CN109935670A - Surface ligand, quantum dot film, QLED device and preparation method thereof - Google Patents
Surface ligand, quantum dot film, QLED device and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of surface ligand, quantum dot film, QLED device and preparation method thereof.The surface ligand is specification Formulas I compound represented: where n is the integer more than or equal to 1；As n=1, R1, R2, R3, R4, R1 ', R2 ', R3 ', in R4 ' at least two for can be with the functional group of the ligand binding of quantum dot or quantum dot surface；As n > 1, R1, R2, R3, R4, R1 ', R2 ', R3 ', at least one in R4 ' is can be with the functional group of the ligand binding of quantum dot or quantum dot surface.The surface ligand is a kind of compound containing conjugated structure, on the one hand can be anchored multiple quantum dots simultaneously, form the quantum dot film of crosslinking, has cross-linked disperse, to improve the stability of quantum dot film；On the other hand, which can effectively improve the transmission of carrier, to improve the luminescent properties of device because having huge conjugated structure.
Description
Technical field
The invention belongs to technology of quantum dots fields, and in particular to a kind of surface ligand, quantum dot film, QLED device and its
Preparation method.
Background technique
Light emitting diode with quantum dots (Quantum dot light-emitting diode, QLED) is a kind of novel hair
Optical device uses quanta point material (Quantum dots, QDs) as luminescent layer, has compared to other luminescent materials and be difficult to
The advantage of analogy, such as internal quantum efficiency, the excellent excitation purity of controllable small-size effect, superelevation, in the following display technology
Field has huge application prospect.
During solwution method prepares QLED device, on the one hand, when preparing each functional layer above quantum dot layer, be easy shadow
It rings and even destroys quantum dot layer, therefore solvent used in functional layer is typically chosen the organic solvent orthogonal with quantum dot layer solvent,
But it is also difficult to avoid that the case where destroying quantum dot layer in this way, and the selection of these functional layer materials and solvent has biggish limit
System；On the other hand, after quantum dot is prepared into film and device, ligand is easy to fall off or in device storage or work process
It is destroyed, greatly influences the performance of QLED device in this way.
Summary of the invention
It is an object of the invention to provide a kind of surface ligands, quantum dot film and preparation method thereof, it is intended to solve existing quantum
Point ligand is easy to fall off or is destroyed, to cause the technical problem that quantum dot film is unstable, luminescent properties are bad.
Another object of the present invention is to provide a kind of QLED device containing above-mentioned quantum dot film and preparation method thereof, aobvious
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 surface ligand, and the surface ligand is such as following formula I compound represented:
Wherein, n is the integer more than or equal to 1；As n=1, R1, R2, R3, R4, R1 ', R2 ', R3 ', in R4 ' at least
Two is can be with the functional groups of the ligand binding of quantum dot or quantum dot surface；As n > 1, R1, R2, R3, R4, R1 ', R2 ',
At least one in R3 ', R4 ' is can be with the functional group of the ligand binding of quantum dot or quantum dot surface.
Correspondingly, a kind of quantum dot film, the quantum dot in the quantum dot film are combined with above-mentioned surface ligand,
In, the surface ligand is in conjunction with the initial ligand of quantum dot surface or quantum dot surface.
And a kind of preparation method of quantum dot film, comprising the following steps:
Quantum dot performed thin film is provided, the quantum dot in the quantum dot performed thin film is combined with initial ligand；
By the quantum dot performed thin film and above-mentioned surface ligand mixed processing, the quantum dot surface or described is obtained
Initial ligand is combined with the quantum dot film of the surface ligand.
On the other hand, the present invention provides a kind of QLED device, including the substrate, hearth electrode, quantum dot light emitting set gradually
Layer and top 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.
Finally, the present invention provides a kind of display screen, including above-mentioned QLED device.
Surface ligand provided by the invention is a kind of long-chain compound containing conjugated structure, on the one hand, it can be simultaneously
Multiple quantum dots are anchored, the quantum dot film of crosslinking is formed, there is cross-linked disperse, to improve the stability of quantum dot film；
On the other hand, which has huge conjugated structure, the transmission of carrier can be effectively improved, to improve device
Luminescent properties.
