaN substrate layer 1 is provided with ZnO film Seed Layer 2, and the top of ZnO film Seed Layer 2 is provided with ZnO nano
Rod 3, the described surrounding of ZnO nanorod 3 cladding ZnS:Mn films shell 4, ZnO nanorod 3 and ZnS:Mn films shell 4 is constituted
ZnO/ZnS:Mn core-shell nanometer rod arrays, ZnS:Mn films shell 4, ZnO nanorod 3, ZnO film Seed Layer 2,1 layer of GaN substrate
Constitute ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices, ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices are in 325nm
Under the ultraviolet excitation of wavelength, the blue light that GaN substrate layer 1 is sent can pass through overlying material, and yellowish green with ZnO nanorod 3
Light and ZnS:The orange light of Mn films shell 4 is superimposed, and obtains white light, described ZnO/ZnS:Mn core-shell nanometer rod arrays
Array gap and top filling be provided with transparent conductive film 5, transparent conductive film 5 is by ZnO/ZnS:Mn core-shell nanometer rod arrays
Between gap filling, make ZnO/ZnS:It is connected with each other between Mn core-shell nanometer rod arrays by transparent conductive film 5, it is described
1 surface of GaN substrate layer is provided with Pt/Ni（50nm/30nm）Electrode 6, the ZnS with transparent conductive film:Mn/ZnO nuclear shell tables
Face is provided with Pt/Ti（50nm/30nm）Electrode 7, under forward voltage excitation, white light emission is presented in the device.
A kind of core shell structure turns white the preparation method of optical device, it is characterised in that described making step is as follows：
Step one：Clean GaN substrate, the p-GaN epitaxial wafers that Mg is adulterated（With sapphire（0001）For substrate, undoped with
The Mg doping p-GaN films of about 1 μ m-thick are grown on GaN cushions）, successively it is put into ultrasonic wave in acetone and ethanol solution and shakes
Cleaning 10-30min is swung, is then rinsed well, is dried up with nitrogen with deionized water, the luminous peak position of GaN substrate layer is 430-
450nm；
Step 2：ZnO film Seed Layer is deposited on GaN substrate layer, the method for deposition ZnO film Seed Layer has：Pulse laser
Sedimentation, magnetron sputtering method, electron-beam vapor deposition method, the ZnO of deposition thickness is 30-50nm；
Step 3：ZnO nanorod is prepared in ZnO film Seed Layer, preparing the method for ZnO nanorod has：Hydrothermal synthesis method, chemistry
Water-bath sedimentation, electrodeposition process, the luminous peak position of ZnO nanorod is 375-387nm and 560-580nm；
Step 4：ZnS is coated on ZnO nanorod:Mn film shells, deposit ZnS:The method of Mn film shells has：Pulse swashs
Photodeposition, magnetron sputtering method, electron-beam vapor deposition method, ZnS:The luminous peak position of Mn film shells is 580-610nm, ZnO nano
Rod and ZnS:Mn films shell constitutes ZnO/ZnS:Mn core-shell nanometer rod arrays, ZnS:Mn films shell, ZnO nanorod, ZnO are thin
Film Seed Layer, GaN substrate layer constitute ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices, ZnS:Mn/ZnO/GaN core-shell nanos
Rod array device is under the ultraviolet excitation of 325nm wavelength, and the blue light that sends of GaN substrate layer can pass through overlying material, and with
The green-yellow light and ZnS of ZnO nanorod:The orange light of Mn film shells is superimposed, and obtains white light, and chromaticity coordinates is（0.31~
0.35,0.30 ~ 0.34）Increase electrode is carried out again carries out production practicality；
Step 5：In ZnO/ZnS:The top deposition transparent conductive film of Mn core-shell nanometer rod arrays, thickness is 100-120nm,
Transparent conductive film is filled in ZnO/ZnS:In Mn core-shell nanometer rod arrays gap, and overlay on ZnO/ZnS:Mn core-shell nanometer rods battle array
The top of row makes ZnO/ZnS:Mn core-shell nanometer rods array is connected with each other；
Step 6：Respectively Pt/Ni is prepared in GaN substrate layer（50nm/30nm）Electrode, in cladding ZnO/ZnS:Mn core-shell nanometer rods
Pt/Ti is prepared on the transparent conductive film of array surface（50nm/30nm）Electrode；
Step 7：ZnS is excited with forward voltage:Mn/ZnO/GaN core-shell nanometer rod arrays, obtain the stronger white light of visible region
Transmitting, obtained white light emission spectral wavelength ranges are 350-800nm, and chromaticity coordinates is（0.335 ~ 0.3393,0.3334 ~
0.3366）.
