CN106848076B - A kind of organo-mineral complexing perovskite LED device and preparation method thereof - Google Patents
A kind of organo-mineral complexing perovskite LED device and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of organo-mineral complexing perovskite LED device and preparation method thereof, the present invention is based on the planar heterojunction light emitting diode of organo-mineral complexing perovskite material, concrete structure is followed successively by substrate, transparent anode, ultrathin insulating layer 1, organic-inorganic perovskite luminescent layer, ultrathin insulating layer 2, electron transfer layer and cathode.Compared to the planar heterojunction perovskite LED device of no ultrathin insulating layer 1 and ultrathin insulating layer 2, light emitting diode of the present invention has high current efficiency and power efficiency, improves 20 times or more.Diode structure disclosed by the invention is a kind of ideal component structure for organo-mineral complexing perovskite material.
Description
Technical field
The invention belongs to LED technology fields, are related to perovskite LED device, especially a kind of organic
Inorganic compounding perovskite LED device and preparation method thereof.
Background technology
2013, perovskite solar cell was by the U.S.《Science》It is chosen as the breakthrough of ten big sciences, perovskite magazine year
This novel organic-inorganic composite material occupies overwhelming in photovoltaic and photoelectric field rapidly due to series of advantages
Advantage.
Before the appearance of organic-inorganic composite perofskite material can trace back to a century, originally, perovskite material master
If being used for photovoltaic art, just developed later to illumination field.At abroad, early start studies organic metal halide perovskite
The electroluminescence characters of material be Cambridge University, Oxford University and University of Munich joint study team, the item of the team
Mesh responsible person, all one's life laboratory Sir Richard professors Friend, which lead the team for the first time and realize perovskite material, to exist
At room temperature shine.The seminar is prepared for a kind of simple three-decker TiO using low temperature solution polycondensation2/CH3NH3PbI3–
The perovskite electroluminescent device (PeLED) of xClx/F8, it is fully compound in perovskite luminescent layer by limiting electron-hole
It shines, obtains the near-infrared PeLED of high brightness.In addition, they also use CH3NH3PbBr3Instead of CH3NH3PbI3- xClx makees
For luminescent layer, it is prepared for green light PeLED, device brightness has reached 364cdm- 2, external quantum efficiency and internal quantum efficiency are distinguished
Reach 0.1% and 0.4%.In addition, Friend seminars by luminescence generated by light the study found that under high excitation intensity, bimolecular
Radiation recombination plays a leading role in the devices.Therefore, the external quantum efficiency of PeLED devices increases under high current densities,
This shows the high-luminous-efficiency of perovskite material and color tunability before low cost display, lighting area have prodigious application
Scape.But the electroluminescent efficiency of device, still well below photoluminescence efficiency, this aspect is due to perovskite luminescent layer
Film forming it is poor, the leakage current in device can cause non-radiative recombination to increase, and on the other hand be the heat due to perovskite material
Stability is poor, and device heating can lead to performance degradation under the conditions of high current.Dinesh Kabra seminars by regulate and control I, Br,
The different ratio of Cl realizes that electroluminescent spectrum is adjustable, has not only prepared green light PeLED, and prepared feux rouges
PeLED, and they are to realize to shine at normal temperatures.Influence one of perovskite material electroluminescent device efficiency because
Element is exactly film morphology, for this purpose, Wei Huang seminars are modified ZnO film by introducing PEI materials, improves parent
It is aqueous, improve the pattern of perovskite thin film, and reduce electrodes work functions and improve charge injection efficiency, the brightness of device reaches
20000cd·m- 2.For the leakage current in suppression device, Friend seminars introduce PIP dielectric materials, are blended with perovskite,
To realize that the inhibiting effect to leakage current, raising device performance, external quantum efficiency have reached 1.2%.
The PeLED reported at present is inefficient, the main reason is that the coverage rate of perovskite thin film prepared by solwution method is not
Completely, and there is cavity, the leakage current for having larger can be caused in this way.These these leakage currents can lead to the inefficiency of device.
Invention content
The shortcomings of film is uneven in above-mentioned technology it is an object of the invention to overcome, and has pin hole, and there are leakage currents, provides
A kind of organo-mineral complexing perovskite LED device and preparation method thereof introduces a pair of of ultrathin insulating layer, reduces device
Leakage current in part, while the injection of carrier and compound, reduction fluorescent quenching are improved, it is final to improve perovskite light emitting diode
Current efficiency.
