CN109935713A - 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 technical field of flat panel display, and in particular to a kind of quantum dot film and preparation method thereof, QLED device and preparation method thereof.Quantum dot surface in the quantum dot film is combined with the conjugated ligand of following general structure: X1‑R‑X2；Wherein, X1And X2For can be with the functional group in conjunction with quantum dot surface；R is alkyl or alkyl derivative with conjugation group.Quantum dot film provided by the invention, its quantum dot surface connects distinctive conjugated ligand, quantum dot is crosslinked by the conjugated ligand, the dissolubility, dispersibility and its conductive capability of quantum dot is set to reach better equilibrium state, further increase the stability and carrier transport ability of quantum dot film, luminous efficiency is correspondingly improved, its overall performance is improved.
Description
Technical field
The invention belongs to technical field of flat panel display, and in particular to a kind of quantum dot film and preparation method thereof, QLED device
Part and preparation method thereof.
Background technique
Quantum dot (Quantum dot) is a kind of quasi-zero dimension nano material, similar superlattices and Quantum Well, granular size
About 1~100nm has the performances such as quantum confined effect, skin effect, quantum size effect and quantum tunneling effect, simultaneously
There is outstanding advantages of monochromaticjty is good, excitation purity is high, luminescent spectrum is narrow, be a kind of very promising nano material.Based on amount
Son point light emitting diode be referred to as light emitting diode with quantum dots (Quantum dots light-emitting diode,
It QLED), is a kind of novel display skill device.The advantage that quantum dot is shown be that colour gamut covering is wide, color is easy to control and
The advantages that excitation purity is high, it is considered to be the nova of display technology, while being also considered as the revolutionary of display technology and representing.
Currently, quantum dot surface typically contains ligand abundant in the technology of preparing of QLED, on the one hand effect is blunt
Change its surface defect；On the other hand it is the stabilization for maintaining quantum dot, prevents reunion between quantum dot, improves its dissolubility.Such as
Fruit uses the organic ligand of long-chain, and the dissolution of quantum dot and dispersibility are more preferable, but its conductive capability also reduces simultaneously；If used
The organic ligand of short chain, although its conductive capability can be improved, it is dissolved and dispersibility substantially reduces, and quantum dot is caused to be easy
Reunite.In order to reach the balance of the two, reasonable design and selection ligand are to quanta point material performance and QLED device
Performance has a major impact.
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 in existing quantum dot membrane-film preparation process, the dissolution of quantum dot and dispersibility are difficult to reach with its conductive capability
The technical issues of balance.
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:
One aspect of the present invention provides a kind of quantum dot film, and the quantum dot surface in the quantum dot film is connected with as follows
The conjugated ligand of general structure:
X1-R-X2
Wherein, X1And X2For can be with the functional group in conjunction with quantum dot surface；R is that the alkyl or alkyl with conjugation group spread out
Biology.
Correspondingly, a kind of preparation method of quantum dot film includes the following steps:
Quantum dot performed thin film and gaseous conjugated ligand, the general structure of the conjugated ligand are as follows: X are provided1-R-X2；
Wherein, X1And X2For can with the functional group in conjunction with quantum dot surface, R be with conjugation group alkyl or alkyl spread out
Biology；
The quantum dot performed thin film, which is placed in, to be passed through the conjugated ligand and carry out gas phase ligand and set in obturator
It changes, so that the quantum dot surface initial ligand in the quantum dot performed thin film is replaced into the conjugated ligand, obtain the quantum
Point film.
Another aspect of the present invention provides a kind of QLED device, including quantum dot light emitting layer, and the quantum dot light emitting layer is upper
State the quantum dot film of preparation method acquisition.
Correspondingly, the preparation method of above-mentioned 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 quantum dot film described above, quantum dot performed thin film is prepared into quantum dot film, is obtained
To quantum dot light emitting 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.
And a kind of display screen, including above-mentioned QLED device.
