CN106876533A - One kind is based on MgO CsPbBr3Luminescent device of structure and preparation method thereof - Google Patents
One kind is based on MgO CsPbBr3Luminescent device of structure and preparation method thereof Download PDFInfo
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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
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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
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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
- H01L33/44—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 coatings, e.g. passivation layer or anti-reflective coating
Abstract
The present invention provides a kind of based on MgO CsPbBr3Luminescent device of structure and preparation method thereof, the impact ionization process using MgO insulating barriers under high electric field produces nonequilibrium carrier, so as to realize the preparation of the perovskite luminescent device without p-type hole mobile material.Luminescent device of the invention includes the substrate of insulation, and the electronics that N-shaped is sequentially provided with substrate provides layer, CsPbBr3Luminescent layer, MgO insulating barriers and contact electrode.Impact ionization process of the one aspect of the present invention using MgO insulating barriers under high electric field produces carrier, on the other hand by CsPbBr3The larger conduction band barrier in/MgO interfaces can be formed to CsPbBr3Effective limitation of electronics is injected in layer, so as to realize nonequilibrium electron and holoe carrier in CsPbBr3High efficiency radiation recombination in layer, overcomes traditional CsPbBr3The larger problem of luminescent device cut-in voltage, to CsPbBr3Luminescent device Simplified flowsheet, enhancing stability, reduction power consumption have very important significance.
Description
Technical field
The invention belongs to technical field of semiconductor luminescence, and in particular to one kind is based on MgO-CsPbBr3The hair of structure
Optical device and preparation method thereof.
Background technology
Nearly 2 years, hybrid perovskite material（CH3NH3PbX3, X=Cl/Br/I）Potential in illumination field should
With the extensive concern for starting to cause people, the luminescent device based on perovskite thin film and quantum dot system has successfully been prepared,
Cover the visible light wave range in from blue light to red range.But, based on CH3NH3PbX3The luminescent device of material is in stability
It is unsatisfactory always, therefore people start the more excellent CsPbX of sight steering stability3（X=Cl/Br/I）System material,
And can prepare based on CsPbBr3The green luminescence device of material.
However, the CsPbBr for having reported at present3Device architecture also there are problems that in terms of carrier transport and injection it is a lot,
Especially hole provides the selection aspect of layer.A kind of suitable hole provides material should ensure the efficient injection in hole, again
There is the effect of electronic blocking, 2 points of the above will directly determine CsPbBr3The cut-in voltage and its efficiency of luminescent device.And it is traditional
Hole provides material PEDOT:PSS and spiro-OMeTAD due to and CsPbBr3The presence of luminous interlayer hole injection barrier will
The cut-in voltage of device can be increased（J. Xing, F. Yan, Y. W. Zhao, S. Chen, H. K. Yu, Q.
Zhang, R. G. Zeng, H. V. Demir, X. W. Sun, A. Huan, and Q. H. Yang, ACS Nano
10, 6623（2016）; O. A. J. Quintero, R. S. Sanchez, M. Rincon, and I. M. Sero,
J. Phys. Chem. Lett. 6, 1883（2015））.Additionally, the electrical conductivity of above two organic polymer material compared with
It is low, and it is unfavorable for the efficient injection of holoe carrier, and also the stability of two kinds of materials is very poor, and pole is influenceed by water oxygen in environment
Greatly.
There are the excellent properties of bipolarity electric charge transmission in view of perovskite material, if it is possible to by device structure design
Realize the preparation without p-type hole mobile material luminescent device, it will to the type device in technique simplification, stability lifting and work(
Depletion is small etc., and aspect has very important meaning.
The content of the invention
It is an object of the invention to be directed to above-mentioned the deficiencies in the prior art, there is provided one kind is based on MgO-CsPbBr3Structure
Luminescent device and preparation method thereof, the impact ionization process using MgO insulating barriers under high electric field produces nonequilibrium carrier, from
And realize the preparation of the perovskite luminescent device without p-type hole mobile material.
The technical scheme is that realize in the following manner：One kind is based on MgO-CsPbBr3The luminescent device of structure,
Including the substrate for insulating, the electronics that N-shaped is sequentially provided with substrate provides layer, CsPbBr3Luminescent layer, MgO insulating barriers and contact
Electrode.
The substrate is the Al of twin polishing2O3Substrate, the thickness of substrate is 300 ~ 400 microns.
It is ZnO or TiO that the electronics of N-shaped provides layer2Semi-conducting material, its thickness is 300 ~ 450 nanometers.
