CN106848076A - 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
- Publication number
- CN106848076A CN106848076A CN201710010843.3A CN201710010843A CN106848076A CN 106848076 A CN106848076 A CN 106848076A CN 201710010843 A CN201710010843 A CN 201710010843A CN 106848076 A CN106848076 A CN 106848076A
- Authority
- CN
- China
- Prior art keywords
- perovskite
- layer
- insulating layer
- substrate
- organo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Led Devices (AREA)
Abstract
The present invention discloses a kind of organo-mineral complexing perovskite LED device and preparation method thereof, planar heterojunction light emitting diode of the present invention based on 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 negative electrode.Compared to the planar heterojunction perovskite LED device without ultrathin insulating layer 1 Yu ultrathin insulating layer 2, light emitting diode of the present invention has current efficiency and power efficiency high, improves more than 20 times.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 field, it is related to perovskite LED device, it is 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 new organic-inorganic composite 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 to illumination field later.Abroad, early start research 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 director, all one's life laboratory Sir Richard professors Friend lead the team to realize perovskite material first to exist
At room temperature luminous.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, is fully combined by limiting electron-hole in perovskite luminescent layer
It is luminous, obtain the near-infrared PeLED of high brightness.In addition, they also use CH3NH3PbBr3Instead of CH3NH3PbI3- xClx makees
It is luminescent layer, is prepared for green glow PeLED, device brightness has reached 364cdm- 2, external quantum efficiency and internal quantum efficiency are distinguished
Reach 0.1% and 0.4%.Additionally, Friend seminars are studied by luminescence generated by light find, under excitation intensity high, 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 that the high-luminous-efficiency and color tunability of perovskite material have very big application preceding in low cost display, lighting field
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 the non-radiative recombination to increase, and on the other hand be the heat due to perovskite material
Less stable, device heating can cause 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 glow PeLED, and prepared feux rouges
PeLED, and they are to realize lighting at normal temperatures.Influence perovskite material electroluminescent device efficiency it is one of because
Element is exactly film morphology, therefore, Wei Huang seminars are modified by introducing PEI materials to ZnO film, improves parent
It is aqueous, improve the pattern of perovskite thin film, and reduce electrodes work functions and improve electric charge injection efficiency, the brightness of device reaches
20000cd·m- 2.In order to the leakage current in suppression device, Friend seminars introduce PIP dielectric materials, it is blended with perovskite,
To realize the inhibitory action to leakage current, device performance is improved, external quantum efficiency has reached 1.2%.
At present report PeLED it is inefficient, its main cause be solwution method prepare perovskite thin film coverage rate not
Completely, and in the presence of cavity, can so cause have larger leakage current.These these leakage currents can cause the inefficiency of device.
The content of the invention
It is uneven it is an object of the invention to film in overcoming above-mentioned technology, there is pin hole, the shortcomings of there is leakage current, there is provided
A kind of organo-mineral complexing perovskite LED device and preparation method thereof, it introduces a pair of ultrathin insulating layers, 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 device：Base is followed successively by 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 negative electrode 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 is used
A kind of metal oxide in expecting for tin indium oxide, zinc oxide or tin oxide, or for gold, copper, silver or zinc in a kind of metal；
The organic conductive polymer that transparent anode is used 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, aluminum 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.