Quantum dot film provided by the invention, QLED device, display screen, since the surface of the quantum dot wherein contained combines
Match on the surface that the initial ligand of the surface ligand and quantum dot surface therein that have aforementioned present invention is combined with aforementioned present invention
Body, therefore it is with good stability, and the surface ligand can effectively improve the transmission of carrier, therefore it has
Good luminescent properties.
The preparation method of quantum dot film provided by the invention and the preparation method of QLED device, including use quantum dot
Performed thin film and above-mentioned surface ligand mixed processing step of the invention, the mixed process liquid phase process or gas phase process are ok
It realizes.After mixed processing, above-mentioned surface ligand can with quantum dot by electrostatic interaction in conjunction with, or with quantum dot surface just
By bonding action anchoring, (bonding action can be regarded as chemically reacting beginning ligand, including addition reaction, substitution reaction, organic oxygen
Change reduction reaction, polymerization reaction, condensation reaction；Generally refer to esterification, acylation reaction, sulfonylation, acyl chloride reaction,
Acyl chlorides substitution reaction, ester substitution reaction, aldol reaction etc.), so that the quantum dot film of crosslinking is formed, it in this way can raising amount
The stability and luminescent properties of son point film or QLED device.Meanwhile the subsequent deposition other function material on quantum dot film
It when material, can be influenced caused by quantum dot film to avoid the introducing of solvent, to extend the solvent of subsequent material to be deposited
Range of choice.
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 surface ligand, the surface ligand is the chemical combination as shown in following formula I
Object:
Wherein, n is the integer more than or equal to 1；As n=1, R1, R2, R3, R4, R1 ', R2 ', R3 ', in R4 ' at least
Two is can be with the functional groups of the ligand binding of quantum dot or quantum dot surface；As n > 1, R1, R2, R3, R4, R1 ', R2 ',
At least one in R3 ', R4 ' is can be with the functional group of the ligand binding of quantum dot or quantum dot surface.
Above-mentioned surface ligand is a kind of long-chain compound containing conjugated structure, on the one hand, it can be anchored multiple amounts simultaneously
It is sub-, the quantum dot film of crosslinking is formed, there is cross-linked disperse, to improve the stability of quantum dot film；On the other hand, should
Surface ligand has huge conjugated structure, the transmission of carrier can be effectively improved, to improve the luminescent properties of device.
Further, in above-mentioned surface ligand, can with the functional group of the ligand binding of quantum dot or quantum dot surface or
The functional group for being connected with saturated carbon chains or unsaturation carbochain, be chosen in particular from halogen atom, hydroxyl, ether, sulfydryl, thioether group,
Aldehyde radical, carbonyl, carboxyl, ester group, nitro, nitroso, amino, imido grpup, sulfenyl, sulfo group, acyl group, amide groups, nitroxyl, sulphonyl
Base, cyano, isocyano group, hydrazone group, phosphino-, phosphate, oximido, epoxy group, azo group, vinyl, acetenyl, in fragrant ring group
It is one or more；It is further preferred that the functional group be sulfydryl, hydroxyl, carboxyl, amino, cyano, and if R1, R2,
R3, R4, R1 ', R2 ', R3 ', also contain carbochain other than functional group in R4 ', then the carbochain is preferably unsaturated carbon chain structure, such as
Vinyl, acetenyl, phenyl ring etc., this is because unsaturated structure can have conjugation, to promote the transmission of electronics.
The specific method of long-chain compound shown in Formulas I above-mentioned for acquisition is not within this case limit of consideration, as long as energy
Enough obtain the compound.In general, above-mentioned Formulas I compound represented can be as follows by 1-4 in the embodiment of the present invention
The monomer of the composition of unit shown in Formula II, is obtained by the reactions such as being condensed or polymerizeing.
