CN109935736A - Quantum dot film and preparation method thereof, QLED device and preparation method thereof - Google Patents
Quantum dot film and preparation method thereof, QLED device and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technology of quantum dots field more particularly to a kind of quantum dot film and preparation method thereof and a kind of QLED devices and preparation method thereof.The preparation method of the quantum dot film includes the following steps: that offer quantum dot performed thin film and the solution containing mineral ligand, the quantum dot in the quantum dot performed thin film contain initial surface ligand；The quantum dot performed thin film and the solution containing mineral ligand are subjected to the displacement of liquid phase ligand, obtain quantum dot surface in conjunction with the quantum dot film of the mineral ligand.The present invention can not only be passivated the place that quantum dot surface organic ligand cannot be passivated, and improve the transmission of carrier, final to improve device overall performance.
Description
Technical field
The invention belongs to technology of quantum dots fields more particularly to a kind of quantum dot film and preparation method thereof, and one kind
QLED device and preparation method thereof.
Background technique
Light emitting diode with quantum dots (Quantum dot light-emitting diode, QLED) is a kind of novel
Luminescent device, uses quanta point material (Quantum dots, QDs) as luminescent layer, has hardly possible compared to other luminescent materials
With internal quantum efficiency, the excellent excitation purity of the advantage of analogy, such as controllable small-size effect, superelevation, skill will be shown in future
Art field has huge application prospect.
Under normal circumstances, quantum dot surface can connect organic ligand by modes such as chelatings.The surface ligand of quantum dot exists
Play the role of in quantum dot synthesis vital, on the one hand, surface ligand can be passivated the defect of quantum dot surface, improve quantum
The luminescent properties of point；On the other hand, surface ligand can reduce between quantum dot and reunite, and increase point of quantum dot in a solvent
The ability of dissipating.In light emitting diode with quantum dots device, surface ligand can further influence the photoelectricity performance of device, therefore rationally
The ligand of quantum dot surface in selection quantum dot film is the weight for improving quantum dot film and light emitting diode with quantum dots luminous efficiency
Want step.Currently, the ligand overwhelming majority of quantum dot is organic molecule, containing longer carbochain, conductivity is lower, one
The transmission that device inside carrier is influenced in degree is determined, to reduce device performance.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of quantum dot film and its preparation side are provided
Method, it is intended to solve the sedimentation easy to reunite of ligand in existing quantum dot membrane-film preparation process, selectively be restricted, so that obtaining quantum
The technical issues of putting bad uniformity of film, low efficiency.
Another object of the present invention is to provide a kind of QLED device containing above-mentioned quantum dot film and preparation method thereof,
Display screen.
For achieving the above object, The technical solution adopted by the invention is as follows:
On the one hand, the present invention provides a kind of preparation method of quantum dot film, comprising the following steps:
Quantum dot performed thin film and the solution containing mineral ligand are provided, the quantum dot in the quantum dot performed thin film contains
There is initial surface ligand；
The quantum dot performed thin film and the solution containing mineral ligand are subjected to the displacement of liquid phase ligand, obtain quantum
Quantum dot film of the point surface in conjunction with the mineral ligand.
Correspondingly, a kind of quantum dot film, the quantum dot film are obtained by above-mentioned preparation method.
On the other hand, the present invention provides a kind of QLED device, including the hearth electrode, quantum dot light emitting layer and top being stacked
Electrode, the quantum dot light emitting layer are the quantum dot film that above-mentioned preparation method obtains.
Correspondingly, a kind of preparation method of QLED device, comprising the following steps:
Hearth electrode is provided；
Quantum dot performed thin film is prepared on the hearth electrode；
According to the preparation method of above-mentioned quantum dot film, quantum dot performed thin film is prepared into quantum dot film, the amount of obtaining
Son point luminescent layer；
Top electrode is prepared on the quantum dot light emitting layer；
Wherein, the hearth electrode is anode, and the top electrode is cathode；Or the hearth electrode is cathode, the top electrode
For anode.