During above-mentioned negative electrode selection metal, selected from gold, silver or aluminium；It is lithium fluoride and gold during the negative electrode selection combination electrode
The combination electrode of category 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 ethanol, acetone ultrasound and deionized water ultrasound, is dried after cleaning, wherein
Ito film above transparent conduction base sheet as device transparent anode layer, the square resistance of ito film is 15 Ω~30 Ω, thickness
It is 80~120nm；
2) preparation of the first ultrathin insulating layer：By step 1) substrate handled well, use ultraviolet-ozone to process 5~10 points
Clock, is then sent to substrate in vacuum chamber, in one layer of insulating materials of deposition on substrate as the first ultrathin insulating layer, speed
In 0.01~0.03nm/s, film thickness is 0.01~10nm for control；
3) preparation of organic-inorganic perovskite luminescent layer：In step 2) prepare the first ultrathin insulating layer on prepare perovskite
Layer：Perovskite precursor solution is spin-coated on into deposition has 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 for annealing temperature control, after the completion of obtain organic
Inorganic perovskite luminescent layer；
4) preparation of the second ultrathin insulating layer：Step 3) the organic-inorganic perovskite luminescent layer for preparing is logical in its substrate
Cross vacuum vapour deposition or magnetron sputtering method prepares insulating barrier as the second ultrathin insulating layer；The perovskite thin film for preparing is turned
Vacuum chamber depositing insulating layer is moved on to, in 0.01~0.03nm/s, film thickness is 0.01~10nm to speed control；After the completion of
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 for preparing：
The evaporation rate of material film is 0.1~0.2nm/s, and thickness is 20~60nm；
6) preparation of negative electrode：Keep step 5) vacuum cavity pressure it is constant, on electron transfer layer evaporation metal or
Person's fluoride and metal composite layer as device cathode layer, thickness is 80~120nm；After the completion of to obtain described machine inorganic multiple
Close perovskite LED device.
Compared with prior art, the invention has the advantages that：
Organo-mineral complexing perovskite LED device of the invention and preparation method thereof solves perovskite thin film
Inhomogeneities, have pin hole, there are problems that, 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, it is possible to achieve prepared by large area, requirement to equipment and environment compared with
It is low.Introduced without ultrathin insulating layer compared to tradition and prepare 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 lifts more than 20 times, can fully meet device it is commercially use the need for.
Brief description of the drawings
Fig. 1 is perovskite luminous diode device structure schematic diagram of the invention；
1 is ITO substrates, and 2 is the first ultrathin insulating layer, and 3 is organic-inorganic perovskite luminescent layer, and 4 is the second ultrathin insulating
Layer, 5 is electron transfer layer, and 6 is negative electrode
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 () is the film morphology on ITO substrates, (b) is the 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 barriers；
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 barriers；
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 barrier；
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 barrier；
Specific embodiment
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 negative electrode.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
Anode uses inorganic material or organic conductive polymer, and the inorganic material is the one kind in tin indium oxide, zinc oxide or tin oxide
Metal oxide or for gold, copper, silver or zinc in a kind of metal, organic conductive polymer be polythiophene, polyvinylbenzenesulfonic acid sodium
Or polyaniline.
First ultrathin insulating layer of the invention and the second ultrathin insulating layer select inorganic or organic compound, such as be fluorinated
Lithium, potassium fluoride, magnesium fluoride, sodium chloride, magnesium chloride, potassium chloride depositable material and silica, aluminum oxide, polytetrafluoroethylene (PTFE)
Can magnetron sputtering material.
The material of organic-inorganic perovskite luminescent layer of the 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。
Electron transport layer materials of the invention are：4,7- diphenyl -1,10- ferrosins (Bphen), (the 1- benzene of 1,3,5- tri-
Base -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi).
Cathode material of the invention is metal or fluoride and metal composite electrode, and metal is selected from gold, silver or aluminium；It is compound
Electrode is lithium fluoride and argent or aluminium.
First and second ultrathin insulating layer of the invention can by magnetron sputtering, vacuum evaporation, spin coating, spraying, soak, scrape
Prepared by the method such as painting or roller coating technology, its thickness is 1-10nm.Organo-mineral complexing perovskite material can be by wet method spin coating
And the mode such as vacuum evaporation is obtained.Its thickness is 10-600nm.Cathode material can be obtained by vacuum deposition method, and it is thick
It is 100~120nm to spend.
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 clearly using the method for ethanol, acetone ultrasound and deionized water ultrasound
Wash, placed it in after cleaning and dry under infrared lamp, wherein the ito film above transparent conduction base sheet 1 as device anode layer,
The square resistance of ito film is 15 Ω~30 Ω, and thickness is 80~120nm.Substrate can also be flexible substrate in addition to from glass,
Wherein flexible substrate can be polyester or poly- phthalimide class compound.Anode layer can be polymerized using inorganic material or organic conductive
Thing, the inorganic material selects tin indium oxide (ITO), and tin oxide fluorine (FTO) can also be poly- thiophene with organic conductive polymer outward
Fen, polyvinylbenzenesulfonic acid sodium or polyaniline.