The purpose of the present invention is achieved through the following technical solutions：
Present invention firstly provides a kind of organo-mineral complexing perovskite LED devices：It is followed successively by base from the bottom to top
Piece, transparent anode, the first ultrathin insulating layer, organic-inorganic perovskite luminescent layer, the second ultrathin insulating layer, electron transfer layer and the moon
Pole；First ultrathin insulating layer and the second ultrathin insulating layer select inorganic or organic compound；The organic-inorganic perovskite
Luminescent layer is methylamine lead halogen or carbonamidine lead halogen；The cathode is the combination electrode of metal or fluoride and metal.
Further, above-mentioned substrate is glass or flexible substrate；The transparent anode uses inorganic material or organic conductive
Polymer.
Further, above-mentioned flexible substrate is polyester or poly- phthalimide class compound；The inorganic material that the transparent anode uses
Material is a kind of metal oxide in tin indium oxide, zinc oxide or tin oxide, or is a kind of metal in gold, copper, silver or zinc；
The organic conductive polymer that transparent anode uses is polythiophene, polyvinylbenzenesulfonic acid sodium or polyaniline.
Above-mentioned first ultrathin insulating layer and the second ultrathin insulating layer can select lithium fluoride, potassium fluoride, magnesium fluoride, chlorination
The depositable materials such as sodium, magnesium chloride, potassium chloride and silica, aluminium oxide, polytetrafluoroethylene (PTFE) etc. can magnetron sputtering materials.
Above-mentioned methylamine lead halogen is CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbBr3-xIx、
CH3NH3PbBr3-xClxOr CH3NH3PbCl3-xIx；The carbonamidine lead halogen is HC (NH2)2PbBr3、HC(NH2)2PbCl3、HC
(NH2)2PbI3、HC(NH2)2PbBr3-XIx、HC(NH2)2PbCl3-XI or HC (NH2)2PbBr3-XClx。
Above-mentioned electron transport layer materials are 4,7- diphenyl -1,10- ferrosins or the (1- phenyl -1H- benzos of 1,3,5- tri-
Imidazoles -2- bases) benzene.
When above-mentioned cathode selection metal, it is selected from gold, silver or aluminium；It is lithium fluoride and gold when the cathode selection combination electrode
Belong to the combination electrode of silver or aluminium.
The present invention also proposes a kind of preparation method of above-mentioned organo-mineral complexing perovskite LED device, including with
Lower step：
1) substrate is cleaned using the method for ethyl alcohol, acetone ultrasound and deionized water ultrasound, is dried after cleaning, wherein
The square resistance of transparent anode layer of the ito film as device above transparent conduction base sheet, ito film is the Ω of 15 Ω~30, film thickness
For 80~120nm；
2) preparation of the first ultrathin insulating layer：The substrate that step 1) is handled well uses ultraviolet -5~10 points of ozone treatment
Then clock is transmitted to substrate in vacuum chamber, in one layer of insulating materials of deposition on substrate as the first ultrathin insulating layer, rate
In 0.01~0.03nm/s, film thickness is 0.01~10nm for control；
3) preparation of organic-inorganic perovskite luminescent layer：Perovskite is prepared on the first ultrathin insulating layer prepared by step 2)
Layer：Perovskite precursor solution, which is spin-coated on deposition, to be had on the ito glass substrate of insulating materials, and substrate rotating speed is 3000rpm, when
Between be 30~60 seconds；At 80~100 DEG C, annealing time was controlled at 10~20 minutes, was obtained after the completion organic for annealing temperature control
Inorganic perovskite luminescent layer；
4) preparation of the second ultrathin insulating layer：The organic-inorganic perovskite luminescent layer that step 3) prepares is logical in its substrate
It crosses vacuum vapour deposition or magnetron sputtering method prepares insulating layer as the second ultrathin insulating layer；The perovskite thin film prepared is turned
Vacuum chamber depositing insulating layer is moved on to, for rate control in 0.01~0.03nm/s, film thickness is 0.01~10nm；After the completion
To the second ultrathin insulating layer；
5) preparation of electron transfer layer：Vacuum evaporation electron transfer layer is carried out on the second ultrathin insulating layer prepared：
The evaporation rate of material film is 0.1~0.2nm/s, and film thickness is 20~60nm；
6) preparation of cathode：Keep step 5) vacuum cavity pressure it is constant, on electron transfer layer evaporation metal or
Person's fluoride and cathode layer of the metal composite layer as device, film thickness are 80~120nm；It is inorganic multiple that the machine is obtained after the completion
Close perovskite LED device.