CsPbBr3The thickness of luminescent layer is 50 ~ 100 nanometers.
The sputter temperature of MgO insulating barriers is 200 ~ 350 DEG C, and thickness is 40 ~ 50 nanometers, and resistivity is 108~1011Ohm li
Rice.
One kind is based on MgO-CsPbBr3The preparation method of the luminescent device of structure, is carried out as steps described below：
（1）Cleaning substrate；
（2）Layer is provided using the electronics of radio frequency magnetron sputtering method depositing n-type on substrate；
（3）There is provided in the electronics of N-shaped and prepare CsPbBr using low temperature solution polycondensation or Gas Evaporation Method on layer3Luminescent layer；
（4）Using radio frequency magnetron sputtering method in CsPbBr3Luminescent layer（3）Upper deposition MgO insulating barriers；
（5）The contact electrode of circle is prepared on MgO insulating barriers using thermal evaporation.
Preferably, step（2）The sputtering that the electronics of middle N-shaped provides layer uses high-purity argon gas as working gas, pure oxygen high
Used as reacting gas, the flow-rate ratio of argon gas and oxygen is 3 to gas:1.
Preferably, step（3）Middle CsPbBr3Luminescent layer is prepared according to a step solwution method：By CsBr and PbBr2Powder
Mixing is dissolved in dimethyl formamide solution；Stirred 24 hours under the conditions of 65 DEG C with magnetic stirring apparatus and obtain mixed solution；
Under inert gas shielding, the mode of mixed solution spin coating is uniformly spin-coated on the electronics of N-shaped and is provided on layer, spincoating conditions are：
Low speed 500 rpms/5 seconds, at a high speed 3000 rpms/25 seconds；Finally the sample after spin coating is made annealing treatment, is annealed
Temperature is 120 DEG C, and the time is 10 minutes.
Or, the CsPbBr3Luminescent layer（3）Prepared using two step solwution methods：By PbBr2Powder is dissolved in dimethyl formyl
Configuration concentration is 1 mole every liter of solution in amine, stirred under the conditions of 65 DEG C with magnetic stirring apparatus 5 hours it is standby；By CsBr powder
End is dissolved in the solution for standby that configuration concentration in isopropanol is 15 milligrams every milliliter；Under inert gas shielding, by what is prepared
PbBr2The mode of solution spin coating is uniformly spin-coated on the electronics of N-shaped offer layer and prepares PbBr2Film, spincoating conditions are：Low speed
500 rpms/5 seconds, at a high speed 3000 rpms/25 seconds；And the sample after spin coating is made annealing treatment, annealing temperature is
120 DEG C, the time is 10 minutes；After sample temperature is down to room temperature, takes CsBr solution with liquid-transfering gun and drop in sample surfaces, and with rotation
The method of painting carries out spin-coat process by low speed 500 rpms/5 seconds, the high speed parameter of 3000 rpms/25 seconds；Spin coating knot
Shu Hou, sample is made annealing treatment, and annealing temperature is 120 DEG C, and the time is 10 minutes.
Or, the CsPbBr3Luminescent layer（3）Preparation using Gas Evaporation Method complete, concretely comprise the following steps：By PbBr2Powder
End is dissolved in the solution that configuration concentration in dimethylformamide is 1 mole every liter, 5 is stirred under the conditions of 65 DEG C with magnetic stirring apparatus small
When it is standby；Under inert gas shielding, the PbBr that will be prepared2The electronics that the mode of solution spin coating is uniformly spin-coated on N-shaped is carried
For layer（2）Upper preparation PbBr2Film, spincoating conditions are：Low speed 500 rpms/5 seconds, high speed 3000 rpms/25 seconds；
And the sample after spin coating is made annealing treatment, annealing temperature is 120 DEG C, and the time is 10 minutes；Treat that sample temperature is down to room temperature
Afterwards, sample is transferred in horizontal pipe furnace；CsBr powder is held in ceramic boat, and ceramic boat is placed on horizontal pipe furnace
Center；Then, spin coating there is into PbBr2The sample of film tips upside down on the top of ceramic boat, and sample surfaces are apart from CsBr powder
0.8 centimetre；In the evaporation process of CsBr powder, the flow of high-purity argon gas is 150sccm, and evaporating temperature is 180 DEG C, during evaporation
Between be 25 minutes；After evaporating, sample is naturally cooling to room temperature.