The preparation of (2) first ultrathin insulating layers：By the good substrate of dried process, 5~10 points are processed using ultraviolet-ozone
Clock, is then sent to substrate in vacuum chamber, then in one layer of insulating materials of deposition on substrate, speed control 0.01~
0.03nm/s, film thickness is 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 is spin-coated on into deposition has on the ito glass substrate of the first ultrathin insulating layer, and substrate rotating speed is
3000rpm, the time is 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 for preparing, 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, aluminum oxide, polytetrafluoroethylene (PTFE) etc. such as potassium can magnetron sputtering material；The calcium titanium for preparing
Ore deposit film is transferred to the ultrathin insulating layer of vacuum chamber vapor deposition second, and speed control is in 0.01~0.03nm/s, film thickness
It is 0.01~10nm.
(5) preparation of electron transfer layer：Vacuum evaporation electron transfer layer is carried out on the second ultrathin insulating layer for preparing.
Electron transport material 4,7- diphenyl -1,10- ferrosins (Bphen), 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene
(TPBi), preferably Bphen, the evaporation rate of material film is 0.1~0.2nm/s, and thickness is 20~60nm.
(6) preparation of negative electrode：Keep above-mentioned vacuum cavity pressure constant, on above-mentioned electron transfer layer evaporation metal,
Or fluoride and metal composite layer, used as the cathode layer of device, thickness is 80~120nm.Wherein metal is selected from gold, silver or aluminium
In, prioritizing selection aluminium；Combination electrode is lithium fluoride and argent or aluminium, preferred fluorinated lithium and aluminium.
For method set out above, the present invention provides several specific embodiments：
Embodiment 1：
With reference now to Fig. 1, it is following structure according to the perovskite LED device of one embodiment of the invention：
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：Using the method pair of ethanol, acetone ultrasound and deionized water ultrasound
Transparent conduction base sheet (ito glass) is cleaned, and drying under infrared lamp is placed it in after cleaning, wherein in transparent conduction base sheet
The ito film in face as device anode layer, the square resistance of ito film is 15 Ω~30 Ω, and thickness is 80~120nm；
(2) preparation of LiF insulating barriers 1 (i.e. the first ultrathin insulating layer)：By the good substrate of dried process, using ultraviolet-smelly
Oxygen is processed 5~10 minutes, then substrate is sent in vacuum chamber, prioritizing selection lithium fluoride (LiF), is then steamed on substrate
One layer of LiF insulating barrier of plated deposition, in 0.01~0.03nm/s, film thickness is 1~10nm to speed control.
(3) preparation of LiF insulating barriers 2 (i.e. the second ultrathin insulating layer)：The perovskite thin film that will be prepared is transferred to vacuum chamber
Room, is deposited with LiF insulating barriers, and in 0.01~0.03nm/s, film thickness is 1~10nm to speed control.
(4) preparation of calcium titanium ore bed：
Calcium titanium ore bed is prepared on LiF insulating barriers 1：By first ammonium lead iodine perovskite (CH3NH3PbBr3) precursor solution spin coating
Have on the ito glass substrate of LiF insulating barriers in deposition, substrate rotating speed is 3000rpm, 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 for preparing.Electronics
Transmission material is 4,7- diphenyl -1,10- ferrosins (Bphen), and the evaporation rate of material film is 0.1~0.2nm/s, thickness
It is 60nm or so.
(6) preparation of negative electrode：Keep above-mentioned vacuum cavity pressure constant, lithium fluoride is deposited with above-mentioned hole blocking layer
And aluminium, the evaporation rate of Al is 0.8~1nm/s, and thickness is 100nm.
Fig. 2 is to whether there is 1 time scanning electron microscope (SEM) photograph of the polycrystalline perovskite thin film of preparation of LiF insulating barriers；It is different referring to Fig. 3
Voltage-the current efficiency (a) of device prepared by perovskite thin film and the contrast of voltage-brightness (b) curve map.
