CN109980105A - A kind of QLED device - Google Patents
A kind of QLED device Download PDFInfo
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- CN109980105A CN109980105A CN201711460056.5A CN201711460056A CN109980105A CN 109980105 A CN109980105 A CN 109980105A CN 201711460056 A CN201711460056 A CN 201711460056A CN 109980105 A CN109980105 A CN 109980105A
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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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
Abstract
The present invention provides a kind of QLED device, the QLED device includes luminescent layer, its, the luminescent layer is laminated in the way of [ABA] n by blue light quantum point material layer A and gold-tinted quantum dot material layer B and is formed, n is 1-3, wherein, the valence band difference of the blue light quantum point material and the gold-tinted quantum dot material is 0, and the blue light quantum point material conduction level is at least 0.5eV higher than the conduction level of the gold-tinted quantum dot material.The combined efficiency of quantum dot and the luminance purity of device are improved by introducing single band difference superlattice structure in luminescent layer, avoids the accumulation of quantum dot layer charge.
Description
Technical field
The present invention relates to QLED device arts more particularly to a kind of QLED devices.
Background technique
Colloidal Quantum Dots because its fluorescence efficiency is high, monochromaticjty is good, emission wavelength is controllable and stability is good and in display
There is considerable application prospect in part field.Light emitting diode (light emitting diode with quantum dots, Quantum dot based on quantum dot
Light-emitting diode, QLED) have many advantages, such as that better color saturation, efficiency colour temperature and service life are long, it is expected to
Mainstream technology as next-generation solid state lighting and FPD.
White light quanta point LED device reports fewer, and one is sent out using three primary colours quantum dot for primary structure
Light, i.e. selection red, green, blue quantum dot are white as three primary colours mixed luminescence；Second using blue colour fluorescent powder as substrate,
In conjunction with yellow quantum dot light emitting, white light is generated with blue colour fluorescent powder excitation collective effect.And current white light quanta point light-emitting diodes
The electron injection ability for the electron transport layer materials that tube device uses generally is better than the Hole injection capacity of hole transport layer material,
Excessive electron injection is caused to cause the self-luminous of device function layer such as hole transmission layer, to influence quantum dot luminescent device
Luminance purity and combined efficiency.In addition, being obstructed if overprimed electronics transports in quantum dot light emitting layer, charge can be made
It is accumulated in quantum dot light emitting layer, seriously affects the characteristics of luminescence of quantum dot.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of QLED device and preparation method thereof,
By introducing single band difference superlattice structure in luminescent layer, the polyelectron of crossing that can not only inject device is limited in quantum dot hair
In photosphere, avoid excess electrons injection hole functional layer to improve the combined efficiency of quantum dot and the luminance purity of device, and
And to injection quantum dot light emitting layer in electronics for, although transport it is relatively limited, in single band difference superlattice structure still
Can be transported by resonance tunneling effect, and with not by the hole for transporting limitation be compounded to form in time it is two or more shine it is compound
White light is formed, the accumulation of quantum dot layer charge is avoided.
Technical scheme is as follows:
A kind of QLED device, the QLED device includes luminescent layer, wherein the luminescent layer by blue light quantum point material layer A and
Gold-tinted quantum dot material layer B is laminated to be formed in the way of [ABA] n, n 1-3, wherein the blue light quantum point material and institute
The valence band difference for stating gold-tinted quantum dot material is 0, and the blue light quantum point material conduction level is than the gold-tinted quantum dot material
Conduction level height at least 0.5eV.
Quantum dot light emitting device provided by the invention, wherein the luminescent layer is by blue light quantum point material layer A and yellow light amount
Son point material layer B forms single band difference superlattice structure as shown shown in Figure 1 and Figure 2 according to [ABA] n stacked system.The list
Valence band difference with two kinds of materials in difference superlattice structure is 0, and hole transports the not scattering by potential barrier in luminescent layer at this time, can
In time with electronics recombination luminescence, the accumulation of charge is avoided.Blue-light-emitting quanta point material in the single band difference superlattice structure
Conduction level at least 0.5eV higher than the conduction level of Yellow luminous quanta point material, to guarantee luminescent layer to the beam of electron transport
Tie up effect.The single band difference superlattice structure of composition can produce it is two or more shine, using it in visible-range institute
The blue-light-emitting of sending and Yellow luminous it is compounded to form white light.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of QLED device preferred embodiment of the invention.
