CN106784391A - Quantum dot light emitting device and preparation method thereof, liquid crystal display device - Google Patents
Quantum dot light emitting device and preparation method thereof, liquid crystal display device Download PDFInfo
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Abstract
The present invention relates to technology of quantum dots field, disclose a kind of quantum dot light emitting device, including the anode, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer, electron injecting layer and the negative electrode that are disposed adjacent successively, the quantum dot of the quantum dot light emitting layer is MA1‑xCsxPbX3, wherein 0 ＜ x ＜ 1, MA are methylamine, X is halogen.The invention also discloses the preparation method of quantum dot light emitting device, the quantum dot light emitting device can be used for liquid crystal display device.The present invention utilizes a kind of high-quality Ca-Ti ore type quantum dot MA1‑ xCsxPbX3Used as emitting layer material, quantum dot light emitting device has high current efficiency, external quantum efficiency high, high brightness, low turn-on voltage, stable performance, simple structure, prepares the characteristic such as simple, there is good application prospect in field of information display.
Description
Technical field
The present invention relates to technology of quantum dots field, in particular to a kind of quantum dot light emitting device and preparation method thereof,
Liquid crystal display device.
Background technology
Quantum dot is the nano material of quasi-zero dimension, there is a small amount of atomic building, and particle diameter is typically in the range of between 1 ~ 10nm, due to
, by quantum confinement, continuous band structure becomes the discrete energy levels with molecular characterization for electronics and hole, can be with after being stimulated
Transmitting fluorescence.Quantum dot LED technology is a kind of brand new technical based on quantum effect, with common inorganic semiconductor light-emitting-diode
Compared to unrivaled technical advantage and application prospect；Quantum dot light emitting layer is that have semiconductor-quantum-point colloidal solution spin coating
Form, therefore there is simple preparation process, low cost, flexible can prepare.Quantum dot LED has luminous excitation simultaneously
High, emission wavelength can be realized by changing quantum dot size.Light emitting diode with quantum dots application widely, can be as aobvious
Show the light emitting source in device, simultaneously because quantum dot LED is the small incandescnet particle on nanometer-scale, it is that a kind of new fluorescence is visited
Pin, can be used in biomolecule and cell imaging.
Because the electroluminescent device prepared using inorganic compound has stabilized structure, long service life, stability is strong
Etc. advantage, it is widely used, but inorganic electroluminescence device is successful height, processing difficulties, inefficiency, it is difficult to
Meet demand of the people to device for display of message, organic electroluminescence device material selection range is wide, with low voltage drive, height
The characteristics such as brightness, wide viewing angle, fast response time, have good application prospect at aspects such as display illuminations, obtain in recent years
Swift and violent development, organic electroluminescence device has become one of current study hotspot.
But the high cost of present electroluminescent device, be difficult to large area production, effectiveness of performance is not high enough, luminosity
Not enough big, cut-in voltage is not small enough, still has greater room for improvement, it is more difficult to large-scale production application.
The content of the invention
The present invention is intended to provide a kind of quantum dot light emitting device, to solve the luminous of quantum dot light emitting device in the prior art
The problems such as efficiency is low, luminosity is small.
It is a further object of the present invention to provide the preparation method of the quantum dot light emitting device.
It is a further object of the present invention to provide a kind of liquid crystal display device using the quantum dot light emitting device.
To reach one of above-mentioned purpose, the present invention uses following technical scheme：
A kind of quantum dot light emitting device, including anode, hole injection layer, hole transmission layer, the quantum dot hair being disposed adjacent successively
Photosphere, electron transfer layer, electron injecting layer and negative electrode, the quantum dot of the quantum dot light emitting layer is MA1-xCsxPbX3, wherein 0 ＜
X ＜ 1, MA are methylamine, and X is halogen.
The thickness of quantum dot light emitting layer is 30~200nm.
Further, the material of the anode is selected from gold, copper, platinum, palladium, ITO, aluminium and mixes zinc oxide, gallium and mix zinc oxide, cadmium and mixes
Zinc oxide, copper indium oxide, the anode material formed in ITO surfaces spin coating conducting polymer.
The thickness of anode is 100~300nm.
Further, the material of the hole injection layer is selected from poly- 3,4-ethylene dioxythiophene/poly styrene sulfonate
（PEDOT：PSS）, doping it is poly-（Perfluoroethylene-perfluor ether sulfonic acid）Polythieno-thiophene.
