CN109935715A - Transoid QLED device and preparation method thereof - Google Patents
Transoid QLED device and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of transoid QLED device, comprising the following steps: provides cathode and displaced ligands solution；Quantum dot performed thin film is deposited on the cathode, the quantum dot performed thin film is made of the quantum dot that initial ligand is contained on surface, displaced ligands in the quantum dot performed thin film and the displaced ligands solution are subjected to ligand exchange in situ, the initial ligand is replaced into displaced ligands, obtains quantum dot light emitting layer；Hole functional layer is prepared in the quantum dot light emitting layer surface, prepares anode in the hole functional layer.
Description
Technical field
The invention belongs to technical field of flat panel display more particularly to a kind of transoid QLED device and preparation method thereof.
Background technique
Light emitting diode with quantum dots (Quantum dot light-emitting diode, QLED) is a kind of novel
Luminescent device, uses quanta point material (Quantum dots, QDs) as luminescent layer, has hardly possible compared to other luminescent materials
With internal quantum efficiency, the excellent excitation purity of the advantage of analogy, such as controllable small-size effect, superelevation, skill will be shown in future
Art field has huge application prospect.
Under normal circumstances, quantum dot surface can connect organic ligand or by forming chemical bond etc. by modes such as chelatings
Mode connects mineral ligand.The surface ligand of quantum dot plays the role of vital in quantum dot synthesis, on the one hand, surface
Defect with physical efficiency passivation quantum dot surface, improves the luminescent properties of quantum dot；On the other hand, surface ligand can reduce quantum
Reunite between point, and increases the dispersibility of quantum dot in a solvent.In light emitting diode with quantum dots device, surface ligand meeting
The photoelectricity performance of device is further influenced, therefore the ligand for reasonably selecting the quantum dot surface in quantum dot film is to improve quantum
The important step of point film and light emitting diode with quantum dots luminous efficiency.
Swap after synthesis terminates to the ligand of quantum dot surface is mode commonplace at present.But this method
It has certain problems.Firstly, the ligand of quantum dot surface influences its dispersibility in organic solvent, therefore in ligand exchange
The ligand introduced in the process is likely to result in the poor dispersion of quantum dot, especially for the shorter ligand of some chain lengths point
Son often will appear the problem of quantum dot can not disperse, therefore can not form quantum dot film with good uniformity.Secondly,
When directly carrying out ligand exchange in solution, selected ligand structure and type are by biggish limitation, for example, solution ligand exchange
Ligand used can only be single ligand, i.e., bridging property ligand (while connection 2 or more QD) cannot be used, because molten
It is added after bridging property ligand between quantum dot or is connected with each other in liquid, and then reunion and coagulation.Simultaneously as quantum dot in solution
It is more, generate the insufficient situation of ligand exchange.In addition, the new ligand for displacement is molten there is also that cannot be dissolved in former quantum dot
Situation in liquid, the selectivity of ligand substantially reduces at this time.
On this basis, at present mainstream transoid QLED device (positive and negative anodes position exchange, be successively on substrate cathode,
Electronic work ergosphere, quantum dot light emitting layer, hole functional layer, hole-injecting material and anode), due on quantum dot light emitting layer
When preparing hole transmission layer and hole injection layer by solwution method, solvent for use, which may re-dissolve, takes away or directly washes away quantum
Quantum dot in point luminescent layer, destroys quantum dot layer, thus influence quantum dot light emitting layer at film uniformity and interface performance, into
And transoid QLED device uniformity of luminance is influenced, especially for the quantum dot light emitting layer of printing technology preparation.
Summary of the invention
The purpose of the present invention is to provide a kind of transoid QLED devices and preparation method thereof, it is intended to solve existing transoid
In the preparation process of QLED device, the solvent damage quantum dot layer of hole functional layer, to influence the film forming of quantum dot light emitting layer
The problem of uniformity and interface performance.