Compared with prior art, the invention has the advantages that：
The organo-mineral complexing perovskite LED device and preparation method thereof of the present invention solves perovskite thin film
Inhomogeneities, have pin hole, the problems such as there are leakage currents, various organic and inorganic perovskite thin films can be expanded to, it is continuous flexibly
Adjustment improves the process conditions of perovskite thin film growth, may be implemented large area preparation, requirement to equipment and environment compared with
It is low.It is introduced without ultrathin insulating layer compared to tradition and prepares planar heterojunction LED device, polycrystalline calcium prepared by the present invention
Titanium ore LED device can fully reduce leakage current, improve the current efficiency of device, the Organic-inorganic composite of preparation
The current efficiency of perovskite LED device promotes 20 times or more, can fully meet the commercially use needs of device.
Description of the drawings
Fig. 1 is the perovskite luminous diode device structure schematic diagram of the present invention；
1 is ITO substrates, and 2 be the first ultrathin insulating layer, and 3 be organic-inorganic perovskite luminescent layer, and 4 be the second ultrathin insulating
Layer, 5 be electron transfer layer, and 6 be cathode
Fig. 2 is the scanning electron microscope (SEM) photograph of the methylamine lead bromine perovskite thin film of the embodiment of the present invention 1；
(a) it is the film morphology on ITO substrates, is (b) film morphology on the first ultrathin insulating layer substrate.
Fig. 3 is the perovskite (CH of the embodiment of the present invention 13NH3PbBr3) LED device vacuum vapour deposition prepare
Voltage-current efficiency (a) and voltage-brightness curve (b) figure under LiF insulating layers；
Fig. 4 is the perovskite (HC (NH of the embodiment of the present invention 12)2PbBr3) LED device is in vacuum evaporation legal system
Voltage-current efficiency (a) and voltage-brightness curve figure (b) under standby LiF insulating layers；
Fig. 5 is the perovskite (CH of the embodiment of the present invention 23NH3PbBr3) LED device is in radio-frequency magnetron sputter method
Prepare SiO2Voltage-current efficiency (a) and voltage-brightness curve figure (b) under insulating layer；
Fig. 6 is the perovskite (HC (NH of the embodiment of the present invention 22)2PbBr3) LED device is in rf magnetron sputtering
Method prepares SiO2Voltage-current efficiency (a) and voltage-brightness curve figure (b) under insulating layer；
Specific implementation mode
The present invention is described in further detail below in conjunction with the accompanying drawings：
Referring to Fig. 1, organo-mineral complexing perovskite LED device of the invention be followed successively by from the bottom to top substrate, thoroughly
Bright anode, the first ultrathin insulating layer, organic-inorganic perovskite luminescent layer, the second ultrathin insulating layer, electron transfer layer and cathode.With
Under each layer is described in detail：
Wherein substrate is glass or flexible substrate, and wherein flexible substrate is polyester or poly- phthalimide class compound；It is transparent
It is one kind in tin indium oxide, zinc oxide or tin oxide that anode, which uses inorganic material or organic conductive polymer, the inorganic material,
Metal oxide is a kind of metal in gold, copper, silver or zinc, and organic conductive polymer is polythiophene, polyvinylbenzenesulfonic acid sodium
Or polyaniline.
The first ultrathin insulating layer and the second ultrathin insulating layer of the present invention selects inorganic or organic compound, for example is fluorinated
Lithium, potassium fluoride, magnesium fluoride, sodium chloride, magnesium chloride, potassium chloride depositable material and silica, aluminium oxide, polytetrafluoroethylene (PTFE)
It can magnetron sputtering material.