Preferably for above compound, it is contemplated that situations such as steric hindrance, there is following preferred structure:
In R1, R2, R3, R4, R1 ', R2 ', R3 ', in R4 ', there is 6 kinds of preferable cases: (1) R1 and R3 ' be can with quantum dot,
Or the functional group of the ligand binding of quantum dot surface, other are H, and concrete structure formula is as shown in Formulas I a；(2) R1 and R2 ' be can be with
The functional group of the ligand binding of quantum dot or quantum dot surface, other are H, and concrete structure formula is as shown in Formulas I b；(3) R1, R3 and
R1 ' is can be with the functional group of the ligand binding of quantum dot or quantum dot surface, other are H, and concrete structure formula is as shown in Formulas I c；
(4) R1, R3, R1 ' and R3 ' be can be with the functional group of the ligand binding of quantum dot or quantum dot surface, other are H, specific structure
Formula is as shown in Formulas I d；(5) R1, R2 and R1 ' be can be with the functional group of the ligand binding of quantum dot or quantum dot surface, other are
H, concrete structure formula is as shown in Formulas I e；(6) R1, R2, R1 ' and R2 ' be can be with the ligand binding of quantum dot or quantum dot surface
Functional group, other are H, and concrete structure formula is as shown in Formulas I f.
Embodiment more preferably lifts the structure of 3 preferred compounds: such as following formula I g, Formulas I h, Formulas I i institute below
Show.
For conventional quantum dot cross-linking method, usually make to react between quantum dot surface ligand, or
The ligand with carbon-carbon double bond etc is introduced in quantum dot, is added crosslinking agent, is promoted by the methods of ultraviolet lighting or heating
It is reacted, and to form the quantum dot film of crosslinking, is very easy to cause between quantum dot during crosslinking between quantum dot
Reunite, and certain cross-linked areas quantum dots easily occurs and assemble situations such as more, certain cross-linked areas quantum dot aggregations are few, though at this moment
So-called crosslinked film so can be formed, but due to the uneven crosslinking between quantum dot, will affect the uniformity of film layer instead
And the uniformity of luminance of device.And in embodiments of the present invention, surface ligand shown in Formulas I of the embodiment of the present invention is introduced, by
In it with long-chain, there is certain steric configuration, be capable of forming reticular structure, and have thereon it is multiple can be with quantum dot knot
The functional group of conjunction can only be anchored on quantum dot on the long-chain of the surface ligand (it is to be understood that for long-chain surface ligand
It is a rope, multiple quantum dots are embedded on this rope), it can't reunite between quantum dot, so as to avoid biography
The drawbacks of system cross-linking method.In general, the electric conductivity of long-chain polymer is not fine, but long-chain with a conjugated structure
Compound is due to containing a large amount of unsaturated bonds, and delocalized electron can be transmitted freely, to greatly improve its electric conductivity；It is based on
This, the structure of the long-chain surface ligand of the embodiment of the present invention is phenyl ring and the spaced long-chain compound of triple carbon-carbon bonds, and
Above with multiple functional groups with quantum dot coordination.In this way, which the electric conductivity of long-chain surface ligand is very high, quantum dot is not only
It can be crosslinked and be anchored on chain, while long-chain surface ligand can improve the transmission of carrier as the channel of carrier transport
Performance, and then improve the uniformity of luminance of device.
Correspondingly, the embodiment of the present invention provides a kind of quantum dot film, and the quantum dot in the quantum dot film is combined with this
Surface ligand shown in formula I in inventive embodiments, wherein the surface ligand and quantum dot surface or quantum dot surface are matched
Body combines.
Quantum dot film provided in an embodiment of the present invention, the above-mentioned surface that quantum dot surface is connected with conjugated structure are matched
On the one hand body can be anchored multiple quantum dots simultaneously, form the quantum dot film of crosslinking, have cross-linked disperse, and film layer
Stablize；On the other hand, with huge conjugated structure, the transmission of carrier can be effectively improved, to improve quantum dot
The luminescent properties of film.
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..