Quantum dot film provided by the invention, quantum dot surface connect distinctive conjugated ligand, which contains
It is conjugated group, and quantum dot is crosslinked by the conjugated ligand, reaches the dissolubility of quantum dot, dispersibility with its conductive capability
Better equilibrium state further increases the stability and carrier transport ability of quantum dot film, correspondingly improves luminous
Efficiency improves its overall performance.
The preparation method of quantum dot film provided by the invention, using vapor phase method to the surface in situ of quantum dot performed thin film
Ligand exchange is displaced ligands, carries out ligand displacement relative to using solwution method, gas phase original position ligand exchange has solvent-free damage
Outstanding advantages of hurting (overall performance for the quantum dot film that raising obtains), low in cost, simple process is handed over using ligand in situ
The initial ligand of quantum dot surface in quantum dot performed thin film of changing commanders is replaced into displaced ligands, thus after changing quantum dot film forming
Surface polarity and surface tension, and then by control quantum dot surface polarity, avoid quantum dot light emitting layer from upper layer electricity
The influence of subfunction material solution solvent, after quantum dot solution forms quantum dot performed thin film by film-forming process, quantum dot
Arrangement and position it is substantially stationary, at this time again with gaseous displaced ligands carry out ligand displacement would not occur solution sedimentation ask
Topic, and quantum dot film forming procedure is not influenced by the ligand structure after exchanging.In addition, carrying out ligand displacement, gas using vapor phase method
Ligand displacement degree is more abundant in phase atmosphere, and the selection of displaced ligands has preferable selection not by the limitation of solution environmental
Scale and industrialized production may be implemented in flexibility；And replaced using distinctive conjugated ligand, keep the quantum dot of preparation thin
Dissolubility, dispersibility and its conductive capability of quantum dot in film reach better equilibrium state, and it is thin to further increase quantum dot
The stability and carrier transport ability of film, correspondingly improve luminous efficiency, improve its overall performance.
QLED device provided by the invention, display screen, comprising by above-mentioned quantum dot film.Due to being measured in the quantum dot film
Son point surface ligand contains distinctive conjugation group, and conjugated ligand makes the dissolubility of the quantum dot in quantum dot film, dispersibility
Reach better equilibrium state with its conductive capability, improves the stability and carrier transport energy of quantum dot film in this way
Power can correspondingly improve device efficiency, further increase the photoelectric properties of QLED device, display screen.
The preparation method of QLED device provided by the invention, on the basis of QLED device customary preparation methods, using gas
Phase method carries out surface ligand displacement to quantum dot performed thin film, is replaced into distinctive conjugated ligand, not only simple process, and uses
Vapor phase method carries out the quantum dot light emitting layer performance more stability that conjugated ligand is replaced, and improves in quantum dot film in this way
Carrier transport ability, device efficiency can be correspondingly improved.
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 quantum dot film, the quantum dot surface in the quantum dot film connects
It is connected to the surface ligand of following general structure:
X1-R-X2
Wherein, X1And X2For can be with the functional group in conjunction with quantum dot surface；R is that the alkyl or alkyl with conjugation group spread out
Biology.
Quantum dot film provided by the invention, quantum dot surface connect distinctive conjugated ligand, which contains
It is conjugated group, and quantum dot is crosslinked by the conjugated ligand, reaches the dissolubility of quantum dot, dispersibility with its conductive capability
Better equilibrium state further increases the stability and carrier transport ability of quantum dot film, correspondingly improves luminous
Efficiency improves its overall performance.
Conjugated ligand, since its electronics has delocalization effect, forms more dense packing of molecules, has compared with generic ligand
Conducive to effective transmission of intermolecular charge, into the transmission for improving carrier in device inside, to improve the luminescent properties of device.