Preferably, the present invention provides a kind of display screen, including above-mentioned QLED device.
The preparation method of quantum dot film provided by the invention is to carry out ligand displacement in situ again after quantum dot film forming,
The ligand introduced in quantum dot synthesis process is replaced as the smaller mineral ligand of volume, on the one hand since its volume is far smaller than
Organic ligand can be passivated the place that quantum dot surface organic ligand cannot be passivated, to more effectively be passivated the table of quantum dot
Planar defect；On the other hand, also due to the volume and steric hindrance of mineral ligand are far smaller than organic ligand, this make quantum dot it
Between the smaller interval that (is especially formed after quantum dot film), i.e. the distance between quantum dot is shorter, to reduce carrier
Transmission range, and then improve the transmission of carrier, it is final to realize the effect for improving device overall performance.When quantum dot solution is logical
Cross film-forming process formed quantum dot performed thin film after, the arrangement of quantum dot and position are substantially stationary, at this time again with mineral ligand into
The problem of solution sedimentation would not occur in the displacement of row ligand；Moreover, the solvent selectivity for displaced ligands is more, the selection of ligand
Range can be wider, has preferable selection flexibility, scale and industrialized production may be implemented.
Quantum dot film provided by the invention, since ligand displacement mineral ligand in situ is carried out after quantum dot forms a film again,
The bad problem of quantum dot film uniformity can be obtained to avoid existing preparation method；Due to the volume and space bit of mineral ligand
Resistance is far smaller than organic ligand, the place that quantum dot surface organic ligand cannot be passivated can be passivated, to more effectively be passivated
The surface defect of quantum dot；Meanwhile the smaller interval (especially formed after quantum dot film) between quantum dot, i.e. quantum dot
The distance between it is shorter, to reduce the transmission range of carrier, and then improve the transmission of carrier, final realize improves device
The effect of overall performance.
QLED device provided by the invention, display screen, include the quantum dot film prepared by the above method.Due to
Ligand displacement in situ is carried out after quantum dot film forming again and introduces the smaller mineral ligand of volume, reduces the transmission distance of carrier in this way
From, and then the transmission of carrier is improved, it is final to realize the effect for improving device overall performance.
The preparation method of QLED device provided by the invention, on the basis of QLED device customary preparation methods, use is molten
Liquid method carries out surface ligand displacement to quantum dot performed thin film and introduces mineral ligand, not only simple process, but also is conducive to improve
The photoelectric properties of QLED device.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, 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.
On the one hand, the embodiment of the invention provides a kind of preparation methods of quantum dot film, comprising the following steps:
S01: quantum dot performed thin film and the solution containing mineral ligand, the quantum dot in the quantum dot performed thin film are provided
Contain initial surface ligand；
S02: the quantum dot performed thin film and the solution containing mineral ligand are subjected to the displacement of liquid phase ligand, obtained
Quantum dot film of the quantum dot surface in conjunction with the mineral ligand.
The preparation method of quantum dot film provided in an embodiment of the present invention is to carry out ligand in situ again after quantum dot film forming
Displacement, is replaced as the smaller mineral ligand of volume for the ligand introduced in quantum dot synthesis process, on the one hand since its volume is remote
Much smaller than organic ligand, it can be passivated the place that quantum dot surface organic ligand cannot be passivated, to more effectively be passivated quantum
The surface defect of point；On the other hand, also due to the volume and steric hindrance of mineral ligand are far smaller than organic ligand, this amount of making
The smaller interval (especially formed after quantum dot film) between son point, i.e. the distance between quantum dot is shorter, to reduce
The transmission range of carrier, and then the transmission of carrier is improved, it is final to realize the effect for improving device overall performance.Work as quantum dot
After solution forms quantum dot performed thin film by film-forming process, the arrangement of quantum dot and position are substantially stationary, at this time again with inorganic
Ligand, which carries out ligand displacement, the problem of solution sedimentation would not occurs；Moreover, the solvent selectivity for displaced ligands is more, ligand
Range of choice can be wider, there is preferable selection flexibility, scale and industrialized production may be implemented.
