CN106531860B - Quantum dot light emitting layer and device and preparation method, illuminating module and display device - Google Patents
Quantum dot light emitting layer and device and preparation method, illuminating module and display device Download PDFInfo
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- CN106531860B CN106531860B CN201611198580.5A CN201611198580A CN106531860B CN 106531860 B CN106531860 B CN 106531860B CN 201611198580 A CN201611198580 A CN 201611198580A CN 106531860 B CN106531860 B CN 106531860B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
Abstract
The present invention discloses quantum dot light emitting layer and device and preparation method, illuminating module and display device, and method is comprising steps of the quantum dot dissolution that surface is coated with ligand in a solvent, obtains quantum dot solution；Quantum dot solution is deposited in substrate or functional layer using solwution method, obtains quantum dot light emitting layer；Quantum dot light emitting is placed in vacuum cavity, it is passed through organometallic complex, handles 0.5 ~ 30 min, wherein the pressure of inside cavity is 0.01 ~ 1 mbar, partial pressure of the organometallic complex after gasifying is 0.001 ~ 0.1 mbar, and the temperature of inside cavity is 10 ~ 25 °C；Quantum dot light emitting layer after the completion of above-mentioned processing is taken out, quantum dot crosslinking luminescent layer is obtained.Quantum dot film of the present invention not only uniform ground, but also film layer stabilization, it is difficult to which solvent when being deposited by subsequent other function layer, which re-dissolves, to be taken away or wash away, and the uniformity of luminance and stability of QLED are effectively improved.
Description
Technical field
The present invention relates to LED technology field more particularly to a kind of quantum dot crosslinking luminescent layer and QLED device and
Preparation method, illuminating module and display device.
Background technique
Quantum dot (Quantum dot, QD) is also referred to as semiconductor nano (Semiconductor
Nanocrystal), be a kind of particle radius be less than or close to Exciton Bohr Radius semi-conductor nano particles, have each
The unique optical characteristics of kind, as forbidden bandwidth easily tunes, extinction spectrum range is wide, spectral purity is high, light/stable chemical performance
Deng.Light emitting diode based on quantum dot is referred to as light emitting diode with quantum dots (Quantum dot light-emitting
Diode, QLED), it is a kind of emerging display device, structure and Organic Light Emitting Diode (Organic light-
Emitting diode, OLED) it is similar, but compared with conventional light emitting diodes and OLED, QLED has excitation purity high, steady
Outstanding advantages of qualitative good, the service life is long, colour temperature is good, preparation process is simple, is expected to substitute traditional inorganic and organic LED as warp
Ji, stable and dynamical next-generation display panel.
The QLED device of current most of researchs is all made of solwution method processing preparation, such as spin-coating method, print process, solwution method
Compared with evaporation coating method, not only method is simple, technique is quick but also low in cost, conducive to the extensive industry of QLED device
Change preparation.Even so, solwution method is more difficult to get the film layer of highly uniform densification, and prepared film often will appear thickness not
Uniformly, covering is not complete, film layer crystallinity is bad, boundary defect is big, is mutually dissolved the unfavorable phenomenons such as infiltration between film layer, and therewith
It compares, evaporation coating method is easy to get that film thickness is uniform, high quality of excellent in crystallinity by accurately controlling deposition velocity and atmosphere
Film.The film forming of solwution method is uneven, eventually results in that prepared QLED device repeatability is bad, performance difference between device
Greatly, and light-emitting area is uneven and performance is unstable.Particularly, core group stratification of the quantum dot light emitting layer as QLED device,
It plays the role of other film layers of following process and the performance of device at film uniformity vital.
For the deposition method of quantum dot light emitting layer, current most of film-forming process are by the quantum of surface ligand functionalization
Point is dissolved in organic solvent, is configured to quantum dot solution or quantum dot ink, is then deposited on lining by spin coating or mode of printing
On bottom or functional layer, other function layer is then sequentially depositing on quantum dot light emitting layer using same film build method, is finally steamed
Plated electrode obtains QLED device.But because quantum dot relies primarily on ligand and is dispersed in solution or ink, still keep
Granular state, particle size is larger compared with conventional ion or small organic molecule, and quantum dot particle is more difficult when film forming uniformly spreads over
On substrate, and with the further volatilization of solvent, the spacing between quantum dot particle gradually can be widened or be shunk, and can aggravate quantum
The inhomogeneities of point luminescent layer.Further, since quantum dot surface organic ligand rich in, post-depositional quantum dot still have very
Big chance re-dissolves in the solwution method film forming procedure of subsequent other function layer to be taken away or directly washes away, and quantum dot film layer is caused
Unevenly and the uniform performance of device luminance nonuniformity is lower.Even if using the solvent of indissoluble solution quantum dot, it is also difficult to avoid the mistake
The generation of journey, and because of this, the selection of follow-up function layer material also will receive the limitation of its optional solvent.