In addition, the steric hindrance of conjugated ligand is often larger, the distance between quantum dot is larger, transmission of the carrier between quantum dot
The effect is unsatisfactory, therefore simple by limited to the promotion effect of device performance using conjugated ligand substitution generic ligand, therefore
By being crosslinked, keep quantum dot closer.On the other hand, in the quantum dot film being commonly crosslinked, the effect of crosslinking first is that formed
Mutually close quantum dot film structure, is connected with each other, still, in the quantum dot film of crosslinking between quantum dot and quantum dot
In, the type and property of the intermediary of crosslinking method and formation cross-linked structure often cause very big difference to the transmission of carrier
It is different, for example, when being crosslinked between quantum dot by long chain alkane structure, although quantum dot crosslinked film is capable of forming, due to length
The carrier transport effect of alkane is poor, and the carrier transmission performance of the film after crosslinking is simultaneously bad.Therefore, using conjugation and friendship
The structure of connection allows the connection bridge between quantum dot to be all when having the conjugated structure of electron delocalization effect, and in the structure
The transmission of carrier can be channel transmission, can largely improve the laser propagation effect of carrier, to improve device
Part performance.
Quantum dot film provided in an embodiment of the present invention, can be adapted for light emitting diode with quantum dots, be readily applicable to
Other electronic devices containing quantum dot layer, including but not limited to quantum point detector, quantum point sensor, quantum dot sun electricity
Pond, quantum dot laser etc..
Further, in the conjugated ligand of above structure general formula, the X1And X2It is connect with quantum dot surface, connection side
Formula includes one of bonding, Electrostatic Absorption, chelating or a variety of.And the X1And X2Be independently selected from halogen atom, hydroxyl, ether,
Sulfydryl, thioether group, aldehyde radical, carbonyl, carboxyl, ester group, nitro, nitroso, amino, imido grpup, sulfo group, acyl group, nitroxyl, sulphonyl
Base, cyano, isocyano group, hydrazone group, phosphino-, phosphate, oximido, epoxy group, azo group, vinyl, acetenyl, in fragrant ring group
It is at least one；That is X1And X2It can be above-mentioned group of the same race, be also possible to group not of the same race.It is preferred that X1With X2It is identical, both sides
It is active consistent, it can react with quantum dot；If both sides activity is inconsistent, need to control reactant dosage and reaction ginseng
Number, when functional group's total overall reaction of high activity finishes, adjusting response parameter can just be such that the functional group of low activity and quantum dot occurs
Reaction.
Meanwhile in the conjugated ligand of above structure general formula, with the alkyl or alkyl derivative for being conjugated group, i.e., R is
Organo units structure with conjugation (electron delocalization effect), such as undersaturated alkyl or alkyl derivative, conjugation effect
It should include but is not limited to that 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
The organo units structure of conjugation includes but is not limited to double bond and the alternately arranged linear structure of singly-bound and/or cyclic structure,
Wherein 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 the present case and three carbon-carbon double bonds alternate the cyclic conjugated structure of connection
One of), wherein the cyclic structure, which can be orderly cyclic structure, is also possible to heterocycle structure；Specifically, described to have
The functional group contained in the organo units structure of conjugation includes but is not limited to phenyl ,-C=C- ,-C ≡ C- ,-C=O ,-N=
One of N- ,-C ≡ N ,-C=N- or a variety of；Particularly, can contain in the organo units structure with conjugation
Ring structure, wherein the ring structure include but is not limited to benzene ring structure, luxuriant and rich with fragrance structure, naphthalene structure, indenes structure, pyrene knot structure, Benzyl structure,
Acenaphthene structure, acenaphthylene structure, fluorene structured, anthracene structure, fluoranthene structure, benzanthracene structure, benzofluoranthrene structure, benzopyran structure, indenes
And pyrene structure, dibenzanthracene structure, benzo structure, pyrrole structure, pyridine structure, pyridazine structure, furan structure, thiophene knot
It is structure, indole structure, porphine structure, porphyrin structure, thiazole structure, glyoxaline structure, pyrazine structure, pyrimidine structure, quinoline structure, different
Quinoline structure, pteridine structure, acridine structure, oxazole structure, carbazole structure, triazole structure, benzofuran structure, benzothiophene knot
One of structure, benzothiazole structure, benzoxazoles structure, benzopyrrole structure, benzimidazole structure are a variety of.
