CN108735907A - A kind of QLED devices, display device and preparation method thereof - Google Patents

A kind of QLED devices, display device and preparation method thereof Download PDF

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Publication number
CN108735907A
CN108735907A CN201710264527.9A CN201710264527A CN108735907A CN 108735907 A CN108735907 A CN 108735907A CN 201710264527 A CN201710264527 A CN 201710264527A CN 108735907 A CN108735907 A CN 108735907A
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China
Prior art keywords
hole
layer
qled devices
hole injection
qled
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CN201710264527.9A
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Chinese (zh)
Inventor
钱磊
杨行
杨一行
曹蔚然
向超宇
陈崧
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TCL Corp
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TCL Corp
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Priority to CN201710264527.9A priority Critical patent/CN108735907A/en
Publication of CN108735907A publication Critical patent/CN108735907A/en
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17Carrier injection layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass

Abstract

The invention belongs to show applied technical field, a kind of QLED devices, display device and preparation method thereof are provided.The QLED devices include the substrate set gradually, hearth electrode, hole transmission layer, quantum dot light emitting layer, electron transfer layer and top electrode, further include hole-injecting material and modifying interface it is material doped made of hole injection layer, wherein, modifying interface material is p-type electric-conducting material.In the present invention, hole injection layer is made by using hole-injecting material and modifying interface are material doped, its cavity transmission ability and ionization energy are improved with this, reduce hole injection barrier, to effectively improve conductance, driving voltage is reduced, the injection balance of carrier is improved, reduce the charged of device simultaneously, improves the power efficiency of device and the service life of device.