The invention is realized in this way a kind of preparation method of transoid QLED device, comprising the following steps:
Cathode and displaced ligands solution are provided；
Quantum dot performed thin film is deposited on the cathode, and the quantum dot performed thin film contains initial ligand by surface
Displaced ligands in the quantum dot performed thin film and the displaced ligands solution are carried out ligand in situ and handed over by quantum dot composition
It changes, the initial ligand is replaced into displaced ligands, obtains quantum dot light emitting layer；
Hole functional layer is prepared in the quantum dot light emitting layer surface, prepares anode in the hole functional layer.
And a kind of transoid QLED device, cathode, quantum dot light emitting layer, hole functional layer and the sun combined including stacking
Pole, wherein the transoid QLED device is prepared by the above method.
The preparation method of transoid QLED device provided by the invention first deposits quantum dot performed thin film, then using in situ
The initial ligand of quantum dot surface in quantum dot performed thin film is replaced into displaced ligands by ligand exchange, thus change quantum dot at
Surface polarity and surface tension after film, so by control quantum dot surface polarity, avoid quantum dot light emitting layer from
The influence of upper layer hole functional material solution solvent, so as to realize the preparation of whole soln method transoid device.Simultaneously as amount
The arrangement of quantum dot and position are substantially stationary in son point performed thin film, are not in quantum dot when using ligand exchange in situ at this time
The problem of sedimentation, to extend the range of choice of ligand, while the solvent selectivity of displaced ligands is more.In addition, passing through original
Position ligand exchange, so that the surface ligand of quantum dot has more selectivity in quantum dot light emitting layer, to improve hole function
The selectivity of material and its dissolution solvent.
Transoid QLED device provided by the invention, is prepared by the above method, so that the hole function of transoid QLED device
Energy the material such as solvent of hole mobile material, hole mobile material and the ink type of formation are no longer limited, to expand anti-
The range of choice of type QLED device hole functional material and ink.
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.
In the present invention, " highly polar " and " low pole " is an opposite description, is indicated using certain displaced ligands as ginseng
According to, another displaced ligands with its carry out Polarity comparision as a result, using certain organic solvent as reference, it is another organic
Solvent carries out the result of Polarity comparision with it.The polarity refers to polar relatively strong and weak, not proper pole on the contrary
Property with nonpolarity on difference.
The embodiment of the invention provides a kind of preparation methods of transoid QLED device, comprising the following steps:
S01., cathode and displaced ligands solution are provided；
S02. quantum dot performed thin film is deposited on the cathode, and the quantum dot performed thin film is contained by surface initially matches
The quantum dot of body forms, and the displaced ligands in the quantum dot performed thin film and the displaced ligands solution are carried out ligand in situ
Exchange, is replaced into displaced ligands for the initial ligand, obtains quantum dot light emitting layer；
S03. hole functional layer is prepared in the quantum dot light emitting layer surface；
S04. anode is prepared in the hole functional layer.
The preparation method of transoid QLED device provided in an embodiment of the present invention first deposits quantum dot performed thin film, then adopts
The initial ligand of quantum dot surface in quantum dot performed thin film is replaced into displaced ligands with ligand exchange in situ, thus knots modification
Surface polarity and surface tension after son point film forming, and then by the polarity of control quantum dot surface, avoid quantum dot light emitting
Layer from upper layer hole functional material solution solvent influence, so as to realize the preparation of whole soln method transoid device.Meanwhile
Since the arrangement of quantum dot and position are substantially stationary in quantum dot performed thin film, be not in when using original position ligand exchange at this time
The problem of quantum dot settles, to extend the range of choice of ligand, while the solvent selectivity of displaced ligands is more.In addition,
By ligand exchange in situ, so that the surface ligand of quantum dot has more selectivity in quantum dot light emitting layer, to improve sky
The selectivity of acupoints material and its dissolution solvent.
Specifically, the cathode can deposit over the substrate in above-mentioned steps S01, cathode base is formed.The lining
Bottom is rigid substrate or flexible substrate, and the rigid substrate includes but is not limited to one of glass, metal foil or a variety of；Institute
Flexible substrate is stated to include but is not limited to polyethylene terephthalate (PET), polyethylene terephthalate (PEN), gather
Ether 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), one in textile fabric
Kind is a variety of.