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 quantum dot crosslinking luminescent layer and QLED
Device and preparation method, illuminating module and display device, it is intended to solve existing quantum dot film layer and cover uneven, uneven thickness
Problem even and that the uniform performance of device luminance nonuniformity is lower.
Technical scheme is as follows:
A kind of preparation method of quantum dot crosslinking luminescent layer, wherein comprising steps of
The quantum dot dissolution that surface is coated with ligand in a solvent, obtains quantum dot solution；
Quantum dot solution is deposited, quantum dot light emitting layer is obtained；
Resulting quantum dot light emitting is placed in vacuum cavity, organometallic complex is passed through, crosslinking Treatment is carried out, obtains
Luminescent layer is crosslinked to quantum dot.
The preparation method of the quantum dot crosslinking luminescent layer, wherein the ligand is organic ligand.
The preparation method of the quantum dot crosslinking luminescent layer, wherein the organic ligand is thioacetic acid, sulfydryl third
Acid, mercaptobutyric acid, sulfydryl oleic acid, mercapto glycerol, glutathione, mercaptoethylmaine, sulfydryl oleyl amine, tri octyl phosphine, trioctylphosphine oxidation
One of phosphine, oleic acid, amino acid, alkyl acid, alkylamine, sulfonic acid, mercaptan are a variety of.
The preparation method of the quantum dot crosslinking luminescent layer, wherein the ligand is mineral ligand.
The preparation method of the quantum dot crosslinking luminescent layer, wherein the mineral ligand is Cl-、Br-、S2-、HS-、
SnS4 4-、Sn2S6 4-、ZnCl4 2−、Zn(OH)4 2−One of or it is a variety of.
The preparation method of the described quantum dot crosslinking luminescent layer, wherein the quantum dot be II-V compound semiconductor,
One of Group III-V compound semiconductor, IV-VI compound semiconductor and its core-shell structure are a variety of.
The preparation method of the described quantum dot crosslinking luminescent layer, wherein the solvent be normal octane, isooctane, toluene,
Benzene, chlorobenzene, dimethylbenzene, chloroform, acetone, hexamethylene, n-hexane, pentane, isopentane, N,N-dimethylformamide, N, N- bis-
Methylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide, n-butyl ether, methyl phenyl ethers anisole, phenetole, benzene second
One of ketone, aniline, diphenyl ether are a variety of.
The preparation method of the quantum dot crosslinking luminescent layer, wherein the organometallic complex is alkyl aluminum, alkyl
One of lithium, alkyl indium, alkyl gallium, alkyl cadmium, alkyl tellurium, alkyl magnesium, zinc alkyl, amido lithium, aryl lithium are a variety of.
The preparation method of the quantum dot crosslinking luminescent layer, wherein the time of the crosslinking Treatment is 0.5 ~ 30 min.
The preparation method of the quantum dot crosslinking luminescent layer, wherein the pressure of the inside cavity is 0.01 ~ 1
mbar。
The preparation method of the described quantum dot crosslinking luminescent layer, wherein partial pressure of the organometallic complex after gasifying be
0.001~0.1 mbar。
The preparation method of the quantum dot crosslinking luminescent layer, wherein the temperature of inside cavity is 10 ~ 25 °C.
A kind of quantum dot crosslinking luminescent layer, wherein the quantum dot crosslinking luminescent layer is handed over using quantum dot as described above
The preparation method of connection luminescent layer is prepared.
A kind of QLED device, wherein including being arranged between anode and cathode and the anode and the cathode as taken up an official post
The quantum dot that quantum dot described in one is crosslinked the preparation method preparation of luminescent layer is crosslinked luminescent layer.
The QLED device, wherein further include being arranged between the anode and quantum dot crosslinking luminescent layer
Hole injection layer and hole transmission layer, and the electron-transport being arranged between luminescent layer and the cathode is crosslinked in the quantum dot
Layer, the hole transmission layer and the quantum dot light emitting layer overlap.
A kind of illuminating module, including QLED device as described above.
A kind of display device, including illuminating module as described above.