It is further preferred that conjugated ligand described in the embodiment of the present invention includes such as any compound represented of following formula 1-4
At least one of,
Wherein, formula 1, formula 2, formula 3, at least contain a conjugation group in formula 4, specifically, in formula 1, R is to be conjugated group；
In formula 2, at least one of R1, R2 are conjugation group；At least one of in formula 3, R, R1, R1 ', R2, R2 ' are conjugated radicle
Group；In formula 4, R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ' at least one of for conjugation group.It is conjugated on group
Face has illustrated, such as R, R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ' can be independently chosen from undersaturated alkyl or
Alkyl derivative, such as alkylene, alkynes base, aryl, heteroaryl and its derivative.X1, X1 ', X2, X2 ', X3, X3 ' it is activity
Functional group, the functional group that can be chelated with quantum dot surface, it is preferred that the active function groups include halogen atom ,-
SH、-COOH、-NH2、-OH、-NO2、-SO3H, at least one of phosphino-, phosphate, ether, cyano, but not limited to this.It is preferred that
Active function groups and quantum dot between have preferable reactivity, and be easy to and the initial ligand that is introduced in quantum dot synthesis process
Displacement in situ is carried out, replacement rate is improved.Correspondingly, the embodiment of the present invention provides a kind of preparation method of quantum dot film, packet
Include following steps:
S01: quantum dot performed thin film and gaseous displaced ligands, the general structure of the displaced ligands are as follows: X are provided1-R-
X2；
Wherein, X1And X2For can with the functional group in conjunction with quantum dot surface, R be with conjugation group alkyl or alkyl spread out
Biology；
S02: above-mentioned quantum dot performed thin film, which is placed in, to be passed through above-mentioned conjugated ligand and carry out gas phase ligand in obturator
Displacement, makes the quantum dot surface initial ligand in the quantum dot performed thin film be replaced into the conjugated ligand, obtains the amount
Son point film.
The preparation method of quantum dot film provided by the invention, using vapor phase method to the surface in situ of quantum dot performed thin film
Ligand exchange is displaced ligands, carries out ligand displacement relative to using solwution method, gas phase original position ligand exchange has solvent-free damage
Outstanding advantages of hurting (overall performance for the quantum dot film that raising obtains), low in cost, simple process is handed over using ligand in situ
The initial ligand of quantum dot surface in quantum dot performed thin film of changing commanders is replaced into displaced ligands, thus after changing quantum dot film forming
Surface polarity and surface tension, and then by control quantum dot surface polarity, avoid quantum dot light emitting layer from upper layer electricity
The influence of subfunction material solution solvent, after quantum dot solution forms quantum dot performed thin film by film-forming process, quantum dot
Arrangement and position it is substantially stationary, at this time again with gaseous displaced ligands carry out ligand displacement would not occur solution sedimentation ask
Topic, and quantum dot film forming procedure is not influenced by the ligand structure after exchanging.In addition, carrying out ligand displacement, gas using vapor phase method
Ligand displacement degree is more abundant in phase atmosphere, and the selection of displaced ligands has preferable selection not by the limitation of solution environmental
Scale and industrialized production may be implemented in flexibility；And replaced using distinctive conjugated ligand, keep the quantum dot of preparation thin
Dissolubility, dispersibility and its conductive capability of quantum dot in film reach better equilibrium state, and it is thin to further increase quantum dot
The stability and carrier transport ability of film, correspondingly improve luminous efficiency, improve its overall performance.