Preferably, the general structure of displaced ligands is X in the displaced ligands solution1-R-X2, wherein the R is
Alkyl or alkyl derivative, the X1For the functional group being crosslinked with the quantum dot, the X2Functional group, and institute are adjusted for polarity
The crosslinking active for stating X1 and quantum dot is greater than the crosslinking active of the X2 and quantum dot (X1 be different functional group with X2), from
And make the anchoring ability of X1 and quantum dot stronger, and X2 is made to be exposed at the outermost of quantum dot ligand shell.The embodiment of the present invention
Pass through the X1The connection for realizing the surface ligand Yu the quantum dot passes through the X2Carry out the surface polarity of quantum point,
To change the surface polarity and surface tension of quantum dot light emitting layer, and then by the polarity of control quantum dot surface, avoid anti-
The quantum dot light emitting layer of lower layer is influenced by upper layer hole functional material solution solvent in type QLED device fabrication process, thus
The solwution method preparation of transoid QLED device may be implemented.
Wherein, the R is alkyl or alkyl derivative, selected from full containing any organo-functional group or without organo-functional group
With alkane, unsaturated alkane, fragrant hydrocarbons and their derivates, it is specifically including but not limited to alkane, alkene, alkynes, aromatic hydrocarbon, cycloalkanes
Hydrocarbon, halogenated hydrocarbons, alcohol, ether, phenol, aldehyde, ketone, carboxylic acid, ester, nitrogenous compound.
Preferably, the X1For-SH ,-COOH ,-NH2、-OH、-NO2、-SO3H, one of phosphino-, phosphate；It is preferred that
, the X2For-COOH ,-OH ,-CN ,-NHCO-CH3、-NH2、-SH、-CHO、-CO-、-COOR、-NO2、-O-、-O-CH3、-
CH3One of.
The case where for the free active function groups of quantum dot surface ligand are adjusted to polar functional group, it is preferred that when
When X1 is-SH, X2 is selected from-COOH ,-OH ,-CN ,-NHCO-CH3、-NH2,-CHO,-CO-；When X1 be-COOH when, X2 be selected from-
OH、-NHCO-CH3、-NH2,-CHO,-CO-；When X1 is-CN, X2 is selected from -- NHCO-CH3、-NH2,-CHO,-CO-；Work as X1
When for-OH, X2 is selected from-NHCO-CH3、-NH2,-CHO,-CO-；When X1 is-NH2, X2 is selected from-NHCO-CH3、-CHO、-CO-。
The case where for the free active function groups of the ligand of quantum dot surface are adjusted to nonpolarity or low pole functional group, it is preferred that
When X1 is-SH, X2 is selected from-COOR ,-NO2、-O-、-O-CH3、-CH3；When X1 is-COOH, X2 is selected from-COOR ,-NO2、-
O-、-O-CH3、-CH3；When X1 is-CN, X2 is selected from-COOR ,-NO2、-O-、-O-CH3、-CH3；When X1 be-OH when, X2 be selected from-
COOR、-NO2、-O-、-O-CH3、-CH3；When X1 is-NH2, X2 is selected from-COOR ,-NO2、-O-、-O-CH3、-CH3.Certainly,
In X1-R-X2 structure, the alkyl chain of R is longer, and nonpolar degree is also relatively bigger.
As an implementation, X2For-COOH ,-OH ,-CN ,-NHCO-CH3、-NH2,-SH ,-CHO when, constituted
Displaced ligands can be understood as highly polar ligand, including but not limited to thioacetic acid, 3- mercaptopropionic acid, 3- mercaptobutyric acid, 6- mercapto
Base caproic acid, mercaptoethylmaine, 3- mercaptopropylamine, 4- mercaptobenzoic acid, mercapto glycerol, 1- Trimethylamine ethyl mercaptan, mercaptoaniline, nitre
At least one of base aniline, aniline sulfonic acid, aminobenzoic acid, 4- (diphenylphosphino) benzoic acid.