Transparent conductive film of the present invention is transparent conductive film, and the transparent conductive film of the superiors is neither
Influence luminous efficiency, and the easy making of device.
ZnS of the present invention:The doping concentration of Mn2+ in Mn film shells is 1% ~ 3%, under the doping concentration
ZnS:Can occur the orange light transmitting of Mn2+ 580-610nm or so appropriate intensity in Mn film shells, such nucleocapsid is received
Rice rod array device will produce preferably luminous chromaticity coordinates.
ZnS of the present invention:The optimization doping concentration of Mn2+ in Mn film shells is 1%, under the doping concentration
ZnS:Can occur the orange light transmitting of Mn2+ 580-610nm or so appropriate intensity in Mn film shells, such nucleocapsid is received
Rice rod array device will produce the luminous chromaticity coordinates of optimization.
Transparent conductive film can be replaced by another cost-effective transparent conductive film in above-mentioned steps five, and it makes step
It is rapid as follows：
Step 1：In ZnO/ZnS:ZnO film layer, the method for deposition ZnO film layer are deposited on the top of Mn core-shell nanometer rod arrays
Have：Pulsed laser deposition, electron-beam vapor deposition method, magnetron sputtering method, the ZnO of deposition thickness is 20-60nm；
Step 2：Au film layers are deposited on ZnO film, the method for deposition Au film layers has：Pulsed laser deposition, electron beam evaporation
Method, magnetron sputtering method.Au thickness degree is 6-30nm；
Step 3：ZnS film layers are deposited on Au films, the method for deposition ZnS film layers has：Pulsed laser deposition, electron beam steam
Hair method, magnetron sputtering method, the ZnS of deposition thickness is 20-60nm.
The advantages of the present invention are as follows：
Core shell structure turns white the advantage of optical device：
1. device architecture is simple, do not need that fluorescent material, pollution-free, cost is low, luminous efficiency is high and stably.
2. use ZnS:Mn/ZnO/GaN core-shell nanometer rod array systems, strengthen efficiency of light absorption, so optical characteristics
It is very excellent, transport electronic capability also stronger.
The ZnS of cladding outside 3.ZnO nanometer rods:Mn layers, the luminous chromaticity coordinates of device can be made closer to standard white light
（0.33, 0.33）.
4. the transparent conductive film of the superiors neither influences luminous efficiency, and the easy making of device.
5. the minimum cut-in voltage of device is about 6V, hence it is evident that less than the cut-in voltage of the device of document report.
No matter 6. with ultraviolet excitation or voltage drive, preferable white light emission can be obtained.
7. reducing production cost, operating efficiency is accelerated.
8. cushion and nucleation inculating crystal layer that GaN substrate layer grows provided with ZnO film Seed Layer as ZnO nanorod,
And the effect of ZnO film Seed Layer can reduce the lattice mismatch between ZnO nanorod and substrate, make ZnO nanorod distribution equal
It is even, vertical in order, grow to marshalling, due to the presence of ZnO film Seed Layer so that the ZnO nanorod row that growth is obtained
Row are neat, compact structure, directionality are more preferable, and this allows for ZnS:The luminescent properties of Mn/ZnO/GaN core-shell nanometer rod arrays are very
It is good.
9. ZnS:Mn2+ doping concentrations in Mn film shells are 1.0%, are caused according to the preparation method and preparation condition
The ZnS arrived:Mn2+ 580-610nm or so orange light transmitting, such core-shell nanometer rod array are occurred in that in Mn film shells
Device will produce the luminous chromaticity coordinates of optimization.