The present invention produces nonequilibrium carrier using the thought of impact ionization, so as to realize the perovskite without hole transmission layer
The preparation of green luminescence device.Device structure design impact ionization process on the one hand using MgO insulating barriers under high electric field
Carrier is produced, on the other hand by CsPbBr3The larger conduction band barrier in/MgO interfaces is formed to CsPbBr3Electricity is injected in layer
Effective limitation of son, so as to realize nonequilibrium electron and holoe carrier in CsPbBr3High efficiency radiation recombination in layer, overcomes
Traditional CsPbBr3The larger problem of luminescent device cut-in voltage.Traditional CsPbBr3The cut-in voltage of luminescent device is 3 ~ 4 volts,
And the MgO-CsPbBr prepared by the present invention3About 2 volts of the cut-in voltage of luminescent device.Device architecture proposed in the present invention sets
It is calculated as CsPbBr3Luminescent device Simplified flowsheet, enhancing stability and reduction power consumption have very important significance.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the structural representation of perovskite green light LED of the present invention.
Fig. 2 is CsPbBr in embodiment 13The electron scanning micrograph of luminescent layer.
Fig. 3 is CsPbBr in embodiment 23The electron scanning micrograph of luminescent layer.
Fig. 4 is CsPbBr in embodiment 33The electron scanning micrograph of luminescent layer.
Fig. 5 is CsPbBr in embodiment 43The electron scanning micrograph of luminescent layer.
Fig. 6 is the current-voltage characteristic curve of the perovskite green luminescence device prepared by embodiment 1,2,3 and 4.
Electroluminescent hair of perovskite green luminescence devices of the Fig. 7 prepared by embodiment 1,2,3 and 4 under same drive voltage
Spectrum.
Luminous strength ratio of perovskite green luminescence devices of the Fig. 8 prepared by embodiment 1,2,3 and 4 under different voltages
Compared with.
Fig. 9 is the external quantum efficiency of the perovskite green luminescence device prepared by embodiment 1,2,3 and 4.
Wherein：1. substrate, 2. the electronics of N-shaped layer is provided, 3. CsPbBr3Luminescent layer, 4. MgO insulating barriers, 5. contact
Electrode.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not paid
Embodiment, belongs to the scope of protection of the invention.
As shown in figure 1, of the invention based on MgO-CsPbBr3The luminescent device of structure, including the substrate 1 for insulating, substrate 1
On be sequentially provided with N-shaped electronics provide layer 2, CsPbBr3Luminescent layer 3, MgO insulating barriers 4 and contact electrode 5.The electronics of N-shaped is carried
It is ZnO or TiO for layer 22Semi-conducting material, its thickness is 300 ~ 450 nanometers.
The substrate 1 is the Al of twin polishing2O3Substrate, the thickness of substrate is 300 ~ 400 microns, a preferably 350 microns left sides
It is right.
The CsPbBr3The thickness of luminescent layer 3 is 50 ~ 100 nanometers.
The sputter temperature of the MgO insulating barriers 4 is 200 ~ 350 DEG C, and thickness is 40 ~ 50 nanometers, and resistivity is 108~1011Europe
Nurse centimetre.
In the present invention, based on MgO-CsPbBr3The preparation method of the luminescent device of structure, is to carry out as steps described below
's：
（1）Cleaning substrate 1；
（2）Using radio frequency magnetron sputtering method on substrate 1 depositing n-type electronics provide layer 2；
（3）There is provided in the electronics of N-shaped and prepare CsPbBr on layer 23Luminescent layer 3；
（4）Using radio frequency magnetron sputtering method in CsPbBr3MgO insulating barriers 4 are deposited on luminescent layer 3；
（5）The contact electrode 5 of circle is prepared on MgO insulating barriers 4 using thermal evaporation.Contact electrode is preferably Au electrodes.
Preferably, step（2）The sputtering that the electronics of middle N-shaped provides layer 2 uses high-purity argon gas as working gas, pure oxygen high
Used as reacting gas, the flow-rate ratio of argon gas and oxygen is 3 to gas:1.
Preferably, step（3）Middle CsPbBr3The preparation of luminescent layer 3 is low temperature solution polycondensation or Gas Evaporation Method.
Preferably, step（3）Middle CsPbBr3Luminescent layer 3 is according to a step solwution method（One step solwution method is low temperature solution polycondensation
One kind）Prepare：
By CsBr and PbBr2Powder mixing is dissolved in dimethyl formamide solution, is stirred under the conditions of 65 DEG C with magnetic stirring apparatus
Obtain mixed solution within 24 hours；
Under inert gas shielding, the mode of mixed solution spin coating is uniformly spin-coated on the electronics of N-shaped and is provided on layer 2, spin coating
Condition is：Low speed 500 rpms/5 seconds, (i.e. spin coating is divided into two stages, first stage within 3000 rpms/25 seconds at a high speed
It is that 500 speed per minute are adhered to 5 seconds, second stage is 3000 rpms and adheres to 25 seconds, the application spin coating described below
It is identical with this)；Finally the sample after spin coating is made annealing treatment, annealing temperature is 120 DEG C, the time is 10 minutes.