Correspondingly, the embodiment of the present invention provides a kind of preparation method of above-mentioned quantum dot film, includes the following steps:
S01: providing quantum dot performed thin film, and the quantum dot in the quantum dot performed thin film is combined with initial ligand；
S02: by surface ligand mixed processing shown in the quantum dot performed thin film and above-mentioned Formulas I, the quantum is obtained
Point surface or the initial ligand are combined with the quantum dot film of the surface ligand.
The preparation method of quantum dot film provided in an embodiment of the present invention, including use quantum dot performed thin film and the present invention
Above-mentioned Formulas I shown in surface ligand mixed processing step, the mixed process liquid phase process or gas phase process can be realized.It is mixed
After conjunction processing, above-mentioned surface ligand can with quantum dot by electrostatic interaction in conjunction with, or the initial ligand with quantum dot surface
It is anchored by bonding action, to form the quantum dot film of crosslinking, the stability of the high quantum dot film of energy energy, raising in this way is sent out
Optical property.Meanwhile it is subsequent when depositing other function material on quantum dot film, it can be thin to quantum dot to avoid the introducing of solvent
It is influenced caused by film, to extend the solvent selection range of subsequent material to be deposited.
Specifically, in above-mentioned steps S02, the process of quantum dot performed thin film and above-mentioned surface ligand mixed processing can be
Gas phase reaction or liquid phase reactor.Specifically, gas phase reaction in this way, the process of the mixed processing are as follows: the quantum dot is prefabricated
Film, which is placed in, to be passed through the gaseous surface ligand in obturator, carry out gas phase reaction.Had using vapor phase method solvent-free
Outstanding advantages of damaging (overall performance for the quantum dot film that raising obtains), low in cost, simple process.In addition, using gas
Phase method is reacted, and ligand displacement degree is more abundant in gas phase atmosphere, and the selection of surface ligand is by the limitation of solution environmental,
With preferable selection flexibility, scale and industrialized production may be implemented.
Specifically, by the quantum dot performed thin film be placed in can be in obturator when, it is described can obturator as reaction
Device, on the one hand, it can prevent water, oxygen from entering, in order to avoid surface ligand is impacted；Importantly, described closed can fill
The closed environment set can form pressurization or vacuum environment, to promote the progress of gas phase reaction.Theoretically, as long as being able to achieve
The airtight chamber of certain vacuum degree could be used for the embodiment of the present invention, can be low vacuum airtight chamber, is also possible to high vacuum
Airtight chamber, the embodiment of the present invention do not limit strictly.In one preferred embodiment, during the gas phase reaction, it is described can
The internal pressure of obturator is 10-4~102Pa, the partial pressure of the surface ligand are 0.01~10Pa.
Specifically, liquid phase reactor in this way, the process of the mixed processing are as follows: by the quantum dot performed thin film be placed in containing
Immersion treatment is carried out in the solution of the surface ligand.The long-chain surface ligand and quantum dot film of the embodiment of the present invention act on simultaneously
The implementation method for being anchored the quantum dot film that multiple quantum dots ultimately form crosslinking simultaneously can be such that firstly, above-mentioned long chained list
The preferred physical state of face ligand is that (can be conventional sense is liquid to liquid, can also be changed by modes such as heating
Liquid can also be dissolved in certain solvent, form solution shape), quantum dot film is then immersed into above-mentioned long-chain surface
(it is also possible to be deposited directly on quantum dot film by the methods of spin coating, printing) in ligand liquid, immersion 5~
It is taken out after 120min, forms the quantum dot film of crosslinking.It further, further include in 60-200 after the immersion treatment
Under conditions of DEG C the step of heating anneal, to remove unbonded surface ligand and solvent.
Specific address, the quantum dot in the quantum dot performed thin film be 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
One of race's simple substance 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, four
The II-VI group compound of member；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-。
And the embodiment of the invention also provides a kind of QLED device, including quantum dot light emitting layer, the quantum dot light emittings
Layer is the quantum dot film that the preparation method of the embodiments of the present invention obtains.