It can be seen that introducing device prepared by the perovskite thin film after LiF insulating barriers, device performance has huge
Lifting：Current efficiency is 8.61cd/A, and luminosity is 35145cd/m2。
Similarly process above is applicable to carbonamidine lead bromine perovskite material and prepares light emitting diode, and its efficiency is 14.62cd/
A, brightness is 41252cd/m2.Such as Fig. 4
Embodiment 2：
With reference now to Fig. 1, it is following structure according to the perovskite LED device of second embodiment of the invention：
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：Using the method pair of ethanol, acetone ultrasound and deionized water ultrasound
Transparent conduction base sheet (ito glass) is cleaned, and drying under infrared lamp is placed it in after cleaning, wherein in transparent conduction base sheet
The ito film in face as device anode layer 2, the square resistance of ito film is 15 Ω~30 Ω, and thickness is 80~120nm；
(2)SiO2The preparation of insulating barrier 1 (i.e. the first ultrathin insulating layer)：By the good substrate of dried process, using it is ultraviolet-
Ozone is processed 5~10 minutes, and then substrate is sent in vacuum chamber, and r. f. magnetron sputtering is then passed through on substrate
One layer of SiO2Insulating barrier, in 0.01~0.03nm/s, film thickness is 0.01~10nm to speed control.
(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 barrier, 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 barrier 2 (i.e. the second ultrathin insulating layer)：The perovskite thin film that will be prepared is transferred to vacuum chamber
Room, by rf magnetron sputtering SiO2Insulating barrier, in 0.01~0.03nm/s, film thickness is 0.01~10nm to speed control.
(5) preparation of electron transfer layer：There is SiO in deposition2Electron transport material, electronics are deposited with the substrate of insulating barrier 2
Transmission material is 4,7- diphenyl -1,10- ferrosins (Bphen), and the evaporation rate of material film is 0.1~0.2nm/s, thickness
It is 20~60nm.
(6) preparation of negative electrode：Keep above-mentioned vacuum cavity pressure constant, lithium fluoride is deposited with above-mentioned hole blocking layer
And aluminium, the evaporation rate of Al is 0.8~1nm/s, and thickness is 100nm.
From figure 5 it can be seen that introducing device prepared by the perovskite thin film after SiO2 insulating barriers, device performance has very big
Lifting：Current efficiency is 0.58cd/A, and brightness is 2080cd/m2。
Similarly process above is applicable to carbonamidine lead bromine perovskite material and prepares light emitting diode, and its efficiency is 1.96cd/
A, brightness is 3807cd/m2, such as Fig. 6.
Claims (8)
1. a kind of organo-mineral complexing perovskite LED device, it is characterised 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 negative electrode；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 negative electrode is the combination electrode of metal or fluoride and metal.
2. organo-mineral complexing perovskite LED device according to claim 1, it is characterised in that the substrate
It is 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, it is characterised in that the flexibility
Substrate is polyester or poly- phthalimide class compound；The inorganic material that the transparent anode is used is tin indium oxide, zinc oxide or oxygen
Change tin in a kind of metal oxide, or for gold, copper, silver or zinc in a kind of metal；The organic conductive that transparent anode is used
Polymer is polythiophene, polyvinylbenzenesulfonic acid sodium or polyaniline.
4. organo-mineral complexing perovskite LED device according to claim 1, it is characterised in that described first
Ultrathin insulating layer and the selection of the second ultrathin insulating layer are lithium fluoride, potassium fluoride, magnesium fluoride, sodium chloride, magnesium chloride, potassium chloride can steam
Plating material and silica, aluminum oxide, polytetrafluoroethylene (PTFE) can magnetron sputtering materials.
5. organo-mineral complexing perovskite material according to claim 1 is：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
Person HC (NH2)2PbBr3-XClx。
6. organo-mineral complexing perovskite LED device according to claim 1, it is characterised in that the electronics
Transmission layer material is 4,7- diphenyl -1,10- ferrosins or 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene.
7. organo-mineral complexing perovskite LED device according to claim 1, it is characterised in that the negative electrode
During selection metal, selected from gold, silver or aluminium；It is lithium fluoride and argent or the compound electric of aluminium during the negative electrode selection combination electrode
Pole.
