CN106910830A - A kind of organic electroluminescence device and preparation method thereof - Google Patents
A kind of organic electroluminescence device and preparation method thereof Download PDFInfo
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- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/18—Carrier blocking layers
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- 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
Abstract
Organic electroluminescence device of the present invention, including material：ABX3And/or A2BX4, wherein, A is at least one in amido cation, the positive monovalent ion of the first major element；B is at least one in the 4th positive divalent ion of major element；X is at least one in the negative monovalent ion of the 7th major element.ABX3With A2BX4With carrier mobility higher, with the energy level matched with other conventional organic photoelectrical materials, it is not only able to realize the use in organic electroluminescence device, and carrier mobility can also be effectively improved.ABX3With A2BX4As inorganic material, with the heat endurance higher than organic material and chemical stability, can effectively extend device lifetime.The preparation method of organic electroluminescence device of the present invention, is formed using rubbing method or altogether vapour deposition method and contains ABX3And/or A2BX4Film, technological temperature is low, and the preparation of other functions layer in the organic electroluminescence device is not influenceed；Meanwhile, technical maturity, preparation cost is low.
Description
Technical field
The present invention relates to field of organic electroluminescence, and in particular to a kind of organic electroluminescence device and its system
Preparation Method.
Background technology
Organic electroluminescence device (English full name Organic Light-Emitting Device, abbreviation OLED)
It is active luminescent device using electroluminescent organic material, with low-power consumption, colour gamut be wide, volume is thinner
The advantages of, it is expected to turn into main flow illumination of future generation and flat panel display.
Most of inorganic semiconductor materials are unable to good match, and system with electroluminescent organic material energy level
Standby process needs the high-temperature technologies such as magnetron sputtering, high annealing mostly, influences the stabilization of other organic materials
Property.Therefore, in current organic electroluminescence device, in addition to electrode, mostly using organic material
Prepare.
The transmission of carrier (hole and electronics) in organic material belongs to Hopping mechanism, in transmitting procedure
Need to overcome various potential barriers, the problem for easily causing mobility relatively low；Simultaneously as organic material point
Minor structure is unstable, and in the organic electroluminescence device course of work, carrier or exciton are gathered in interface
Place, is also easy to cause the structure of organic molecule to change (oxidation is reduced), influences the life-span of device.
The content of the invention
Therefore, the invention solves the problems that technology in carrier mobility is low in organic electroluminescence device, device
The problem of part short life, so as to provide the organic electroluminescence hair that a kind of carrier mobility is high, device lifetime is long
Optical device and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of organic electroluminescence device, including material：ABX3And/or A2BX4,
Wherein,
A is at least one in amido cation, the positive monovalent ion of the first major element；
B is at least one in the 4th positive divalent ion of major element；
X is at least one in the negative monovalent ion of the 7th major element.
The A is CH3NH3 +、CH3NH=CH2 +、CH3CH2NH3 +、C6H5NH3 +、
C6H5CH2NH3 +、Cs+、Rb+、K+、Na+、Li+In at least one.
The B is Pb2+、Sn2+、Ge2+In at least one.
The X is I-、Br-、Cl-In at least one.
The ABX3With the A2BX4It is carrier transmission material and/or material of main part.
The ABX3With the A2BX4Highest occupied molecular orbital (HOMO) energy level be
- 4eV~-7eV, lowest unoccupied molecular orbital (LUMO) energy level is -1eV~-4eV.
The ABX3With the A2BX4Energy gap be respectively 1eV~4eV, exciton bind energy is
10meV~30meV.
A kind of preparation method of described organic electroluminescence device, comprises the following steps：
By AX and BX2Mixed dissolution is obtained contains AX and BX in a solvent in proportion2Mixed solution；
By the mixed solution coating film forming, it is obtained and contains ABX3And/or A2BX4Film；
Wherein,
A is at least one in amido cation, the positive monovalent ion of the first major element；
B is at least one in the 4th positive divalent ion of major element；
X is at least one in the negative monovalent ion of the 7th major element.