In addition, the CsPbBr3Luminescent layer 3 can also be prepared using two step solwution methods（Two step solwution methods are cryogenic fluids
One kind of method）：
By PbBr2Powder is dissolved in the solution that configuration concentration in dimethylformamide is 1 mole every liter, with magnetic stirring apparatus at 65 DEG C
Under the conditions of stirring 5 hours it is standby；CsBr powder is dissolved in the solution for standby that configuration concentration in isopropanol is 15 milligrams every milliliter；
Under inert gas shielding, the PbBr that will be prepared2The electronics that the mode of solution spin coating is uniformly spin-coated on N-shaped provides layer
PbBr is prepared on 22Film, spincoating conditions are：Low speed 500 rpms/5 seconds, at a high speed 3000 rpms/25 seconds；And to rotation
Sample after painting is made annealing treatment, and annealing temperature is 120 DEG C, and the time is 10 minutes；
After sample temperature is down to room temperature, takes CsBr solution with liquid-transfering gun and drop in sample surfaces, and 500 turns are pressed with the method for spin coating
Per minute/5 seconds, 3000 rpms/25 seconds parameters carry out spin-coat process；After spin coating terminates, sample is made annealing treatment,
Annealing temperature is 120 DEG C, and the time is 10 minutes.
In addition, the CsPbBr3The preparation of luminescent layer 3 can be completed using Gas Evaporation Method, be concretely comprised the following steps：
By PbBr2Powder is dissolved in the solution that configuration concentration in dimethylformamide is 1 mole every liter, with magnetic stirring apparatus at 65 DEG C
Under the conditions of stirring 5 hours it is standby；
Under inert gas shielding, the PbBr that will be prepared2The electronics that the mode of solution spin coating is uniformly spin-coated on N-shaped provides layer
PbBr is prepared on 22Film, spincoating conditions are：Low speed 500 rpms/5 seconds, at a high speed 3000 rpms/25 seconds；And to rotation
Sample after painting is made annealing treatment, and annealing temperature is 120 DEG C, and the time is 10 minutes；
After sample temperature is down to room temperature, sample is transferred in horizontal pipe furnace；CsBr powder is held in ceramic boat, and will
Ceramic boat is placed on the center of horizontal pipe furnace；Then, spin coating there is into PbBr2The sample of film tips upside down on the top of ceramic boat,
Sample surfaces are 0.8 centimetre apart from CsBr powder；In the evaporation process of CsBr powder, the flow of high-purity argon gas is 150sccm,
Evaporating temperature is 180 DEG C, and evaporation time is 25 minutes；After evaporating, sample is naturally cooling to room temperature.
Preparation method of the present invention and performance are illustrated with reference to specific embodiment.
Embodiment 1：
（1）Cleaning dielectric substrate 1, the substrate 1 for being used is double Al for throwing2O3Piece.
Using the Al of double throwings2O3Piece is carried out Chemical cleaning as substrate 1, and cleaning step is：Place the substrate in first
Cleaning agent（Vertical person who is not a member of any political party's liquid detergent）Middle immersion 10 minutes, then rinsed well with running water；Then acetone and ethanol are used successively
Solution is respectively cleaned by ultrasonic 10 minutes, and recycling is once；After being rinsed well with deionized water afterwards, standby is dried up through high pure nitrogen
With.
（2）The ZnO electronics for preparing N-shaped provides layer.
Double throwing Al after by cleaning2O3Substrate 1 is put into magnetron sputtering cavity, and completing ZnO electronics using radio-frequency power supply provides
The sputtering of layer, concretely comprises the following steps：ZnO ceramic targets are installed, by the position adjustment between target and substrate to 12 centimetres；Open machinery
Pump, vacuumizes to sputter chamber, after chamber vacuum degree is less than 5 Pascal, opens molecular pump and continues to vacuumize, until cavity is true
Reciprocal of duty cycle is less than 1.0 × 10-3Pascal；To appropriate high-purity argon gas and oxygen are passed through in cavity, adjust the flow proportional of the two to
3:1 so that the pressure stabilization of cavity is in 1.0 Pascals；Radio frequency source is opened, is 150 watts by its power setting, and by underlayer temperature
It is set as 400 DEG C, sputtering time is set as 2 hours.The thickness that obtained N-shaped ZnO electronics provides layer is 370 nanometers, its electronics
Concentration is 7.2 × 1017cm-3。
（3）CsPbBr is prepared using a step solwution method3Luminescent layer 3.