Further, the material of the hole transmission layer is selected from 4- butyl-N, N- diphenyl aniline homopolymers（Poly-
TPD）, N, N '-bis-（1- how base）- N, N '-diphenyl -1,1 '-diphenyl -4,4 '-diamines, N, N '-bis-（3- aminomethyl phenyls）- N,
N '-diphenyl -1,1 '-diphenyl -4,4 '-diamines（TPD）, it is poly-（9,9- dioctyl fluorene -co- N-（4- butyl phenyls）Diphenyl
Amine）（TFB）.
The gross thickness of hole injection layer and hole transmission layer is 50~100nm.
Further, the material of the electron transfer layer is selected from TPBi（1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals -
Base) benzene）、Alq3（8-hydroxyquinoline aluminium）、TAZ、PBD、Beq2（8-hydroxyquinoline beryllium）、DPVBi（4,4'- bis- (2,2- hexichol second
Alkenyl) -1,1'- biphenyl）.
Further, the material of the electron injecting layer is LiF.
The gross thickness of electron injecting layer and electron transfer layer is 5~10nm.
Further, the material of the negative electrode is selected from Al, Ag, Mg, Li, Ca, In.
The thickness of negative electrode is 100~200nm.
Further, the quantum dot is prepared according to following steps：
S1, HX and methylamine reaction prepare MAX；
S2, MAX and CsX, PbX2Mix to obtain solution A, add oleic acid and oleyl amine to obtain solution B, solution B is added drop-wise in toluene solution
Form Ca-Ti ore type quantum dot；
S3, to Ca-Ti ore type quantum dot purify.
A kind of method for preparing above-mentioned quantum dot light emitting device, comprises the following steps：
S1, will ITO electro-conductive glass clean after be placed in UV ozone machine process；
S2, the spin coating hole injection layer material on ITO electro-conductive glass, baking；
S3, the spin coating hole transport layer material on hole injection layer, baking；
S4, the spin coating quantum dot solution on hole transmission layer, form quantum dot light emitting layer；
S5, under vacuum conditions thermal evaporation, are sequentially depositing electron transport layer materials, electron injecting layer material and cathode material；
S6, use uv-curable glue packaging.
A kind of liquid crystal display device, including above-mentioned quantum dot light emitting device.
The invention has the advantages that：
The present invention utilizes a kind of high-quality Ca-Ti ore type quantum dot MA1-xCsxPbX3Used as emitting layer material, the quantum dot is used
Conventional chemical reagent, it is with low cost, and can prepare at normal temperatures, process is simple.With reference to spin-coating film preparation technology with
Technique for vacuum coating, is capable of achieving the production of high-volume large area, effectively reduces cost.With MA1-xCsxPbX3For prepared by luminescent layer
Quantum dot light emitting device there is high current efficiency, external quantum efficiency high, high brightness, low turn-on voltage, stable performance, knot
Structure is simple, prepare the characteristic such as simple, there is good application prospect in field of information display.
Brief description of the drawings
Fig. 1 is the structural representation of the quantum dot light emitting device of embodiment 1；
Fig. 2 is the TEM figures and HRTEM figures of the quantum dot of embodiment 2；
Fig. 3 is the performance test results of embodiment 3.
Specific embodiment
With reference to specific embodiment, the present invention is described further.
Embodiment 1
A kind of quantum dot light emitting device, structure are as shown in figure 1, anode 6, hole injection layer 5, hole including being disposed adjacent successively
Transport layer 4, quantum dot light emitting layer 3, electron transfer layer 2, electron injecting layer and negative electrode 1.
The quantum dot of quantum dot light emitting layer is MA1-xCsxPbX3, wherein 0 ＜ x ＜ 1, MA are methylamine, X is halogen；Quantum dot
The thickness of luminescent layer is 30~200nm.
Anode material is ITO, can also mix zinc oxide, gallium using the metal of high work function such as gold, copper, platinum, palladium, and aluminium
Mix zinc oxide, cadmium and mix zinc oxide, copper indium oxide, or use two-layer electrode, formed in ITO surfaces spin coating conducting polymer
Anode material；The thickness of anode is 100~300nm.
The material of hole injection layer is poly- 3,4-ethylene dioxythiophene/poly styrene sulfonate, can also be poly- using doping
（Perfluoroethylene-perfluor ether sulfonic acid）Polythieno-thiophene.
The material of hole transmission layer is 4- butyl-N, N- diphenyl aniline homopolymers, can also be moved using other high holes
The aromatic multi-amine class compound of shifting rate, such as N, N '-bis-（1- how base）- N, N '-diphenyl -1,1 '-diphenyl -4,4 '-diamines,
N, N '-bis-（3- aminomethyl phenyls）- N, N '-diphenyl -1,1 '-diphenyl -4 are 4 '-diamines, poly-（9,9- dioctyl fluorene -co- N-
（4- butyl phenyls）Diphenylamine）.