This product is in the case of the whole identicals of preparation method and preparation condition other factors of this patent, according to ZnS:Mn
The difference of Mn2+ doping concentrations in film shell show that the form of electroluminescent peak position and luminous chromaticity coordinates is as follows（Table one）：
Table one：
It can be seen that according to table one：In the case where Mn2+ doping concentrations are 1% ~ 3%, electroluminescent long wavelength's peak position is in 600nm
Left and right, this is due to the ZnS of product:Mn2+ 600nm or so orange light transmitting is occurred in that in Mn film shells, wherein adulterating
When concentration is 1.0%, the luminous chromaticity coordinates of core-shell nanometer rod array device is closest to standard white light（0.33, 0.33）.
This product is in the case of the whole identicals of the other factors such as the preparation method and preparation condition of this patent, according to excitation
The different colors coordinate form that voltage difference is produced is as follows（Table two）：
Table two：
It can be seen that according to table two：In the case of relatively low 6 ~ 20V of driving voltage driving voltage, it can be produced close to mark
Quasi- white light（0.33, 0.33）Luminous chromaticity coordinates, under high voltage excitation, higher heat will be produced because of high voltage, to device
Part is also easy to produce damage, and the service life reduction of device meets green energy resource production standard.
The advantage of transparent conductive film：
In original utilization transparent conductive film, containing In elements in transparent conductive film, but In contents in nature
Seldom, it is expensive, and be easily oxidized under the transparent conductive oxide film high temperature of individual layer, it is difficult to stable doping is realized, this
Apply for the transparent conductive film sandwich structure made, its simple in construction, cost is low；Transmitance is high（>86.6%）, surface resistance is low
（<26Ω/sq）, quality factor height（>6.562×10-3Ω-1）；Heat endurance, corrosion resistance are stronger；It is situated between ZnO as bottom
Matter, ZnS can effectively prevent metal Au layers in preparation process of oxidation as surface materials, improve three layers of electrically conducting transparent and be combined
The photoelectric properties of film.
The embodiment of core shell structure luminescent device in the present invention：
Embodiment 1
Step one：GaN substrate is cleaned, cleaned by ultrasonic vibration 10-30min, Ran Houyong in acetone and ethanol solution is successively put into
Deionized water rinsing is clean, is dried up with nitrogen；
Step 2：The deposited by electron beam evaporation method deposition ZnO film Seed Layer on GaN substrate layer, the purity of ZnO target is 99.99%,
Vacuum is better than 1.0 × 10-4Pa, and electronic beam current is 8 mA during plated film, and anode voltage is 6 kV, and evaporation time is 10-20
Min, underlayer temperature is RT-300 DEG C, and the thickness of ZnO film is 30-50nm；
Step 3：ZnO nanorod is prepared with electrodeposition process in ZnO film Seed Layer, a certain amount of Zn (NO3) is accurately weighed
2 6H2 O are dissolved in deionized water, prepare certain density electric depositing solution；The temperature for controlling electric depositing solution is 60-80
DEG C electrodeposition time is 1-2 h, using the cm electro-conductive glass of 2.0 cm × 2.5 as working electrode, Pt electrodes be to electrode, it is full
It is reference electrode with calomel electrode, ZnO nano-rod array is prepared using potentiostatic method.