As another embodiment, X2For-CO- ,-COOR ,-NO2、-O-、-O-CH3、-CH3When, the displacement that is constituted
Ligand can be understood as low pole displaced ligands, including but not limited to octylame, propylamine, cetylamine, 4- sulfydryl methyl phenyl ethers anisole, 1- hydroxyl
At least one of base -3- methoxy-propa.Certainly, the embodiment of the present invention can also be come real by the carbon chain lengths of adjusting R
The existing polar adjusting of surface ligand, specifically, the carbochain of R is longer, the polarity of the surface ligand constituted is accordingly reduced.
As another preferred situation, conjugation group is contained in the R.In the embodiment of the present invention, since the conjugation is matched
The electronics of body have delocalization effect, more dense packing of molecules can be formed, be conducive to effective transmission of intermolecular charge, into
Device inside improves the transmission of carrier, to improve the luminescent properties of device.The carrier in quantum dot film is improved in this way
Transmission, can correspondingly improve the luminescent properties of device, and extend the solvent selection range of subsequent material to be deposited.However,
Since the steric hindrance of the conjugated ligand is often larger, it is larger to be combined with the distance between quantum dot of the conjugated ligand,
Laser propagation effect of the carrier between quantum dot is unsatisfactory, therefore simple by substituting generic ligand to device using conjugated ligand
The promotion effect of performance is limited.In view of this, the embodiment of the present invention keeps quantum dot tighter by being cross-linked with each other between conjugated ligand
It is close, to preferably play the advantage of organic ligand.But a quantum dot is distinguished by two crosslinked groups of conjugated ligand
In the quantum dot film being cross-linked to form with adjacent quantum dot, the type and property of the intermediary of crosslinking method and formation cross-linked structure
Matter often causes very big difference to the transmission of carrier, for example, when being crosslinked between quantum dot by long chain alkane structure, although
It is capable of forming quantum dot crosslinked film, but since the carrier transport effect of long chain alkane is poor, the carrier of the film after crosslinking
Transmission performance is simultaneously bad.Therefore, multiple active officials are arranged by the conjugated ligand end of the chain in quantum dot surface in the embodiment of the present invention
It can roll into a ball, be crosslinked with multiple active function groups on adjacent quantum dot surface, so that the transmission of carrier is can be channel transmission, simultaneously
Connection bridge between quantum dot can play electron delocalization effect (conjugated ligand), to largely improve carrier
Laser propagation effect, improve 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 group
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, 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, contain in the R
But one of it is not limited to phenyl ring ,-C=C- ,-C ≡ C- ,-C=O ,-N=N- ,-C ≡ N ,-C=N- group or a variety of；Especially
Ground, 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 knot
Structure, indenes structure, pyrene Jie Gou, Benzyl structure, acenaphthene structure, acenaphthylene structure, fluorene structured, anthracene structure, fluoranthene structure, benzanthracene structure, benzene
And it fluoranthene structure, benzopyran structure, indeno pyrene structure, dibenzanthracene structure, benzo structure, pyrrole structure, pyridine structure, rattles away
Piperazine structure, furan structure, thiophene-structure, indole structure, porphine structure, porphyrin structure, thiazole structure, glyoxaline structure, pyrazine knot
Structure, pyrimidine structure, quinoline structure, isoquinoline structure, pteridine structure, acridine structure, oxazole structure, carbazole structure, triazole structure,
Benzofuran structure, benzothiophene structure, benzothiazole structure, benzoxazoles structure, benzopyrrole structure, benzimidazole structure
One of or it is a variety of.
Specifically, the displaced ligands are selected to 2- mercaptobenzoic acid, 4- mercaptobenzoic acid, 4-aminobenzoic acid, 4- hydroxyl
Yl benzoic acid, to sulfosalicylic acid, paranitrobenzoic acid, 4- mercaptoaniline, 4- hydroxyanilines, 4- cyano-aniline, 4- sulfydryl benzene
Hexenoic acid, 4-Vinyl phenol acid, 2- (4- hydroxy phenyl) pyridine, the chloro- 5- cyano thiazole of 2-, 2- Amino 3 cyano thiophene, 3-
At least one of amino -5- sulfydryl -1,2,4- triazole.