The gross thickness of hole injection layer and hole transmission layer is 50~100nm.
The material of electron transfer layer is TPBi, can also use Alq3、TAZ、PBD、Beq2、DPVBi。
The material of electron injecting layer is LiF.
The gross thickness of electron injecting layer and electron transfer layer is 5~10nm.
Cathode material is Al, using the single-layer metal negative electrode of the low work functions such as Ag, Mg, Li, Ca, In, or can also be made
With the alloy cathode for the metal and high work function of low work function and the metal of stable chemical nature being deposited with together formation, or
Using mixed compound electrode, by mixed with the metal clip of low work function between negative electrode and luminescent layer, to improve device performance.
The thickness of negative electrode is 100~200nm.
Quantum dot light emitting device is prepared according to following steps：
1st, prepare the ITO electro-conductive glass that light is carved with electrode, rinsed using ionized water, acetone, isopropanol successively, make ITO layer upward
Place, ito glass piece is placed on 20min is processed in UV ozone machine, clean ITO, make glass that there is surface hydrophilicity, take out glass
Glass piece, ITO is used as transparent anode material；
2nd, using sol evenning machine on ito glass one layer of PEDOT of spin coating：PSS, then puts and toasts on hot plate（Sample 1）,
PEDOT：PSS as device hole injection layer material；
3rd, the chlorobenzene solution of Poly-TPD, one layer of Poly-TPD of spin coating on sample 1 are drawn with liquid-transfering gun（Sample 2）, Ran Houfang
Toast on hot plate, Poly-TPD is used as hole transport layer material；
4th, the colloidal solution of perovskite quantum dot, the spin coating perovskite quantum dot on sample 2, quantum dot conduct are drawn with liquid-transfering gun
Emitting layer material；
5th, thermal evaporation deposition material under vacuum conditions, is sequentially depositing TPBi, LiF and Al, and they are respectively electron transfer layer materials
Material, electron injecting layer material, cathode material；
6th, sample is taken out, uv-curable glue packaging is used.
Embodiment 2
The MA of embodiment 11-xCsxPbX3Quantum dot can be prepared according to the following steps：
1st, it is the HX of 50 ~ 70wt% by concentration（X=Cl、Br、I）It is the methylamine methanol solution of 25 ~ 40wt% with content（HX and methylamine
Mol ratio be 1 ~ 1.1：1~1.1）Mix at 0 DEG C, stirring reaction 1 ~ 3 hour, then solvent evaporated, obtains white solid,
Cleaned with ether 3 times, and dried 24 hours in vacuum drying chamber；
2nd, by MAX and CsX, PbX2It is dissolved into DMF and forms solution A（MAX、CsX、PbX2Consumption according to needed for quantum dot
Structure composition is adjusted）, add 200 ~ 500 μ L oleic acid and 15 ~ 50 μ L oleyl amines to obtain solution B, solution B is added drop-wise in toluene solution
Form Ca-Ti ore type quantum dot；
3rd, isometric tert-butyl alcohol, ethyl acetate or acetonitrile are added in the stoste of S2, under the rotating speed of 5000 ~ 10000rpm from
, be redispersed in sediment in n-hexane, toluene, tetrahydrofuran or normal octane after centrifugation, in 3000 ~ 6000rpm by the heart 2 ~ 5 minutes
Rotating speed under be centrifuged 0.5 ~ 3 minute, then sediment is redispersed in n-hexane, toluene, tetrahydrofuran or normal octane,
It is centrifuged 3 ~ 5 minutes under the rotating speed of 5000 ~ 10000rpm, takes supernatant.
Obtained quantum dot TEM figures and HRTEM figures（Upper left corner illustration）It is Fig. 2.
Embodiment 3
The performance of the device of testing example 1, obtains result as shown in Figure 3, the cut-in voltage of light emitting diode with quantum dots device
4.0V can be reduced to, electroluminescent peak is 520nm（Fig. 3-a）, halfwidth 20nm, luminosity（Fig. 3-b）, external quantum efficiency
（Fig. 3-d）, current efficiency（Fig. 3-c）24500 cd/m can most preferably be respectively reached2, 1.3% and 4.1cd/A.
It can be seen that, quantum dot light emitting device current efficiency high of the present invention, external quantum efficiency is high, luminosity is high, cut-in voltage
It is low.