Step 4：Deposited by electron beam evaporation method coats ZnS on ZnO nanorod:Mn film layers, ZnS:The purity of Mn targets is
99.99%, vacuum is better than 1.0 × 10-4Pa, and electronic beam current is 8 mA during plated film, and anode voltage is 6 kV, and evaporation time is
20-40 min, underlayer temperature is 200-300 DEG C, after evaporation is finished, ZnS:Mn film samples are in 7.5 × 10-5Pa vacuum conditions
Lower 300-400 DEG C of annealing 0.5-1h, ZnS:The luminous peak position of Mn films is 580-610nm, ZnO nanorod and ZnS:Mn film shells
Layer constitutes ZnO/ZnS:Mn core-shell nanometer rod arrays, ZnS:Mn films shell, ZnO nanorod, ZnO film Seed Layer, GaN substrate
Layer constitutes ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices, ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices exist
Under the ultraviolet excitation of 325nm wavelength, the blue light that sends of GaN substrate layer can pass through overlying material, and with the Huang of ZnO nanorod
Green glow and ZnS:The orange light of Mn film shells is superimposed, and obtains white light, then carry out increase electrode progress production practicality；
Step 5：In ZnO/ZnS:The top deposited by electron beam evaporation method deposition transparent conductive film of Mn core-shell nanometer rod arrays,
Thickness is 100-120nm, and transparent conductive film is filled in ZnO/ZnS:In Mn core-shell nanometer rod arrays gap, and overlay on ZnO/
ZnS:The top of Mn core-shell nanometer rod arrays makes ZnO/ZnS:Mn core-shell nanometer rods array is connected with each other.
Step 6：Respectively Pt/Ni is prepared in GaN substrate layer surface deposited by electron beam evaporation method（50nm/30nm）Electrode, in bag
Cover ZnO/ZnS:Deposited by electron beam evaporation method prepares Pt/Ti on the transparent conductive film of Mn core-shell nanometer rod array surfaces（50nm/
30nm）Electrode, in order to ensure preferable Ohmic contact, sample is in 300-500 DEG C of annealing 10-30min；
Step 7：ZnS is excited with 6-20V forward voltage:Mn/ZnO/GaN core-shell nanometer rod arrays, obtain visible region wavelength
350-900nm white light.
Embodiment 2
Step one：GaN substrate is cleaned, cleaned by ultrasonic vibration 10-30min, Ran Houyong in acetone and ethanol solution is successively put into
Deionized water rinsing is clean, is dried up with nitrogen；
Step 2：ZnO film Seed Layer is deposited with pulsed laser deposition on GaN substrate layer, the use of wavelength is 248 nm, arteries and veins
A width of 10 ns krypton fluoride excimer laser, focuses on ZnO ceramic targets（99.99%）On, pulsed laser energy is 250-
350 mJ, laser pulse repetition frequency 5-10Hz, the area focused on ceramic target be 4 mm2, the J/cm2 of energy density 6,
Vacuum chamber back end vacuum is 10-7 Pa, and source-cardinal distance during ZnO deposition is 4-6 cm, and growth temperature is RT-300 DEG C, ZnO film
Thickness be 30-50nm；
Step 3：ZnO nanorod is prepared with hydrothermal synthesis method in ZnO film Seed Layer, respectively prepare Zn (NO3) 2 solution and
Hexa（HMT）Solution, concentration is 0.01 ~ 0.03mol/L, is 1 by mol ratio:1 solution mixing is fallen back
In thermal response kettle, ready GaN substrate is then placed in, reactor is put into electric constant-temp air dry oven and 90-120 is warming up to
DEG C, growth time is 2-5h, and question response terminates reactor naturally cooling to room temperature, takes out sample and is rushed with a large amount of deionized waters
Wash, be then placed in baking oven and 0.5-1h is dried at 80-100 DEG C, the luminous peak position of ZnO nanorod is 373-387nm and 560-
580nm；
Step 4：On ZnO nanorod ZnS is coated with pulsed laser deposition:Mn film layers, are 248 nm, arteries and veins using wavelength
A width of 10 ns krypton fluoride excimer laser, focuses on ZnS:Mn ceramic targets（99.99%）On, pulsed laser energy is
250-350mJ, laser pulse repetition frequency 5Hz, the area focused on ceramic target are 4 mm2, the J/cm2 of energy density 6.
