CN109928903A - Quantum dot surface ligand, quantum dot film and its preparation method and application - Google Patents
Quantum dot surface ligand, quantum dot film and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of quantum dot surface ligands, comprise the following structure at least one of any compound represented of formula 1-4,
Description
Technical field
The invention belongs to technical field of quantum dot preparation more particularly to a kind of quantum dot surface ligand, quantum dot film and
Preparation method and application.
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 by chelating etc. modes connect organic ligand or
Person connects mineral ligand by forming the modes such as chemical bond.The surface ligand of quantum dot plays most important in quantum dot synthesis
Effect, on the one hand, surface ligand can be passivated the defect of quantum dot surface, improve the luminescent properties of quantum dot；On the other hand, table
Face ligand, which can be reduced between quantum dot, reunites, and increases the dispersibility of quantum dot in a solvent.In two pole of quantum dot light emitting
In tube device, surface ligand can further influence the photoelectricity performance of device, therefore reasonably select the quantum dot in quantum dot film
The ligand on surface is the important step for improving quantum dot film and light emitting diode with quantum dots luminous efficiency.It is right after synthesis terminates
It is mode commonplace at present that the ligand of quantum dot surface, which swaps, but there is also certain problems for this method.Quantum dot
The ligand on surface influences its dispersibility in organic solvent, therefore the ligand introduced in ligand exchange processes is likely to result in
The poor dispersion of quantum dot, especially for the shorter ligand molecular of some chain lengths, often will appear quantum dot can not disperse
The problem of, therefore quantum dot film with good uniformity can not be formed.
The self stability of quantum dot is improved using normal ligand during synthesizing quantum dot and is guaranteed in a solvent
Good dispersion, and ligand displacement in situ is the method to solve the above problems.After quantum dot film forming, in situ match is carried out
Body displacement, the ligand introduced in quantum dot synthesis process is replaced as being ordered according to film or light emitting diode with quantum dots requirement on devices
The photoelectric properties of quantum dot film or light emitting diode with quantum dots device can be improved in the surface ligand of system.It is more universal at present
The end of the chain for the ligand replaced in situ generally comprises a kind of functional group combined with quantum dot, the combination of the functional group and quantum dot
Power is greater than the binding force of original ligand, so that displacement reaction occur.
Summary of the invention
The purpose of the present invention is to provide a kind of quantum dot surface ligands, it is intended to solve the chain of existing quantum dot surface ligand
End only includes a kind of functional group combined with quantum dot, and when leading in situ replace, ligand is opposite with the binding ability of quantum dot
Problem weaker, exchange rate is slower.
Another object of the present invention is to provide a kind of quantum dot films and its system containing above-mentioned quantum dot surface ligand
Preparation Method.
A further object of the present invention is to provide a kind of QLED device containing above-mentioned quantum dot film and one kind contain
The display device of above-mentioned QLED device.
The invention is realized in this way a kind of quantum dot surface ligand, comprise the following structure formula 1-4 it is any shown in chemical combination
At least one of object,
Wherein, R, R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ' it is independently chosen from as alkyl or alkyl derivative；
X1, X1 ', X2, X2 ', X3, X3 ' be can be with the active function groups in conjunction with quantum dot.
And a kind of quantum dot film, the quantum dot film are made of the quantum dot containing surface ligand, the surface
Ligand is above-mentioned quantum dot surface ligand, and the quantum dot surface ligand and one or more quantum dot chelatings connect
It connects.
Correspondingly, a kind of preparation method of quantum dot film, comprising the following steps:
Quantum dot performed thin film is provided, configures quantum dot surface ligand solution, wherein the quantum dot surface ligand solution
In quantum dot surface ligand be above-mentioned quantum dot surface ligand；
The quantum dot surface ligand is deposited on quantum dot performed thin film surface, after cleaning treatment, obtains quantum
Point film.
And a kind of QLED device, including the hearth electrode, quantum dot light emitting layer and top electrode being stacked, wherein described
Quantum dot light emitting layer is above-mentioned quantum dot film.
And a kind of display device, including above-mentioned QLED device.