In the embodiment of the present invention, by selecting the X2 big with the material polarity spectrum of hole transmission layer, according to the displacement
The polar difference of ligand, choosing to the property of can choose has the function of opposite (or difference is larger) polar solvent as hole material
The solvent of material realizes that the dipole inversion of adjacent materials layer configures the hole function of later layer so as to avoid in preparation process
When layer solution, due to polarity similar compatibility, the quantum dot of lower layer is caused to be dissolved or wash away, to influence the property of quantum dot film
Energy.
As an implementation, when the material of the hole transmission layer is highly polar organic material, the displaced ligands
In the displaced ligands of solution, X2 is low pole or non-polar functional group, the low pole or non-polar functional group be selected from-CO- ,-
COOR、-NO2、-O-、-O-CH3、-CH3At least one of.
As another embodiment, when the material of the hole transmission layer is low pole organic material, the displacement is matched
In the displaced ligands of liquid solution, X2 is highly polar functional group, and the highly polar functional group is selected from-COOH ,-OH ,-CN ,-NHCO-
CH3、-NH2,-SH, at least one of-CHO.
As another embodiment, when the material of the hole transmission layer is inorganic compound, the displaced ligands are molten
In the displaced ligands of liquid, X2 is low pole or non-polar functional group, the low pole or non-polar functional group be selected from-CO- ,-
COOR、-NO2、-O-、-O-CH3、-CH3At least one of.
In the embodiment of the present invention, the displaced ligands solution is according to the difference of the quantum dot film for carrying out ligand exchange in situ
And it is different, it can be the combination (displaced ligands are highly polar ligand) of highly polar ligand and intensive polar solvent, be also possible to low pole
The combination of ligand and weak polar solvent (displaced ligands are low pole ligand).Specifically, the solvent of the displaced ligands solution is
Organic solvent, the organic solvent include but is not limited to saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbon, alcohols solvent, ether solvent, ketone
The mixing of one of class solvent, nitrile solvents, esters solvent and their derivative either a variety of compositions is organic molten
Agent.Wherein, the organic solvent include but is not limited to hexane, toluene, dimethylbenzene, ethylbenzene, methylene chloride, chloroform, propyl alcohol,
Isopropanol, phenetole, acetonitrile, diethylamine, triethylamine, aniline, pyridine, picoline, ethylenediamine, N,N-dimethylformamide,
At least one of DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide.
The cathode be selected from one of metal material, carbon material, wherein the metal material include but is not limited to Al,
Ag, Cu, Mo, Au or their alloy；The carbon material include but is not limited to graphite, carbon nanotube, graphene, in carbon fiber
It is one or more.
In above-mentioned steps S02, in the quantum dot performed thin film, the initial ligand of quantum dot surface includes but unlimited
In tetradecene, hexadecylene, octadecylene, octadecylamine, octadecenic acid, trioctylamine, trioctylphosphine oxide (TOPO), tri octyl phosphine, octadecane
One of base phosphonic acids, 9- octadecenyl amine, mercaptoundecylic acid are a variety of.
In the embodiment of the present invention, the quantum dot in the quantum dot performed thin film is II-VI group compound, iii-v
Close object, II-V compounds of group, III-VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI race chemical combination
One of object or IV race simple substance are 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, three
The II-VI group compound of member, quaternary；Nanocrystalline including but not limited to GaP, GaAs of III-V compound (semiconductor material),
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-。
Displaced ligands in the quantum dot performed thin film and the displaced ligands solution are subjected to ligand exchange in situ, it can
To be realized by the way that the quantum dot performed thin film to be immersed in the displaced ligands solution, but not limited to this.Matched by situ
Body is replaced, and the displaced ligands in initial ligand and the displaced ligands solution in the quantum dot performed thin film occur ligand and hand over
It changes, forms the quantum dot light emitting film that quantum dot surface is connected with displaced ligands.