Vacuum chamber back end vacuum is 10-7 Pa, ZnS:Source-cardinal distance when Mn is deposited is 4-6 cm, and growth temperature is 200-300 DEG C,
ZnS:The luminous peak position of Mn films is 580-610nm, ZnO nanorod and ZnS:Mn films shell constitutes ZnO/ZnS:Mn nucleocapsids are received
Rice rod array, ZnS:Mn films shell, ZnO nanorod, ZnO film Seed Layer, GaN substrate layer constitute ZnS:Mn/ZnO/GaN cores
Shell nanometer stick array device, ZnS:Mn/ZnO/GaN core-shell nanometer rods array device under the ultraviolet excitation of 325nm wavelength,
The blue light that sends of GaN substrate layer can pass through overlying material, and with the green-yellow light and ZnS of ZnO nanorod:The orange of Mn film shells
Feux rouges is superimposed, and obtains white light, then carry out increase electrode progress production practicality；
Step 5：In ZnO/ZnS:The top of Mn core-shell nanometer rod arrays deposits transparent conductive thin with pulsed laser deposition
Film, thickness is 100-120nm, and transparent conductive film is filled in ZnO/ZnS:In Mn core-shell nanometer rod arrays gap, and overlay on
ZnO/ZnS:The top of Mn core-shell nanometer rod arrays makes ZnO/ZnS:Mn core-shell nanometer rods array is connected with each other.
Step 6：Respectively Pt/Ni is prepared in GaN substrate layer surface with pulsed laser deposition（50nm/30nm）Electrode,
Coat ZnO/ZnS:On the transparent conductive film of Mn core-shell nanometer rod array surfaces Pt/Ti is prepared with pulsed laser deposition
（50nm/30nm）Electrode, in order to ensure preferable Ohmic contact, sample is in 300-500 DEG C of annealing 10-30min；
Step 7：ZnS is excited with 6-20V forward voltage:Mn/ZnO/GaN core-shell nanometer rod arrays, obtain visible region wavelength
350-900nm white light.
Embodiment 3
Step one：GaN substrate is cleaned, cleaned by ultrasonic vibration 10-30min, Ran Houyong in acetone and ethanol solution is successively put into
Deionized water rinsing is clean, is dried up with nitrogen.
Step 2：ZnO film Seed Layer is deposited with magnetron sputtering method on GaN substrate layer, the purity of ZnO target is
99.99%, base vacuum is 6 × 10- 4Pa, and using 99.9% high-purity argon gas, ar pressure is 0.1-0.3Pa, argon flow amount
For 20sccm, sputtering power is 100W, and distance is 4-6cm between target and substrate, and depositing temperature is RT-300 DEG C, and sedimentation time is
0.5-1h, the thickness of ZnO film is 30-50nm；
Step 3：ZnO nanorod is prepared with chemical bath deposition in ZnO film Seed Layer, a certain proportion of nitric acid is configured
The aqueous solution of zinc (in this, as Zn sources) and hexamethylenetetramine (C6H12N4), wherein Zn (NO3) 2 and C6H12N4 thing
The amount ratio of matter is 1: 1, the GaN substrate layer with ZnO film Seed Layer is placed in above-mentioned solution vertically, in certain water
2-4 h are stood under bath temperature (20-90 DEG C), after sample takes out from solution, are rinsed with deionized water, are attached to removing
The deposit on surface, is then placed in baking oven and 0.5-1h is dried at 60-80 DEG C, the luminous peak position of ZnO nanorod is 373-387nm
And 560-580nm.
Step 4：On ZnO nanorod ZnS is coated with magnetron sputtering method:Mn film layers, utilize mechanical pump and molecular pump two
Level pumped vacuum systems, is evacuated to ~ 10-4Pa by back end vacuum, is passed through high-purity 20sccm Ar gas, sputtering chamber vacuum is maintained at 2.0-
3.0Pa, underlayer temperature is maintained at 200-300 DEG C, and rf frequency is adjusted to 120W.Sedimentation time is 0.5-1h, ZnS:Mn films
Luminous peak position is 595nm；, ZnO nanorod and ZnS:Mn films shell constitutes ZnO/ZnS:Mn core-shell nanometer rod arrays, ZnS:Mn
Film shell, ZnO nanorod, ZnO film Seed Layer, GaN substrate layer constitute ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices
Part, ZnS:Mn/ZnO/GaN core-shell nanometer rods array device is under the ultraviolet excitation of 325nm wavelength, and GaN substrate layer is sent
Blue light can pass through overlying material, and with the green-yellow light and ZnS of ZnO nanorod:The orange light of Mn film shells is superimposed,
White light is obtained, then carries out increase electrode and carries out production practicality；
Step 5：In ZnO/ZnS:The top of Mn core-shell nanometer rod arrays deposits transparent conductive film with magnetron sputtering method, thick
Spend for 100-120nm, transparent conductive film is filled in ZnO/ZnS:In Mn core-shell nanometer rod arrays gap, and overlay on ZnO/ZnS:
The top of Mn core-shell nanometer rod arrays makes ZnO/ZnS:Mn core-shell nanometer rods array is connected with each other.