The self stability of quantum dot generally is improved using normal ligand in quantum dot synthesis process and is guaranteed in a solvent
Good dispersion.When directly carrying out ligand exchange in quantum dot solution, selected ligand structure and type receive biggish
Limitation cannot use bridging property ligand (to connect simultaneously for example, ligand used in solution ligand exchange can only be single ligand
Meet 2 or more QD) because being added after such ligand between quantum dot or being connected with each other in the solution, and then roll into a ball poly and poly
It is heavy.Simultaneously as quantum dot is more in solution, solution generates the insufficient situation of ligand exchange.In addition, can have a problem that
It is exactly that new for displacement there is a situation where to be dissolved in former quantum dot solution with cognition, and the selectivity of ligand is big at this time
It is big to reduce.And after quantum dot solution forms quantum dot layer by film-forming process, the arrangement of quantum dot and position are substantially stationary, this
Shi Zaiyong mineral ligand, which carries out ligand displacement, the problem of solution sedimentation would not occurs.In addition, being used for the molten of the new ligand of displacement
Agent selectively can be mostly very much, and the range of choice of ligand can be wider.After quantum dot film forming, ligand displacement in situ is carried out
The ligand introduced in quantum dot synthesis process is replaced as to the table customized according to film or light emitting diode with quantum dots requirement on devices
Face ligand, to improve the photoelectric properties of quantum dot film or light emitting diode with quantum dots device.
Further, in above-mentioned steps S01, the mineral ligand includes SnS4 4-、Sn2S6 4-、SnTe4 4-、AsS3 3-、
MoS4 2-、In2Se4 2-、CN-、SCN-、S2-、P3-、F-、Cl-、Br-、I-At least one of.These mineral ligand volumes are far smaller than
Organic ligand can not only be passivated the place that quantum dot surface organic ligand cannot be passivated, and can effectively be passivated the table of quantum dot
Planar defect；And it is shorter the distance between to make quantum dot, to reduce the transmission range of carrier, and then improves the biography of carrier
It is defeated, it is final to realize the effect for improving device overall performance.
Further, it is the ionic compound for containing following structural formula containing mineral ligand in above-mentioned steps S01:
AxBy
Wherein, A includes Li+、Na+、K+、NH4 +、N2H5 +、TMS2+At least one of, B be the mineral ligand (i.e.
SnS4 4-、Sn2S6 4-、SnTe4 4-、AsS3 3-、MoS4 2-、In2Se4 2-、CN-、SCN-、S2-、P3-、F-、Cl-、Br-、I-In at least one
Kind), x and y are the anion and cationic proportion obtained according to charge balance.Such as (NH4)2In S, x 2, y 1.It will be above-mentioned
It is the solution containing mineral ligand that selectable ionic compound, which is dissolved in ionic compound solution obtained in solvent,.
Further, in above-mentioned steps S01, the solvent for dissolving above-mentioned ionic compound can be organic solvent；Specifically
Ground, organic solvent include but is not limited to saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbon, alcohols solvent, ether solvent, ketones solvent, nitrile
The mixed organic solvents of one of solvent, esters solvent and their derivative either a variety of compositions.Wherein, described
Organic solvent includes but is not limited to hexane, hexamethylene, heptane, normal octane, isooctane, pentane, methylpentane, ethylpentane, ring
Pentane, methyl cyclopentane, ethyl cyclopentane, benzene,toluene,xylene, ethylbenzene, methylene chloride, chloroform, carbon tetrachloride, two
Chloroethanes, trichloroethanes, chloropropane, dichloropropane, trichloropropane, chlorobutane, methylene bromide, bromoform, bromoethane, bromine third
Alkane, iodomethane, chlorobenzene, bromobenzene, benzyl chloride, benzyl bromide, benzotrifluoride, methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol,
Sec-butyl alcohol, the tert-butyl alcohol, amylalcohol, isoamyl alcohol, tert-pentyl alcohol, cyclohexanol, octanol, benzylalcohol, ethylene glycol, phenol, o-cresol, ether, benzene
Methyl ether, phenetole, diphenyl ether, tetrahydrofuran, glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol diethyl ether, ethoxy ether,
Propylene glycol monopropyl ether, glycol monobutyl ether, acetaldehyde, benzaldehyde, acetone, butanone, cyclohexanone, acetophenone, formic acid, acetic acid,
Ethyl acetate, diethy-aceto oxalate, diethyl malonate, propyl acetate, methyl propyl ester, butyl acetate, methyl amyl acetate, nitro
Benzene, acetonitrile, diethylamine, triethylamine, aniline, pyridine, picoline, ethylenediamine, N,N-dimethylformamide, N, N- dimethyl second
Amide, N-Methyl pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide, carbon disulfide, methyl sulfide, ethyl sulfide, dimethyl sulfoxide,
At least one of mercaptan, ethyl mercaptan, methoxyl group tetrahydrofuran.