The utility model has the advantages that quantum dot light emitting prepared by solwution method is placed on volatile organometallic complex atmosphere by the present invention
In, the organometallic complex vivaciously and easily hydrolyzed reacts after gasifying with quantum dot surface ligand abundant, makes point
Not independent quantum dot is crosslinked together, and the quantum dot after formation gas phase is cementing is crosslinked luminescent layer.Quantum dot film of the present invention is not
Only uniform ground, and film layer is stablized, it is difficult to and solvent when being deposited by subsequent other function layer, which re-dissolves, to be taken away or washes away, and is had
Effect ground improves the uniformity of luminance and stability of QLED device, in addition, the introducing of organometallic complex can be effectively passivated
Quantum dot surface defect improves the luminous efficiency and luminescent lifetime of QLED device.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of QLED device of the present invention.
Fig. 2 is the cross-linking process schematic diagram of QLED device in the embodiment of the present invention 1.
Fig. 3 is the structural schematic diagram of QLED device in the embodiment of the present invention 1.
Specific embodiment
The present invention provides a kind of quantum dot crosslinking luminescent layer and QLED device and preparation method, illuminating module and display fill
It sets, to make the purpose of the present invention, technical solution and effect clearer, clear and definite, the present invention is described in more detail below.It answers
Work as understanding, the specific embodiments described herein are merely illustrative of the present invention, is not intended to limit the present invention.
A kind of preparation method preferred embodiment of quantum dot crosslinking luminescent layer of the invention, wherein comprising steps of
The quantum dot dissolution that surface is coated with ligand first in a solvent, obtains quantum dot solution；
Then quantum dot solution is deposited in substrate or functional layer using solwution method, obtains quantum dot light emitting layer；
Then resulting quantum dot light emitting is placed in vacuum cavity, is passed through organometallic complex, processing 0.5 ~ 30
Min, wherein the pressure of inside cavity is 0.01 ~ 1 mbar, and partial pressure of the organometallic complex after gasifying is 0.001 ~ 0.1
Mbar, the temperature of inside cavity are 10 ~ 25 °C；
Quantum dot light emitting layer after the completion of above-mentioned processing is taken out, quantum dot crosslinking luminescent layer is obtained.
The present invention is placed on quantum dot light emitting prepared by solwution method in volatile organometallic complex atmosphere, it is active and
The organometallic complex easily hydrolyzed reacts after gasifying with quantum dot surface ligand abundant, makes amount independently
Son point is crosslinked together, and the quantum dot after formation gas phase is cementing is crosslinked luminescent layer.In the present invention, the work of organometallic complex
With being on the one hand to be crosslinked quantum dot with ligand together, quality of forming film is improved, makes institute at quantum dot film not only uniform ground,
And film layer is stablized, it is difficult to which solvent when being deposited by subsequent other function layer, which re-dissolves, to be taken away or wash away, and is effectively improved
The uniformity of luminance and stability of QLED device, on the other hand, the introducing of organometallic complex can effectively be passivated quantum
Point surface defect, improves the luminous efficiency and luminescent lifetime of QLED device.
Specifically, it is dissolved in toluene or chloroform equal solvent, matches after surface to be coated with to the quantum dot drying weighing of ligand
Quantum dot solution is made, wherein the concentration of quantum dot solution is 1 ~ 50 mg/mL.Preferably, the ligand is organic ligand or nothing
Machine ligand, the organic ligand are long-chain organic ligand and/or short chain organic ligand；The organic ligand can be but be not limited to
It is thioacetic acid, mercaptopropionic acid, mercaptobutyric acid, sulfydryl oleic acid, mercapto glycerol, glutathione, mercaptoethylmaine, sulfydryl oleyl amine, three pungent
One of base phosphine, trioctyl phosphine oxide, oleic acid, amino acid, alkyl acid, alkylamine, sulfonic acid, mercaptan etc. are a variety of；The nothing
Machine ligand can be but be not limited to Cl-、Br-、S2-、HS-、SnS4 4-、Sn2S6 4-、ZnCl4 2−、Zn(OH)4 2−One of or it is a variety of.
Wherein, the organic ligand contains-OH ,-COOH ,-NH2、-NH-、-SH、-CN、-SO3H、-SOOH、-NO2、-CONH2、-
One or more coordinating groups in CONH- ,-COCl ,-CO- ,-CHO ,-Cl ,-Br etc..It is highly preferred that the ligand is short chain
Organic ligand or mineral ligand.
Specifically, quantum dot of the present invention can be doped or non-doped II-V compound semiconductor, iii-v
One of compound semiconductor, IV-VI compound semiconductor and its core-shell structure are a variety of.