Step 6：Respectively Pt/Ni is prepared in GaN substrate layer surface with magnetron sputtering method（50nm/30nm）Electrode, in cladding
ZnO/ZnS:On the transparent conductive film of Mn core-shell nanometer rod array surfaces Pt/Ti is prepared with magnetron sputtering method（50nm/30nm）
Electrode, in order to ensure preferable Ohmic contact, sample is in 300-500 DEG C of annealing 10-30min.
Step 7：ZnS is excited with 6-20V forward voltage:Mn/ZnO/GaN core-shell nanometer rod arrays, obtain visible region
Wavelength 350-900nm white light.
The embodiment of transparent conductive film in core shell structure luminescent device of the present invention
Embodiment 1
Step 1：In ZnO/ZnS:ZnO film layer is deposited with pulsed laser deposition on the top of Mn core-shell nanometer rod arrays, is made
It is 248 nm with wavelength, pulsewidth is 10 ns krypton fluoride excimer laser, focuses on ZnO ceramic targets（99.99%）On, swash
Optical pulse energy is 250-300 mJ, and laser pulse repetition frequency 5-10Hz, the area focused on ceramic target is 4 mm2,
The J/cm2 of energy density 6, vacuum chamber back end vacuum is 10-7 Pa, and source-cardinal distance during ZnO deposition is 4-6 cm, and growth temperature is
RT-300 DEG C of room temperature, the thickness of ZnO film is 20-60nm；
Step 2：Au film layers are deposited with pulsed laser deposition on ZnO film layer, the use of wavelength are 248 nm, pulsewidth is 10
Ns krypton fluoride excimer laser, focuses on Au targets（99.999%）On, pulsed laser energy is 300-350 mJ, laser
Pulse recurrence frequency 5-10Hz, the area focused on ceramic target is 4 mm2, the J/cm2 of energy density 6.Vacuum chamber back end is true
Sky is 10-7 Pa, and source-cardinal distance when Au is deposited is 4-6 cm, and growth temperature is RT-100 DEG C of room temperature.The thickness of Au films is 6-
30nm。
Step 3：ZnS film layers are deposited with pulsed laser deposition in Au film layers, the use of wavelength are 248 nm, pulsewidth is
10 ns krypton fluoride excimer laser, focuses on ZnS ceramic targets（99.99%）On, pulsed laser energy is 250-350
MJ, laser pulse repetition frequency 5-10Hz, the area focused on ceramic target are 4 mm2, the J/cm2 of energy density 6.Vacuum
Room back end vacuum is 10-7 Pa, and source-cardinal distance when ZnS is deposited is 4-6 cm, and growth temperature is RT-300 DEG C of room temperature, ZnS films
Thickness be 20-60nm.