First by 1.33 grams of CsBr（Aladdin boards）PbBr with 2.30 grams2（Aladdin boards）Powder mixing is dissolved in 4
In the dimethyl formamide solution of milliliter；Then stirred 24 hours under the conditions of 65 DEG C with magnetic stirring apparatus；Then in indifferent gas
In the glove box of body protection, the mode of the mixed solution spin coating that will be prepared uniformly is spin-coated on the ZnO electronics offer layer of N-shaped
On, spincoating conditions are：Low speed 500 rpms/5 seconds, at a high speed 3000 rpms/25 seconds；Finally to spin coating in glove box
Sample afterwards is made annealing treatment, and annealing temperature is 120 DEG C, and the time is 10 minutes.
Fig. 2 is the CsPbBr prepared using a step solwution method3The electron scanning micrograph of luminescent layer 3.
（4）By the complete CsPbBr of spin coating3The sample of luminescent layer 3 is positioned in magnetron sputtering cavity, is completed using radio-frequency power supply
The sputtering of MgO insulating barriers 4.
Concretely comprise the following steps：MgO ceramic targets are installed, by the position adjustment between target and substrate to 10 centimetres；Open machinery
Pump, vacuumizes to sputter chamber, after chamber vacuum degree is less than 5 Pascal, opens molecular pump and continues to vacuumize, until cavity is true
Reciprocal of duty cycle is less than 1.0 × 10-3Pascal；To appropriate high-purity argon gas and oxygen are passed through in cavity, adjust the flow proportional of the two to
1:1 so that the pressure stabilization of cavity is in 1.0 Pascals；Radio frequency source is opened, is 120 watts by its power setting, and by underlayer temperature
It is set as 250 DEG C, sputtering time is set as 0.5 hour.The thickness of prepared MgO insulating barriers 4 is 45 nanometers, and resistivity is
6.2×109Ohmcm.
（5）Translucent Au is deposited on the surface of MgO insulating barriers 4 using thermal evaporation and combination mask plate and contacts electrode,
The shape of Au contact electrodes is a diameter of 1.5 millimeters of circle, and its thickness is 40 nanometers.
Embodiment 2：
（1）Using double throwing Al of insulation2O3Piece is used as substrate 1.To double throwing Al in the present embodiment2O3The cleaning method and reality of substrate
Apply example 1 identical.
（2）Double throwing Al after cleaning2O3TiO is sputtered on substrate 12Electronics provides layer.
Double throwing Al after by cleaning2O3Substrate 1 is put into magnetron sputtering cavity, and TiO is completed using radio-frequency power supply2Electronics is carried
For the sputtering of layer, concretely comprise the following steps：TiO is installed2Ceramic target, by the position adjustment between target and substrate to 12 centimetres；Open
Mechanical pump, vacuumizes to sputter chamber, after chamber vacuum degree is less than 5 Pascal, opens molecular pump and continues to vacuumize, until chamber
Body vacuum is less than 1.0 × 10-3Pascal；To appropriate high-purity argon gas and oxygen are passed through in cavity, the flow-rate ratio of the two is adjusted
Example is to 3:1 so that the pressure stabilization of cavity is in 1.0 Pascals；Radio frequency source is opened, is 150 watts by its power setting, and by substrate
Temperature is set as 400 DEG C, and sputtering time is set as 2 hours.Obtained N-shaped TiO2The thickness that electronics provides layer is 350 nanometers, its
Electron concentration is 2.6 × 1017cm-3。
（3）CsPbBr is prepared using a step solwution method3Luminescent layer 3.The technical process and preparation parameter of the part and implementation
Example 1 is identical.
Fig. 3 is the CsPbBr prepared using a step solwution method3The electron scanning micrograph of luminescent layer 3.
（4）By the complete CsPbBr of spin coating3The sample of luminescent layer 3 is positioned in magnetron sputtering cavity, is completed using radio-frequency power supply
The sputtering of MgO insulating barriers 4.The method and embodiment 1 that MgO insulating barriers 4 are obtained in the present embodiment are identical.