The material of the organic-inorganic perovskite luminescent layer of the present invention：Methylamine lead halogen is CH3NH3PbI3、CH3NH3PbBr3、
CH3NH3PbCl3、CH3NH3PbBr3-xIx、CH3NH3PbBr3-xClxOr CH3NH3PbCl3-xIx；Carbonamidine lead halogen is HC (NH2)2PbBr3、HC(NH2)2PbCl3、HC(NH2)2PbI3、HC(NH2)2PbBr3-XIx、HC(NH2)2PbCl3-XI or HC (NH2)2PbBr3-XClx。
The present invention electron transport layer materials be：4,7- diphenyl -1,10- ferrosins (Bphen), (the 1- benzene of 1,3,5- tri-
Base -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi).
The cathode material of the present invention is metal or fluoride and metal composite electrode, and metal is in gold, silver or aluminium；It is compound
Electrode is lithium fluoride and metallic silver or aluminium.
The first and second ultrathin insulating layer of the present invention can by magnetron sputtering, vacuum evaporation, spin coating, spraying, impregnate, scrape
Prepared by the methods of painting or roller coating technology, thickness 1-10nm.Organo-mineral complexing perovskite material can pass through wet method spin coating
And the modes such as vacuum evaporation obtain.Its thickness is 10-600nm.Cathode material can be obtained by vacuum deposition method, thick
Degree is 100~120nm.
For organo-mineral complexing perovskite LED device set forth above, the present invention is proposed below for the knot
The preparation method of structure diode component：
(1) transparent conduction base sheet (ito glass) is carried out using the method for ethyl alcohol, acetone ultrasound and deionized water ultrasound clear
It washes, places it under infrared lamp and dry after cleaning, wherein anode layer of the ito film above transparent conduction base sheet 1 as device,
The square resistance of ito film is the Ω of 15 Ω~30, and film thickness is 80~120nm.Substrate can also be flexible substrate in addition to selecting glass,
Wherein flexible substrate can be polyester or poly- phthalimide class compound.Inorganic material or organic conductive polymerization may be used in anode layer
Object, the inorganic material select tin indium oxide (ITO), and outside, it is poly- thiophene that can also use organic conductive polymer to tin oxide fluorine (FTO)
Pheno, polyvinylbenzenesulfonic acid sodium or polyaniline.
The preparation of (2) first ultrathin insulating layers：The substrate that will be dried uses ultraviolet -5~10 points of ozone treatment
Then clock is transmitted to substrate in vacuum chamber, then in one layer of insulating materials of deposition on substrate, rate control 0.01~
0.03nm/s, film thickness are 0.01~10nm.
(3) preparation of perovskite thin film (i.e. organic-inorganic perovskite luminescent layer)：Calcium is prepared on the first ultrathin insulating layer
Titanium ore layer：Perovskite precursor solution, which is spin-coated on deposition, to be had on the ito glass substrate of the first ultrathin insulating layer, and substrate rotating speed is
3000rpm, time are 30~60 seconds；At 80~100 DEG C, annealing time was controlled at 10~20 minutes for annealing temperature control.
The preparation of (4) second ultrathin insulating layers：The perovskite thin film prepared, its substrate by vacuum vapour deposition or
Magnetron sputtering method prepares the second ultrathin insulating layer.Insulating materials is lithium fluoride, potassium fluoride, magnesium fluoride, sodium chloride, magnesium chloride, chlorine
Changing the depositable materials and silica, aluminium oxide, polytetrafluoroethylene (PTFE) etc. such as potassium can magnetron sputtering material；The calcium titanium prepared
Mine film is transferred to the second ultrathin insulating layer of vacuum chamber vapor deposition, and rate control is in 0.01~0.03nm/s, film thickness
For 0.01~10nm.
(5) preparation of electron transfer layer：Vacuum evaporation electron transfer layer is carried out on the second ultrathin insulating layer prepared.
Electron transport material 4,7- diphenyl -1,10- ferrosins (Bphen), 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene
(TPBi), the evaporation rate of preferably Bphen, material film are 0.1~0.2nm/s, and film thickness is 20~60nm.
(6) preparation of cathode：Keep above-mentioned vacuum cavity pressure constant, on above-mentioned electron transfer layer evaporation metal,
Or fluoride and cathode layer of the metal composite layer as device, film thickness are 80~120nm.Wherein metal is selected from gold, silver or aluminium
In, preferentially select aluminium；Combination electrode is lithium fluoride and metallic silver or aluminium, preferred fluorinated lithium and aluminium.