Fig. 2 is a kind of structural schematic diagram of QLED device another preferred embodiment of the invention.
Specific embodiment
The present invention provides a kind of QLED device and preparation method thereof, to make the purpose of the present invention, technical solution and effect more
Add clear, clear, the present invention is described in more detail below.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
Luminescent layer of the invention can be applied to a variety of existing QLED device architectures.Specifically, Fig. 1 is one kind of the invention
The structural schematic diagram of QLED device preferred embodiment, as shown in Figure 1, the embodiment of the present invention is by taking eurymeric QLED device as an example, it is described
QLED device successively includes anode grid substrate 101, hole functional layer 102, luminescent layer 103, electronic work ergosphere 104, yin from bottom to up
Pole layer 105 and encapsulated layer 106, wherein the luminescent layer 103 is pressed by blue light quantum point material layer A and gold-tinted quantum dot material layer B
It is laminated and to be formed according to the mode of [ABA] n, n 1-3, wherein the valence of the blue light quantum point material and the gold-tinted quantum dot material
Band difference is 0, and the blue light quantum point material conduction level is at least 0.5eV higher than the conduction level of the gold-tinted quantum dot material.
Specifically, quantum dot light emitting device provided by the invention, wherein the luminescent layer 103 is by blue light quantum point material
Layer A and gold-tinted quantum dot material layer B forms single band difference superlattice as shown shown in Figure 1 and Figure 2 according to [ABA] n stacked system
Structure.The valence band difference of two kinds of materials is 0 in the single band difference superlattice structure, at this time hole transporting not by gesture in luminescent layer
The scattering at base can avoid the accumulation of charge in time with electronics recombination luminescence.Blue-light-emitting amount in the single band difference superlattice structure
The conduction level at least 0.5eV higher than the conduction level of Yellow luminous quanta point material of son point material, to guarantee luminescent layer to electricity
The constraint effect that son transports.The single band difference superlattice structure of composition can produce it is two or more shine, using it visible
The blue-light-emitting that is issued in optical range and Yellow luminous it is compounded to form white light.
Further, as shown in Figure 1, the structure of the luminescent layer 103 is blue light quantum point material layer A and gold-tinted quantum dot material
The luminescent layer 103 to be formed is laminated in bed of material B in the way of [ABA] n, and wherein n is 1-3, it is preferable that n is in the luminescent layer 103
2。
Further, in the present invention, the blue light quantum point material selection luminescent spectrum peak value is in blue-light-emitting section
II-VI group compound, III-V compound, II-V compounds of group, the III-VI compound, group IV-VI of 420nm ~ 520nm
Close one of object, I-III-VI group compound, II-IV-VI compounds of group and IV race simple substance or a variety of.Preferably, the indigo plant
Light quanta point material is selected from ZnS or ZnSe.
Further, in the present invention, the gold-tinted quantum dot material selection luminescent spectrum peak value is in Yellow luminous section
II-VI group compound, III-V compound, II-V compounds of group, the III-VI compound, group IV-VI of 520nm ~ 630nm
Close one of object, I-III-VI group compound, II-IV-VI compounds of group and IV race simple substance or a variety of.Preferably, the Huang
Light quanta point material is selected from CdSe or CdS.
The semiconductor material that luminescent layer of the present invention uses includes but is not limited to the nanocrystalline of II-VI semiconductor, such as CdS,
The II- of CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe and other binary, ternary, quaternary
VI compound；Nanocrystalline, such as GaP, GaAs, InP, InAs and other binary, ternary, the quaternary of Group III-V semiconductor
III-V compound；It is described for electroluminescent semiconductor material be also not limited to II-V compounds of group, III- VI compound,
Group IV-VI compound, I-III-VI group compound, II-IV-VI compounds of group, IV race simple substance etc..