Description

A kind of QLED devices, display device and preparation method thereof
Technical field
The invention belongs to show applied technical field more particularly to a kind of QLED devices, display device and preparation method thereof.
Background technology
Light emitting diode with quantum dots (Quantum Dot Light Emitting Diode, QLED) has excitation purity height, Frivolous can be flexible the advantages that, and solwution method may be used to prepare, it is the next-generation display technology placed high hopes.
Currently, QLED devices generally use quantum dot as luminescent material, meanwhile, the charge in order to improve QLED devices moves Shifting rate generally use PEDOT (polymer of 3,4- ethene dioxythiophene monomers):PSS (kayexalate) is noted as hole Enter material.However, the ionization energy due to quanta point material is very high, and PEDOT:The ito anode work function of PSS modifications is relatively low, Effective hole injection can not be formed, in addition the hole mobility of quantum dot itself is again relatively low compared to electron mobility so that Electrons and holes injection is uneven in QLED devices, and electronics is mostly sub, thus the current efficiency of device can not further increase.This Outside, its luminescent quantum yield is very sensitive for extra electric field as luminescent material for quantum dot, under high electric field, due to quantum this Plutarch effect, luminous efficiency decline is very fast, and therefore, under high driving voltage, QLED devices are extremely unstable, exists to shine and decline Subtract phenomenon, shortens the service life of device.
Therefore, that there are carrier injections is uneven, power efficiency is low and service life is short asks for existing QLED devices Topic.
Invention content
The purpose of the present invention is to provide a kind of QLED devices, display device and preparation method thereof, it is intended to solve existing QLED devices have that carrier injection is uneven, power efficiency is low and service life is short.
The purpose of the present invention is to provide a kind of QLED devices, including set gradually substrate, hearth electrode, hole transport Layer, quantum dot light emitting layer, electron transfer layer and top electrode, the QLED devices further include being repaiied by hole-injecting material and interface Hole injection layer made of exterior material doping, wherein the modifying interface material is p-type electric-conducting material.
Another object of the present invention, which also resides in, provides a kind of display device, and the display device includes QLED as described above Device.
Third object of the present invention, which also resides in, provides a kind of preparation method based on QLED devices as described above, described Preparation method includes following step:
Substrate, depositions of bottom electrode are provided;
Modifying interface material is added in hole-injecting material and obtains mixed solution, the mixed solution is deposited on described Hole injection layer is formed on hearth electrode;
Hole transmission layer, quantum dot light emitting layer, electron transfer layer and top electricity are sequentially depositing on the hole injection layer Pole;
Wherein, the modifying interface material is p-type electric-conducting material.
QLED provided by the invention repaiies hole-injecting material and interface using p-type electric-conducting material as modifying interface material Exterior material is doped to form hole injection layer, on the one hand can improve conductance, reduces device drive voltage;On the other hand, lead to Overdoping can improve the work function that hole-injecting material is modified, and reduce hole injection barrier, the carrier note of balancing device Enter, improves its current efficiency.Based on this, the carrier injection balance of the QLED devices is improved, and device has lower drive Dynamic voltage and less transmission loss are all greatly improved to the whole efficiency and service life of device.
QLED provided by the invention, only need to be material doped in hole by modifying interface on the basis of the preparation of original QLED To form hole injection layer in injection material, method is simple and easy to control, has preferable application prospect.
Description of the drawings
Fig. 1 is the structural schematic diagram of QLED devices provided in an embodiment of the present invention;
The flow chart of Fig. 2 preparation methods provided in an embodiment of the present invention based on QLED devices.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
In conjunction with Fig. 1, an embodiment of the present invention provides a kind of QLED, as shown in Figure 1, including the substrate 1, the bottom electricity that set gradually Pole 2, hole transmission layer 3, quantum dot light emitting layer 4, electron transfer layer 5 and top electrode 6, QLED devices further include being injected by hole Material and modifying interface it is material doped made of hole injection layer 7, wherein modifying interface material is p-type electric-conducting material, hole note Enter layer 7 to be arranged between hearth electrode 2 and hole transmission layer 3.
In embodiments of the present invention, QLED devices are not limited to top emitting or bottom emitting;It is also not necessarily limited to eurymeric device or anti- Type device.
In embodiments of the present invention, hole-injecting material and modifying interface material are doped, form hole injection layer 7.Wherein, modifying interface material is p-type electric-conducting material, and the hole concentration of p-type electric-conducting material is much larger than free electronic concentration, a side Face can improve conductance, reduce device drive voltage;On the other hand the work function that hole-injecting material is modified can be improved, subtracted Few hole injection barrier, the carrier injection of balancing device, improves its current efficiency.Therefore, it is different from using individual hole The hole injection layer 7 of injection material, the embodiment of the present invention can not only pass through equilbrium carrier by doped interface decorative material The whole efficiency for injecting and reducing transmission loss, improving device, and device can be improved by the driving voltage of reduction device Service life.
In embodiments of the present invention, the content of modifying interface material, to the shadow of the injection efficiency of 7 carrier of hole injection layer Sound it is larger, it is preferable that by the gross mass of hole injection layer 7 be 100% in terms of, the mass percentage of modifying interface material is 0.1%-50%.Further, conductance is preferably improved in order to obtain, the carrier injection of balancing device, it is preferred that with hole The gross mass of implanted layer 7 is 100% meter, and the mass percentage of modifying interface material is 0.1%-10%.The preferred interface The contribution of the content of decorative material, the balance injection of electric conductivity and carrier to whole system is very big, largely Conductance is improved, the driving voltage of device is reduced while reducing hole injection barrier.
In embodiments of the present invention, modifying interface material is p-type electric-conducting material, can be specifically polyethylene glycol, methyl Asia Sulfone, N, at least one of N-dimethylformamide, multi-walled carbon nanotube, sorbierite, bromine, PFI.Preferably, modifying interface material Can be carbon nanotube, carbon nanotube has very outstanding electric conductivity.
In embodiments of the present invention, hole-injecting material can be PEDOT:PSS, molybdenum oxide, vanadium oxide, tungsten oxide, oxygen Change at least one of chromium, molybdenum disulfide, tungsten disulfide, selenizing molybdenum, two tungsten selenides.Preferably, hole-injecting material can be PEDOT:PSS。
In embodiments of the present invention, for the ease of the making of hole injection layer 7, modifying interface material and hole-injecting material It is preferred that can be dissolved in homogeneous solvent, of course it is to be understood that homogeneous solvent herein, can be single solvent, can also be a variety of The mixed solvent that single solvent is formed.
In embodiments of the present invention, the thickness of hole injection layer is preferably 5-200nm.
In embodiments of the present invention, the selection of substrate 1 is unrestricted, and flexible base board may be used, and can also use hard Substrate.Hard substrate can be specifically glass substrate.
In embodiments of the present invention, hearth electrode 2 can be used conventional anode material and be made.Preferably, hearth electrode 2 can be At least one of conductive metal oxide, graphene, carbon nanotube, high-work-function metal and conducting polymer.It is highly preferred that It can be the ito transparent electrode that thickness is 10-200nm.
In embodiments of the present invention, the material of hole transmission layer 3 can be conducting polymer, including TFB, poly-TPD, At least one of TCTA, CBP, PVK;Can also be copper, iron, aluminium, nickel doping inorganic oxide, such as:Molybdenum oxide, oxidation Nickel, tungsten oxide, vanadium oxide etc..Preferably, the thickness of hole transmission layer is 5-200nm.
In embodiments of the present invention, the selection of the material of quantum dot light emitting layer 4 is unrestricted, it is preferable that quantum dot light emitting Layer 4 material can be in nucleocapsid semi-conducting material, including II-VI group nucleocapsid semiconductor and V-VI races nucleocapsid semi-conducting material extremely Few one kind, such as can be at least one of CdSe/ZnS, CdZnS/ZnS, CdxZn1-xSeyS1-y/ZnS, and/or At least one of PbSe, PbS, PbSe/CdS, PbSe/ZnS;It can also be the perovskites luminescent material such as MAPbX3 and CsPbX3 And luminescent quantum dot;The either I-IV-VI races semi-conducting material such as Cu-In-S.The material of the preferred quantum dot light emitting layer 4 has There is higher luminous efficiency.Preferably, the thickness of quantum dot light emitting layer 4 is 5-100nm.
In embodiments of the present invention, the material selection of electron transfer layer 5 is unrestricted, can be organic conductive material, packet Include at least one of NET5, Alq3, OXD-7 of LiF, CsF, CsCOs, NDN1 doping;Can also be aluminium, lithium, lanthanum, indium, gadolinium And the inorganic oxide of the doping such as magnesium, such as:At least one of nickel oxide, tungsten oxide, vanadium oxide.Preferably, electronics passes The thickness of defeated layer 5 is 5-200nm.
In embodiments of the present invention, conventional cathode material can be used in top electrode 6, it is preferable that can be Al, Ag, Ca, At least one of Ba, Mg.
It is illustrated with reference to specific embodiment.
Embodiment one:
A kind of QLED devices, including set gradually substrate 1, hearth electrode 2, hole transmission layer 3, quantum dot light emitting layer 4, electricity Sub- transport layer 5 and top electrode 6, further include by PEDOT:PSS:PFI adulterates hole injection layer 7 made of 5wt%DMSO.Its In, substrate 1 is substrate of glass;The material of hearth electrode 2 is ITO, thickness 120nm;The thickness of hole injection layer 7 is 40nm, PEDOT:PSS:The weight ratio of PFI is 1:2.5:11.2;The material of hole transmission layer 3 is TFB, thickness 25nm;Quantum dot is sent out The material of photosphere 4 is CdSe/ZnS QDs, thickness 40nm;The material of electron transfer layer 5 is nano zine oxide, and thickness is 20nm;The material of top electrode 6 is Al.
In embodiments of the present invention, pass through PEDOT:PSS:PFI adulterates the DMSO of 5wt% so that the hole injection layer 7 Work function is compared to only comprising PEDOT:The work function of the hole injection layer of PSS has been increased to 5.8eV, conductivity from 4.7eV Up to 50scm-1
Embodiment two:
A kind of QLED devices, including set gradually substrate 1, hearth electrode 2, hole transmission layer 3, quantum dot light emitting layer 4, electricity Sub- transport layer 5 and top electrode 6 further include the PEDOT by thickness for 40nm:The multi-wall carbon nano-tube of PSS film dopings 0.1wt% Hole injection layer 7 made of pipe.Wherein, substrate 1 is substrate of glass;The material of hearth electrode 2 is ITO, thickness 120nm;Hole The material of transmitting layer 3 is TFB, thickness 25nm;The material of quantum dot light emitting layer 4 is CdSe/ZnS QDs, thickness 40nm;Electricity The material of sub- transport layer 5 is nano zine oxide, and thickness is 20nm;The material of top electrode 6 is Al.
In the present embodiment, pass through PEDOT:The multi-walled carbon nanotube of PSS film dopings 0.1wt% so that note in the hole Enter the conductivity of layer 7 compared to only comprising PEDOT:The conductivity of the hole injection layer of PSS improves 30 times, and light transmittance then from Original 92% drops to 86%.
Embodiment three:
A kind of QLED devices, including set gradually substrate 1, hearth electrode 2, hole transmission layer 3, quantum dot light emitting layer 4, electricity Sub- transport layer 5 and top electrode 6 further include the PEDOT by thickness for 40nm:Made of the liquid bromine of PSS film dopings 6wt% Hole injection layer 7.Wherein, substrate 1 is substrate of glass;The material of hearth electrode 2 is ITO, thickness 120nm;Hole transmission layer 3 Material is TFB, thickness 25nm;The material of quantum dot light emitting layer 4 is CdSe/ZnS QDs, thickness 40nm;Electron transfer layer 5 Material be nano zine oxide, thickness is 20nm;The material of top electrode 6 is Al.
In the present embodiment, pass through PEDOT:The liquid bromine of PSS film dopings 6wt% so that the electricity of the hole injection layer 7 Conductance is compared to only comprising PEDOT:The conductivity of the hole injection layer of PSS improves 300 times, and light transmittance is then from original 92% improves extremely to 97%.
QLED provided by the invention repaiies hole-injecting material and interface using p-type electric-conducting material as modifying interface material Exterior material is doped, and forms hole injection layer 7, on the one hand can improve conductance, reduces device drive voltage;On the other hand, The work function that hole-injecting material is modified can be improved by doping, reduces hole injection barrier, the carrier of balancing device Injection, improves its current efficiency.Based on this, the carrier injection balance of the QLED devices is improved, and device has lower Driving voltage and less transmission loss are all greatly improved to the whole efficiency and service life of device.
The embodiment of the present invention additionally provides a kind of display device, which includes QLED devices as described above.
The QLED of the embodiment of the present invention can be prepared by following methods.
Correspondingly, in conjunction with Fig. 2, an embodiment of the present invention provides a kind of preparation method based on QLED as above, including it is following Step:
Step S01:Substrate, depositions of bottom electrode are provided.
Step S02:Modifying interface material is added in hole-injecting material and obtains mixed solution, mixed solution is deposited on Hole injection layer is formed on hearth electrode.Wherein, modifying interface material is p-type electric-conducting material.
Step S03:Be sequentially depositing on hole injection layer hole transmission layer, quantum dot light emitting layer, electron transfer layer and Top electrode.
The selection of layers of material and its preferred type, thickness are for example above in the embodiment of the present invention, in order to save length, herein It repeats no more.
QLED provided by the invention, only need to be material doped in hole by modifying interface on the basis of the preparation of original QLED To form hole injection layer in injection material, method is simple and easy to control, has preferable application prospect.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " specific example ", Or the description of " first embodiment ", " second embodiment " etc. mean specific features described in conjunction with this embodiment or example, structure, Material or feature are included at least one embodiment or example of the invention.In the present specification, above-mentioned term is shown The statement of meaning property may not refer to the same embodiment or example.Moreover, particular features, structures, materials, or characteristics described It can be combined in any suitable manner in any one or more of the embodiments or examples.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and All any modification, equivalent and improvement made by within principle etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of QLED devices, including set gradually substrate, hearth electrode, hole transmission layer, quantum dot light emitting layer, electron-transport Layer and top electrode, which is characterized in that the QLED devices further include by hole-injecting material and the material doped system of modifying interface At hole injection layer, wherein the modifying interface material be p-type electric-conducting material.
2. QLED devices as described in claim 1, which is characterized in that by the gross mass of the hole injection layer be 100% in terms of, The mass percentage of the modifying interface material is 0.1%-50%.
3. QLED devices as described in claim 1, which is characterized in that the modifying interface material includes polyethylene glycol, methyl Sulfoxide, N, at least one of N-dimethylformamide, multi-walled carbon nanotube, sorbierite, bromine, PFI.
4. such as claims 1 to 3 any one of them QLED devices, which is characterized in that the hole-injecting material is PEDOT: PSS。
5. QLED devices as described in claim 1, which is characterized in that the thickness of the hole injection layer is 5-200nm.
6. QLED devices as described in claim 1, which is characterized in that the quantum dot light emitting layer includes II-VI group nucleocapsid half At least one of conductor material, V-VI races nucleocapsid semi-conducting material, I-IV-VI races semi-conducting material, perovskite luminescent material.
7. QLED devices as claimed in claim 6, which is characterized in that the II-VI group nucleocapsid semiconductor include CdSe/ZnS, At least one of CdZnS/ZnS, CdxZn1-xSeyS1-y/ZnS;And/or
The V-VI races nucleocapsid semi-conducting material includes at least one of PbSe, PbS, PbSe/CdS, PbSe/ZnS;And/or
I-IV-VI races semi-conducting material includes Cu-In-S;And/or
The perovskite luminescent material includes MAPbX3、CsPbX3At least one of.
8. QLED devices as described in claim 1, which is characterized in that the hole transmission layer include TFB, poly-TPD, At least one of TCTA, CBP, PVK;And/or
The hole transmission layer includes at least one in copper, iron, aluminium, the molybdenum oxide of nickel doping, nickel oxide, tungsten oxide, vanadium oxide Kind.
9. a kind of display device, which is characterized in that the display device includes such as claim 1~8 any one of them QLED Device.
10. a kind of preparation method based on such as claim 1~8 any one of them QLED devices, which is characterized in that the system Preparation Method includes following step:
Substrate, depositions of bottom electrode are provided;
Modifying interface material is added in hole-injecting material and obtains mixed solution, the mixed solution is deposited on the bottom electricity Hole injection layer is formed on extremely;
Hole transmission layer, quantum dot light emitting layer, electron transfer layer and top electrode are sequentially depositing on the hole injection layer;
Wherein, the modifying interface material is p-type electric-conducting material.
CN201710264527.9A 2017-04-21 2017-04-21 A kind of QLED devices, display device and preparation method thereof Pending CN108735907A (en)

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CN111384260A (en) * 2018-12-28 2020-07-07 Tcl集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
CN111725433A (en) * 2019-03-19 2020-09-29 Tcl集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
CN112280025A (en) * 2020-12-30 2021-01-29 南京贝迪新材料科技股份有限公司 High-stability quantum dot hybrid nanostructure, QLED device and preparation method thereof
CN112397617A (en) * 2019-08-19 2021-02-23 Tcl集团股份有限公司 Doped tungsten oxide nano material, preparation method thereof and inorganic hole transport material
WO2021114387A1 (en) * 2019-12-10 2021-06-17 深圳市华星光电半导体显示技术有限公司 Perovskite light emitting device and preparation method therefor, and display
CN113054119A (en) * 2019-12-28 2021-06-29 Tcl集团股份有限公司 Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof
WO2022143824A1 (en) * 2020-12-31 2022-07-07 Tcl科技集团股份有限公司 Optoelectronic device
WO2022143828A1 (en) * 2020-12-31 2022-07-07 Tcl科技集团股份有限公司 Photoelectric device

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WO2020108069A1 (en) * 2018-11-28 2020-06-04 Tcl科技集团股份有限公司 Nano metal oxide, preparation method therefor, and quantum dot light-emitting diode
CN111384260A (en) * 2018-12-28 2020-07-07 Tcl集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
CN111384260B (en) * 2018-12-28 2022-04-01 Tcl科技集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
CN111725433B (en) * 2019-03-19 2021-06-11 Tcl科技集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
CN111725433A (en) * 2019-03-19 2020-09-29 Tcl集团股份有限公司 Quantum dot light-emitting diode and preparation method thereof
CN112397617B (en) * 2019-08-19 2022-02-18 Tcl科技集团股份有限公司 Doped tungsten oxide nano material, preparation method thereof and inorganic hole transport material
CN112397617A (en) * 2019-08-19 2021-02-23 Tcl集团股份有限公司 Doped tungsten oxide nano material, preparation method thereof and inorganic hole transport material
WO2021114387A1 (en) * 2019-12-10 2021-06-17 深圳市华星光电半导体显示技术有限公司 Perovskite light emitting device and preparation method therefor, and display
CN113054119A (en) * 2019-12-28 2021-06-29 Tcl集团股份有限公司 Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof
CN113054119B (en) * 2019-12-28 2022-05-17 Tcl科技集团股份有限公司 Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof
CN112280025B (en) * 2020-12-30 2021-03-19 南京贝迪新材料科技股份有限公司 High-stability quantum dot hybrid nanostructure, QLED device and preparation method thereof
CN112280025A (en) * 2020-12-30 2021-01-29 南京贝迪新材料科技股份有限公司 High-stability quantum dot hybrid nanostructure, QLED device and preparation method thereof
WO2022143824A1 (en) * 2020-12-31 2022-07-07 Tcl科技集团股份有限公司 Optoelectronic device
WO2022143828A1 (en) * 2020-12-31 2022-07-07 Tcl科技集团股份有限公司 Photoelectric device

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Application publication date: 20181102