Specifically, the quantum dot surface in the quantum dot performed thin film contains initial ligand, institute in above-mentioned steps S01
Stating initial ligand is the surface ligand introduced after synthesizing quantum dot, or the surface of ligand exchange introducing is carried out by solwution method
Ligand, the embodiment of the present invention do not have considered critical, generally organic ligand, including but not limited to tetradecene, hexadecylene, 18
Alkene, octadecylamine, octadecenic acid, trioctylamine, trioctylphosphine oxide (TOPO), tri octyl phosphine, octadecylphosphonic acid, 9- octadecenyl amine, mercapto
At least one of base undecanoic acid.
Quantum dot in the quantum dot performed thin film is II-VI group compound, III-V compound, II-V race chemical combination
In object, III-VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI compounds of group or IV race simple substance
It is one or more.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 the II-VI of other binary, ternary, quaternary
Compounds of group；Nanocrystalline including but not limited to GaP, GaAs, InP, InAss of III-V compound (semiconductor material), but not
It is limited to this, can also is 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-。
In above-mentioned steps S02, by the quantum dot performed thin film be placed in can in obturator, it is described can obturator conduct
Reaction unit, on the one hand, can prevent water, oxygen from entering, ligand displacement is impacted；Importantly, described closed can fill
The closed environment set can form pressurization or vacuum environment, to promote the progress of ligand displacement reaction.Theoretically, as long as energy
It realizes that the airtight chamber of certain vacuum degree could be used for the embodiment of the present invention, can be low vacuum airtight chamber, be also possible to height
Vacuum tightness chamber, the embodiment of the present invention do not limit strictly.
Further, the process for providing gaseous conjugated ligand includes: that liquid conjugated ligand is evaporated or boiled
Gaseous conjugated ligand is obtained after processing；Conjugated ligand in the embodiment of the present invention is organic ligand, and part room temperature is liquid, can
It is evaporated processing to it, forms gaseous conjugated ligand, then is passed into and can carry out the displacement of gas phase ligand in obturator.
The process that gaseous conjugated ligand is provided can also include: by solid-state conjugated ligand through distillation processing or successively through liquefaction at
Gaseous conjugated ligand is obtained after reason, evaporation process.Conjugated ligand part room temperature in the embodiment of the present invention is solid, can be to it
Distillation processing is successively evaporated processing through liquefaction processing, evaporation, forms gaseous conjugated ligand, then being passed into can be closed
In device, the displacement of gas phase ligand is carried out.
Preferably, the embodiment of the present invention is using progress gas phase ligand displacement under vacuum conditions.Specifically, the gas phase is matched
Body replace during, it is described can obturator internal pressure be 10-5-103Pa, the partial pressure of the conjugated ligand are 10-4-
102Pa.By control described in can obturator internal pressure, the content of positive direction product is effectively reduced；And by adjusting institute
The partial pressure for stating conjugated ligand guarantees appropriate level of the conjugated ligand in reaction environment, thus from product source and raw material
Source bilayer promotes displacement reaction to carry out to positive direction (direction of the quantum dot in conjunction with the conjugated ligand).Further preferably
, during gas phase ligand displacement, it is described can the internal pressure of obturator be 10-4-102Pa, the conjugated ligand
Partial pressure be 0.01-10Pa, thus be more advantageous to displacement reaction towards positive direction carry out.
In the embodiment of the present invention, the gas phase ligand displacement can carry out at normal temperature, it is preferred that in order to improve reaction speed
Rate can heat it.To sum up, during gas phase ligand displacement, it is described can obturator inside temperature
Degree is 5-200 DEG C.In the embodiment of the present invention, time of gas phase ligand displacement according to the type of initial ligand, conjugated ligand,
And it is described can the internal pressure of obturator, the partial pressure of conjugated ligand and it is different, between 0.5-360min.