Quantum dot surface ligand provided by the invention, the end of the chain contain multiple active function groups, are passing through ligand displacement in situ
Mode when preparing quanta point material such as quantum dot film, multiple active function groups shape in conjunction with one or more quantum dots
It at the quantum dot film structure of crosslinking, can not only increase the exchange rate of quantum dot surface ligand molecule, but also can be improved
The binding force of quantum dot surface ligand and quantum dot, to improve two pole of thus obtained quantum dot film or quantum dot light emitting
The stability of tube device.
Quantum dot film provided by the invention, due to containing above-mentioned quantum dot surface ligand, the quantum dot surface ligand
It can be crosslinked and be combined with one or more quantum dots, to improve the stability of quantum dot film.
The preparation method of quantum dot film provided by the invention contains the quantum dot table of multiple active function groups using the end of the chain
The original organic ligand of face ligand and quantum dot surface is replaced, and exchange rate and quantum dot surface ligand and quantum are improved
Binding force between point, the good stability of the quantum dot film assigned.
QLED device provided by the invention, display device, due to containing quantum dot film, it is thus possible to improve device
Stability.
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.
The embodiment of the invention provides a kind of quantum dot surface ligand, comprise the following structure formula 1-4 it is any shown in chemical combination
At least one of object,
Wherein, R, R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ' it is independently chosen from alkyl or alkyl derivative；X1,
X1 ', X2, X2 ', X3, X3 ' are can be with the active function groups in conjunction with quantum dot.
Quantum dot surface ligand provided in an embodiment of the present invention, the end of the chain contain multiple active function groups, match by situ
When the mode of body displacement prepares quanta point material such as quantum dot film, multiple active function groups and one or more quantum dots
In conjunction with the quantum dot film structure for forming crosslinking, it can not only increase the exchange rate of quantum dot surface ligand molecule, Er Qieneng
The binding force of quantum dot surface ligand and quantum dot is enough improved, to improve thus obtained quantum dot film or quantum dot hair
The stability of optical diode device.
In the embodiment of the present invention, R, R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ' it can be independently chosen from as saturation
Or undersaturated alkyl or alkyl derivative, such as alkyl, alkylene, alkynes base, aryl, heteroaryl and its derivative.
In the embodiment of the present invention, X1, X1 ', X2, X2 ', X3, X3 ' it is the function that can be chelated with quantum dot surface
Group, it is preferred that the active function groups include halogen atom ,-SH ,-COOH ,-NH2、-OH、-NO2、-SO3H, phosphino-, phosphoric acid
At least one of base, ether, cyano, but not limited to this.There is preferable react between preferred active function groups and quantum dot
Property, and it is easy to carry out displacement in situ in quantum dot synthesis process with the initial ligand introduced, improve replacement rate.
Specifically, the surface ligand includes but is not limited to 2,3-dimercaptosuccinic acid, 2,3- dyhydrobutanedioic acid, season penta
Tetrol four (3- mercaptopropionic acid) ester, pentaerythritol tetraacrylate, pentaerythritol tetrabenzoate, five propylene of dipentaerythrite
Acid esters, four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 3,5- diformazan sulfydryl -2,6- diamino first
Benzene, 2,4- diamino -6- mercaptopyrimidine, the chloro- 4- aminopyrimidine of 2-, 2,3- dichloro dimethyl succinate, 2,3- dichloro succinic acid
At least one of bis- (4- amino-benzene oxygen) ethane of diethylester, 1,2-.Preferred surface ligand is passing through ligand displacement in situ
Mode when preparing quanta point material such as quantum dot film, can effectively match with the original of quantum dot introduced in the synthesis process
Displacement occurs between body, simultaneously because it is preferred that the activity of active function groups is stronger, and quantum dot binding force with higher,
And then through same quantum dot surface ligand in conjunction with multiple quantum dots, and stable quantum dot film structure is formed, improves film
The stability and dispersion performance of layer.