It further, further include that the initial ligand that will be cemented out is purged after ligand exchange.The removing
Mode can be to remain in the initial ligand of the quantum dot light emitting film surface using solvent cleaning, or by the quantum of preparation
Point light-emitting film is placed in vacuum plant, and the pressure and temperature by regulating and controlling vacuum chamber removes the quantum dot light emitting film surface
Initial ligand (by vacuumize it is loosely organized in quantum dot film or have neither part nor lot in coordination ligand remove, finally obtain
One more stable quantum dot layer).
It preferably, further include that electronic work ergosphere is prepared between the cathode and quantum dot light emitting layer, the electric function
Layer includes at least one of electron injecting layer, electron transfer layer.Wherein, the electron transfer layer, which is selected from, has electron-transporting
The material of energy, it is however preferred to have the inorganic material or organic material of electronic transmission performance, the inorganic material include but is not limited to n
Type ZnO, TiO2、SnO2、Ta2O3、AlZnO、ZnSnO、InSnO、Ca、Ba、CsF、LiF、Cs2CO3At least one of；It is described to have
Machine material includes being not limited to Alq3、TPBi、BCP、BPhen、PBD、TAZ、OXD-7、3TPYMB、BP4mPy、TmPyPB、
At least one of BmPyPhB, TQB.
In above-mentioned steps S03, the hole functional layer preferably selects solution processing method deposition, improves the thin of hole functional layer
Film thickness uniformity, to assign the hole functional layer excellent stability.Specifically, the preparation of the hole functional layer
Method are as follows: functional material solution in hole is provided, by the hole functional material liquid deposition in the quantum dot light emitting layer surface,
Annealed processing prepares hole functional layer.
Wherein, the solvent of the hole functional material solution includes intensive polar solvent or weak polar solvent, when the quantum
When the displaced ligands of the luminous layer surface of point are highly polar ligand, the solvent of the hole functional material solution is preferably that low pole is molten
Agent, including but not limited to hexane, hexamethylene, heptane, normal octane, isooctane, isopentane, pentane, methylpentane, ethylpentane,
Pentamethylene, methyl cyclopentane, ethyl cyclopentane, benzene,toluene,xylene, ethylbenzene, carbon disulfide, carbon tetrachloride, methylene chloride,
Dichloroethanes, chlorobutane, methylene bromide, N-Propyl Bromide, iodomethane, diphenyl ether, trichloro ethylene, n-butyl ether, disulfide, isopropyl ether,
One of dimethyl carbonate, trioctylamine, methyl ethyl ketone, tri-n-butylamine, tetrahydrofuran, chlorobenzene are a variety of；When the quantum dot light emitting
When the displaced ligands of layer surface are low pole ligand, the solvent of the hole functional material solution is preferably intensive polar solvent, packet
Include but be not limited to methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, amylalcohol, isoamyl alcohol, tert-pentyl alcohol,
Cyclohexanol, octanol, benzylalcohol, ethylene glycol, phenol, o-cresol, ether, methyl phenyl ethers anisole, phenetole, diphenyl ether, glycol dimethyl ether, third
Glycol methyl ether, ethylene glycol diethyl ether, ethoxy ether, propylene glycol monopropyl ether, glycol monobutyl ether, acetaldehyde, benzaldehyde, third
Ketone, butanone, cyclohexanone, acetophenone, formic acid, acetic acid, ethyl acetate, diethy-aceto oxalate, diethyl malonate, propyl acetate, first
Base propyl ester, butyl acetate, methyl amyl acetate, nitrobenzene, acetonitrile, diethylamine, triethylamine, aniline, pyridine, picoline, N,
Dinethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide, curing
At least one of carbon, methyl sulfide, ethyl sulfide, dimethyl sulfoxide, mercaptan, ethyl mercaptan, methoxyl group tetrahydrofuran.
Specifically, the hole functional layer includes hole transmission layer, at least one layer in hole injection layer.