Specifically, QLED device includes the hearth electrode, quantum dot light emitting layer and top electrode being stacked, the embodiment of the present invention
In, the QLED device can be eurymeric QLED device, or transoid QLED device.It is described as a kind of implementation situation
QLED device can be eurymeric QLED device, i.e., the described hearth electrode is anode, and the top electrode is cathode.Implement as another kind
Situation, the QLED device can be transoid QLED device, i.e., the described hearth electrode is cathode, and the 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；
E03: preparing top electrode 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.
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 carrier transport, the efficiency of display screen 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 initial ligand of the quantum dot surface in the quantum dot performed thin film is sulfydryl
Ethamine；
By poly- (2,5- 12 carbonic acyl radical -1,4- benzene Asia acetylene -2- (11- hydroxyl hendecane epoxide carbonyl) -1,4- benzene Asia second
Alkynes) [poly (2,5-didodecanoxy-1,4-phenyleneethynylene-2- (11-
Hydroxyundecyloxycarbonyl)-Isosorbide-5-Nitrae-phenyleneethynylene)] it dissolves in ethanol, being configured to concentration is
The solution of 15mg/ml；
Above-mentioned quantum dot performed thin film is immersed in above-mentioned solution, is taken out after impregnating 20min, then be transferred into vacuum
It in chamber, adjusts vacuum degree and is 10Pa and maintains 30min, have neither part nor lot in the ligand of reaction and molten in quantum dot performed thin film to remove
Agent obtains quantum dot film.
Embodiment 2
A kind of preparation method of quantum dot film, comprising the following steps:
CdSe quantum dot performed thin film is provided, the initial ligand of the quantum dot surface in the quantum dot performed thin film is sulfydryl
Ethamine；
The quantum dot performed thin film is transferred in vacuum chamber, gaseous poly- (2,5- 10 two carbonic acyl radicals-Isosorbide-5-Nitraes-benzene are passed through
Sub- acetylene -2- (11- hydroxyl hendecane epoxide carbonyl)-Isosorbide-5-Nitrae-benzene Asia acetylene), wherein vacuum chamber internal pressure is 5Pa, gathers
Point of (2,5- 12 carbonic acyl radical -1,4- benzene Asia acetylene -2- (11- hydroxyl hendecane epoxide carbonyl) -1,4- benzene Asia acetylene) gas
Pressure is 1Pa, and chamber interior temperature is 25 DEG C, and the processing time is 30min, and after treatment is taken out, and obtains CdSe quantum dot film.
Embodiment 3
A kind of preparation method of light emitting diode with quantum dots, comprising the following steps:
By poly- (2,5- 12 carbonic acyl radical -1,4- benzene Asia acetylene -2- (11- hydroxyl hendecane epoxide carbonyl) -1,4- benzene Asia second
Alkynes) dissolve the solution for being configured to that concentration is 15mg/ml in ethanol；
It is sulfydryl second that PEDOT hole injection layer, TFB hole transmission layer, initial surface ligand are successively printed on ito anode
Quantum dot film, is then immersed in above-mentioned solution by the CdSe quantum dot film of amine, takes out after impregnating 20min, then by its turn
Move on in vacuum chamber, adjust vacuum degree and be 10Pa and maintain 30min, with remove participated in quantum dot film reaction ligand and
Solvent obtains CdSe quantum dot luminescent layer.
Printing ZnO electron transfer layer on the quantum dot light emitting layer obtained after chemical reaction crosslinking, last evaporating Al cathode,
Obtain light emitting diode with quantum dots.
In above-described embodiment, by poly- (2, the 5- 10 two carbonic acyl radicals-Isosorbide-5-Nitraes-benzene for introducing conjugated structure in quantum dot film
Sub- acetylene -2- (11- hydroxyl hendecane epoxide carbonyl)-Isosorbide-5-Nitrae-benzene Asia acetylene), on the one hand, it can be anchored multiple quantum simultaneously
Point forms the quantum dot film of crosslinking, has cross-linked disperse, to improve the stability of quantum dot film；On the other hand, have
There is huge conjugated structure, the transmission of carrier can be effectively improved, to improve the luminescent properties of device.