Embodiment 2
Step 1：In ZnO/ZnS:Deposited by electron beam evaporation method deposition ZnO film layer, ZnO target on the top of Mn core-shell nanometer rod arrays
Purity be 99.99%, vacuum be better than 1.0 × 10-4Pa, during plated film electronic beam current be 8 mA, anode voltage be 6 kV, substrate
Temperature is RT-300 DEG C, and the thickness of ZnO film is 20-60nm.After evaporation is finished, ZnO film layer sample is true in 7.5 × 10-5Pa
300-500 DEG C of annealing 0.5-1h under empty condition；
Step 2：The deposited by electron beam evaporation method deposition Au film layers on ZnO film layer, the purity of Au targets is 99.999%, and vacuum is excellent
Electronic beam current is 8 mA when 1.0 × 10-4Pa, plated film, and anode voltage is 6 kV, and underlayer temperature is RT-100 DEG C, Au films
Thickness is 6-30nm.After evaporation is finished, Au film samples 200-300 DEG C of annealing 0.5-1h under 7.5 × 10-5Pa vacuum conditions；
Step 3：Deposited by electron beam evaporation method deposits ZnS film layers in Au film layers, and the purity of ZnS targets is 99.99%, and vacuum is excellent
Electronic beam current is 8 mA when 1.0 × 10-4Pa, plated film, and anode voltage is 6 kV, and underlayer temperature is RT-300 DEG C, ZnS films
Thickness be 20-60nm.After evaporation is finished, the 300-500 DEG C of annealing under 7.5 × 10-5Pa vacuum conditions of ZnS film samples
0.5-1h。
Embodiment 3
Step 1：In ZnO/ZnS:ZnO film layer is deposited with magnetron sputtering method on the top of Mn core-shell nanometer rod arrays, ZnO target
Purity is 99.99%, and base vacuum is 6 × 10- 4Pa, and using 99.9% high-purity argon gas, ar pressure is 0.1-0.2Pa, argon
Throughput is 20sccm, and sputtering power is 100W, and distance is 4-6 cm between target and substrate, and depositing temperature is RT-300 DEG C, and ZnO is thin
The thickness of film is 20-60nm；
Step 2：Au film layers are deposited with magnetron sputtering method on ZnO film layer, the purity of Au targets is 99.999%, and base vacuum is 6
× 10- 4Pa, using 99.9% high-purity argon gas, ar pressure is 0.1-0.2Pa, and argon flow amount is 20sccm, and sputtering power is
100W, distance is 4-6cm between target and substrate, and depositing temperature is RT-100 DEG C, and the thickness of Au films is 6-30nm；
Step 3：ZnS film layers are deposited with magnetron sputtering method in Au film layers, the purity of ZnS targets is 99.99%, and base vacuum is 6
× 10- 4Pa, using 99.9% high-purity argon gas, ar pressure is 0.1-0.2Pa, and argon flow amount is 20sccm, and sputtering power is
100W, distance is 4-6cm between target and substrate, and depositing temperature is RT-300 DEG C, and the thickness of ZnS films is 20-60nm.
The present invention makes ZnS in actual production process:Mn/ZnO/GaN core-shell nanometer rods array device and electrically conducting transparent
During film, the film layer of use and the preparation method of ZnO nanorod are not limited to the method in this patent document, it is every can system
Making the method for film layer can use in this patent, and the Au film layers in transparent conductive film are also not limited to Au metals,
It can be replaced by other permeabilities, the metal conducted electricity very well, prepare ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices are complete
Into rear progress ultraviolet excitation inspection, if non-whitening light carries out experiment adjustment again, transparent conductive film is increased by if emitting white light
Actual test and application are carried out with electrode, the disqualification rate for producing product is so reduced, production cost is reduced.
Claims (6)
- The optical device 1. a kind of core shell structure turns white, it is characterised in that the base substrate of the described optical device that turns white is GaN substrate Layer, the top of GaN substrate layer, which is provided with above ZnO film Seed Layer, ZnO film Seed Layer, is provided with ZnO nanorod, described ZnO ZnS is coated around nanometer rods:Mn film shells, ZnO nanorod and ZnS:Mn films shell constitutes ZnO/ZnS:Mn core-shell nanos Rod array, ZnS:Mn films shell, ZnO nanorod, ZnO film Seed Layer, GaN substrate layer constitute ZnS:Mn/ZnO/GaN nucleocapsids Nanometer stick array device, ZnS:Mn/ZnO/GaN core-shell nanometer rods array device is under the ultraviolet excitation of 325nm wavelength, GaN The blue light that substrate layer is sent can pass through overlying material, and with the green-yellow light and ZnS of ZnO nanorod:Mn film shells it is orange red Optical superposition together, obtains white light.