It is further preferred that at least containing a conjugation group, i.e. formula 1, formula 2, formula 3, formula 4 in formula 1, formula 2, formula 3, formula 4
For conjugated ligand.Specifically, R is conjugation group in formula 1；In formula 2, at least one of R1, R2 are conjugation group；In formula 3,
R, at least one of R1, R1 ', R2, R2 ' are conjugation group；In formula 4, R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5,
At least one of R5 ' is conjugation group.In the embodiment of the present invention, since the electronics of the conjugated ligand has delocalization effect,
More dense packing of molecules can be formed, is conducive to effective transmission of intermolecular charge, and then improve carrier in device inside
Transmission, to improve the luminescent properties of device.However, being combined with since the steric hindrance of the conjugated ligand is often larger
The distance between the quantum dot of the conjugated ligand is larger, and laser propagation effect of the carrier between quantum dot is unsatisfactory, therefore
It is simple limited to the promotion effect of device performance by substituting generic ligand using conjugated ligand.In view of this, the embodiment of the present invention
By being cross-linked with each other between conjugated ligand, keep quantum dot closer, to preferably play the advantage of organic ligand.But one
In the quantum dot film that quantum dot is cross-linked to form respectively by two crosslinked groups of conjugated ligand with adjacent quantum dot, crosslinking side
The type and property of the intermediary of formula and formation cross-linked structure often cause very big difference to the transmission of carrier, for example,
When being crosslinked between quantum dot by long chain alkane structure, although quantum dot crosslinked film is capable of forming, due to long chain alkane
Carrier transport effect is poor, and the carrier transmission performance of the film after crosslinking is simultaneously bad.Therefore, the embodiment of the present invention is by measuring
Multiple active function groups are arranged in the conjugated ligand end of the chain on son point surface, hand over multiple active function groups on adjacent quantum dot surface
Connection, makes the transmission of carrier can be channel transmission, while the connection bridge between quantum dot can play electron delocalization effect
(conjugated ligand) is answered, to largely improve the laser propagation effect of carrier, improves device performance.
It should be appreciated that the conjugation group of the embodiment of the present invention is the group that can generate conjugation, the conjugation
Including but not limited to π-is pi-conjugated, p- is pi-conjugated, one of sigma-pi conjugated, σ-p conjugation, p-p conjugation or a variety of；It is described to have altogether
The organo units structure of yoke effect includes but is not limited to double bond and the alternately arranged linear structure of singly-bound and/or cyclic structure,
In can also further contain in this configuration three bond structures (particularly, it should be appreciated that it is theoretical by classical organic chemistry,
Benzene ring structure is considered as three carbon-carbon single bonds in this case and three carbon-carbon double bonds alternate in the cyclic conjugated structure of connection
One kind), wherein the cyclic structure, which can be orderly cyclic structure, is also possible to heterocycle structure；Specifically, the conjugated radicle
Group, which is selected from but not limited to, contains one of phenyl ring, C=C, C ≡ C, C=O, N=N, C ≡ N, C=N- or a variety of groups；It is special
Not, the conjugation group can contain circular structure, wherein the ring structure includes but is not limited to benzene ring structure, luxuriant and rich with fragrance structure, naphthalene
Structure, indenes structure, pyrene Jie Gou, Benzyl structure, acenaphthene structure, acenaphthylene structure, fluorene structured, anthracene structure, fluoranthene structure, benzanthracene structure,
Benzofluoranthrene structure, benzopyran structure, indeno pyrene structure, dibenzanthracene structure, benzo structure, pyrrole structure, pyridine structure,
Pyridazine structure, furan structure, thiophene-structure, indole structure, porphine structure, porphyrin structure, thiazole structure, glyoxaline structure, pyrazine
Structure, pyrimidine structure, quinoline structure, isoquinoline structure, pteridine structure, acridine structure, oxazole structure, carbazole structure, triazole knot
Structure, benzofuran structure, benzothiophene structure, benzothiazole structure, benzoxazoles structure, benzopyrrole structure, benzimidazole
One of structure is a variety of.
And the embodiment of the invention also provides a kind of quantum dot films, the quantum dot film is by containing surface ligand
Quantum dot be made, the surface ligand be above-mentioned quantum dot surface ligand, and the quantum dot surface ligand and one or
Multiple quantum dot chelating connections.
Quantum dot film provided in an embodiment of the present invention, due to containing above-mentioned quantum dot surface ligand, the quantum dot table
Face ligand can be crosslinked with one or more quantum dots and be combined, the quantum dot film that forming properties are stable, dispersion performance improves, from
And improve the stability of quantum dot film.