8. the preparation method of organo-mineral complexing perovskite LED device described in a kind of claim 1-7 any one,
It is characterised in that it includes following steps：
1) substrate is cleaned using the method for ethanol, acetone ultrasound and deionized water ultrasound, is dried after cleaning, wherein transparent
Ito film above conductive substrate as device transparent anode layer, the square resistance of ito film is 15 Ω~30 Ω, and thickness is 80
~120nm；
2) preparation of the first ultrathin insulating layer：By step 1) substrate handled well, processed 5~10 minutes using ultraviolet-ozone,
Then substrate is sent in vacuum chamber, Bamboo platings or one layer of insulating materials of magnetron sputtering deposition are ultra-thin as first Shang Ji Pian
Insulating barrier, in 0.01~0.03nm/s, film thickness is 0.01-10nm to speed control；
3) preparation of organic-inorganic perovskite luminescent layer：In step 2) prepare the first ultrathin insulating layer on prepare calcium titanium ore bed：
Perovskite precursor solution is spin-coated on into deposition has 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 for annealing temperature control, after the completion of obtain organic nothing
Machine perovskite luminescent layer；
4) preparation of the second ultrathin insulating layer：Step 3) the organic-inorganic perovskite luminescent layer for preparing, in its substrate by true
Empty vapour deposition method or magnetron sputtering method prepare insulating barrier as the second ultrathin insulating layer；On the premise of not ingress of air, preparation
Good perovskite thin film is transferred to vacuum chamber depositing insulating layer, and speed control is in 0.01~0.03nm/s, film thickness
0.01-10nm；After the completion of obtain 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 for preparing：Material
The evaporation rate of film is 0.1~0.2nm/s, and thickness is 30-60nm；
6) preparation of negative electrode：Keep step 5) vacuum cavity pressure it is constant, evaporation metal or fluorine on electron transfer layer
Compound and metal composite layer as device cathode layer, thickness is 80~120nm；After the completion of obtain described machine inorganic compounding calcium
Titanium ore LED device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710010843.3A CN106848076B (en) | 2017-01-06 | 2017-01-06 | A kind of organo-mineral complexing perovskite LED device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710010843.3A CN106848076B (en) | 2017-01-06 | 2017-01-06 | A kind of organo-mineral complexing perovskite LED device and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106848076A true CN106848076A (en) | 2017-06-13 |
| CN106848076B CN106848076B (en) | 2018-07-17 |
Family
ID=59117885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710010843.3A Active CN106848076B (en) | 2017-01-06 | 2017-01-06 | A kind of organo-mineral complexing perovskite LED device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106848076B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101919100B1 (en) | 2018-10-17 | 2018-11-19 | 한국과학기술정보연구원 | Apparatus and method for simulating lead halide perovskite compound |
| 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 |
| CN109360889A (en) * | 2018-07-28 | 2019-02-19 | 西安交通大学 | A kind of perovskite solar battery of high fill factor and preparation method thereof |
| 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 |
| CN111834501A (en) * | 2020-06-16 | 2020-10-27 | 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 |
| CN114335370A (en) * | 2021-12-28 | 2022-04-12 | 合肥维信诺科技有限公司 | Light emitting device, display substrate and display panel |
| CN114388707A (en) * | 2021-12-30 | 2022-04-22 | 华南理工大学 | White light electroluminescent device and preparation method and application thereof |
| TWI793801B (en) * | 2021-10-14 | 2023-02-21 | 國立東華大學 | Perovskite optical component and manufacturing method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003077669A (en) * | 2001-09-03 | 2003-03-14 | Toppan Printing Co Ltd | High polymer electroluminescent element and manufacturing method therefor |
| CN101826550A (en) * | 2010-04-29 | 2010-09-08 | 电子科技大学 | ABO3/TiO2/MgO/III-V group nitride semiconductor heterostructure and preparation method |
| CN105185908A (en) * | 2015-08-10 | 2015-12-23 | 华南理工大学 | Solution-processed organic-inorganic planar heterojunction light emitting diode and manufacturing method thereof |
| CN105957973A (en) * | 2016-06-16 | 2016-09-21 | 中国华能集团公司 | Flexible luminescent device structure and preparation method thereof |
-
2017