Wherein, the hole injection layer is selected from the organic material with Hole injection capacity.Prepare the hole injection layer
Including but not limited to poly- (3,4- the ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS) of hole-injecting 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.
In above-mentioned steps S04, the anode is selected from one of blended metal oxide, the blended metal oxide packet
Include but be 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 adulterate magnesia
(AMO).The anode can also be the combination electrode containing metal sandwich in transparent metal oxide, wherein the transparent gold
Belonging to oxide can be doping transparent metal oxide, or undoped transparent metal oxide.The combination electrode
Including but 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/TiO2。
In the embodiment of the present invention, the anode, cathode, hole injection layer, hole transmission layer, electron transfer layer, electronics note
Enter the deposition method of layer and quantum dot performed thin film, can be realized with chemical method or physical method, wherein the chemical method includes
But it is not limited to chemical vapour deposition technique, successive ionic layer adsorption and reaction method, anodizing, strike, coprecipitation
One of or it is a variety of；The physical method includes but is not limited to physical coating method or solution processing method, wherein solution processing method packet
Include but be not limited to spin-coating method, print process, knife coating, dip-coating method, infusion method, spray coating method, roll coating process, casting method, slit
Rubbing method, strip rubbing method；Physical coating method includes but is not limited to that thermal evaporation coating method, electron beam evaporation deposition method, magnetic control splash
Penetrate one of method, multi-arc ion coating embrane method, physical vaporous deposition, atomic layer deposition method, pulsed laser deposition or a variety of.
And the embodiment of the invention provides a kind of transoid QLED device, the cathodes combined including stacking, quantum dot light emitting
Layer, hole functional layer and anode, wherein the transoid QLED device is prepared by the above method.
Transoid QLED device provided in an embodiment of the present invention, is prepared by the above method, so that transoid QLED device
Hole the functional material such as solvent of hole mobile material, hole mobile material and the ink type of formation are no longer limited, to open up
The range of choice of transoid QLED device hole functional material and ink is opened up.
Specifically, transoid QLED device described in the embodiment of the present invention further includes interface-modifying layer, the interface-modifying layer is
Electronic barrier layer, hole blocking layer, electrode modification layer, at least one layer in isolated protective layer.
The packaged type of the transoid QLED device can be partial encapsulation, full encapsulation or not encapsulate, the embodiment of the present invention
Do not limit strictly.
The embodiment of the invention also provides a kind of printing quantum dot display screens, including above-mentioned transoid QLED device.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of reciprocal form structure light emitting diode with quantum dots, comprising the following steps:
Cathode is provided；In ethanol by the dissolution of 3- mercaptopropionic acid, it is configured to displaced ligands solution；
CdSe quantum dot performed thin film is printed on cathode, and quantum dot performed thin film is immersed in the ligand substitutional solution
In, it is taken out after impregnating 10min, then be transferred into vacuum chamber, adjusts vacuum degree and be 10Pa and maintain 30min, removal amount
The ligand and solvent not being coordinated in son point luminescent layer, prepare CdSe quantum dot luminescent layer；
Hole functional layer is printed on the CdSe quantum dot luminescent layer, and anode is finally deposited, obtains reciprocal form structure quantum
Point luminescent diode.
Embodiment 2
A kind of preparation method of reciprocal form structure light emitting diode with quantum dots, comprising the following steps:
Cathode is provided；In ethanol by the dissolution of 3- mercaptopropionic acid, it is configured to displaced ligands solution；
ZnO electron transfer layer, CdSe quantum dot performed thin film are successively printed on ITO cathode, by quantum dot performed thin film
It is immersed in the ligand substitutional solution, is taken out after impregnating 10min, then be transferred into vacuum chamber, adjusting vacuum degree is
10Pa simultaneously maintains 30min, removes the ligand and solvent not being coordinated in quantum dot light emitting layer, prepares CdSe quantum dot luminescent layer；
TFB hole transmission layer and PEDOT:PSS hole injection layer are printed on the CdSe quantum dot luminescent layer, are finally steamed
Al cathode is plated, whole soln method reciprocal form structure light emitting diode with quantum dots is obtained.