Specifically, the quanta point material in the quantum dot film is II-VI group compound, III-V compound, II-V
Compounds of group, III-VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI compounds of group or IV race are single
One of matter is a variety of.Specifically, the II-VI group compound (semiconductor material) include CdS, CdSe, CdTe, ZnS,
ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, but not limited to this, it can also be other binary, ternary, quaternary
II-VI group compound；III-V compound (semiconductor material) it is nanocrystalline include but is not limited to GaP, GaAs, InP,
InAss, but not limited to this, it can also be other binary, ternary, the III-V compound of quaternary.
As a kind of preferred implementation situation, the quantum dot be doped or non-doped inorganic Ca-Ti ore type semiconductor and/
Or hybrid inorganic-organic Ca-Ti ore type semiconductor.Specifically, the inorganic Ca-Ti ore type semiconductor structure general formula is AMX3,
Wherein, A 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 calcium
Titanium ore 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 cation M is located at the octahedral body-centered of halogen, and organic amine cation B is filled in the gap between octahedron, and it is unlimited to be formed
The three-dimensional structure of extension；As n > 2, the inorganic metal hal ide octahedron MX that is connected in a manner of total top6 4-In two-dimensional directional
Extend to form layer structure, Intercalation reaction organic amine cation bilayer (protonation monoamine) or organic amine cation unimolecule
Layer (protonation diamine), organic layer and inorganic layer mutually overlap and form stable two-dimensional layered structure；M be divalent metal sun from
Son, including but not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, X is halogen yin
Ion, including but not limited to Cl-、Br-、I-。
Correspondingly, the embodiment of the invention also provides a kind of preparation methods of quantum dot film, comprising the following steps:
S01., quantum dot performed thin film is provided, configures quantum dot surface ligand solution, wherein the quantum dot surface ligand
Quantum dot surface ligand in solution is above-mentioned quantum dot surface ligand；
S02. the quantum dot surface ligand is deposited on quantum dot performed thin film surface, after cleaning treatment, obtained
Quantum dot film.
The preparation method of quantum dot film provided in an embodiment of the present invention contains the amount of multiple active function groups using the end of the chain
The original organic ligand of son point surface ligand and quantum dot surface is replaced, and exchange rate and quantum dot surface ligand are improved
Binding force between quantum dot, the good stability of the quantum dot film assigned.
Specifically, the quantum dot performed thin film is contained the quantum dot of initial organic ligand by surface in above-mentioned steps S01
Be made, and the initial organic ligand be tetradecene, it is hexadecylene, octadecylene, octadecylamine, octadecenic acid, trioctylamine, three pungent
At least one of base phosphine oxide, tri octyl phosphine, octadecylphosphonic acid, 9- octadecenyl amine, mercaptoundecylic acid, but not limited to this.
In the quantum dot surface ligand solution, solvent is organic solvent, and the organic solvent preferably includes hexane, hexamethylene
Alkane, heptane, normal octane, isooctane, pentane, methylpentane, ethylpentane, pentamethylene, methyl cyclopentane, ethyl cyclopentane, benzene,
Toluene, dimethylbenzene, ethylbenzene, methylene chloride, chloroform, carbon tetrachloride, dichloroethanes, trichloroethanes, chloropropane, dichloro third
Alkane, trichloropropane, chlorobutane, methylene bromide, bromoform, bromoethane, N-Propyl Bromide, 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, uncle
Amylalcohol, cyclohexanol, octanol, benzylalcohol, ethylene glycol, phenol, o-cresol, ether, methyl phenyl ethers anisole, phenetole, diphenyl ether, tetrahydrofuran,
Glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol diethyl ether, ethoxy ether, propylene glycol monopropyl ether, propyleneglycol monobutyl base
Ether, acetaldehyde, benzaldehyde, acetone, butanone, cyclohexanone, acetophenone, formic acid, acetic acid, ethyl acetate, diethy-aceto oxalate, malonic acid two
Ethyl ester, propyl acetate, methyl propyl ester, butyl acetate, methyl amyl acetate, nitrobenzene, acetonitrile, diethylamine, triethylamine, aniline,
Pyridine, picoline, ethylenediamine, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl
Sulfoxide, hexamethyl phosphoramide, carbon disulfide, methyl sulfide, ethyl sulfide, dimethyl sulfoxide, mercaptan, ethyl mercaptan, methoxyl group tetrahydrofuran
At least one of, but not limited to this.