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 surface ligand, which is characterized in that the surface ligand is such as following formula I compound represented:
Wherein, n is the integer more than or equal to 1；As n=1, R1, R2, R3, R4, R1 ', R2 ', R3 ', at least two in R4 '
For can be with the functional group of the ligand binding of quantum dot or quantum dot surface；As n > 1, R1, R2, R3, R4, R1 ', R2 ', R3 ',
At least one in R4 ' is can be with the functional group of the ligand binding of quantum dot or quantum dot surface.
2. surface ligand as described in claim 1, which is characterized in that the functional group include: halogen atom, hydroxyl, ether,
Sulfydryl, thioether group, aldehyde radical, carbonyl, carboxyl, ester group, nitro, nitroso, amino, imido grpup, sulfenyl, sulfo group, acyl group, amide
Base, nitroxyl, sulfonyl, cyano, isocyano group, hydrazone group, phosphino-, phosphate, oximido, epoxy group, azo group, vinyl, acetylene
At least one of base, fragrant ring group；And/or
In Formulas I compound represented, n=1-4.
3. a kind of quantum dot film, which is characterized in that the quantum dot in the quantum dot film is combined with claims 1 or 2 institute
The surface ligand stated, wherein the surface ligand is in conjunction with the initial ligand of quantum dot surface or quantum dot surface.
4. a kind of preparation method of quantum dot film, which comprises the following steps:
Quantum dot performed thin film is provided, the quantum dot in the quantum dot performed thin film is combined with initial ligand；
By the quantum dot performed thin film and surface ligand mixed processing of any of claims 1 or 2, the quantum dot table is obtained
Face or the initial ligand are combined with the quantum dot film of the surface ligand.
5. the preparation method of quantum dot film as claimed in claim 4, which is characterized in that the process of the mixed processing are as follows:
The quantum dot performed thin film, which is placed in, to be passed through the gaseous surface ligand in obturator, carry out gas phase reaction；Or
The quantum dot performed thin film is placed in the solution containing the surface ligand and carries out immersion treatment.
6. the preparation method of quantum dot film as claimed in claim 5, which is characterized in that during the gas phase reaction,
It is described can obturator internal pressure be 10-4~102Pa, the partial pressure of the surface ligand are 0.01~10Pa.
7. the preparation method of quantum dot film as claimed in claim 5, which is characterized in that the time of the immersion treatment is 5-
120min；And/or
After the immersion treatment, further include the steps that heating under conditions of 60-200 DEG C.
8. a kind of QLED device, including quantum dot light emitting layer, which is characterized in that the quantum dot light emitting layer is by claim 4-
The quantum dot film that 7 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 4-7, 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 QLED device according to any one of claims 8.
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| CN113831907A (en) * | 2020-06-24 | 2021-12-24 | Tcl科技集团股份有限公司 | Quantum dot material and preparation method thereof, quantum dot light-emitting diode and preparation method thereof |
| CN114058373A (en) * | 2020-07-31 | 2022-02-18 | 京东方科技集团股份有限公司 | Quantum dot structure, quantum dot light-emitting device and manufacturing method |
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| CN105070849A (en) * | 2015-07-14 | 2015-11-18 | Tcl集团股份有限公司 | Light-emitting device with compactly arranged quantum dot light-emitting layer and preparation method thereof |
| CN106531860A (en) * | 2016-12-22 | 2017-03-22 | Tcl集团股份有限公司 | Quantum dot luminescent layer and device, and preparation methods thereof, luminescence module and display device |
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| CN105070849A (en) * | 2015-07-14 | 2015-11-18 | Tcl集团股份有限公司 | Light-emitting device with compactly arranged quantum dot light-emitting layer and preparation method thereof |
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Cited By (3)
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| CN113831907A (en) * | 2020-06-24 | 2021-12-24 | Tcl科技集团股份有限公司 | Quantum dot material and preparation method thereof, quantum dot light-emitting diode and preparation method thereof |
| 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 |
| CN114058373A (en) * | 2020-07-31 | 2022-02-18 | 京东方科技集团股份有限公司 | Quantum dot structure, quantum dot light-emitting device and manufacturing method |
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