- The optical device 2. a kind of core shell structure according to claim 1 turns white, it is characterised in that described ZnO/ZnS:Mn cores The array gap of shell nanometer stick array and top filling are provided with transparent conductive film, and described GaN substrate layer surface is provided with Pt/Ni （50nm/30nm）Electrode, the ZnS with transparent conductive film:Mn/ZnO nucleocapsids layer surface is provided with Pt/Ti（50nm/30nm）Electricity Pole, under forward voltage excitation, white light emission is presented in the device.
- The preparation method of device 3. kind of core shell structure emits white light, it is characterised in that described making step is as follows：Step one：Clean GaN substrate, the p-GaN epitaxial wafers that Mg is adulterated（With sapphire（0001）For substrate, undoped with The Mg doping p-GaN films of about 1 μ m-thick are grown on GaN cushions）, successively it is put into supersonic oscillations in acetone and ethanol solution 10-30min is cleaned, is then rinsed well, is dried up with nitrogen with deionized water, the luminous peak position of GaN substrate layer is 430- 450nm；Step 2：ZnO film Seed Layer is deposited on GaN substrate layer, the method for deposition ZnO film Seed Layer has：Pulse laser Sedimentation, magnetron sputtering method, electron-beam vapor deposition method, the ZnO of deposition thickness is 30-50nm；Step 3：ZnO nanorod is prepared in ZnO film Seed Layer, preparing the method for ZnO nanorod has：Hydrothermal synthesis method, change Water-bath sedimentation, electrodeposition process are learned, the luminous peak position of ZnO nanorod is 375-387nm and 560-580nm；Step 4：ZnS is coated on ZnO nanorod:Mn film shells, deposit ZnS:The method of Mn film shells has：Pulse swashs Photodeposition, magnetron sputtering method, electron-beam vapor deposition method, ZnS:The luminous peak position of Mn film shells is 580-610nm, ZnO nano Rod and ZnS:Mn films shell constitutes ZnO/ZnS:Mn core-shell nanometer rod arrays, ZnS:Mn films shell, ZnO nanorod, ZnO are thin Film Seed Layer, GaN substrate layer constitute ZnS:Mn/ZnO/GaN core-shell nanometer rod array devices, ZnS:Mn/ZnO/GaN core-shell nanos Rod array device is under the ultraviolet excitation of 325nm wavelength, and the blue light that sends of GaN substrate layer can pass through overlying material, and with The green-yellow light and ZnS of ZnO nanorod:The orange light of Mn film shells is superimposed, and obtains white light, and chromaticity coordinates is（0.31~ 0.35,0.30 ~ 0.34）Increase electrode is carried out again carries out production practicality；Step 5：In ZnO/ZnS:The top deposition transparent conductive film of Mn core-shell nanometer rod arrays, thickness is 100-120nm, Transparent conductive film is filled in ZnO/ZnS:Mn core-shell nanometer rod arrays gap, and overlay on ZnO/ZnS:Mn core-shell nanometer rod arrays Top make ZnO/ZnS:Mn core-shell nanometer rods array is connected with each other；Step 6：Respectively Pt/Ni is prepared in GaN substrate layer（50nm/30nm）Electrode, in cladding ZnO/ZnS:Mn core-shell nanometer rods Pt/Ti is prepared on the transparent conductive film of array surface（50nm/30nm）Electrode；Step 7：ZnS is excited with forward voltage:Mn/ZnO/GaN core-shell nanometer rod arrays, obtain the stronger white light of visible region Transmitting, obtained white light emission spectral wavelength ranges are 350-800nm, and chromaticity coordinates is（0.335 ~ 0.3393,0.3334 ~ 0.3366）.
- Optical device and preparation method thereof 4. a kind of core shell structure according to Claims 2 or 3 turns white, it is characterised in that described Transparent conductive film be transparent conductive film.
- Optical device and preparation method thereof 5. a kind of core shell structure according to claim 1,2 or 3 turns white, it is characterised in that institute The ZnS stated:The doping concentration of Mn2+ in Mn film shells is 1% ~ 3%.
- Optical device and preparation method thereof 6. a kind of core shell structure according to claim 5 turns white, it is characterised in that described ZnS:The optimization doping concentration of Mn2+ in Mn film shells is 1%..
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