（5）Finally, transparent Au is deposited on the surface of MgO insulating barriers 4 using thermal evaporation and contacts electrode.The work of the part
Skill process and preparation parameter and embodiment 1 are identical.
This example and embodiment 1 except that, it is TiO that the electronics of N-shaped provides layer 22, due to TiO2Have with ZnO material
It is different can band feature, when the two respectively and CsPbBr3When luminescent layer 3 is contacted, it is possible to achieve to CsPbBr3Luminescent layer 3 is different
Electron injection effect.
Embodiment 3：
This example and embodiment 1 except that, CsPbBr3The preparation of luminescent layer 3 is completed using two step solwution methods, specific steps
For：First, by 2.30 grams of PbBr2（Aladdin boards）Configuration concentration is 1 mole every liter during powder is dissolved in dimethylformamide
Solution, stirred under the conditions of 65 DEG C with magnetic stirring apparatus 5 hours it is standby；By 1.33 grams of CsBr（Aladdin boards）Powder is dissolved in
Configuration concentration is 15 milligrams every milliliter of solution for standby in isopropanol；In the glove box of inert gas shielding, by what is prepared
PbBr2The mode of solution spin coating is uniformly spin-coated on the ZnO electronics of N-shaped offer layer 2 and prepares PbBr2Film, spincoating conditions are：
Low speed 500 rpms/5 seconds, at a high speed 3000 rpms/25 seconds；And in glove box to spin coating after sample anneal
Treatment, annealing temperature is 120 DEG C, and the time is 10 minutes；After sample temperature is down to room temperature, 300 microlitres are taken with liquid-transfering gun
CsBr solution drops in sample surfaces, and with the method for spin coating（Low speed 500 rpms/5 seconds, high speed 3000 rpms/25
Second）Carry out spin-coat process；After spin coating terminates, sample is made annealing treatment, annealing temperature is 120 DEG C, the time is 10 minutes.
Fig. 4 is the CsPbBr prepared using two step solwution methods3The electron scanning micrograph of luminescent layer 3.Other each layers
The step of preparation process of film is with embodiment 1.
In the present embodiment, CsPbBr3The preparation of luminescent layer 3 is completed using two step solwution methods, so can be by controlling every layer
Spincoating conditions to CsPbBr3The shape characteristic of luminescent layer 3 is regulated and controled.
Embodiment 4：
This example and embodiment 1 except that, CsPbBr3The preparation of luminescent layer 3 is completed using Gas Evaporation Method, specific steps
For：First, by 2.30 grams of PbBr2（Aladdin boards）Configuration concentration is 1 mole every liter during powder is dissolved in dimethylformamide
Solution, stirred under the conditions of 65 DEG C with magnetic stirring apparatus 5 hours it is standby；In the glove box of inert gas shielding, will prepare
PbBr2The mode of solution spin coating is uniformly spin-coated on the ZnO electronics of N-shaped offer layer 2 and prepares PbBr2Film, spincoating conditions
For：Low speed 500 rpms/5 seconds, at a high speed 3000 rpms/25 seconds；And in glove box to spin coating after sample move back
Fire treatment, annealing temperature is 120 DEG C, and the time is 10 minutes；After sample temperature is down to room temperature, sample is transferred to horizontal tube
In stove；3.5 grams of CsBr are held in ceramic boat（Aladdin boards）Powder, and ceramic boat is placed on the center of horizontal pipe furnace；
Then, spin coating there is into PbBr2The sample of film tips upside down on the top of ceramic boat, and sample surfaces are apart from CsBr（Aladdin boards）Powder
End is 0.8 centimetre；In CsBr（Aladdin boards）In the evaporation process of powder, the flow of high-purity argon gas is 150sccm, evaporation temperature
It is 180 degrees Celsius to spend, and evaporation time is 25 minutes；After evaporating, sample is naturally cooling to room temperature.
Fig. 5 is the CsPbBr prepared using Gas Evaporation Method3The electron scanning micrograph of luminescent layer 3.Other each layers
The step of preparation process of film is with embodiment 1.
In the present embodiment, CsPbBr3The preparation of luminescent layer 3 is completed using Gas Evaporation Method, so can be by controlling CsBr
The evaporating temperature of layer and time are to CsPbBr3The crystallization property of luminescent layer 3 is controlled.
Fig. 6 is the current-voltage characteristic curve of prepared device in embodiment 1,2,3,4, and four devices show bright
Aobvious rectification characteristic, cut-in voltage is about 1.9 ~ 2.2 volts, and the numerical value is significantly lower than tradition CsPbBr3The result of luminescent device.