Specifically, solvent of the present invention can be but be not limited to normal octane, isooctane, toluene, benzene, chlorobenzene, dimethylbenzene,
Chloroform, acetone, hexamethylene, n-hexane, pentane, isopentane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- first
Base pyrrolidones, dimethyl sulfoxide, hexamethyl phosphoramide, n-butyl ether, methyl phenyl ethers anisole, phenetole, acetophenone, aniline, diphenyl ether etc.
One of or it is a variety of.
Specifically, the above-mentioned solwution method of the present invention can be but be not limited to spin-coating method, dip-coating method, impact system, print process,
One of ink-jet method, spray coating method, roll coating process, knife coating, casting method, strike, slit coating method, strip rubbing method
Or it is a variety of.
Specifically, substrate of the present invention can be rigid substrate or flexible substrate, wherein the rigid substrate can be
But one of it is not limited to glass, metal foil or a variety of；The flexible substrate can be but be not limited to poly terephthalic acid second
Diol ester (PET), ethylene glycol terephthalate (PEN), polyether-ether-ketone (PEEK), polystyrene (PS), polyether sulfone (PES),
Polycarbonate (PC), poly- aryl acid esters (PAT), polyarylate (PAR), polyimides (PI), polyvinyl chloride (PVC), polyethylene
(PE), one of polyvinylpyrrolidone (PVP), textile fabric or a variety of.
Specifically, functional layer of the present invention can pass for conductive glass layer, metal electrode layer, hole injection layer, hole
Defeated layer, hole blocking layer, electron transfer layer, electron injecting layer, electronic barrier layer, electrode modification layer, one in isolated protective layer
Kind is a variety of；Wherein, the conductive glass layer can be but be not limited to indium doping tin oxide (ITO), fluorine-doped tin oxide
(FTO), one of antimony-doped tin oxide (ATO), aluminium-doped zinc oxide (AZO) or a variety of.
Specifically, organometallic complex of the present invention is active and volatile organometallic complex, Ke Yiwei
But it is not limited to alkyl aluminum, lithium alkylide, alkyl indium, alkyl gallium, alkyl cadmium, alkyl tellurium, alkyl magnesium, zinc alkyl, amido lithium, aryl lithium
One of or it is a variety of；More specifically, the organometallic complex can be but be not limited to trimethyl aluminium, triethyl aluminum, three
Aluminium isobutyl, diethyl zinc, lithium methide, ethyl-lithium, butyl lithium, three chloromethane lithiums, vinyl lithium, cyclopropyl lithium, phenyl lithium, diformazan
Base zinc, diethyl zinc, dimethyl cadmium, diethyl cadmium, tellurium diethyl, diisopropyl tellurium, trimethyl gallium, triethyl-gallium, trimethyl
Indium, dimethyl ethyl indium, antimony triethyl, diamyl magnesium, dimethyl diamyl magnesium, dimethylethyl amine match one of aluminium alkane or more
Kind.The above-mentioned organometallic complex of the present invention can react with ligand as described above.
A kind of quantum dot of the invention is crosslinked luminescent layer, wherein the quantum dot crosslinking luminescent layer is using any institute as above
The preparation method for the quantum dot crosslinking luminescent layer stated is prepared.It is equal that the present invention prepares resulting quantum dot crosslinking luminescent layer covering
It is even, thickness is uniform, quality of forming film is high；It is used in QLED device, can effectively improve the uniformity of luminance of QLED device, shine
Efficiency and stability.
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of QLED device of the invention, as shown, it is wrapped
It includes:
Step S100, hole injection layer and hole transmission layer are sequentially prepared on the substrate containing anode；
Step S200, quantum dot crosslinking luminescent layer as described above is prepared on the hole transport layer；
Step S300, it is sequentially prepared electron transfer layer and cathode on quantum dot crosslinking luminescent layer, obtains QLED device.
A kind of QLED device preferred embodiment of the invention, successively includes: the substrate containing anode, hole from bottom to top
Implanted layer, hole transmission layer, quantum dot as described above crosslinking luminescent layer, electron transfer layer and cathode.The present invention is as described above
Quantum dot crosslinking luminescent layer in QLED device, manufactured QLED device not only uniformity of luminance with higher and stabilization
Property, also there is high luminous efficiency and luminescent lifetime.
Specifically, substrate of the present invention can be rigid substrate or flexible substrate, wherein the rigid substrate can be
But one of it is not limited to glass, metal foil or a variety of；The flexible substrate can be but be not limited to poly terephthalic acid second
Diol ester (PET), ethylene glycol terephthalate (PEN), polyether-ether-ketone (PEEK), polystyrene (PS), polyether sulfone (PES),
Polycarbonate (PC), poly- aryl acid esters (PAT), polyarylate (PAR), polyimides (PI), polyvinyl chloride (PVC), polyethylene
(PE), one of polyvinylpyrrolidone (PVP), textile fabric or a variety of.
Specifically, anode of the present invention can be selected from indium doping tin oxide (ITO), fluorine-doped tin oxide (FTO), Sb doped
One of tin oxide (ATO), aluminium-doped zinc oxide (AZO) etc. are a variety of.
Specifically, hole injection layer of the present invention can be poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid
(PEDOT:PSS), CuPc (CuPc), tetra- cyanogen quinone of 2,3,5,6- tetra- fluoro- 7,7', 8,8'--bismethane (F4-TCNQ), 2,3,6,
Six cyano -1,4,5,8,9,12- of 7,10,11-, six azepine benzophenanthrene (HATCN), is mixed doped or non-doped transition metal oxide
One of miscellaneous or undoped metal chalcogenide is a variety of；Wherein, the transition metal oxide can be but be not limited to
MoO3、VO2、WO3、CrO3, one of CuO or their mixture or a variety of；The metal chalcogenide can be but not
It is limited to MoS2、MoSe2、WS2、WSe2, one of CuS or their mixture or a variety of.
Specifically, the material of hole transmission layer of the present invention can be selected from the organic material with cavity transmission ability, can
Think but be not limited to poly- (9,9- dioctyl fluorene-CO-N- (4- butyl phenyl) diphenylamines) (TFB), polyvinylcarbazole (PVK), gather
(bis- bis- (phenyl) benzidine of (4- butyl phenyl)-N, N'- of N, N') (poly-TPD), it is poly- (double-N of 9,9- dioctyl fluorene -co-,
N- phenyl -1,4- phenylenediamine) (PFB), 4,4 ', 4 ' '-three (carbazole -9- base) triphenylamine (TCTA), 4,4'- bis- (9- carbazole) connection
Benzene (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, C60 or theirs is mixed
Close one of object or a variety of.The hole transport layer material is further selected from the inorganic material with cavity transmission ability, can be with
For but be not limited to NiO, MoO3、VO2、WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2, in CuS or their mixture one
Kind is a variety of.
Specifically, the material of electron transfer layer of the present invention can be but be not limited to N-shaped ZnO, TiO2、SnO2、Ta2O3、
AlZnO、Zn2SnO4、InSnO2、Alq3、Ca、Ba、CsF、LiF、CsCO3One of or it is a variety of；Preferably, the electronics passes
Defeated layer is N-shaped ZnO, N-shaped TiO2。
Specifically, cathode of the present invention can be but be not limited to various conductive carbon materials, conductive metal oxide material,
One of metal material is a variety of；Wherein conductive carbon material can be but be not limited to doped or non-doped carbon nanotube, doping
Or undoped graphene, doped or non-doped graphene oxide, C60, graphite, carbon fiber, in more empty carbon or their mixture
It is one or more；Conductive metal oxide material can be but be not limited in ITO, FTO, ATO, AZO or their mixture
It is one or more；Metal material can be but be not limited to one of Al, Ag, Cu, Mo, Au or their alloy or a variety of；
Wherein in the metal material, form can be but be not limited to dense film, nano wire, nanosphere, nanometer rods, nanocone,
One of nano-hollow ball or their mixture are a variety of；Preferably, the cathode is Ag or Al.
Specifically, QLED device of the present invention with partial encapsulation, full encapsulation or can not encapsulate.
Specifically, the preparation method of above layers of the present invention can be chemical method or physical method, and wherein chemical method can be
But it is not limited to sol-gel method, chemical bath deposition method, chemical vapour deposition technique, hydro-thermal method, coprecipitation, electrochemical deposition method
One of or it is a variety of；Physical method can be but be not limited to thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering method,
One of multi-arc ion coating embrane method, electrolysis method, method of electrostatic spinning are a variety of.
It should be noted that the present invention is not limited to the QLED devices of above structure, can also further comprise interfactial work ergosphere or
One of interface-modifying layer, including but not limited to electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer or
It is a variety of.
It should be noted that reciprocal form structure can also be prepared the present invention is not limited to prepare above-mentioned autologous QLED device
QLED device.And the QLED device of reciprocal form structure can also further comprise interfactial work ergosphere or interface-modifying layer, including but not
It is limited to one of electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer or a variety of.
A kind of illuminating module of the invention, wherein including QLED device as described above.
A kind of display device of the invention, wherein including illuminating module as described above.
Below by embodiment, the present invention is described in detail.
Embodiment 1
The preparation step of QLED device is as follows:
One layer of PEDOT:PSS film of spin coating is as hole injection layer on ITO substrate；
One layer of PVK of spin coating is as hole transmission layer on PEDOT:PSS layer；
The CdSe@ZnS of spin coating layer of surface cladding mercaptopropionic acid (MPA) ligand is as quantum dot light emitting layer on PVK layer；
Then, the CdSe@ZnS of surface cladding mercaptopropionic acid (MPA) ligand of above-mentioned preparation is placed in vacuum cavity,
It is passed through trimethyl aluminium ((CH3)3Al) gas, wherein inside cavity pressure is 0.05 mbar, and the partial pressure of trimethylaluminum gas is
0.01 mbar, inside cavity temperature are 16 °C, and the processing time is 5 min, and after treatment is taken out, and obtain quantum dot crosslinking hair
Photosphere；
Then, above-mentioned preparation quantum dot crosslinking luminescent layer on spin coating layer of ZnO as electron transfer layer；
Finally, one layer of Al is deposited in ZnO layer, QLED device is obtained.Wherein, the cross-linking process schematic diagram of the present embodiment is shown in
The structural schematic diagram of Fig. 2, QLED device is shown in Fig. 3,1 is ITO substrate in Fig. 3,2 is PEDOT:PSS layers, 3 is PVK layers, 4 amounts of being
Son point crosslinking luminescent layer, 5 be ZnO layer, 6 be Al layers.
Embodiment 2
The preparation step of QLED device is as follows:
One layer of PEDOT:PSS film of spin coating is as hole injection layer on ITO substrate；
Hole transmission layer is used as one layer TFB layers of spin coating on PEDOT:PSS layer；
The CdSe@ZnS of spin coating layer of surface cladding mercaptopropionic acid (MPA) ligand is as quantum dot light emitting layer on TFB layer；
Then, the CdSe@ZnS of surface cladding mercaptopropionic acid (MPA) ligand of above-mentioned preparation is placed in vacuum cavity,
It is passed through trimethyl aluminium ((CH3)3Al) gas, wherein inside cavity pressure is 0.05 mbar, and the partial pressure of trimethylaluminum gas is
0.02 mbar, inside cavity temperature are 18 °C, and the processing time is 10 min, and after treatment is taken out, and obtain quantum dot crosslinking
Luminescent layer；
Then, above-mentioned preparation quantum dot crosslinking luminescent layer on spin coating layer of ZnO as electron transfer layer；
Finally, one layer of Al is deposited in ZnO layer, QLED device is obtained.
Embodiment 3
The preparation step of QLED device is as follows:
One layer of PEDOT:PSS film of spin coating is as hole injection layer on ITO substrate；
One layer of TFB of spin coating is as hole transmission layer on PEDOT:PSS layer；
The CdSe@ZnS of spin coating layer of surface oleic acid-coated (OA) ligand is as quantum dot light emitting layer on TFB layer；
Then, the CdSe@ZnS of coated with oleic acid (OA) ligand of above-mentioned preparation is placed in vacuum cavity, is passed through
Triethyl aluminum ((CH3CH2)3Al) gas, wherein inside cavity pressure is 0.05 mbar, and the partial pressure of triethyl aluminum gas is 0.01
Mbar, inside cavity temperature are 18 °C, and the processing time is 20 min, and after treatment is taken out, and obtain quantum dot crosslinking and shine
Layer；
Then, above-mentioned preparation quantum dot crosslinking luminescent layer on spin coating layer of ZnO as electron transfer layer；
Finally, one layer of Al is deposited in ZnO layer, QLED device is obtained.
Embodiment 4
The preparation step of QLED device is as follows:
One layer of PEDOT:PSS film of spin coating is as hole injection layer on ITO substrate；
One layer of PVK of spin coating is as hole transmission layer on PEDOT:PSS layer；
The CdSe@CdS of layer of surface cladding thioacetic acid (TGA) ligand is printed on PVK layer as quantum dot light emitting layer；
Then, the CdSe@CdS layer of surface cladding thioacetic acid (TGA) ligand of above-mentioned preparation is placed in vacuum cavity,
It is passed through triethyl aluminum ((CH3CH2)3Al) gas, wherein inside cavity pressure is 0.05 mbar, and the partial pressure of triethyl aluminum gas is
0.01 mbar, inside cavity temperature are 18 °C, and the processing time is 20 min, and after treatment is taken out, and obtain quantum dot crosslinking
Luminescent layer；
Then, above-mentioned preparation quantum dot crosslinking luminescent layer on spin coating layer of ZnO as electron transfer layer；
Finally, one layer of Al is deposited in ZnO layer, QLED device is obtained.
Embodiment 5
The preparation step of QLED device is as follows:
One layer of PEDOT:PSS film of spin coating is as hole injection layer on ITO substrate；
Hole transmission layer is used as one layer PVK layers of spin coating on PEDOT:PSS layer；
The CdSe@CdS of layer of surface cladding dihydrolipoic acid (DHLA) ligand is printed on PVK layer as quantum dot light emitting
Layer；
Then, the CdSe@CdS layer of surface cladding dihydrolipoic acid (DHLA) ligand of above-mentioned preparation is placed in vacuum cavity
In, it is passed through triethyl aluminum ((CH3CH2)3Al) gas, wherein inside cavity pressure is 0.1 mbar, the partial pressure of triethyl aluminum gas
For 0.02 mbar, inside cavity temperature is 18 °C, and the processing time is 30 min, and after treatment is taken out, and obtains quantum dot friendship
Join luminescent layer；
Then, above-mentioned preparation quantum dot crosslinking luminescent layer on spin coating layer of ZnO as electron transfer layer；
Finally, one layer of Al is deposited in ZnO layer, QLED device is obtained.
In conclusion a kind of quantum dot crosslinking luminescent layer provided by the invention and QLED device and preparation method, luminous mould
Group and display device.The present invention is placed on quantum dot light emitting prepared by solwution method in volatile organo-metallic compound atmosphere,
The organo-metallic compound vivaciously and easily hydrolyzed reacts after gasifying with quantum dot surface organic ligand abundant, makes point
Not independent quantum dot is crosslinked together, and the quantum dot after formation gas phase is cementing is crosslinked luminescent layer.In the present invention, organic metal
On the one hand the effect of compound is to be crosslinked quantum dot with ligand together, improve quality of forming film, make institute at quantum dot film not
Only uniform ground, and film layer is stablized, it is difficult to and solvent when being deposited by subsequent other function layer, which re-dissolves, to be taken away or washes away, and is had
Effect ground improves the uniformity of luminance and stability of QLED device, and on the other hand, the introducing of organo-metallic compound can be effectively
It is passivated quantum dot surface defect, improves the luminous efficiency and luminescent lifetime of quantum dot device.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (17)
1. a kind of preparation method of quantum dot crosslinking luminescent layer, which is characterized in that comprising steps of
The quantum dot dissolution that surface is coated with ligand in a solvent, obtains quantum dot solution；
Quantum dot solution is deposited, quantum dot light emitting layer is obtained；
Resulting quantum dot light emitting is placed in vacuum cavity, organometallic complex is passed through, carries out crosslinking Treatment, the amount of obtaining
Son point crosslinking luminescent layer.
2. the preparation method of quantum dot crosslinking luminescent layer according to claim 1, which is characterized in that the ligand is organic
Ligand.
3. the preparation method of quantum dot according to claim 2 crosslinking luminescent layer, which is characterized in that the organic ligand is
It is thioacetic acid, mercaptopropionic acid, mercaptobutyric acid, sulfydryl oleic acid, mercapto glycerol, glutathione, mercaptoethylmaine, sulfydryl oleyl amine, three pungent
One of base phosphine, trioctyl phosphine oxide, oleic acid, amino acid, alkyl acid, alkylamine, sulfonic acid, mercaptan are a variety of.
4. the preparation method of quantum dot crosslinking luminescent layer according to claim 1, which is characterized in that the ligand is inorganic
Ligand.
5. the preparation method of quantum dot according to claim 4 crosslinking luminescent layer, which is characterized in that the mineral ligand is
Cl-、Br-、S2-、HS-、SnS4 4-、Sn2S6 4-、ZnCl4 2-、Zn(OH)4 2-One of or it is a variety of.
6. the preparation method of quantum dot according to claim 1 crosslinking luminescent layer, which is characterized in that the quantum dot is
One in II-V compound semiconductor, Group III-V compound semiconductor, group IV-VI compound semiconductor and its core-shell structure
Kind is a variety of.
7. the preparation method of quantum dot crosslinking luminescent layer according to claim 1, which is characterized in that the solvent is positive pungent
Alkane, isooctane, toluene, benzene, chlorobenzene, dimethylbenzene, chloroform, acetone, hexamethylene, n-hexane, pentane, isopentane, N, N- diformazan
Base formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide, n-butyl ether, benzene first
One of ether, phenetole, acetophenone, aniline, diphenyl ether are a variety of.