For method set out above, the present invention provides several specific embodiments：
Embodiment 1：
Referring now to Figure 1, the perovskite LED device of one embodiment according to the present invention is such as lower structure：
Glass (plastics) substrate/ITO (100nm)/LiF (5nm)/CH3NH3PbBr3(100nm)/LiF(8nm)/Bphen
(60nm)/LiF(1nm)/Al(100nm)
(1) cleaning of the pre- glass substrate for being carved with ITO：Utilize ethyl alcohol, the method pair of acetone ultrasound and deionized water ultrasound
Transparent conduction base sheet (ito glass) is cleaned, and is placed it under infrared lamp and is dried after cleaning, wherein in transparent conduction base sheet
The square resistance of anode layer of the ito film in face as device, ito film is the Ω of 15 Ω~30, and film thickness is 80~120nm；
(2) preparation of LiF insulating layers 1 (i.e. the first ultrathin insulating layer)：The substrate that will be dried, using ultraviolet-smelly
Oxygen is handled 5~10 minutes, and then substrate is transmitted in vacuum chamber, is preferentially selected lithium fluoride (LiF), is then steamed on substrate
One layer of LiF insulating layer of plated deposition, for rate control in 0.01~0.03nm/s, film thickness is 1~10nm.
(3) preparation of LiF insulating layers 2 (i.e. the second ultrathin insulating layer)：The perovskite thin film prepared is transferred to vacuum chamber
LiF insulating layers are deposited in room, and for rate control in 0.01~0.03nm/s, film thickness is 1~10nm.
(4) preparation of calcium titanium ore bed：
Calcium titanium ore bed is prepared on LiF insulating layers 1：By first ammonium lead iodine perovskite (CH3NH3PbBr3) precursor solution spin coating
Have on the ito glass substrate of LiF insulating layers in deposition, substrate rotating speed is 3000rpm, and the time is 30~60 seconds；Annealing temperature control
At 80~100 DEG C, annealing time was controlled at 10~20 minutes system.
(5) preparation of electron transfer layer：Vacuum evaporation electron transfer layer is carried out on the perovskite thin film prepared.Electronics
Transmission material is 4,7- diphenyl -1,10- ferrosin (Bphen), and the evaporation rate of material film is 0.1~0.2nm/s, film thickness
For 60nm or so.
(6) preparation of cathode：It keeps above-mentioned vacuum cavity pressure constant, lithium fluoride is deposited on above-mentioned hole blocking layer
And aluminium, the evaporation rate of Al is 0.8~1nm/s, film thickness 100nm.
Fig. 2 is that whether there is or not the scanning electron microscope (SEM) photographs of the polycrystalline perovskite thin film of 1 time preparation of LiF insulating layers；It is different referring to Fig. 3
The comparison of the voltage-current efficiency (a) and voltage-brightness (b) curve graph of device prepared by perovskite thin film.
It can be seen from the figure that introducing device prepared by the perovskite thin film after LiF insulating layers, device performance has huge
It is promoted：Current efficiency is 8.61cd/A, light emission luminance 35145cd/m2。
Similarly process above is applicable to carbonamidine lead bromine perovskite material and prepares light emitting diode, efficiency 14.62cd/
A, brightness 41252cd/m2.Such as Fig. 4
Embodiment 2：
Referring now to Figure 1, the perovskite LED device of second embodiment according to the present invention is such as lower structure：
Glass (plastics) substrate/ITO (100nm)/SiO2(0.06nm)/CH3NH3PbBr3(100nm)/SiO2(1nm)/
Bphen(60nm)/LiF(1nm)/Al(100nm)
(1) cleaning of the pre- glass substrate for being carved with ITO：Utilize ethyl alcohol, the method pair of acetone ultrasound and deionized water ultrasound
Transparent conduction base sheet (ito glass) is cleaned, and is placed it under infrared lamp and is dried after cleaning, wherein in transparent conduction base sheet
The square resistance of anode layer 2 of the ito film in face as device, ito film is the Ω of 15 Ω~30, and film thickness is 80~120nm；
(2)SiO2The preparation of insulating layer 1 (i.e. the first ultrathin insulating layer)：The substrate that will be dried, using it is ultraviolet-
Ozone treatment 5~10 minutes, is then transmitted to substrate in vacuum chamber, then passes through r. f. magnetron sputtering on substrate
One layer of SiO2Insulating layer, for rate control in 0.01~0.03nm/s, film thickness is 0.01~10nm.