Fig. 7 is device prepared in embodiment 1,2,3,4 in same drive voltage（5.0 volts）Under electroluminescence spectrum,
Now the Au contact electrodes in device connect the positive pole of dc source, the ZnO or TiO of N-shaped2Layer connection negative pole.Can be with from Fig. 7
See, four devices show obvious green emission, and luminous peak position is in 522 rans.But due to four device architectures
Middle layers of material characteristic has differences, and the luminous intensity of device has obvious difference under same drive voltage.
Fig. 8 is the luminous intensity contrast of prepared device under different driving voltage in embodiment 1,2,3,4, now device
Au electrodes in part connect the positive pole of power supply, the ZnO or TiO of N-shaped2Layer connection negative pole.By to device under different driving voltage
Luminous spectrum be integrated treatment, it can be found that four luminous intensities of device have different variation tendencies with driving voltage.This
Mainly due to caused by being had differences between four structure designs and layers of material characteristic of device.
Fig. 9 is that the external quantum efficiency of prepared device in embodiment 1,2,3,4 compares.As can see from Figure 8, embodiment
Perovskite green luminescence device prepared in 3 has highest external quantum efficiency 1.66%, calcium titanium prepared in embodiment 2
The external quantum efficiency of ore deposit green luminescence device is relatively low（0.36%）.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (10)
1. it is a kind of to be based on MgO-CsPbBr3The luminescent device of structure, including the substrate for insulating（1）, it is characterised in that：Substrate（1）On
The electronics for being sequentially provided with N-shaped provides layer（2）、CsPbBr3Luminescent layer（3）, MgO insulating barriers（4）And contact electrode（5）.
2. according to claim 1 a kind of based on MgO-CsPbBr3The luminescent device of structure, it is characterised in that：The substrate
（1）It is the Al of twin polishing2O3Substrate, the thickness of substrate is 300 ~ 400 microns.
3. according to claim 1 a kind of based on MgO-CsPbBr3The luminescent device of structure, it is characterised in that：The electricity of N-shaped
Son provides layer（2）It is ZnO or TiO2Semi-conducting material, its thickness is 300 ~ 450 nanometers.
4. according to claim 1 a kind of based on MgO-CsPbBr3The luminescent device of structure, it is characterised in that：CsPbBr3
Luminescent layer（3）Thickness be 50 ~ 100 nanometers.
5. according to claim 1 a kind of based on MgO-CsPbBr3The luminescent device of structure, it is characterised in that：MgO insulate
Layer（4）Sputter temperature be 200 ~ 350 DEG C, thickness be 40 ~ 50 nanometers, resistivity is 108~1011Ohmcm.
6. it is a kind of to be based on MgO-CsPbBr3The preparation method of the luminescent device of structure, it is characterised in that be to carry out as steps described below
's：
（1）Cleaning substrate（1）；
（2）Using radio frequency magnetron sputtering method in substrate（1）The electronics of upper depositing n-type provides layer（2）；
（3）Layer is provided in the electronics of N-shaped（2）Upper utilization low temperature solution polycondensation or Gas Evaporation Method prepare CsPbBr3Luminescent layer（3）；
（4）Using radio frequency magnetron sputtering method in CsPbBr3Luminescent layer（3）Upper deposition MgO insulating barriers（4）；
（5）Using thermal evaporation in MgO insulating barriers（4）It is upper to prepare circular contact electrode（5）.
7. according to claim 6 a kind of based on MgO-CsPbBr3The preparation method of the luminescent device of structure, its feature exists
In：Step（2）The electronics of middle N-shaped provides layer（2）Sputtering using high-purity argon gas as working gas, high purity oxygen gas are used as reaction
The flow-rate ratio of gas, argon gas and oxygen is 3:1.
8. according to claim 6 a kind of based on MgO-CsPbBr3The preparation method of the luminescent device of structure, its feature exists
In：Step（3）Middle CsPbBr3Luminescent layer（3）It is to be prepared using a step solwution method：
By CsBr and PbBr2Powder mixing is dissolved in dimethyl formamide solution, and 24 are stirred under the conditions of 65 DEG C with magnetic stirring apparatus
Hour obtains mixed solution；
Under inert gas shielding, layer is provided by the electronics that the mode of mixed solution spin coating is uniformly spin-coated on N-shaped（2）On, rotation
Painting condition is：500 rpms/5 seconds, 3000 rpms/25 seconds；Finally the sample after spin coating is made annealing treatment, is moved back
Fiery temperature is 120 DEG C, and the time is 10 minutes.