Further, the overall thickness of the luminescent layer is 12-165nm, wherein single [ABA] lamination layer structure with a thickness of
12-55nm.Blue light quantum point material layer A to the luminescent layer for forming the single band difference superlattice structure, to guarantee superlattices knot
The formation of structure, thickness are unsuitable blocked up, it is preferred that blue light quantum point material layer A with a thickness of 1-5nm, blocked up blue light quantum
Point material layer A will be unfavorable for the formation of superlattice structure, and the resistance that will cause device is excessive, reduce device performance.It is described
Gold-tinted quantum dot material layer B with a thickness of 10-25nm, can be adjusted flexibly according to the thickness of luminescent layer.
Further, in the present invention, 101 material of anode grid substrate can be selected from indium doping tin oxide (ITO), Fluorin doped
One of tin oxide (FTO), antimony-doped tin oxide (ATO), aluminium-doped zinc oxide (AZO) are a variety of；The hole injection
Layer is poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), undoped transition metal oxide, adulterated
Cross one of metal oxide, metal sulfide, doping metals sulfide or a variety of.
Further, in the present invention, 102 material of hole functional layer can be selected from having the organic of cavity transmission ability
Material, including but not limited to poly- (9,9- dioctyl fluorene-CO-N- (4- butyl phenyl) diphenylamines) (TFB), polyvinylcarbazole
(PVK), poly- (bis- bis- (phenyl) benzidine of (4- butyl phenyl)-N, N'- of N, N') (poly- TPD), poly- (9,9- dioctyl fluorene-
Co- double-N, N- phenyl -1,4- phenylenediamine) (PFB), 4,4 ', 4 ' '-three (carbazole -9- base) triphenylamine (TCTA), 4,4'- bis-
(9- carbazole) biphenyl (CBP), N, N '-diphenyl-N, N '-two (3- aminomethyl phenyl) -1,1 '-biphenyl -4,4 '-diamines (TPD),
N, N '-diphenyl-N, N '-(1- naphthalene) -1,1 '-biphenyl -4,4 '-diamines (NPB), doped graphene, undoped graphene,
C60Or their mixture；The hole functional layer material is further selected from the inorganic material with cavity transmission ability, including
But it is not limited to doped or non-doped NiO, WO3、MoO3, CuO or their mixture；
Further, 104 material of electronic work ergosphere described in the present invention is N-shaped ZnO, TiO2、SnO、Ta2O3、AlZnO、
ZnSnO, InSnO, Alq3 tri- (8-hydroxyquinoline) aluminium, Ca, Ba, CsF, LiF, CsCO3One of or it is a variety of；Preferably, institute
Stating electronic work ergosphere is N-shaped ZnO, N-shaped TiO2；The cathode is Al or Ag；
Further, in the above-described embodiment, the hole functional layer can be hole injection layer, hole transmission layer, electronics resistance
One or more of barrier.
Further, in the above-described embodiment, the electronic work ergosphere can be electron injecting layer, electron transfer layer, sky
One or more of cave barrier layer.
It should be noted that the hole injection layer, hole transmission layer, electronic barrier layer, electron injecting layer, electron transfer layer,
Hole blocking layer is all not required, and can be increased or be reduced according to the actual situation.
It is also provided based on a kind of above-mentioned composite quantum dot LED device in conjunction with a specific embodiment of the invention
A kind of preparation method of QLED device, wherein comprising steps of
S10 is in 101 surface deposition of hole functional layer 102 of anode grid substrate；
S20 is in 102 surface depositing light emitting layer 103 of hole functional layer；
S30 deposits electronic work ergosphere 104 on 103 surface of luminescent layer；
S40 obtains the QLED device in 104 surface deposited cathode layer 105 of electronic work ergosphere.