And the embodiment of the invention also provides a kind of QLED devices, including the substrate, hearth electrode, quantum set gradually
Point luminescent layer and top electrode, wherein the quantum dot light emitting layer is the quantum dot film of the embodiments of the present invention.
QLED device provided in an embodiment of the present invention, comprising by above-mentioned quantum dot film.Due to being measured in the quantum dot film
Distinctive conjugated ligand is contained on son point surface, conjugated ligand make the dissolubility of the quantum dot in quantum dot film, dispersibility and its
Conductive capability reaches better equilibrium state, improves the stability and carrier transport ability of quantum dot film in this way, can
Device efficiency is correspondingly improved, the photoelectric properties of QLED device, display screen are further increased.
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 by the invention, on the basis of QLED device customary preparation methods, using gas
Phase method carries out surface ligand displacement to quantum dot performed thin film, is replaced into distinctive conjugated ligand, not only simple process, and uses
Vapor phase method carries out the quantum dot light emitting layer performance more stability that conjugated ligand is replaced, and improves in quantum dot film in this way
Carrier transport ability, device efficiency can be correspondingly improved.
Specifically, in QLED device after quantum dot film forming, ligand is carried out to quantum dot layer by gas phase reaction method
Exchange, by quantum dot synthesize in the initial ligand (such as oleic acid) that coats by gas phase reaction ligand exchange be band is conjugated group
Common rail crosslinking ligand (such as HS-CH=CH-SH), two sections of the common rail crosslinking ligand can connect two different quantum dots, thus
Quantum dot is crosslinked by conjugated ligand, quantum dot-surface conjugated ligand reticular structure of crosslinking is formed, improves in device
The stability and carrier transport ability of quantum dot light emitting layer improve device performance.
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 display screens, including above-mentioned QLED device.
Display screen provided in an embodiment of the present invention, due to containing above-mentioned quantum dot film, this improves quantum dot films
In stability and carrier transport ability, device efficiency can be correspondingly improved.
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, comprising the following steps:
CdSe quantum dot performed thin film is provided, the quantum dot performed thin film is transferred in vacuum chamber, is passed through 1,2-
Dithioglycol gas, wherein vacuum chamber internal pressure is 5Pa, the partial pressure of 1,2- dithioglycol gas is 1Pa, chamber interior
Temperature is 25 DEG C, and the processing time is 30min, and after treatment is taken out, and obtains the CdSe amount that ligand is replaced into 1,2- dithioglycol
Son point film.
Embodiment 2
A kind of preparation method of eurymeric structure quantum point light emitting diode, comprising the following steps:
PEDOT hole injection layer is successively printed on ito anode, TFB hole transmission layer, surface are coated with oleic acid ligand
CdSe quantum dot performed thin film；
The quantum dot performed thin film of above-mentioned preparation is transferred in vacuum chamber, Isosorbide-5-Nitrae-dimercaptobenzene gas is passed through, wherein
Chamber interior pressure is 5Pa, Isosorbide-5-Nitrae-dimercaptobenzene gas partial pressure is 1Pa, and chamber interior temperature is 25 DEG C, and the processing time is
30min, after treatment are taken out, and Isosorbide-5-Nitrae-dimercaptobenzene ligand crosslinking CdSe quantum dot luminescent layer is obtained；
ZnO electron transfer layer, last evaporating Al are printed on the quantum dot light emitting layer of ligand obtained above conjugation crosslinking
Cathode obtains eurymeric structure quantum point light emitting diode.