The solvent is anhydrous aprotic polar solvent.
A kind of preparation method of described organic electroluminescence device, comprises the following steps：
By AX and BX2It is respectively placed in two containers, by controlling AX and BX2Evaporation rate,
Evaporation is obtained and contains ABX3And/or A2BX4Film；
Wherein,
A is at least one in amido cation, the positive monovalent ion of the first major element；
B is at least one in the 4th positive divalent ion of major element；
X is at least one in the negative monovalent ion of the 7th major element.
Above-mentioned technical proposal of the invention has advantages below compared to existing technology：
1st, organic electroluminescence device of the present invention, including material：ABX3And/or A2BX4,
Wherein, A is at least one in amido cation, the positive monovalent ion of the first major element；B is the 4th
At least one in the positive divalent ion of major element；X be in the negative monovalent ion of the 7th major element at least
It is a kind of.ABX3With A2BX4With carrier mobility higher, with other conventional organic photoelectrics
The energy level of match materials, meanwhile, can film forming at a lower temperature, be not only able to realize in Organic Electricity
Use in electroluminescence device, and carrier mobility can also be effectively improved.In addition, ABX3With
A2BX4As inorganic material, with the heat endurance higher than organic material and chemical stability, can
Effectively extend device lifetime.
2nd, the preparation method of organic electroluminescence device of the present invention, using rubbing method or common evaporation
Method is formed and contains ABX3And/or A2BX4Film, technological temperature is low, and the organic electroluminescence is not influenceed
The preparation of other functions layer in luminescent device；Meanwhile, technical maturity, preparation cost is low.
Brief description of the drawings
In order that present disclosure is more likely to be clearly understood, below according to specific implementation of the invention
Example and with reference to accompanying drawing, the present invention is further detailed explanation, wherein
Fig. 1 is the structural representation of organic electroluminescence device of the present invention；
Reference is expressed as in figure：1- first electrode layers, 2- hole injection layers, 3- hole transmission layers,
4- electronic barrier layers, 5- luminescent layers, 6- hole blocking layers, 7- electron transfer layers, 8- electron injecting layers,
9- the second electrode lays.
Specific embodiment
In order that the object, technical solutions and advantages of the present invention are clearer, below in conjunction with accompanying drawing to this
The implementation method of invention is described in further detail.
The present invention can be embodied in many different forms, and should not be construed as limited to set forth herein
Embodiment.Conversely, there is provided these embodiments so that the disclosure will be thorough and complete, and will be
Design of the invention is fully conveyed to those skilled in the art, and the present invention will only be defined by the appended claims.
In the accompanying drawings, for clarity, the size and relative size in layer and region can be exaggerated.
Embodiment 1
The present embodiment provides a kind of organic electroluminescence device, as shown in figure 1, including be stacked the
One electrode layer 1, hole injection layer 2, hole transmission layer 3, electronic barrier layer 4, luminescent layer 5, hole
Barrier layer 6, electron transfer layer 7, electron injecting layer 8 and the second electrode lay 9.
ABX3Section bar material (CH3NH3)PbI3Used as hole transmission layer 3, specific device architecture is：
ITO(180nm)/HATCN(10nm)/(CH3NH3)PbI3(40nm)/TCTA(20nm)/CBP(30n
m):Ir(ppy)3(10%)/BCP (20nm)/Alq3(50nm)/LiF(0.7nm)/Al(150nm)。
Wherein, ITO be first electrode layer 1, HATCN as hole injection layer 2, by evaporation process
Prepare 10nm；(CH3NH3)PbI3It is hole transmission layer 3, by common evaporation PbI2And CH3NH3I's
Method forms film, and thickness is 40nm；TCTA is electronic barrier layer 4, and 20nm is prepared by being deposited with；
CBP is the material of main part of luminescent layer 5, Ir (ppy)3It is the guest materials of luminescent layer 5, is prepared by common evaporation
30nm, wherein Ir (ppy)3Mass concentration is 10%；BCP is hole blocking layer 6, is prepared by being deposited with
20nm；Alq3It is electron transfer layer 7,50nm is prepared by being deposited with；LiF is electron injecting layer 8, is led to
Cross evaporation and prepare 0.7nm；Al is the second electrode lay 9, and 150nm is prepared by being deposited with.