In above-mentioned steps S02, the quantum dot surface ligand is deposited on quantum dot performed thin film surface, the amount
Son point surface ligand occurs displacement in situ with the original organic ligand on quantum dot performed thin film surface and reacts, finally, described
Quantum dot surface ligand cements out the original organic ligand, forms quantum dot surface ligand-quantum dot cross-linking products.
The embodiment of the present invention due to the quantum dot surface ligand have various active functional group, can be efficiently by quantum dot
The original organic ligand on performed thin film surface is replaced, and forms that binding force is stronger, stability-enhanced quantum dot film.
Preferably, in the described the step of quantum dot surface ligand is deposited on the quantum dot performed thin film surface,
Deposition method is solution processing method, and the solution processing method includes immersion, Best-Effort request, printing, spin coating, spraying, roller coating, scrapes
At least one of painting, silk-screen printing.
Further, the ligand of quantum dot connection is located at by cleaning treatment removal, original is had including be replaced out
Machine ligand and the quantum dot surface ligand of not fully reacting provided in an embodiment of the present invention.The preferred cleaning treatment
For at least one of solvent cleaning, vacuum processing, annealing.Specifically, the cleaning treatment can be clear for solvent single
It washes, solvent is cleaned multiple times, single is vacuum-treated, is repeatedly vacuum-treated, vacuum and annealing, vacuum and low-temperature treatment.
And the embodiment of the invention also provides a kind of QLED devices, including hearth electrode, the quantum dot light emitting being stacked
Layer and top electrode, wherein the quantum dot light emitting layer is above-mentioned quantum dot film.
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 is selected from blended metal oxide.Specifically, the hearth electrode can choose the field QLED routine
Hearth electrode material.As a kind of implementation situation, the hearth electrode is blended metal oxide, and the blended metal oxide includes
But it is not limited to indium doping tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminium-doped zinc oxide
(AZO), Ga-doped zinc oxide (GZO), indium doping zinc oxide (IZO), magnesium doping zinc-oxide (MZO), aluminium doping magnesia (AMO)
One of or it is a variety of.As another implementation situation, the hearth electrode is to contain metal sandwich in transparent metal oxide
Combination electrode, wherein the transparent metal oxide can be doping transparent metal oxide, or undoped is 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.
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.
At least one of the top electrode selection metal material, carbon material.Wherein, the metal material includes but unlimited
In Al, Ag, Cu, Mo, Au or their alloy；The carbon material includes but is not limited to graphite, carbon nanotube, graphene, carbon fiber
One of dimension is a variety of.
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.
Corresponding, the embodiment of the invention also provides a kind of preparation methods of QLED device, comprising the following steps:
E01. hearth electrode is prepared on substrate；
E02. according to the preparation method of above-mentioned quantum dot film, quantum dot light emitting layer is prepared on the hearth electrode；
E03. top electrode is prepared on the quantum dot light emitting layer.
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 display devices, including above-mentioned QLED device.
QLED device provided in an embodiment of the present invention, display device, due to containing quantum dot film, it is thus possible to improve
The stability of device.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of quantum dot surface ligand, comprising the following structure compound represented, (compound name is four -3- of pentaerythrite
Mercaptopropionic acid ester):
Embodiment 2
A kind of QLED device, including the anode, quantum dot light emitting layer and cathode being stacked, the preparation of the QLED device
Method the following steps are included:
E11. in ethanol by 2,3-dimercaptosuccinic acid dissolution, it is configured to quantum dot surface ligand solution；
E12. the luminous preformed layer of CdSe quantum dot is successively printed on ito anode, then soaks quantum dot light emitting preformed layer
Enter into the quantum dot surface ligand solution in step E11, taken out after impregnating 10min, then be transferred into vacuum chamber, is adjusted
Section vacuum degree is 10Pa and maintains 30min, removes the ligand and solvent not being coordinated in quantum dot light emitting layer, obtains quantum dot light emitting
Layer；
E13. the evaporating Al cathode on quantum dot light emitting layer obtains eurymeric structure quantum point light emitting diode.