Specifically, when preparing composite quantum dot LED device as described in Figure 1, by taking magnetron sputtering method as an example,
Then the step S20 is specifically included: substrate is the transparent glass of deposited ITO and hole functional layer.Target is purity
The gold-tinted quantum dot material B such as CdS target of 99.99% blue light quantum point materials A such as ZnS circle target and purity 99.9%.Substrate is taken out,
It is put into sputtering equipment after being dried with vacuum oven or infrared lamp.Ionization power supply is first opened, by substrate alignment cleaning rod cleaning
12min removes the particle of substrate surface attachment.Target between substrate at a distance from be 4.5 ~ 5cm, Ar throughput be 25.0ml/min,
Penetrating deposition pressure is 0.5 ~ 0.6Pa, and effective radio-frequency power is about 100W.In a cycle, according to required thickness selection CdS and
The radio-frequency sputtering time of ZnS, repetition sputter several periods, the luminescent layer of ZnS/CdS superlattice film have just been made.
Further, in the present invention, each deposition method can be chemical method or physical method, wherein chemical method packet
Include but be not limited to chemical vapour deposition technique, successive ionic layer adsorption and reaction method, anodizing, strike, co-precipitation
One of method is a variety of；Physical method includes but is not limited to spin-coating method, print process, knife coating, dip-coating method, infusion method, spray
Coating, roll coating process, casting method, slit coating method, strip rubbing method, thermal evaporation coating method, electron beam evaporation deposition method, magnetic control
One of sputtering method, multi-arc ion coating embrane method, physical vaporous deposition, atomic layer deposition method, pulsed laser deposition are more
Kind.
Below by specific embodiment, further explanation is made to the present invention program:
Embodiment 1
The structure of the present embodiment QLED device are as follows: stack gradually the ito anode layer to be formed, the hole PEDOT:PSS in glass substrate
Implanted layer, TFB hole transmission layer, [ZnSCdSZnS] luminescent layer, ZnO electron transfer layer and Al cathode layer.
The present embodiment QLED device the preparation method is as follows:
A. on ITO substrate one layer of PEDOT:PSS film of spin coating as hole injection layer；
B. on PEDOT:PSS layer one layer of TFB film of spin coating as hole transmission layer；
C. one layer of quantum dot light emitting layer based on single band difference superlattice structure is deposited by magnetron sputtering method, wherein quantum dot hair
Photosphere is three layers of single band difference superlattice level structure functional layer, including the ZnSCdSZnS set gradually, with a thickness of 50nm, wherein
Two sides ZnS thickness is all 5nm, intermediate CdS with a thickness of 40nm；
D. then, on quantum dot light emitting layer spin coating layer of ZnO film as electron transfer layer；
E. finally, one layer of Al is deposited on ZnO, light emitting diode with quantum dots is obtained.
Embodiment 2
The structure of the present embodiment QLED device are as follows: stack gradually the ito anode layer to be formed, the hole PEDOT:PSS in glass substrate
Implanted layer, TFB hole transmission layer, [ZnSCdSZnS] 2 luminescent layer, ZnO electron transfer layer and Al cathode layer.
The present embodiment QLED device the preparation method is as follows:
A. on ITO substrate one layer of PEDOT:PSS film of spin coating as hole injection layer；
B. on PEDOT:PSS layer one layer of TFB film of spin coating as hole transmission layer；
C. one layer of quantum dot light emitting layer based on single band difference superlattice structure is deposited by magnetron sputtering method, wherein quantum dot hair
Photosphere is six layers of single band difference superlattice level structure functional layer, including [ZnSCdSZnS] 2 set gradually, with a thickness of 40nm,
In, two sides ZnS thickness is all 5nm, intermediate CdS with a thickness of 10nm；
D. then, on quantum dot light emitting layer spin coating layer of ZnO film as electron transfer layer；
E. finally, one layer of Al is deposited on ZnO, light emitting diode with quantum dots is obtained.
Embodiment 3
The structure of the present embodiment QLED device are as follows: stack gradually the ito anode layer to be formed, the hole PEDOT:PSS in glass substrate
Implanted layer, TFB hole transmission layer, [ZnSCdSZnS] 2 luminescent layer, ZnO electron transfer layer and Al cathode layer.