Further, the initial surface ligand that the quantum dot in the quantum dot performed thin film contains, including but not limited to
Tetradecene, hexadecylene, octadecylene, octadecylamine, octadecenic acid, trioctylamine, trioctylphosphine oxide (TOPO), tri octyl phosphine, octadecyl
At least one of phosphonic acids, 9- octadecenyl amine, mercaptoundecylic acid.Quantum dot in the quantum dot performed thin film is II-VI group
Compound, III-V compound, II-V compounds of group, III-VI compound, group IV-VI compound, I-III-VI race chemical combination
One of object, II-IV-VI compounds of group or IV race simple substance are a variety of.Specifically, II-VI group compound (the semiconductor material
Material) it include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, but not limited to this, also
It can be the II-VI group compound of other binary, ternary, quaternary；The nanocrystalline of III-V compound (semiconductor material) include
But it is not limited to GaP, GaAs, InP, InAss, but not limited to this, it can also be the III-V chemical combination of other binary, ternary, quaternary
Object.As a kind of preferred implementation situation, the quantum dot is doped or non-doped inorganic Ca-Ti ore type semiconductor, and/or has
Machine-inorganic hybridization Ca-Ti ore type semiconductor.Specifically, the inorganic Ca-Ti ore type semiconductor structure general formula is AMX3, wherein
A is Cs+Ion, M are divalent metal, including but not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、
Fe2+、Ge2+、Yb2+、Eu2+, X is halide anion, including but not limited to Cl-、Br-、I-.The hybrid inorganic-organic perovskite
Type semiconductor structure general formula is BMX3, wherein B is organic amine cation, including but not limited to CH3(CH2)n-2NH3 +(n≥2)
Or NH3(CH2)nNH3 2+(n≥2).As n=2, inorganic metal hal ide octahedron MX6 4-It is connected by way of total top, metal
Cationic M is located at the octahedral body-centered of halogen, and organic amine cation B is filled in the gap between octahedron, forms unlimited extend
Three-dimensional structure；As n > 2, the inorganic metal hal ide octahedron MX that is connected in a manner of total top6 4-Extend in two-dimensional directional
Form layer structure, Intercalation reaction organic amine cation bilayer (protonation monoamine) or organic amine cation monolayer
(protonation diamine), organic layer and inorganic layer mutually overlap and form stable two-dimensional layered structure；M is divalent metal,
Including but not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, X be halogen yin from
Son, including but not limited to Cl-、Br-、I-。
Further, in above-mentioned steps S02, the process of the liquid phase ligand displacement are as follows: the quantum dot is prefabricated thin
Film, which is placed in the solution, carries out immersion treatment.Preferably, the time of immersion treatment is 5-20min.In the soaking time range
It is interior, mineral ligand can be made preferably to replace quantum dot initial surface ligand.In a preferred embodiment, immersion treatment is best
Time is 10min.
Further, in the preparation method of above-mentioned quantum dot film, after the liquid phase ligand displacement, further including will be described
Quantum dot performed thin film, which is placed in vacuum plant, to be vacuum-treated, and the vacuum degree of the vacuum processing is 5-20Pa.Further
Preferably, the time of vacuum processing is after 20-40min mineral ligand is replaced, to carry out vacuumize Deng post processing modes, cannot be simple
Be interpreted as being dried in vacuo, quantum dot film layer has been drying regime in fact, the purpose vacuumized be in quantum dot film,
Ligand that is loosely organized or having neither part nor lot in coordination removes, and finally obtains a more stable quantum dot film.
Correspondingly, the embodiment of the invention also provides a kind of quantum dot films, and the quantum dot film is by above-mentioned preparation side
Method obtains.The quantum dot film can be to avoid existing due to carrying out ligand displacement mineral ligand in situ again after quantum dot forms a film
Preparation method obtains the bad problem of quantum dot film uniformity；Since the volume and steric hindrance of mineral ligand far smaller than have
Machine ligand can be passivated the place that quantum dot surface organic ligand cannot be passivated, to more effectively be passivated the surface of quantum dot
Defect；Meanwhile the smaller interval (especially formed after quantum dot film) between quantum dot, i.e. the distance between quantum dot are more
It is short, to reduce the transmission range of carrier, and then the transmission of carrier is improved, it is final to realize the effect for improving device overall performance
Fruit.
On the other hand, the embodiment of the invention also provides a kind of QLED devices, including hearth electrode, the quantum dot being stacked
Luminescent layer and top electrode, wherein the quantum dot light emitting layer is the quantum dot film prepared by the above method.
QLED device provided in an embodiment of the present invention introduces body due to carrying out ligand displacement in situ again after quantum dot forms a film
The smaller mineral ligand of product reduces the transmission range of carrier in this way, and then improves the transmission of carrier, and final realize is improved
The effect of device overall performance.
Specifically, in QLED device after quantum dot film forming, ligand exchange in situ is carried out to quantum dot film, by quantum
The surface ligand (such as oleic acid) coated in point synthesis replaces with mineral ligand.One of example are as follows: CdSe/CdS nucleocapsid knot
Structure, general surface ligand can be with Cd (OA)2Form and quantum dot core in nominal price metal ion complexation.The quantum dot forms a film it
Afterwards, if film and such as (NH4)2The contact of S sulfides, can be with Cd (OA)2It chemically reacts, Cd (OA)2+(NH4)2S=CdS
+NH4- OA, so that the OA ligand of quantum dot surface is substituted for inorganic matter.Inorganic surfaces are with the load known from experience in raising quantum dot film
Stream transmission, improves device efficiency.
In the embodiment of the present invention, the QLED device can be eurymeric QLED device, or transoid QLED device.Make
For a kind of implementation situation, the QLED device can be eurymeric QLED device, i.e., the described hearth electrode is anode, and the top electrode is
Cathode.As another implementation situation, the QLED device can be transoid QLED device, i.e., the described hearth electrode is cathode, institute
Stating top electrode is anode.
On the basis of the above embodiments, it is further preferred that the QLED device further includes functionalized modification layer, the function
Energy decorative layer includes at least one of hole injection layer, hole transmission layer, electron injecting layer, electron transfer layer.The hole
Implanted layer, hole transmission layer are arranged between anode and quantum dot light emitting layer, and the electron injecting layer, electron transfer layer setting exist
Between quantum dot light emitting layer and cathode.
Wherein, the quantum dot film is as described above, and in order to save length, details are not described herein again.
The substrate is rigid substrate or flexible substrate, and the rigid substrate includes but is not limited to glass, in metal foil
It is one or more；The flexible substrate includes but is not limited to polyethylene terephthalate (PET), poly terephthalic acid second
Diol ester (PEN), polyether-ether-ketone (PEEK), polystyrene (PS), polyether sulfone (PES), polycarbonate (PC), poly- aryl acid esters
(PAT), polyarylate (PAR), polyimides (PI), polyvinyl chloride (PV), polyethylene (PE), polyvinylpyrrolidone (PVP), spinning
One of textured fiber is a variety of.
The hearth electrode, the top electrode are independently chosen from least one of metal material, carbon material, metal oxide.
Wherein, the metal material includes but is not limited to Al, Ag, Cu, Mo, Au or their alloy；The carbon material includes but unlimited
In one of graphite, carbon nanotube, graphene, carbon fiber or a variety of.The metal oxide is doped or non-doped gold
Belong to oxide, specifically, the blended metal oxide includes but is not limited to indium doping tin oxide as a kind of implementation situation
(ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminium-doped zinc oxide (AZO), Ga-doped zinc oxide
(GZO), one of indium doping zinc oxide (IZO), magnesium doping zinc-oxide (MZO), aluminium doping magnesia (AMO) or a variety of.Make
For another implementation situation, the hearth electrode, the top electrode, which can be independently chosen from transparent metal oxide, contains metal clip
The combination electrode of layer, wherein the transparent metal oxide can be doping transparent metal oxide, or undoped
Transparent metal oxide.The combination electrode includes but is not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/
Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、
TiO2/Ag/TiO2、TiO2/Al/TiO2One of or it is a variety of.It, can be according to different quantum dot light emittings in the embodiment of the present invention
The luminous characteristics of diode, including top emitting device, bottom emitting device, all-transparent device, select different materials hearth electrode and
Top electrode, collocation building have the light emitting diode with quantum dots of different components structure.
The hole injection layer is selected from the organic material with Hole injection capacity.Prepare the hole of the hole injection layer
Including but not limited to poly- (3,4- the ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS) of injection material, CuPc
(CuPc), tetra- cyanogen quinone of 2,3,5,6- tetra- fluoro- 7,7', 8,8'--bismethane (F4-TCNQ), six cyano -1 2,3,6,7,10,11-,
One of six azepine benzophenanthrene (HATCN) of 4,5,8,9,12-, transition metal oxide, transition metal chalcogenide compound are more
Kind.Wherein, the transition metal oxide includes but is not limited to MoO3、VO2、WO3、CrO3, at least one of CuO；The gold
Belonging to chalcogenide compound includes but is not limited to MoS2、MoSe2、WS2、WSe2, at least one of CuS.
The hole transmission layer is selected from the organic material with cavity transmission ability, and including but not limited to poly- (9,9- bis- is pungent
Base fluorenes-CO-N- (4- butyl phenyl) diphenylamines) (TFB), polyvinylcarbazole (PVK), it is poly- (bis- (4- the butyl phenyl)-N of N, N',
Bis- (phenyl) benzidine of N'-) (poly-TPD), poly- (double-N of 9,9- dioctyl fluorene -co-, N- phenyl -1,4- phenylenediamine) (PFB),
4,4 ', 4 "-three (carbazole -9- base) triphenylamines (TCTA), 4,4'- bis- (9- carbazole) biphenyl (CBP), N, N '-diphenyl-N, N ' -
Two (3- aminomethyl phenyl) -1,1 '-biphenyl -4,4 '-diamines (TPD), N, N '-diphenyl-N, N '-(1- naphthalene) -1,1 '-biphenyl -
At least one of 4,4 '-diamines (NPB), doped graphene, undoped graphene, C60.It is described as another embodiment
Hole transmission layer 4 is selected from the inorganic material with cavity transmission ability, including but not limited to doped or non-doped MoO3、VO2、
WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2, at least one of CuS.
The electron transfer layer be selected from electronic transmission performance material, it is however preferred to have electronic transmission performance it is inorganic
Material or organic material, the inorganic material include but is not limited to N-shaped ZnO, TiO2、SnO2、Ta2O3、AlZnO、ZnSnO、
InSnO、Ca、Ba、CsF、LiF、Cs2CO3At least one of；The organic material includes being not limited to Alq3、TPBi、BCP、
At least one of BPhen, PBD, TAZ, OXD-7,3TPYMB, BP4mPy, TmPyPB, BmPyPhB, TQB.
It is further preferred that QLED device described in the embodiment of the present invention further includes interface-modifying layer, the interface-modifying layer
For at least one layer in electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer.
The packaged type of the QLED device can be partial encapsulation, full encapsulation or not encapsulate that the embodiment of the present invention does not have
Stringent limitation.
Correspondingly, the embodiment of the invention provides a kind of preparation methods of QLED device, comprising the following steps:
E01., hearth electrode is provided；
E02. quantum dot performed thin film is prepared on the hearth electrode；
E03. according to the preparation method of above-mentioned quantum dot film, quantum dot performed thin film is prepared into quantum dot film, is obtained
To quantum dot light emitting layer；
E04. top electrode is prepared on the quantum dot light emitting layer,
Wherein, the hearth electrode is anode, and the top electrode is cathode；Or the hearth electrode is cathode, the top electrode
For anode.
The preparation method of QLED device provided in an embodiment of the present invention, on the basis of QLED device customary preparation methods,
Surface ligand displacement is carried out to quantum dot performed thin film using solwution method and introduces inorganic body, not only simple process, but also is conducive to
Improve the photoelectric properties of QLED device.
Specifically, depositing quantum dot film on the hearth electrode in above-mentioned steps E02, quantum dot light emitting layer is prepared, is joined
It is carried out according to the preparation method of the quantum dot film, in order to save length, details are not described herein again.
It preferably, further include the setting functionalized modification layer between quantum dot light emitting layer and electrode, e.g., when hearth electrode is sun
It further include in deposition of hole implanted layer and hole transmission layer before preparing quantum dot light emitting layer when pole, top electrode are cathode
It is at least one layer of；It further include electron transfer layer being deposited on quantum dot light emitting layer, in electron injecting layer before preparing top electrode
It is at least one layer of.It further include deposition electronics before preparing quantum dot light emitting layer when hearth electrode is cathode, top electrode is anode
At least one layer in transport layer, electron injecting layer；It further include the deposition of hole on quantum dot light emitting layer before preparing top electrode
At least one layer in implanted layer and hole transmission layer.
The top electrode, hearth electrode, hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer, Yi Jiliang
The deposition method of son point performed thin film, can be realized, wherein the chemical method includes but is not limited to chemistry with chemical method or physical method
One of vapour deposition process, successive ionic layer adsorption and reaction method, anodizing, strike, coprecipitation are more
Kind；The physical method includes but is not limited to physical coating method or solution processing method, wherein solution processing method includes but is not limited to revolve
Coating, print process, knife coating, dip-coating method, infusion method, spray coating method, roll coating process, casting method, slit coating method, strip apply
Cloth method；Physical coating method includes but is not limited to thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering method, multi sphere ion
One of coating method, physical vaporous deposition, atomic layer deposition method, pulsed laser deposition are a variety of.
And the embodiment of the invention also provides a kind of quantum dot display devices, including above-mentioned QLED device.
Quantum dot display device provided in an embodiment of the present invention, due to containing above-mentioned quantum dot film, it is thus possible to improve
The photoelectric properties of device.
The present invention successively carried out test of many times, and it is further detailed as reference pair invention progress now to lift A partial experiment result
Thin description, is described in detail combined with specific embodiments below.
Embodiment 1
A kind of preparation method of quantum dot film:
CdSe quantum dot performed thin film and mineral ligand solution (i.e. (NH are provided4)2S ethanol solution), the quantum dot is prefabricated thin
Initial surface ligand in film is OA；
Quantum dot performed thin film is immersed in mineral ligand solution, is taken out after impregnating 10min, then be transferred into vacuum
In chamber, adjusts vacuum degree and be 10Pa and maintain 30min, remove the ligand and solvent not being coordinated in quantum dot film.