Embodiment 3
A kind of QLED device, including cathode, electron transfer layer, quantum dot light emitting layer, hole transmission layer, the sky being stacked
Cave implanted layer and cathode, the preparation method of the QLED device the following steps are included:
E11. in ethanol by 2,3-dimercaptosuccinic acid dissolution, it is configured to quantum dot surface ligand solution；
E12. ZnO electron transfer layer and quantum dot light emitting preformed layer are successively printed on cathode, then by quantum dot light emitting
Preformed layer is immersed in the quantum dot surface ligand solution in step E11, 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 light emitting layer, obtain
Quantum dot light emitting layer；
E13. TFB hole transmission layer, PEDOT hole injection layer are successively printed in quantum dot light emitting layer, in hole injection layer
Anode is prepared, reciprocal form structure light emitting diode with quantum dots is obtained.
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 quantum dot surface ligand, which is characterized in that comprise the following structure in any compound represented of formula 1-4 at least
One kind,
Wherein, R, R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ' it is independently chosen from alkyl or alkyl derivative；
X1, X1 ', X2, X2 ', X3, X3 ' be can be with the active function groups in conjunction with quantum dot.
2. quantum dot surface ligand as described in claim 1, which is characterized in that the active function groups include halogen atom ,-
SH、-COOH、-NH2、-OH、-NO2、-SO3H, at least one of phosphino-, phosphate, ether, cyano.
3. quantum dot surface ligand as claimed in claim 1 or 2, which is characterized in that the quantum dot surface ligand is selected from 2,
3- dimercaptosuccinic acid, 2,3 dihydroxybutanedioic acid, pentaerythrite four (3- mercaptopropionic acid) ester, pentaerythritol tetraacrylate,
Pentaerythritol tetrabenzoate, five acrylate of dipentaerythrite, four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid]
Pentaerythritol ester, 3,5- diformazan sulfydryl -2,6- diaminotoluene, 2,4- diamino -6- mercaptopyrimidine, the chloro- 4- aminopyrimidine of 2-,
At least one in bis- (4- amino-benzene oxygen) ethane of 2,3- dichloro dimethyl succinate, 2,3- dichloro diethyl succinate, 1,2-
Kind.
4. quantum dot surface ligand as claimed in claim 1 or 2, which is characterized in that in formula 1, R is conjugation group；And/or
In formula 2, at least one of R1, R2 are conjugation group；And/or
At least one of in formula 3, R, R1, R1 ', R2, R2 ' are conjugation group；And/or
In formula 4, R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ' at least one of for conjugation group.
5. quantum dot surface ligand as claimed in claim 4, which is characterized in that the conjugation group, which is selected from, contains conjugate ring, C
The group of at least one of=C, C ≡ C, C=O, N=N, C ≡ N, C=N-.
6. quantum dot surface ligand as claimed in claim 4, which is characterized in that the conjugate ring is selected from benzene ring structure, luxuriant and rich with fragrance knot
Structure, naphthalene structure, indenes structure, pyrene Jie Gou, Benzyl structure, acenaphthene structure, acenaphthylene structure, fluorene structured, anthracene structure, fluoranthene structure, benzanthracene
Structure, benzofluoranthrene structure, benzopyran structure, indeno pyrene structure, dibenzanthracene structure, benzo structure, pyrrole structure, pyridine
Structure, pyridazine structure, furan structure, thiophene-structure, indole structure, porphine structure, porphyrin structure, thiazole structure, glyoxaline structure,
Pyrazine structure, pyrimidine structure, quinoline structure, isoquinoline structure, pteridine structure, acridine structure, oxazole structure, carbazole structure, three
Azoles structure, benzofuran structure, benzothiophene structure, benzothiazole structure, benzoxazoles structure, benzopyrrole structure, benzo
At least one of glyoxaline structure.
7. a kind of quantum dot film, which is characterized in that the quantum dot film is made of the quantum dot containing surface ligand, described
Surface ligand be quantum dot surface ligand described in any one of claims 1-6, and the quantum dot surface ligand and one or
Multiple quantum dot chelating connections.