8. the preparation method of quantum dot crosslinking luminescent layer according to claim 1, which is characterized in that the organometallic ligand
Conjunction object is alkyl aluminum, in lithium alkylide, alkyl indium, alkyl gallium, alkyl cadmium, alkyl tellurium, alkyl magnesium, zinc alkyl, amido lithium, aryl lithium
It is one or more.
9. the preparation method of quantum dot crosslinking luminescent layer according to claim 1, which is characterized in that the crosslinking Treatment
Time is 0.5~30min.
10. the preparation method of quantum dot crosslinking luminescent layer according to claim 1, which is characterized in that the inside cavity
Pressure be 0.01~1mbar.
11. the preparation method of quantum dot crosslinking luminescent layer according to claim 1, which is characterized in that organic metal cooperation
Partial pressure of the object after gasifying is 0.001~0.1mbar.
12. the preparation method of quantum dot crosslinking luminescent layer according to claim 1, which is characterized in that the temperature of inside cavity
Degree is 10~25 DEG C.
13. a kind of quantum dot is crosslinked luminescent layer, which is characterized in that the quantum dot crosslinking luminescent layer use as claim 1~
The preparation method of 12 any quantum dot crosslinking luminescent layers is prepared.
14. a kind of QLED device, which is characterized in that including what is be arranged between anode and cathode and the anode and the cathode
Quantum dot as prepared by the preparation method of the described in any item quantum dot crosslinking luminescent layers of claim 1~12 is crosslinked luminescent layer.
15. QLED device according to claim 14, which is characterized in that further include being handed in the anode and the quantum dot
The hole injection layer and hole transmission layer that are arranged between connection luminescent layer, and quantum dot crosslinking luminescent layer and the cathode it
Between the electron transfer layer that is arranged, the hole transmission layer and quantum dot crosslinking luminescent layer overlapping.
16. a kind of illuminating module, which is characterized in that including the QLED device as described in claim 14~15 is any.
17. a kind of display device, which is characterized in that including illuminating module as claimed in claim 16.
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| PCT/CN2017/099079 WO2018113334A1 (en) | 2016-12-22 | 2017-08-25 | Quantum dot light-emitting layer and component, manufacturing method, light-emitting module, and display device |
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| CN106531860B (en) * | 2016-12-22 | 2019-10-11 | Tcl集团股份有限公司 | Quantum dot light emitting layer and device and preparation method, illuminating module and display device |
| CN109935719A (en) * | 2017-12-15 | 2019-06-25 | Tcl集团股份有限公司 | Quantum dot film and preparation method thereof, QLED device and preparation method thereof |
| CN109935670B (en) * | 2017-12-15 | 2021-03-26 | Tcl科技集团股份有限公司 | Surface ligand, quantum dot film, QLED device and preparation method thereof |
| CN109935724B (en) * | 2017-12-15 | 2020-07-14 | Tcl科技集团股份有限公司 | Quantum dot light-emitting layer and preparation method and application thereof |
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| CN109988573A (en) * | 2017-12-29 | 2019-07-09 | Tcl集团股份有限公司 | Composite quantum dot, quantum dot solid film and its application |
| WO2020048527A1 (en) * | 2018-09-07 | 2020-03-12 | Tcl集团股份有限公司 | Composite material and quantum dot light emitting diode |
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| CN112186118B (en) * | 2020-09-30 | 2023-06-16 | 京东方科技集团股份有限公司 | Quantum dot light emitting device, manufacturing method thereof and display device |
| US20220320453A1 (en) * | 2020-10-28 | 2022-10-06 | Boe Technology Group Co., Ltd. | Hole transport material, quantum dot light-emitting device and manufacturing method thereof, and display apparatus |
| US20220403230A1 (en) * | 2020-10-30 | 2022-12-22 | Beijing Boe Technology Development Co., Ltd. | Quantum dot material and related applications |
| US20230389406A1 (en) * | 2020-12-15 | 2023-11-30 | Boe Technology Group Co., Ltd. | Quantum dot film layer, quantum dot light-emitting device, and fabrication method |
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| CN113572014A (en) * | 2021-07-19 | 2021-10-29 | 南通大学 | Preparation method of all-inorganic semiconductor quantum dot laser |
| CN115700270A (en) * | 2021-07-27 | 2023-02-07 | 北京京东方技术开发有限公司 | Quantum dot film and preparation method thereof, photoelectric device, display device and preparation method of quantum dot light-emitting device |
| CN113644213A (en) * | 2021-08-13 | 2021-11-12 | 合肥福纳科技有限公司 | Quantum dot light-emitting device and preparation method thereof |
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