ABX3Section bar material (CH3NH3)PbI3HOMO=-5.4eV, LUMO=-3.9eV, Eg=1.6eV,
Heat decomposition temperature Td=240 DEG C, hole mobility is 0.18cm2·V-1·s-1, electron mobility is
0.17cm2·V-1·s-1, compared to conventional hole transmission material, performance is more excellent.
Embodiment 2
The present embodiment provides a kind of organic electroluminescence device, as shown in figure 1, including be stacked the
One electrode layer 1, hole injection layer 2, hole transmission layer 3, electronic barrier layer 4, luminescent layer 5, hole
Barrier layer 6, electron transfer layer 7, electron injecting layer 8 and the second electrode lay 9.
ABX3Section bar material (CH3NH3)PbBr3Used as electron transfer layer, specific device architecture is：
ITO(180nm)/HATCN(10nm)/NPB(40nm)/TCTA(20nm)/CBP(30nm):Ir(ppy
)3(10%)/BCP (20nm)/(CH3NH3)PbBr3(50nm)/LiF(0.7nm)/Al(150nm)。
Wherein, ITO be first electrode layer 1, HATCN as hole injection layer 2, by evaporation process
Prepare 10nm；NPB is hole transmission layer 3, and 40nm is prepared by being deposited with；TCTA is electronic blocking
Layer 4,20nm is prepared by being deposited with；CBP is the material of main part of luminescent layer 5, Ir (ppy)3It is luminescent layer 5
Guest materials, 30nm, wherein Ir (ppy) are prepared by common evaporation3Mass concentration is 10%；BCP is
Hole blocking layer 6,20nm is prepared by being deposited with；(CH3NH3)PbBr3It is electron transfer layer 7, passes through
PbBr is deposited with altogether2And CH3NH3The method of Br forms film, and evaporation prepares 50nm；LiF is noted for electronics
Enter layer 8,0.7nm is prepared by being deposited with；Al is the second electrode lay 9, and 150nm is prepared by being deposited with.
ABX3Section bar material (CH3NH3)PbBr3HOMO=-5.4eV, LUMO=-3.1eV,
Eg=2.24eV, heat decomposition temperature Td=257 DEG C, carrier mobility is about 1cm2·V-1·s-1,
Compared to conditional electronic transmission material, performance is more excellent.
Embodiment 3
The present embodiment provides a kind of organic electroluminescence device, including first electrode layer, the sky being stacked
Cave implanted layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer with
And the second electrode lay.
ABX3Section bar material (CH3NH3)Sn0.3Pb0.7I3Used as hole injection layer, specific device architecture is：
ITO(180nm)/Sn0.3Pb0.7I3(40nm)/poly-TPD(30nm)/PVK:OXD-7 (40%):Ir(pp
y)3(10%) (30nm)/TPBi (40nm) //LiF (0.7nm)/Al (150nm).
Wherein, (CH3NH3)Sn0.3Pb0.7I3As hole injection layer, by CH3NH3I、SnI2、PbI2
According to 159:111:323 ratio is dissolved in DMF, is then spin coated onto the solution and is formed film, gross thickness
It is 40nm.Poly-TPD is hole transmission layer, and 30nm is prepared by the toluene solution of spin coating poly-TPD
Thick film；PVK and OXD-7 is luminescent layer material of main part, and Ir (ppy) 3 is luminescent layer guest materials,
By by them according to 5:4:1 mass ratio is dissolved in toluene, is then spin coated onto the solution and is formed film,
Gross thickness is 40nm；TPBi is electron transfer layer, and 40nm is prepared by the toluene solution of spin coating TPBi
Thick film；LiF is electron injecting layer, and 0.7nm is prepared by being deposited with；Al is the second electrode lay, is led to
Cross evaporation and prepare 150nm.