- 2017-01-06 CN CN201710010843.3A patent/CN106848076B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003077669A (en) * | 2001-09-03 | 2003-03-14 | Toppan Printing Co Ltd | High polymer electroluminescent element and manufacturing method therefor |
| CN101826550A (en) * | 2010-04-29 | 2010-09-08 | 电子科技大学 | ABO3/TiO2/MgO/III-V group nitride semiconductor heterostructure and preparation method |
| CN105185908A (en) * | 2015-08-10 | 2015-12-23 | 华南理工大学 | Solution-processed organic-inorganic planar heterojunction light emitting diode and manufacturing method thereof |
| CN105957973A (en) * | 2016-06-16 | 2016-09-21 | 中国华能集团公司 | Flexible luminescent device structure and preparation method thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109360889A (en) * | 2018-07-28 | 2019-02-19 | 西安交通大学 | A kind of perovskite solar battery of high fill 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 |
| US11912733B2 (en) | 2018-10-17 | 2024-02-27 | Korea Institute Of Science & Technology Information | LHP synthesis simulating method and apparatus |
| WO2020080694A1 (en) * | 2018-10-17 | 2020-04-23 | 한국과학기술정보연구원 | Lhp synthesis simulating method and apparatus |
| 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 |
| CN111834501A (en) * | 2020-06-16 | 2020-10-27 | 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 |
| US11719880B2 (en) | 2021-10-14 | 2023-08-08 | National Dong Hwa University | Perovskite optical element and manufacturing method thereof |
| CN114335370A (en) * | 2021-12-28 | 2022-04-12 | 合肥维信诺科技有限公司 | Light emitting device, display substrate and display panel |
| 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 |
| CN114388707A (en) * | 2021-12-30 | 2022-04-22 | 华南理工大学 | White light electroluminescent device and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106848076B (en) | 2018-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106848076B (en) | A kind of organo-mineral complexing perovskite LED device and preparation method thereof | |
| CN107507918B (en) | A kind of perovskite light emitting diode and preparation method thereof | |
| CN106450009B (en) | A kind of Double Perovskite light emitting diode and preparation method thereof | |
| CN105161629B (en) | Exchange driving QLED and preparation method thereof | |
| CN105552185A (en) | Full-inorganic quantum dot light emitting diode based on inorganic perovskite material and preparation method of full-inorganic quantum dot light emitting diode | |
| CN105470400B (en) | A kind of preparation method and application of perovskite film | |
| CN108417739B (en) | A kind of perovskite light emitting diode and preparation method thereof based on spraying process | |
| CN106803546A (en) | A kind of light emitting diode with quantum dots and preparation method thereof | |
| CN107046101B (en) | The blue light organic emissive diode and preparation method thereof of plasma resonance enhancing | |
| CN103824969B (en) | There is the organic electroluminescence device of multilayer metal compound electrode | |
| CN111341942B (en) | Electric injection yellow light-emitting diode (LED) based on lead-free copper-based iodide and preparation method thereof | |
| CN106384769B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN206293474U (en) | The enhanced blue light organic emissive diode of plasma resonance | |
| CN109378392A (en) | A kind of organic electroluminescence device and display device | |
| CN107068884B (en) | A kind of ultraviolet organic electroluminescence device of high efficiency and preparation method thereof | |
| CN106450012A (en) | Organic light-emitting device with double hole injection layers and preparation method of organic light-emitting device | |
| CN109256473B (en) | White organic light emitting diode and preparation method thereof | |
| CN106340594A (en) | White-light organic electroluminescent device and preparation method thereof | |
| CN102881841A (en) | Semiconductor photoelectric device using copper/graphene composite electrode as anode | |
| Jiang et al. | High-efficiency and stable quantum dot light-emitting diodes with staircase V2O5/PEDOT: PSS hole injection layer interface barrier | |
| CN110190198A (en) | A kind of perovskite Quantum Well electroluminescent device and preparation method thereof | |
| CN105895817A (en) | Perovskite green LED with Ni(Mg)O as hole providing layer and preparation method | |
| US20030168973A1 (en) | High-qualty aluminum-doped zinc oxide layer as transparent conductive electrode for organic light-emitting devices | |
| CN105374949A (en) | Organic light-emitting device and preparation method thereof | |
| CN102169969A (en) | Anode modification method of organic electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |