CN106784191A - QLED devices and preparation method thereof - Google Patents
QLED devices and preparation method thereof Download PDFInfo
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- CN106784191A CN106784191A CN201611226239.6A CN201611226239A CN106784191A CN 106784191 A CN106784191 A CN 106784191A CN 201611226239 A CN201611226239 A CN 201611226239A CN 106784191 A CN106784191 A CN 106784191A
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- 239000002096 quantum dot Substances 0.000 claims abstract description 45
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 40
- 239000011257 shell material Substances 0.000 claims abstract description 27
- 239000011258 core-shell material Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 24
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- 239000000463 material Substances 0.000 claims description 19
- 238000010129 solution processing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000005525 hole transport Effects 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- -1 anode Substances 0.000 claims 2
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- 239000002994 raw material Substances 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001451 molecular beam epitaxy Methods 0.000 description 4
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
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- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- 229910004576 Cd1-xZnxS Inorganic materials 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/28—Materials of the light emitting region containing only elements of Group II and Group VI of the Periodic Table
- H01L33/285—Materials of the light emitting region containing only elements of Group II and Group VI of the Periodic Table characterised by the doping materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a kind of QLED devices, including anode, hole transmission layer, quantum dot light emitting layer, electron transfer layer and the negative electrode being cascading, the quantum dot light emitting layer is core-shell quanta dots, and its shell is ZnS；The hole transmission layer, the electron transfer layer are used and are made with the Shell Materials identical compound of the core-shell quanta dots, wherein, the electron transfer layer is made up of N-type ZnS, and the hole transmission layer is made up of p-type ZnS, and the p-type ZnS is Sb doping ZnS.
Description
Technical field
The invention belongs to technical field of flat panel display, more particularly to a kind of QLED devices and preparation method thereof.
Background technology
Light emitting diode with quantum dots (QLED) due to peak width at half height is narrow, Color tunable and can solution method prepare etc. it is excellent
Point, the contenders as next generation's display science and technology.Researcher launches to study from different angles to QLED, including QDs,
The research of HTL, ETL and electrode；And the research of the properity and stability to device.
United States Patent (USP) (US7880377) reports a kind of QLED devices of substrate/anode/HTL/QDs/ETL/ cathode constructions
Part；Wherein, the shell of HTL, ETL, QD is made of same compound.Because HTL, QDs, ETL are inorganic material layer, should
Invention prepares quantum dot light emitting layer by the method for electron spray, and HTL and ETL layers is prepared by the method for molecular beam epitaxy (MBE).
Although the QLED for obtaining, the efficiency of device can be to a certain extent improved.But, due to using electron spray and molecular beam epitaxy
Device is prepared, very complicated equipment is required to, and molecular beam epitaxy also needs to the vacuum of superelevation and can just carry out, therefore, hinder
Its further popularization and application.Therefore on the premise of the device architecture is ensured, a kind of preparation of simple possible how is provided
Method is still urgent problem.
The content of the invention
It is an object of the invention to provide a kind of QLED devices and preparation method thereof, it is intended to solve prior art and prepare composition
During compound identical HTL, ETL, the QLED devices of QD shells, prepared by electron spray, molecular beam epitaxy inorganic
, it is necessary to the equipment of complexity, harsh vacuum condition, cause method to be difficult to the problem of popularization and application during layer.
The present invention is achieved in that a kind of QLED devices, including anode, hole transmission layer, the amount being cascading
Son point luminescent layer, electron transfer layer and negative electrode, the quantum dot light emitting layer is core-shell quanta dots, and its shell is ZnS；
The hole transmission layer, the electron transfer layer are using the Shell Materials identical chemical combination with the core-shell quanta dots
Thing is made, wherein, the electron transfer layer is made up of N-type ZnS, and the hole transmission layer is made up of p-type ZnS, and the p-type
ZnS is Sb doping ZnS.
And, a kind of preparation method of QLED devices is comprised the following steps：
P-type ZnS solution, N-type ZnS solution are prepared respectively；
Cathode substrate is provided, the deposited n-type ZnS solution in the cathode substrate after heating anneal treatment, uses 365nm
Ultra violet lamp treatment, obtain electron transfer layer；
Quanta point material is deposited by solution processing method on the electron transport layer, quantum dot light emitting layer is prepared；
P-type ZnS solution is deposited on the quantum dot light emitting layer, after heating anneal treatment, is shone using the uviol lamp of 365nm
Treatment is penetrated, hole transmission layer is obtained；
Anode is prepared on the hole transport layer；
Or
P-type ZnS solution, N-type ZnS solution are prepared respectively；
Anode substrate is provided, p-type ZnS solution is sequentially depositing in the anode substrate, after heating anneal treatment, use
The ultra violet lamp treatment of 365nm, obtains hole transmission layer；
Quanta point material is deposited by solution processing method on the hole transport layer, quantum dot light emitting layer is prepared；
The deposited n-type ZnS solution on the quantum dot light emitting layer, after heating anneal treatment, is shone using the uviol lamp of 365nm
Treatment is penetrated, electron transfer layer is obtained；
Negative electrode is prepared on the electron transport layer.
The QLED devices that the present invention is provided, using this ambipolar materials of ZnS as hole transmission layer and electric transmission
The raw material of layer, reduces the anisotropy between different bed boundarys, the more conducively transmission of carrier, improves electronics and hole
Mobility, reduces defect and is combined and Interface composites, and then improve the efficiency of QLED devices.Additionally, using ZnS conducts simultaneously
The raw material of hole transmission layer and electron transfer layer, can improve the stability of the QLED devices.
The preparation method of the QLED devices that the present invention is provided, first, hole transmission layer, electronics is prepared by solution processing method
Transport layer, quantum dot light emitting layer shell raw material identical QLED devices, can not only avoid the use of complicated vacuum equipment, simplify
Production technology and flow, reduce manufacturing cost；And the mobility of carrier can be improved, reduce that defect is compound and interface
It is compound.Secondly, the preparation method of the QLED devices that the present invention is provided, is carried out at ultraviolet irradiation to the ZnS films after annealing
Reason, can be reduced the organic ligand on its surface, the more conducively transmission of carrier and compound, raising QLED device efficiencies.According to
QLED devices prepared by the inventive method, with stabilization efficiency and stability higher.
Brief description of the drawings
Fig. 1 is the eurymeric QLED structural representations without hole injection layer provided in an embodiment of the present invention；
Fig. 2 is the eurymeric QLED structural representations containing hole injection layer provided in an embodiment of the present invention；
Fig. 3 is transoid QLED structural representations provided in an embodiment of the present invention.
Specific embodiment
In order that the technical problem to be solved in the present invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention, is not intended to limit the present invention.
With reference to Fig. 1-3, a kind of QLED devices, including the anode 2, hole being cascading are the embodiment of the invention provides
Transport layer 4, quantum dot light emitting layer 5, electron transfer layer 6 and negative electrode 7, the quantum dot light emitting layer 5 are core-shell quanta dots, and its shell
Layer is ZnS；
The hole transmission layer 4, the electron transfer layer 6 are using the Shell Materials identical with the core-shell quanta dots
Compound is made, wherein, the electron transfer layer 6 is made up of N-type ZnS, and the hole transmission layer 4 is made up of p-type ZnS, and the P
Type ZnS is Sb doping ZnS.
The embodiment of the present invention is passed using ambipolar semi-conducting material ZnS as QLED devices hole-transporting layer 4, electronics
The raw material of defeated layer 6, while as the Shell Materials of the core-shell quanta dots of quantum dot light emitting layer 5, so as to reduce different bed boundarys it
Between anisotropy, the more conducively transmission of carrier improves the mobility in electronics and hole, reduces that defect is compound and interface
It is compound, and then improve the efficiency of QLED devices.Additionally, simultaneously using ZnS as hole transmission layer 4 and electron transfer layer 6
Raw material, can improve the stability of the QLED devices.
Semi-conducting material ZnS in QLED devices described in the embodiment of the present invention, can be using unformed phase ZnS semiconductors
Material, it would however also be possible to employ crystal ZnS semi-conducting materials.Preferably, N-type ZnS, p-type ZnS described in the embodiment of the present invention are unformed
Phase ZnS semi-conducting materials.The unformed phase ZnS semi-conducting materials do not have obvious band edge, with isotropism, defect
It is few, therefore by the use of the unformed phase ZnS semi-conducting materials as the Shell Materials and transport layer material of QLED device luminescent layers
Material, can reduce the anisotropy between different bed boundarys, be more beneficial for the injection in electronics and hole, reduce defect and be combined,
And then increased the efficiency of QLED devices.
Specifically, in the embodiment of the present invention, the ZnS semi-conducting materials for preparing the electron transfer layer 6 are N-type ZnS.
Inherently one N-type semiconductor of ZnS, its band gap is 3.7eV, thus its have to ultraviolet, visible ray, infrared light can be saturating
Cross, can be as transport layer material, particularly electron transfer layer 6.When using ZnS as 4 material of hole transmission layer, need to be to it
It is doped treatment.Specifically, the ZnS semi-conducting material p-type ZnS for preparing the electron transfer layer 6, and the p-type ZnS
It is Sb doping ZnS.Further, in the Sb doping ZnS, counted as 100% with mole total amount of Sb, Zn, Sb accounts for Sb, Zn mole
The 0.5-20% of total amount.The preferred doping ratio can assign the hole on the premise of ZnS bulk material characteristics are ensured
The good p-type effect of transport layer 4.
In the embodiment of the present invention, the quantum dot light emitting layer 5 is core-shell quanta dots, and its shell is ZnS.Thus, obtain
QLED structures in, quantum dot Shell Materials in the electron transfer layer 6, hole transmission layer 4, quantum dot light emitting layer 5 are consistent,
The anisotropy of different bed boundarys is reduced, is more beneficial for improving device efficiency.Further, the core-shell quanta dots are preferably
Oil-soluble core-shell quanta dots, so as to ensure in the preparation process of QLED devices, are protected from being deposited thereon water-soluble ZnS
The influence that material is caused to quantum dot light emitting layer.
In the embodiment of the present invention, it is preferred that the QLED devices also include being arranged on the anode 2 and the hole transport
Hole injection layer 3 between layer 4.
On the basis of above-mentioned specific embodiment, as a specific preferred situation, as shown in figure 1, the QLED devices
It is eurymeric QLED devices, including substrate 1, anode 2, hole transmission layer 4, quantum dot light emitting layer 5, the electronics biography being cascading
Defeated layer 6 and negative electrode 7, wherein, the quantum dot light emitting layer 5 is core-shell quanta dots, and its shell is ZnS；The hole transmission layer
4th, the electron transfer layer 6 is used and is made with the Shell Materials identical compound of the core-shell quanta dots, wherein, the electronics
Transport layer 6 is made up of N-type ZnS, and the hole transmission layer 4 is made up of p-type ZnS, and the p-type ZnS is Sb doping ZnS.
As another specific preferred situation, as shown in Fig. 2 the QLED devices are eurymeric QLED devices, including successively
Substrate 1, anode 2, hole injection layer 3, hole transmission layer 4, quantum dot light emitting layer 5, electron transfer layer 6 and the negative electrode being stacked
7, wherein, the quantum dot light emitting layer 5 is core-shell quanta dots, and its shell is ZnS；The hole transmission layer 4, the electronics are passed
Defeated layer 6 is used and is made with the Shell Materials identical compound of the core-shell quanta dots, wherein, the electron transfer layer 6 is by N-type
ZnS is made, and the hole transmission layer 4 is made up of p-type ZnS, and the p-type ZnS is Sb doping ZnS.
As another specific preferred situation, as shown in figure 3, the QLED devices are transoid QLED devices, including successively
Substrate 1, negative electrode 7, electron transfer layer 6, quantum dot light emitting layer 5, hole transmission layer 4 and the anode 2 being stacked, wherein, it is described
Quantum dot light emitting layer 5 is core-shell quanta dots, and its shell is ZnS；The hole transmission layer 4, the electron transfer layer 6 using with
The Shell Materials identical compound of the core-shell quanta dots is made, wherein, the electron transfer layer 6 is made up of N-type ZnS, institute
Hole transmission layer 4 is stated to be made up of p-type ZnS, and the p-type ZnS is Sb doping ZnS.
Specifically, in above-described embodiment, the selection of the substrate 1 is not limited clearly, and can be hard substrate 1, also may be used
Think flexible base board 1.
The material of the anode 2 is different because of eurymeric QLED, transoid QLED, specifically, when the QLED is eurymeric QLED,
Anode material can be ITO or FTO；When the QLED is transoid QLED, anode material is silver, aluminium, copper, gold and its alloy.
Core in the core-shell quanta dots is CdSe, CdTe, CdTe/CdS, CdSe/CdS, Cd1-xZnxS、PbSe、InX、
GaX, certainly, not limited to this, wherein, X is P, As or Sb.The thickness of the quantum dot light emitting layer 5 is 20-40nm.
The material of the hole injection layer 3 can be selected from any one in NiO, CuO, CuS；Can also for TFB, PVK,
At least one in Poly-TPD, TCTA, CBP.
The material of the negative electrode 7 is different because of eurymeric QLED, transoid QLED, specifically, when the QLED is transoid QLED,
Cathode material preferably can be ITO or FTO；When the QLED is eurymeric QLED, cathode material is silver, aluminium, copper, gold and its closes
Gold.
QLED devices provided in an embodiment of the present invention, using this ambipolar materials of ZnS as hole transmission layer and electricity
The raw material of sub- transport layer, reduces the anisotropy between different bed boundarys, the more conducively transmission of carrier, improve electronics and
The mobility in hole, reduces defect and is combined and Interface composites, and then improve the efficiency of QLED devices.Additionally, use simultaneously
ZnS can improve the stability of the QLED devices as hole transmission layer and the raw material of electron transfer layer.
QLED devices described in the embodiment of the present invention, can be prepared by following methods.
And, difference of the embodiment of the present invention always according to QLED type of device, there is provided two kinds of preparation sides of QLED devices
Method.
Wherein, a kind of preparation method of transoid QLED devices is comprised the following steps：
S01. p-type ZnS solution, N-type ZnS solution are prepared respectively；
S02. cathode substrate is provided, the deposited n-type ZnS solution in the cathode substrate after heating anneal treatment, is used
The ultra violet lamp treatment of 365nm, obtains electron transfer layer；
S03. quanta point material is deposited by solution processing method on the electron transport layer, prepares quantum dot light emitting layer；
S04. p-type ZnS solution is deposited on the quantum dot light emitting layer, after heating anneal treatment, the ultraviolet of 365nm is used
Light irradiation treatment, obtains hole transmission layer；
S05. anode is prepared on the hole transport layer.
Specifically, in above-mentioned steps S01, it is preferred that the preparation method of the N-type ZnS solution is as follows：
It is 1-5 by mol ratio:1-5:The ZnCl of 5-302、Na2S and TGA are added in reaction vessel, are added ultrapure
After water is stirred to clarify, microwave heating treatment prepares water miscible ZnS, wherein, the temperature of the microwave heating treatment is 50-80
DEG C, heat 3-30min.
Wherein, the TGA is a kind of water miscible acid, its dispersiveness that ZnS solution is provided as part.Specifically
, in building-up process, combined by the Zn on-SH and the ZnS surface of the TGA so that the ZnS of synthesis is water solubility.
Microwave heating treatment described in the embodiment of the present invention can be vibrated by intramolecule and provide energy, make what reaction occurred
More fully, so as to make the ZnS uniformities for obtaining more preferably, performance is more stable.
Used as specific embodiment, the preparation method of the N-type ZnS solution is as follows：By 1mmol ZnCl2、1mmol Na2S and
10mmol MPA (TGA) are added in vial, are subsequently adding the ultra-pure water of 100mL, first stir to clarify solution, so
Water miscible ZnS is prepared by heating using microwave afterwards, the condition of wherein heating using microwave is：65 DEG C of heating 10min.By adding acetone
Cleaned with ethanol and then to the ZnS of preparation, be then dissolved in ethanol solution.
Preferably, the preparation method of the p-type ZnS solution is as follows：
By ZnCl2、SbCl5、Na2S and TGA are added in reaction vessel, micro- after adding ultra-pure water to stir to clarify
Wave heating treatment prepares water miscible Sb doping ZnS, wherein, the temperature of the microwave heating treatment is 50-80 DEG C, heats 3-
30min, the ZnCl2、Na2The mol ratio of S and TGA is 1-5:1-5:5-30, the SbCl5Addition meet：With
Mole total amount of Sb, Zn is 100% meter, and Sb accounts for Sb, Zn mole of 0.5-20% of total amount.
Wherein, the TGA is a kind of water miscible acid, its dispersiveness that ZnS solution is provided as part.Specifically
, in building-up process, combined by the Zn on-SH and the ZnS surface of the TGA so that the ZnS of synthesis is water solubility.
Microwave heating treatment described in the embodiment of the present invention can be vibrated by intramolecule and provide heat, so that Sb can
Being dispersed in ZnS evenly, improves the uniformity of p-type ZnS, and then improve stability of material.
Used as specific embodiment, the preparation method of the p-type ZnS solution is as follows：By 1mmol ZnCl2、0.1mmol
SbCl5、1mmol Na2S and 10mmol MPA are added in vial, are subsequently adding the ultra-pure water of 100mL, are first stirred to clarify
Solution, then prepares water miscible ZnS by heating using microwave, and the condition of wherein heating using microwave is：65 DEG C of heating 10min.Pass through
Add acetone and ethanol and then the ZnS to preparing to clean, be then dissolved in ethanol solution.
In above-mentioned steps S02, in the embodiment of the present invention, the selection of the cathode substrate is unrestricted, in negative electrode lining
Deposited n-type ZnS solution on bottom, obtains N-type ZnS films after heating anneal.Of course it is to be understood that the N-type ZnS solution is heavy
Product, is realized using solution processing method.Solution processing method of the present invention, including but not limited to spin coating.Wherein, the heating is moved back
Fire treatment can be carried out under the conditions of 80 DEG C.Further, processed by the ultra violet lamp of 365nm, so as to reduce N-type ZnS
The organic ligand (TGA) of film surface, improves the transmission of its carrier and is combined, and then improve device efficiency.The purple
Outer light irradiation treatment can be 10-30min, concretely 15min.
In above-mentioned steps S03, the quantum dot light emitting layer can be realized using conventional solution processing method.
In above-mentioned steps S04, p-type ZnS solution is deposited on the quantum dot light emitting layer, p-type ZnS is obtained after heating anneal
Film.Wherein, the heating anneal treatment can be carried out under the conditions of 80 DEG C.Further, at by the ultra violet lamp of 365nm
Reason, so as to reduce the organic ligand (TGA) of p-type ZnS film surfaces, improves the transmission of its carrier and is combined, and then
Improve device efficiency.The ultra violet lamp treatment can be 10-30min, concretely 15min.
In above-mentioned steps S05, anode is prepared on the hole transport layer, can be realized by this area conventional method,
As being deposited with.
Further, the QLED devices that can be obtained to the embodiment of the present invention are packaged treatment.
The preparation method of another eurymeric QLED devices is comprised the following steps：
Q01. p-type ZnS solution, N-type ZnS solution are prepared respectively；
Q02., anode substrate is provided, p-type ZnS solution is sequentially depositing in the anode substrate, after heating anneal treatment, make
Processed with the ultra violet lamp of 365nm, obtain hole transmission layer；
Q03. quanta point material is deposited by solution processing method on the hole transport layer, prepares quantum dot light emitting layer；
Q04. the deposited n-type ZnS solution on the quantum dot light emitting layer, after heating anneal treatment, uses the ultraviolet of 365nm
Light irradiation treatment, obtains electron transfer layer；
Q05. negative electrode is prepared on the electron transport layer.
Specifically, in above-mentioned steps Q01, p-type ZnS solution, the same S01 of preparation method of N-type ZnS solution.
In above-mentioned steps Q02, in the embodiment of the present invention, the selection of the anode substrate is unrestricted, in anode lining
P-type ZnS solution is deposited on bottom, p-type ZnS films are obtained after heating anneal.Wherein, the heating anneal treatment can be in 80 DEG C of conditions
Under carry out.Further, processed by the ultra violet lamp of 365nm, so as to reduce the organic ligand (sulfydryl on p-type ZnS surfaces
Acetic acid), improve the transmission of its carrier and be combined, and then improve device efficiency.The ultra violet lamp treatment can be 10-
30min, concretely 15min.
In above-mentioned steps Q03, the quantum dot light emitting layer can be realized using conventional solution processing method.
In above-mentioned steps Q04, the deposited n-type ZnS solution on the quantum dot light emitting layer obtains N-type ZnS after heating anneal
Film.Wherein, the heating anneal treatment can be carried out under the conditions of 80 DEG C.Further, at by the ultra violet lamp of 365nm
Reason, so as to reduce the organic ligand (TGA) on N-type ZnS surfaces, improves the transmission of its carrier and is combined, and then improve
Device efficiency.The ultra violet lamp treatment can be 10-30min, concretely 15min.
In above-mentioned steps Q05, negative electrode is prepared on the electron transport layer, can be realized by this area conventional method,
As being deposited with.
Further, the QLED devices that can be obtained to the embodiment of the present invention are packaged treatment.
Preferably, in above-described embodiment, can be in the anode and the hole transmission layer intervening deposition hole injection layer.
The preparation method of QLED devices provided in an embodiment of the present invention, first, hole transport is prepared by solution processing method
Layer, electron transfer layer, quantum dot light emitting layer shell raw material identical QLED devices, can not only avoid making for complicated vacuum equipment
With, production technology and flow are simplified, reduce manufacturing cost；And the mobility of carrier can be improved, reduce defect and answer
Close and Interface composites.Secondly, the preparation method of QLED devices provided in an embodiment of the present invention, to the ZnS films after annealing
Ultraviolet irradiation treatment is carried out, the organic ligand on its surface, the more conducively transmission of carrier and compound, raising QLED is can be reduced
Device efficiency.According to QLED devices prepared by present invention method, with stabilization efficiency and stability higher.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of QLED devices, including anode, hole transmission layer, quantum dot light emitting layer, the electron transfer layer being cascading
And negative electrode, it is characterised in that the quantum dot light emitting layer is core-shell quanta dots, and its shell is ZnS；
The hole transmission layer, the electron transfer layer are using the Shell Materials identical compound system with the core-shell quanta dots
Into, wherein, the electron transfer layer is made up of N-type ZnS, and the hole transmission layer is made up of p-type ZnS, and the p-type ZnS is
Sb doping ZnS.
2. QLED devices as claimed in claim 1, it is characterised in that the N-type ZnS, p-type ZnS partly lead for unformed phase ZnS
Body material.
3. QLED devices as claimed in claim 1, it is characterised in that in the Sb doping ZnS, with mole total amount of Sb, Zn
It is 100% meter, Sb accounts for Sb, Zn mole of 0.5-20% of total amount.
4. QLED devices as described in claim 1-3 is any, it is characterised in that the QLED devices also include being arranged on described
Hole injection layer between anode and the hole transmission layer.
5. QLED devices as described in claim 1-3 is any, it is characterised in that the QLED devices are eurymeric QLED devices,
Including the substrate, anode, hole transmission layer, quantum dot light emitting layer, electron transfer layer and the negative electrode that are cascading, wherein, institute
Quantum dot light emitting layer is stated for core-shell quanta dots, and its shell is ZnS；The hole transmission layer, the electron transfer layer use with
The Shell Materials identical compound of the core-shell quanta dots is made, wherein, the electron transfer layer is made up of N-type ZnS, described
Hole transmission layer is made up of p-type ZnS, and the p-type ZnS is Sb doping ZnS.
6. QLED devices as described in claim 1-3 is any, it is characterised in that the QLED devices are eurymeric QLED devices,
Including substrate, anode, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and the moon for being cascading
Pole, wherein, the quantum dot light emitting layer is core-shell quanta dots, and its shell is ZnS；The hole transmission layer, the electronics are passed
Defeated layer is used and is made with the Shell Materials identical compound of the core-shell quanta dots, wherein, the electron transfer layer is by N-type
ZnS is made, and the hole transmission layer is made up of p-type ZnS, and the p-type ZnS is Sb doping ZnS.
7. QLED devices as described in claim 1-3 is any, it is characterised in that the QLED devices are transoid QLED devices,
Including the substrate, negative electrode, electron transfer layer, quantum dot light emitting layer, hole transmission layer and the anode that are cascading, wherein, institute
Quantum dot light emitting layer is stated for core-shell quanta dots, and its shell is ZnS；The hole transmission layer, the electron transfer layer use with
The Shell Materials identical compound of the core-shell quanta dots is made, wherein, the electron transfer layer is made up of N-type ZnS, described
Hole transmission layer is made up of p-type ZnS, and the p-type ZnS is Sb doping ZnS.
8. a kind of preparation method of QLED devices, comprises the following steps：
P-type ZnS solution, N-type ZnS solution are prepared respectively；
Cathode substrate is provided, the deposited n-type ZnS solution in the cathode substrate after heating anneal treatment, uses the purple of 365nm
Outer light irradiation treatment, obtains electron transfer layer；
Quanta point material is deposited by solution processing method on the electron transport layer, quantum dot light emitting layer is prepared；
P-type ZnS solution is deposited on the quantum dot light emitting layer, after heating anneal treatment, at the ultra violet lamp of 365nm
Reason, obtains hole transmission layer；
Anode is prepared on the hole transport layer；
Or
P-type ZnS solution, N-type ZnS solution are prepared respectively；
Anode substrate is provided, p-type ZnS solution is sequentially depositing in the anode substrate, after heating anneal treatment, use 365nm
Ultra violet lamp treatment, obtain hole transmission layer；
Quanta point material is deposited by solution processing method on the hole transport layer, quantum dot light emitting layer is prepared；
The deposited n-type ZnS solution on the quantum dot light emitting layer, after heating anneal treatment, at the ultra violet lamp of 365nm
Reason, obtains electron transfer layer；
Negative electrode is prepared on the electron transport layer.
9. the preparation method of QLED devices as claimed in claim 8, it is characterised in that the preparation method of the N-type ZnS solution
It is as follows：
It is 1-5 by mol ratio:1-5:The ZnCl of 5-302、Na2S and TGA are added in reaction vessel, add ultra-pure water to stir
Mix to clarification, microwave heating treatment prepares water miscible ZnS, wherein, the temperature of the microwave heating treatment is 50-80 DEG C,
Heating 3-30min.
10. the preparation method of QLED devices as claimed in claim 8, it is characterised in that the preparation side of the p-type ZnS solution
Method is as follows：
By ZnCl2、SbCl5、Na2S and TGA are added in reaction vessel, and after adding ultra-pure water to stir to clarify, microwave adds
Heat treatment prepares water miscible Sb doping ZnS, wherein, the temperature of the microwave heating treatment is 50-80 DEG C, heats 3-30min,
Wherein, ZnCl2、Na2The mol ratio of S and TGA is 1-5:1-5:5-30, the SbCl5Addition meet：With
Mole total amount of Sb, Zn is 100% meter, and Sb accounts for Sb, Zn mole of 0.5-20% of total amount.
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