(3) preparation of calcium titanium ore bed：
Calcium titanium ore bed is prepared on the insulating layer：By methylamine lead bromine perovskite (CH3NH3PbBr3) precursor solution be spin-coated on it is heavy
Product has SiO2On the substrate of insulating layer, substrate rotating speed is 3000rpm, and the time is 30~60 seconds；Annealing temperature is controlled 80~100
DEG C, annealing time was controlled at 10~20 minutes.
(4)SiO2The preparation of insulating layer 2 (i.e. the second ultrathin insulating layer)：The perovskite thin film prepared is transferred to vacuum chamber
Room passes through rf magnetron sputtering SiO2Insulating layer, for rate control in 0.01~0.03nm/s, film thickness is 0.01~10nm.
(5) preparation of electron transfer layer：There is SiO in deposition2Electron transport material, electronics are deposited on the substrate of insulating layer 2
Transmission material is 4,7- diphenyl -1,10- ferrosin (Bphen), and the evaporation rate of material film is 0.1~0.2nm/s, film thickness
For 20~60nm.
(6) preparation of cathode：It keeps above-mentioned vacuum cavity pressure constant, lithium fluoride is deposited on above-mentioned hole blocking layer
And aluminium, the evaporation rate of Al is 0.8~1nm/s, film thickness 100nm.
From figure 5 it can be seen that introducing device prepared by the perovskite thin film after SiO2 insulating layers, device performance has very big
Promotion：Current efficiency is 0.58cd/A, brightness 2080cd/m2。
Similarly process above is applicable to carbonamidine lead bromine perovskite material and prepares light emitting diode, efficiency 1.96cd/
A, brightness 3807cd/m2, such as Fig. 6.
Claims (5)
1. a kind of organo-mineral complexing perovskite LED device, which is characterized in that be followed successively by substrate, transparent from the bottom to top
Anode, the first ultrathin insulating layer, organic-inorganic perovskite luminescent layer, the second ultrathin insulating layer, electron transfer layer and cathode；It is described
First ultrathin insulating layer and the second ultrathin insulating layer select inorganic or organic compound；The organic-inorganic perovskite luminescent layer is
Methylamine lead halogen or carbonamidine lead halogen；The cathode is the combination electrode of metal or fluoride and metal；
First ultrathin insulating layer and the second ultrathin insulating layer are selected as lithium fluoride, potassium fluoride, magnesium fluoride, sodium chloride, chlorination
Magnesium, potassium chloride depositable material and silica, aluminium oxide, polytetrafluoroethylene (PTFE) can magnetron sputtering materials；The electron-transport
Layer material is 4,7- diphenyl -1,10- ferrosins or 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene；
The methylamine lead halogen is CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbBr3-xIx、CH3NH3PbBr3- xClxOr CH3NH3PbCl3-xIx；The carbonamidine lead halogen is HC (NH2)2PbBr3、HC(NH2)2PbCl3、HC(NH2)2PbI3、HC
(NH2)2PbBr3-XIx、HC(NH2)2PbCl3-XI or HC (NH2)2PbBr3-XClx。
2. organo-mineral complexing perovskite LED device according to claim 1, which is characterized in that the substrate
For glass or flexible substrate；The transparent anode uses inorganic material or organic conductive polymer.
3. organo-mineral complexing perovskite LED device according to claim 2, which is characterized in that the flexibility
Substrate is polyester or poly- phthalimide class compound；The inorganic material that the transparent anode uses is tin indium oxide, zinc oxide or oxygen
Change a kind of metal oxide in tin, or is a kind of metal in gold, copper, silver or zinc；The organic conductive that transparent anode uses
Polymer is polythiophene, polyvinylbenzenesulfonic acid sodium or polyaniline.