8. a kind of preparation method of quantum dot film, which comprises the following steps:
Quantum dot performed thin film is provided, configures quantum dot surface ligand solution, wherein in the quantum dot surface ligand solution
Quantum dot surface ligand is quantum dot surface ligand described in any one of claims 1-6；
The quantum dot surface ligand is deposited on quantum dot performed thin film surface, after cleaning treatment, it is thin to obtain quantum dot
Film.
9. a kind of QLED device, which is characterized in that including the hearth electrode, quantum dot light emitting layer and top electrode being stacked, wherein
The quantum dot light emitting layer is quantum dot film as claimed in claim 7.
10. a kind of display device, which is characterized in that including QLED device as claimed in claim 9.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112071998A (en) * | 2020-09-18 | 2020-12-11 | 京东方科技集团股份有限公司 | Light-emitting device and display device |
| CN113054115A (en) * | 2019-12-27 | 2021-06-29 | Tcl集团股份有限公司 | Preparation method of quantum dot light-emitting diode |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070295266A1 (en) * | 2004-12-13 | 2007-12-27 | Nanosquare Co. Ltd. | Method for Synthesizing Semiconductor Quantom Dots |
| CN101798511A (en) * | 2010-03-04 | 2010-08-11 | 上海大学 | Method for preparing group II-VI soluble selenide semiconductor quantum dots by gas phase method |
| CN105185918A (en) * | 2015-08-27 | 2015-12-23 | Tcl集团股份有限公司 | Quantum dot light-emitting layer, preparation method thereof and QLED |
| CN106873242A (en) * | 2017-03-30 | 2017-06-20 | 广东普加福光电科技有限公司 | A kind of edge sealing structure of quantum dot fluorescence film |
| CN107089039A (en) * | 2017-04-24 | 2017-08-25 | 宁波东旭成新材料科技有限公司 | A kind of multi-functional quantum dot film and preparation method thereof |
-
2017
- 2017-12-15 CN CN201711351536.8A patent/CN109928903A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070295266A1 (en) * | 2004-12-13 | 2007-12-27 | Nanosquare Co. Ltd. | Method for Synthesizing Semiconductor Quantom Dots |
| CN101798511A (en) * | 2010-03-04 | 2010-08-11 | 上海大学 | Method for preparing group II-VI soluble selenide semiconductor quantum dots by gas phase method |
| CN105185918A (en) * | 2015-08-27 | 2015-12-23 | Tcl集团股份有限公司 | Quantum dot light-emitting layer, preparation method thereof and QLED |
| CN106873242A (en) * | 2017-03-30 | 2017-06-20 | 广东普加福光电科技有限公司 | A kind of edge sealing structure of quantum dot fluorescence film |
| CN107089039A (en) * | 2017-04-24 | 2017-08-25 | 宁波东旭成新材料科技有限公司 | A kind of multi-functional quantum dot film and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| EDMOND GRAVEL 等: "Compact tridentate ligands for enhanced aqueous stability of quantum dots and in vivo imaging", 《CHEMICAL SCIENCE》 * |
| MARC THIRY 等: "Fluorescence Properties of Hydrophilic Semiconductor Nanoparticles with Tridentate Polyethylene Oxide Ligands", 《ACS NANO》 * |
| RAFAEL S. SANCHEZ 等: "All solution processed low turn-on voltage near infrared LEDs based on core–shell PbS–CdS quantum dots with inverted device structure", 《NANOSCALE》 * |
| 林伟: "配体结构对量子点化学性能影响的研究", 《北京化工大学硕士研究生学位论文》 * |
| 靳贝贝: "化合物", 《STN 检索报告》 * |
| 靳贝贝: "化合物", 《STN检索报告》 * |
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| WO2021258690A1 (en) * | 2020-06-24 | 2021-12-30 | Tcl科技集团股份有限公司 | Quantum dot material and preparation method, and quantum dot light-emitting diode and preparation method |
| CN112071998A (en) * | 2020-09-18 | 2020-12-11 | 京东方科技集团股份有限公司 | Light-emitting device and display device |
| CN112071998B (en) * | 2020-09-18 | 2024-06-11 | 京东方科技集团股份有限公司 | Light-emitting device and display device |
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