The present embodiment QLED device the preparation method is as follows:
A. on ITO substrate one layer of PEDOT:PSS film of spin coating as hole injection layer；
B. on PEDOT:PSS layer one layer of TFB film of spin coating as hole transmission layer；
C. one layer of quantum dot light emitting layer based on single band difference superlattice structure is deposited by magnetron sputtering method, wherein quantum dot hair
Photosphere is six layers of single band difference superlattice level structure functional layer, including [ZnSCdSZnS] 2 set gradually, with a thickness of 36nm,
In, two sides ZnS thickness is all 4nm, intermediate CdS with a thickness of 10nm；
D. then, on quantum dot light emitting layer spin coating layer of ZnO film as electron transfer layer；
E. finally, one layer of Al is deposited on ZnO, light emitting diode with quantum dots is obtained.
In conclusion a kind of QLED device provided by the invention and preparation method thereof, wherein the luminescent layer is by blue light amount
Son puts the single band difference superlattice structure that material layer A and gold-tinted quantum dot material layer B is formed according to [ABA] n stacked system, wherein n
For the number of plies of lamination.The valence band difference of two kinds of materials is 0 in the single band difference superlattice structure, and hole is defeated in luminescent layer at this time
Fortune can avoid the accumulation of charge in time with electronics recombination luminescence not by the scattering of potential barrier.It is blue in the single band difference superlattice structure
The conduction level of color luminescent quantum dot material at least 0.5eV higher than the conduction level of Yellow luminous quanta point material, to guarantee to send out
Photosphere acts on the constraint of electron transport.The single band difference superlattice structure of composition can produce two or more luminous, utilizations
Its blue-light-emitting issued in visible-range and Yellow luminous it is compounded to form white light.
Claims (10)
1. a kind of QLED device, the QLED device includes luminescent layer, which is characterized in that the luminescent layer is by blue light quantum point material
Bed of material A and gold-tinted quantum dot material layer B is laminated to be formed in the way of [ABA] n, n 1-3, wherein the blue light quantum point material
The valence band difference of material and the gold-tinted quantum dot material is 0, and the blue light quantum point material conduction level is than the gold-tinted quantum dot
The conduction level height at least 0.5eV of material.
2. QLED device according to claim 1, which is characterized in that n 2.
3. QLED device according to claim 1, which is characterized in that the luminescent spectrum wave crest of the blue light quantum point material
For 420nm ~ 520nm；And/or the luminescent spectrum wave crest of the gold-tinted quantum dot material is 520nm ~ 630nm.
4. QLED device according to claim 1, which is characterized in that the blue light quantum point material and the yellow light quantum
Point material is independently selected from II-VI group compound, III-V compound, II-V compounds of group, III-VI compound, group IV-VI
One of compound, I-III-VI group compound, II-IV-VI compounds of group and IV race simple substance are a variety of.
5. QLED device according to claim 4, which is characterized in that the blue light quantum point material is selected from ZnS or ZnSe；
And/or the gold-tinted quantum dot material is selected from CdSe or CdS.
6. QLED device according to claim 1, which is characterized in that the overall thickness of the luminescent layer is 12-165nm.
7. QLED device according to claim 1, which is characterized in that single [ABA] lamination layer structure with a thickness of 12-
55nm。
8. QLED device according to claim 1, which is characterized in that blue light quantum point material layer A with a thickness of 1-5nm；
And/or the gold-tinted quantum dot material layer B with a thickness of 10-25nm.
9. QLED device according to claim 1-8, which is characterized in that the QLED device includes cathode and sun
Pole, and the luminescent layer being arranged between the cathode and the anode, wherein the cathode and the luminescent layer it
Between be additionally provided with electronic work ergosphere.
10. QLED device according to claim 1-8, which is characterized in that the QLED device include cathode and
Anode, and the luminescent layer being arranged between the cathode and the anode, wherein in the anode and the luminescent layer
Between be additionally provided with hole functional layer.
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| WO2021136119A1 (en) * | 2019-12-31 | 2021-07-08 | Tcl科技集团股份有限公司 | Quantum dot light emitting diode and preparation method therefor |
| WO2022011991A1 (en) * | 2020-07-16 | 2022-01-20 | Tcl科技集团股份有限公司 | Light-emitting device and preparation method therefor |
| WO2023193427A1 (en) * | 2022-04-07 | 2023-10-12 | Tcl科技集团股份有限公司 | Light-emitting device and preparation method therefor, and display apparatus |
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