(CH3NH3)Sn0.3Pb0.7I3HOMO be -5.12eV, the work content of ITO is -4.8eV,
The HOMO of poly-TPD is -5.3eV, (CH3NH3)Sn0.3Pb0.7I3As hole injection layer, effectively
The Schottky barrier at interface is reduced, strengthens the injection in hole, improve device performance.
Embodiment 4
The present embodiment provides a kind of organic electroluminescence device, as shown in figure 1, including be stacked the
One electrode layer 1, hole injection layer 2, hole transmission layer 3, electronic barrier layer 4, luminescent layer 5, hole
Barrier layer 6, electron transfer layer 7, electron injecting layer 8 and the second electrode lay 9.
A2BX4Section bar material (C4H9NH3)2PbBr4Used as electronic barrier layer 4, specific device architecture is：
ITO(180nm)/HATCN(10nm)/NPB(40nm)/(C4H9NH3)2PbBr4(20nm)/CBP(3
0nm):Ir(ppy)3(10%)/BCP (20nm)/Alq3(50nm)/LiF(0.7nm)/Al(150nm)。
Wherein, ITO be first electrode layer 1, HATCN as hole injection layer 2, by evaporation process
Prepare 10nm；NPB is hole transmission layer 3, and 40nm is prepared by being deposited with；(C4H9NH3)2PbBr4
It is electronic barrier layer 4, by common evaporation PbBr2And C4H9NH3The method of Br forms film, and thickness is
20nm；CBP is the material of main part of luminescent layer 5, Ir (ppy)3It is the guest materials of luminescent layer 5, by common steaming
Plating prepares 30nm, wherein Ir (ppy)3Mass concentration is 10%；BCP is hole blocking layer 6, by steaming
Plating prepares 20nm；Alq3It is electron transfer layer 7,50nm is prepared by being deposited with；LiF is electron injection
Layer 8,0.7nm is prepared by being deposited with；Al is the second electrode lay 9, and 150nm is prepared by being deposited with.
A2BX4Section bar material (C4H9NH3)2PbBr4HOMO=5.6eV, LUMO=2.6eV, Eg=
3.0eV, energy level is wide, and hole mobility is big, can effectively stop exciton without hindering hole transport, energy
Enough boost device performances.
Comparative example 1
This comparative example provides a kind of organic electroluminescence device, and device architecture is unique different with embodiment 1
Be：The material of hole transmission layer 3 is NPB (N, N'- diphenyl-N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'-
Diamines).
The HOMO of NPB is -5.4eV, and hole mobility is 1 × 10-3cm2V-1s-1。
Comparative example 2
This comparative example provides a kind of organic electroluminescence device, and device architecture is unique different with embodiment 2
Be：The material of electron transfer layer 7 is Alq3(three (8-hydroxyquinoline) aluminium)。
Alq3LUMO be -3.2eV, (CH3NH3)PbBr3LUMO for -3.1eV energy levels it is close,
The potential barrier of electric transmission is close；But Alq3Electron mobility be 1 × 10-6cm2V-1s-1。
Comparative example 3
This comparative example provides a kind of organic electroluminescence device, and device architecture is unique different with embodiment 3
Be：The material of hole injection layer 2 is PEDOT:PSS.PEDOT:The HOMO of PSS is -5.1eV,
It is a conventional hole injection layer, but material pH value ≈ 2, can be rotten during long-term use
Erosion anode ITO, causes the decay of device lifetime.The perovskite material that embodiment 3 is used does not corrode
Property, device lifetime is long.