Embodiment 2
A kind of preparation method of light emitting diode with quantum dots, comprising the following steps:
By (NH4)2S dissolves in ethanol, is configured to mineral ligand solution；
PEDOT hole injection layer, TFB hole transmission layer, CdSe quantum dot film, CdSe are successively printed on ito anode
The surface ligand of quantum dot film is OA, and then quantum dot film is immersed in the ligand solution in step S1, impregnates 10min
After take out, then be transferred into vacuum chamber, adjust vacuum degree and be 10Pa and maintain 30min, remove in quantum dot light emitting layer
The ligand and solvent not being coordinated, obtain quantum dot light emitting layer；
ZnO electron transfer layer is printed on the quantum dot light emitting layer after above-mentioned ligand exchange, last evaporating Al cathode obtains
Eurymeric structure quantum point light emitting diode.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of quantum dot film, which comprises the following steps:
Quantum dot performed thin film and the solution containing mineral ligand are provided, the quantum dot in the quantum dot performed thin film contains just
Beginning surface ligand；
The quantum dot performed thin film and the solution containing mineral ligand are subjected to the displacement of liquid phase ligand, obtain quantum dot table
Quantum dot film of the face in conjunction with the mineral ligand.
2. preparation method as described in claim 1, which is characterized in that the mineral ligand includes SnS4 4-、Sn2S6 4-、
SnTe4 4-、AsS3 3-、MoS4 2-、In2Se4 2-、CN-、SCN-、S2-、P3-、F-、Cl-、Br-、I-At least one of.
3. preparation method as claimed in claim 2, which is characterized in that it is described containing mineral ligand be contain following structural formula
Ionic compound:
AxBy
Wherein, A includes Li+、Na+、K+、NH4 +、N2H5 +、TMS2+At least one of, B is the mineral ligand.
4. preparation method as described in any one of claims 1-3, which is characterized in that after the liquid phase ligand displacement, further include
The quantum dot performed thin film is placed in vacuum plant and is vacuum-treated, the vacuum degree of the vacuum processing is 5-20Pa.
5. a kind of quantum dot film, which is characterized in that the quantum dot film is by the described in any item preparation sides claim 1-4
Method obtains.
6. a kind of QLED device, including the hearth electrode, quantum dot light emitting layer and top electrode being stacked, which is characterized in that described
Quantum dot light emitting layer is the quantum dot film obtained by the described in any item preparation methods of claim 1-4.
7. QLED device as claimed in claim 6, which is characterized in that further include hole transmission layer, hole injection layer, electronics biography
At least one layer in defeated layer, electron injecting layer.
8. QLED device as claimed in claims 6 or 7, which is characterized in that the hearth electrode is anode, and the top electrode is yin
Pole；Or
The hearth electrode is cathode, and the top electrode is anode.
9. a kind of preparation method of QLED device, which comprises the following steps:
Hearth electrode is provided；
Quantum dot performed thin film is prepared on the hearth electrode；
According to any one of claim 1-4 the method, quantum dot performed thin film is prepared into quantum dot film, obtains quantum dot
Luminescent layer；
Top electrode is prepared on the quantum dot light emitting layer,
Wherein, the hearth electrode is anode, and the top electrode is cathode；Or the hearth electrode is cathode, the top electrode is sun
Pole.
10. a kind of display screen, which is characterized in that including the described in any item QLED devices of claim 6-8.
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| CN113611807A (en) * | 2021-07-12 | 2021-11-05 | 深圳大学 | Blue-light perovskite light-emitting diode and preparation method thereof |
| CN115588702A (en) * | 2022-09-30 | 2023-01-10 | 中芯热成科技(北京)有限责任公司 | Infrared quantum dot layer, device, preparation method and application thereof |
| WO2023024113A1 (en) * | 2021-08-27 | 2023-03-02 | 京东方科技集团股份有限公司 | Light emitting device and manufacturing method therefor, display substrate, and display apparatus |
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| CN111117598A (en) * | 2019-12-19 | 2020-05-08 | 华中科技大学 | ABX based on room temperature methodnY3-nLigand regulation method and application of perovskite nano particles |
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Application publication date: 20190625 |