Embodiment 3
A kind of preparation method of reciprocal form structure light emitting diode with quantum dots, comprising the following steps:
ZnO electron transfer layer is successively printed on ITO cathode, surface is coated with the CdSe quantum dot performed thin film of oleic acid；
The quantum dot performed thin film of above-mentioned preparation is transferred in vacuum chamber, Isosorbide-5-Nitrae-dimercaptobenzene gas is passed through, wherein
Chamber interior pressure is 5Pa, Isosorbide-5-Nitrae-dimercaptobenzene gas partial pressure is 1Pa, and chamber interior temperature is 25 DEG C, and the processing time is
30min, after treatment are taken out, and Isosorbide-5-Nitrae-dimercaptobenzene ligand crosslinking CdSe quantum dot luminescent layer is obtained；
TFB hole transmission layer and PEDOT are successively printed on the quantum dot light emitting layer of ligand obtained above conjugation crosslinking
Hole injection layer, last evaporating Al anode, obtains reciprocal form structure light emitting diode with quantum dots.
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 film, which is characterized in that the quantum dot surface in the quantum dot film is connected with as flowering structure is logical
The conjugated ligand of formula:
X1-R-X2
Wherein, X1And X2For can be with the functional group in conjunction with quantum dot surface；R is alkyl or alkyl derivative with conjugation group.
2. quantum dot film as described in claim 1, which is characterized in that the X1And X2Be independently selected from halogen atom, hydroxyl,
Ether, sulfydryl, thioether group, aldehyde radical, carbonyl, carboxyl, ester group, nitro, nitroso, amino, imido grpup, sulfo group, acyl group, nitryl
Base, sulfonyl, cyano, isocyano group, hydrazone group, phosphino-, phosphate, oximido, epoxy group, azo group, vinyl, acetenyl, fragrance
At least one of ring group；And/or
The R is to include double bond and the alternately arranged linear structure of singly-bound and/or cyclic structure.
3. a kind of preparation method of quantum dot film, which comprises the steps of:
Quantum dot performed thin film and gaseous conjugated ligand, the general structure of the conjugated ligand are as follows: X are provided1-R-X2；
Wherein, X1And X2For can with the functional group in conjunction with quantum dot surface, R be with conjugation group alkyl or alkyl derivative；
The quantum dot performed thin film, which is placed in, to be passed through the conjugated ligand and carry out the displacement of gas phase ligand, make in obturator
Quantum dot surface initial ligand in the quantum dot performed thin film is replaced into the conjugated ligand, and it is thin to obtain the quantum dot
Film.
4. the preparation method of quantum dot film as claimed in claim 3, which is characterized in that it is described can stagnation pressure in obturator
It is 10-5-103Pa, the partial pressure of the conjugated ligand are 10-4-102Pa。
5. the preparation method of quantum dot film as claimed in claim 3, which is characterized in that
The temperature of the gas phase ligand displacement is 5-200 DEG C；And/or
The time of the gas phase ligand displacement is 0.5-360min.
6. the preparation method of quantum dot film as claimed in claim 3, which is characterized in that the X in the conjugated ligand1And X2
Be independently selected from halogen atom, hydroxyl, ether, sulfydryl, thioether group, aldehyde radical, carbonyl, carboxyl, ester group, nitro, nitroso, amino,
Imido grpup, sulfo group, acyl group, nitroxyl, sulfonyl, cyano, isocyano group, hydrazone group, phosphino-, phosphate, oximido, epoxy group, azo
At least one of base, vinyl, acetenyl, fragrant ring group；And/or
The R is to include double bond and the alternately arranged linear structure of singly-bound and/or cyclic structure.
7. the preparation method of quantum dot film as claimed in claim 3, which is characterized in that described to provide gaseous conjugated ligand
Process include: by liquid conjugated ligand evaporated or boiling processing after obtain gaseous conjugated ligand；Or
Solid-state conjugated ligand is obtained into gaseous conjugated ligand through distillation processing or successively after liquefaction processing, evaporation process.
8. a kind of QLED device, including quantum dot light emitting layer, which is characterized in that the quantum dot light emitting layer is claim 3-7
The quantum dot film that described in any item preparation methods obtain.
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 the described in any item preparation methods of claim 3-7, quantum dot performed thin film is prepared into quantum dot film, is obtained
Quantum dot light emitting 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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