9. according to claim 6 a kind of based on MgO-CsPbBr3The preparation method of the luminescent device of structure, its feature exists
In：Step（3）Middle CsPbBr3Luminescent layer（3）It is to be prepared using two step solwution methods：
By PbBr2Powder is dissolved in dimethylformamide, is stirred 5 hours under the conditions of 65 DEG C with magnetic stirring apparatus, obtains concentration
It is 1 mole every liter of PbBr2Solution for standby；CsBr powder is dissolved in the CsBr that configuration concentration in isopropanol is 15 milligrams every milliliter
Solution for standby；
Under inert gas shielding, the PbBr that will be prepared2The electronics that the mode of solution spin coating is uniformly spin-coated on N-shaped provides layer
（2）Upper preparation PbBr2Film, spincoating conditions are：500 rpms/5 seconds, 3000 rpms/25 seconds；And to spin coating after
Sample is made annealing treatment, and annealing temperature is 120 DEG C, and the time is 10 minutes；
After sample temperature is down to room temperature, takes CsBr solution with liquid-transfering gun and drop in sample surfaces, and revolved with the method for spin coating
Painting is processed, and spincoating conditions are：500 rpms/5 seconds, 3000 rpms/25 seconds；After spin coating terminates, sample is annealed
Treatment, annealing temperature is 120 DEG C, and the time is 10 minutes.
10. according to claim 6 a kind of based on MgO-CsPbBr3The preparation method of the luminescent device of structure, its feature exists
In：Step（3）Middle CsPbBr3Luminescent layer（3）It is to be prepared using Gas Evaporation Method, concretely comprises the following steps：
By PbBr2Powder is dissolved in dimethylformamide, is stirred 5 hours under the conditions of 65 DEG C with magnetic stirring apparatus, and configuration concentration is
1 mole every liter of PbBr2Solution for standby；
Under inert gas shielding, the PbBr that will be prepared2The electronics that the mode of solution spin coating is uniformly spin-coated on N-shaped provides layer
（2）Upper preparation PbBr2Film, spincoating conditions are：500 rpms/5 seconds, 3000 rpms/25 seconds；And to spin coating after
Sample is made annealing treatment, and annealing temperature is 120 DEG C, and the time is 10 minutes；
After sample temperature is down to room temperature, sample is transferred in horizontal pipe furnace；CsBr powder is held in ceramic boat, and will
Ceramic boat is placed on the center of horizontal pipe furnace；Then, spin coating there is into PbBr2The sample of film tips upside down on the top of ceramic boat,
Sample surfaces are 0.8 centimetre apart from CsBr powder；In the evaporation process of CsBr powder, the flow of high-purity argon gas is 150sccm,
Evaporating temperature is 180 DEG C, and evaporation time is 25 minutes；After evaporating, sample is naturally cooling to room temperature.
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| CN109638116A (en) * | 2018-11-27 | 2019-04-16 | 华灿光电（浙江）有限公司 | A kind of preparation method and epitaxial wafer of the epitaxial wafer of light emitting diode |
| CN114456800A (en) * | 2022-02-10 | 2022-05-10 | 齐鲁工业大学 | Preparation method and application of perovskite quantum dot-molecularly imprinted fluorescent coding microsphere for detecting Sudan red I |
| CN115056042A (en) * | 2022-05-30 | 2022-09-16 | 西北工业大学 | Reduce full inorganic CsPbBr 3 Surface treatment method for leakage current of perovskite device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108682791A (en) * | 2018-03-23 | 2018-10-19 | 合肥国轩高科动力能源有限公司 | A kind of method that vapor phase method prepares the inorganic perovskite negative material of layer structure |
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| CN109638116A (en) * | 2018-11-27 | 2019-04-16 | 华灿光电（浙江）有限公司 | A kind of preparation method and epitaxial wafer of the epitaxial wafer of light emitting diode |
| CN114456800A (en) * | 2022-02-10 | 2022-05-10 | 齐鲁工业大学 | Preparation method and application of perovskite quantum dot-molecularly imprinted fluorescent coding microsphere for detecting Sudan red I |
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| CN115056042A (en) * | 2022-05-30 | 2022-09-16 | 西北工业大学 | Reduce full inorganic CsPbBr 3 Surface treatment method for leakage current of perovskite device |
| CN115056042B (en) * | 2022-05-30 | 2023-11-14 | 西北工业大学 | Reduce full inorganic CsPbBr 3 Surface treatment method for leakage current of perovskite device |
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