4. organo-mineral complexing perovskite LED device according to claim 1, which is characterized in that the cathode
When selecting metal, it is selected from gold, silver or aluminium；It is lithium fluoride and metallic silver or the compound electric of aluminium when the cathode selection combination electrode
Pole.
5. the preparation method of organo-mineral complexing perovskite LED device described in a kind of claim 1-4 any one,
It is characterized by comprising the following steps：
1) substrate is cleaned using the method for ethyl alcohol, acetone ultrasound and deionized water ultrasound, is dried after cleaning, wherein transparent
The square resistance of transparent anode layer of the ito film as device above conductive substrate, ito film is the Ω of 15 Ω~30, film thickness 80
~120nm；
2) preparation of the first ultrathin insulating layer：The substrate that step 1) is handled well, using ultraviolet-ozone treatment 5~10 minutes,
Then substrate is transmitted in vacuum chamber, Bamboo platings or one layer of insulating materials of magnetron sputtering deposition are ultra-thin as first Shang Ji Pian
Insulating layer, rate control is in 0.01~0.03nm/s, film thickness 0.01-10nm；
3) preparation of organic-inorganic perovskite luminescent layer：Calcium titanium ore bed is prepared on the first ultrathin insulating layer prepared by step 2)：
Perovskite precursor solution, which is spin-coated on deposition, to be had on the ito glass substrate of insulating materials, and substrate rotating speed is 3000rpm, time
It is 30~60 seconds；At 80~100 DEG C, annealing time was controlled at 10~20 minutes, obtained organic nothing after the completion for annealing temperature control
Machine perovskite luminescent layer；
4) preparation of the second ultrathin insulating layer：The organic-inorganic perovskite luminescent layer that step 3) prepares, passes through true in its substrate
Empty vapour deposition method or magnetron sputtering method prepare insulating layer as the second ultrathin insulating layer；Under the premise of not ingress of air, preparation
Good perovskite thin film is transferred to vacuum chamber depositing insulating layer, and rate control is in 0.01~0.03nm/s, film thickness
0.01-10nm；The second ultrathin insulating layer is obtained after the completion；
5) preparation of electron transfer layer：Vacuum evaporation electron transfer layer is carried out on the second ultrathin insulating layer prepared：Material
The evaporation rate of film is 0.1~0.2nm/s, film thickness 30-60nm；
6) preparation of cathode：Keep the vacuum cavity pressure of step 5) constant, evaporation metal or fluorine on electron transfer layer
Compound and cathode layer of the metal composite layer as device, film thickness are 80~120nm；The machine inorganic compounding calcium is obtained after the completion
Titanium ore LED device.
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| CN201710010843.3A CN106848076B (en) | 2017-01-06 | 2017-01-06 | A kind of organo-mineral complexing perovskite LED device and preparation method thereof |
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| CN109360889B (en) * | 2018-07-28 | 2020-04-28 | 西安交通大学 | Perovskite solar cell with high filling factor and preparation method thereof |
| CN109244255A (en) * | 2018-07-31 | 2019-01-18 | 华南理工大学 | Organic planar heterojunction white light parts and its dimmer application suitable for pulsed drive |
| KR101919100B1 (en) | 2018-10-17 | 2018-11-19 | 한국과학기술정보연구원 | Apparatus and method for simulating lead halide perovskite compound |
| CN109671855A (en) * | 2018-12-20 | 2019-04-23 | 电子科技大学 | Perovskite luminescent device and preparation method thereof based on ultra-thin dielectric wall |
| CN111725409A (en) * | 2020-06-04 | 2020-09-29 | Tcl华星光电技术有限公司 | White light LED device and its making method |
| CN111834501B (en) * | 2020-06-16 | 2021-10-15 | 华中科技大学 | Rare earth electro-induced blue light device |
| CN113948663A (en) * | 2020-07-15 | 2022-01-18 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| TWI793801B (en) | 2021-10-14 | 2023-02-21 | 國立東華大學 | Perovskite optical component and manufacturing method thereof |
| CN114335370B (en) * | 2021-12-28 | 2023-08-29 | 合肥维信诺科技有限公司 | Light emitting device, display substrate and display panel |
| CN114388707B (en) * | 2021-12-30 | 2024-06-04 | 华南理工大学 | White light electroluminescent device and preparation method and application thereof |
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