The above, specific embodiment only of the invention, but protection scope of the present invention is not limited thereto, and it is any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in, all should
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (10)
1. a kind of quantum dot light emitting device, including anode, hole injection layer, hole transmission layer, the quantum dot being disposed adjacent successively
Luminescent layer, electron transfer layer, electron injecting layer and negative electrode, it is characterised in that the quantum dot of the quantum dot light emitting layer is MA1- xCsxPbX3, wherein 0 ＜ x ＜ 1, MA are methylamine, X is halogen.
2. quantum dot light emitting device according to claim 1, it is characterised in that the material of the anode be selected from gold, copper,
Platinum, palladium, ITO, aluminium mix zinc oxide, gallium mix zinc oxide, cadmium mix zinc oxide, copper indium oxide, in ITO surfaces spin coating conducting polymer
The anode material of formation.
3. quantum dot light emitting device according to claim 1, it is characterised in that the material of the hole injection layer is selected from poly-
3,4-ethylene dioxythiophene/poly styrene sulfonate, doping are poly-（Perfluoroethylene-perfluor ether sulfonic acid）Polythieno-thiophene.
4. quantum dot light emitting device according to claim 1, it is characterised in that the material of the hole transmission layer is selected from 4-
Butyl-N, N- diphenyl aniline homopolymers, N, N '-bis-（1- how base）- N, N '-diphenyl -1,1 '-diphenyl -4,4 '-diamines,
N, N '-bis-（3- aminomethyl phenyls）- N, N '-diphenyl -1,1 '-diphenyl -4 are 4 '-diamines, poly-（9,9- dioctyl fluorene -co- N-
（4- butyl phenyls）Diphenylamine）.
5. quantum dot light emitting device according to claim 1, it is characterised in that the material of the electron transfer layer is selected from
TPBi、Alq3、TAZ、PBD、Beq2、DPVBi。
6. quantum dot light emitting device according to claim 1, it is characterised in that the material of the electron injecting layer is LiF.
7. quantum dot light emitting device according to claim 1, it is characterised in that the material of the negative electrode be selected from Al, Ag,
Mg、Li、Ca、In。
8. quantum dot light emitting device according to claim 1, it is characterised in that the quantum dot is according to following steps system
It is standby：
S1, HX and methylamine reaction prepare MAX；
S2, MAX and CsX, PbX2Mix to obtain solution A, add oleic acid and oleyl amine to obtain solution B, solution B is added drop-wise in toluene solution
Form Ca-Ti ore type quantum dot；
S3, to Ca-Ti ore type quantum dot purify.
9. the method that one kind prepares the quantum dot light emitting device described in claim 1 ~ 8 any one, it is characterised in that including with
Lower step：
S1, will ITO electro-conductive glass clean after be placed in UV ozone machine process；
S2, the spin coating hole injection layer material on ITO electro-conductive glass, baking；
S3, the spin coating hole transport layer material on hole injection layer, baking；
S4, the spin coating quantum dot solution on hole transmission layer, form quantum dot light emitting layer；
S5, under vacuum conditions thermal evaporation, are sequentially depositing electron transport layer materials, electron injecting layer material and cathode material；
S6, use uv-curable glue packaging.
10. a kind of liquid crystal display device, it is characterised in that the liquid crystal display device includes claim 1 ~ 8 any one institute
The quantum dot light emitting device stated.
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Cited By (4)
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| CN109370309A (en) * | 2017-09-22 | 2019-02-22 | 苏州星烁纳米科技有限公司 | Composition for ink and electroluminescent device |
| CN110718648A (en) * | 2019-10-18 | 2020-01-21 | 南昌航空大学 | In-situ synthesis manufacturing method of perovskite quantum dot light-emitting diode based on inorganic hole transport material |
| CN111430558A (en) * | 2020-03-19 | 2020-07-17 | 电子科技大学 | Perovskite material doped structure-based dual-function device and preparation method thereof |
| CN118215319A (en) * | 2024-05-20 | 2024-06-18 | 江苏上达半导体有限公司 | High-performance quantum dot light emitting diode and preparation method thereof |
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| CN110718648A (en) * | 2019-10-18 | 2020-01-21 | 南昌航空大学 | In-situ synthesis manufacturing method of perovskite quantum dot light-emitting diode based on inorganic hole transport material |
| CN111430558A (en) * | 2020-03-19 | 2020-07-17 | 电子科技大学 | Perovskite material doped structure-based dual-function device and preparation method thereof |
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