Device described in above-described embodiment and comparative example is tested, test result is as shown in the table：
| Current efficiency (cd/A) | Power consumption (lm/W) | Life-span (hour) | |
| Embodiment 1 | 31.6 | 30.9 | 3674 |
| Embodiment 2 | 38.9 | 42.5 | 6421 |
| Embodiment 3 | 18.4 | 14.3 | 162 |
| Comparative example 1 | 29.1 | 28.5 | 2215 |
| Comparative example 2 | 29.1 | 28.5 | 2215 |
| Comparative example 3 | 16.2 | 14.8 | 38 |
As can be seen from the above table, the organic electroluminescence device described in the above embodiment of the present invention, not only can
Enough realize the use in organic electroluminescence device, and the current efficiency of device can also be effectively improved,
Power consumption is reduced, extends device lifetime.
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to implementation method
Restriction.For those of ordinary skill in the field, can also do on the basis of the above description
Go out the change or variation of other multi-forms.There is no need and unable to be exhaustive to all of implementation method.
And the obvious change thus extended out or among changing still in protection scope of the present invention.
Claims (10)
1. a kind of organic electroluminescence device, it is characterised in that including material：ABX3And/or A2BX4,
Wherein,
A is at least one in amido cation, the positive monovalent ion of the first major element；
B is at least one in the 4th positive divalent ion of major element；
X is at least one in the negative monovalent ion of the 7th major element.
2. organic electroluminescence device according to claim 1, it is characterised in that the A is
CH3NH3 +、CH3NH=CH2 +、CH3CH2NH3 +、C6H5NH3 +、C6H5CH2NH3 +、Cs+、Rb+、
K+、Na+、Li+In at least one.
3. organic electroluminescence device according to claim 1 and 2, it is characterised in that the B
It is Pb2+、Sn2+、Ge2+In at least one.
4. the organic electroluminescence device according to claim any one of 1-3, it is characterised in that described
X is I-、Br-、Cl-In at least one.
5. the organic electroluminescence device according to claim any one of 1-4, it is characterised in that described
ABX3With the A2BX4It is carrier transmission material and/or material of main part.
6. the organic electroluminescence device according to claim any one of 1-5, it is characterised in that described
ABX3With the A2BX4Highest occupied molecular orbital (HOMO) energy level be -4eV~-7eV, it is minimum
Molecular orbit (LUMO) energy level is not accounted for for -1eV~-4eV.
7. the organic electroluminescence device according to claim any one of 1-6, it is characterised in that described
ABX3With the A2BX4Energy gap be respectively 1eV~4eV, exciton bind energy is 10meV~30meV.
8. a kind of preparation method of the organic electroluminescence device described in any one of claim 1-7, its feature
It is to comprise the following steps：
By AX and BX2Mixed dissolution is obtained contains AX and BX in a solvent in proportion2Mixed solution；
By the mixed solution coating film forming, it is obtained and contains ABX3And/or A2BX4Film；
Wherein,
A is at least one in amido cation, the positive monovalent ion of the first major element；
B is at least one in the 4th positive divalent ion of major element；
X is at least one in the negative monovalent ion of the 7th major element.
9. the preparation method of organic electroluminescence device according to claim 8, it is characterised in that institute
Solvent is stated for anhydrous aprotic polar solvent.
10. a kind of preparation method of the organic electroluminescence device described in any one of claim 1-7, its feature
It is to comprise the following steps：
By AX and BX2It is respectively placed in two containers, by controlling AX and BX2Evaporation rate, steam
Plating is obtained and contains ABX3And/or A2BX4Film；
Wherein,
A is at least one in amido cation, the positive monovalent ion of the first major element；
B is at least one in the 4th positive divalent ion of major element；
X is at least one in the negative monovalent ion of the 7th major element.
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Cited By (1)
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| CN110931649A (en) * | 2019-11-29 | 2020-03-27 | 昆山国显光电有限公司 | Organic electroluminescent device and display device |
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Application publication date: 20170630 |