Embodiment 3
A kind of preparation method of reciprocal form structure light emitting diode with quantum dots, comprising the following steps:
Cathode is provided；In ethanol by 3- mercaptopropionic acid, M-phthalic acid dissolution, it is configured to displaced ligands solution；
ZnO electron transfer layer, CdSe quantum dot performed thin film are successively printed on ITO cathode, by quantum dot performed thin film
It is immersed in the ligand substitutional solution, is taken out after impregnating 10min, then be transferred into vacuum chamber, adjusting vacuum degree is
10Pa simultaneously maintains 30min, removes the ligand and solvent not being coordinated in quantum dot light emitting layer, prepares CdSe quantum dot luminescent layer；
TFB hole transmission layer and PEDOT:PSS hole injection layer are printed on the CdSe quantum dot luminescent layer, are finally steamed
Al cathode is plated, whole soln method reciprocal form structure light emitting diode with quantum dots is obtained.
Embodiment 4
A kind of preparation method of reciprocal form structure light emitting diode with quantum dots, comprising the following steps:
Cathode is provided；In ethanol by M-phthalic acid dissolution, it is configured to displaced ligands solution；
ZnO electron transfer layer, CdSe quantum dot performed thin film are successively printed on ITO cathode, by quantum dot performed thin film
It is immersed in the ligand substitutional solution, is taken out after impregnating 10min, then be transferred into vacuum chamber, adjusting vacuum degree is
10Pa simultaneously maintains 30min, removes the ligand and solvent not being coordinated in quantum dot light emitting layer, prepares CdSe quantum dot luminescent layer；
TFB hole transmission layer and PEDOT:PSS hole injection layer are printed on the CdSe quantum dot luminescent layer, are finally steamed
Al cathode is plated, whole soln method 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 preparation method of transoid QLED device, which comprises the following steps:
Cathode and displaced ligands solution are provided；
Quantum dot performed thin film is deposited on the cathode, and the quantum dot performed thin film is contained the quantum of initial ligand by surface
Displaced ligands in the quantum dot performed thin film and the displaced ligands solution are carried out ligand exchange in situ by point composition, will
The initial ligand is replaced into displaced ligands, obtains quantum dot light emitting layer；
Hole functional layer is prepared in the quantum dot light emitting layer surface；
Anode is prepared in the hole functional layer.
2. the preparation method of transoid QLED device as described in claim 1, which is characterized in that the structure of the displaced ligands is logical
Formula is X1-R-X2, wherein the R is alkyl or alkyl derivative, the X1For the function being crosslinked with the quantum dot
Group, the X2Functional group is adjusted for polarity, and the crosslinking active of the X1 and quantum dot is greater than the crosslinking of the X2 and quantum dot
Activity.
3. the preparation method of transoid QLED device as claimed in claim 2, which is characterized in that the X1Selected from-SH ,-COOH ,-
NH2、-OH、-NO2、-SO3H, one of phosphino-, phosphate；And/or
The X2Selected from-COOH ,-OH ,-CN ,-NHCO-CH3、-NH2、-SH、-CHO、-CO-、-COOR、-NO2、-O-、-O-
CH3、-CH3One of.
4. white light quanta point light emitting diode as described in claim 1, which is characterized in that contain conjugate ring ,-C=in the R
At least one of C- ,-C ≡ C- ,-C=O ,-N=N- ,-C ≡ N ,-C=N- group.
5. the preparation method of transoid QLED device as claimed in claim 2, which is characterized in that the displaced ligands are sulfydryl second
Acid, 3- mercaptopropionic acid, 3- mercaptobutyric acid, 6- mercaptohexanoic acid, mercaptoethylmaine, 3- mercaptopropylamine, 4- mercaptobenzoic acid, sulfydryl are sweet
Oil, 1- Trimethylamine ethyl mercaptan, mercaptoaniline, nitroaniline, aniline sulfonic acid, aminobenzoic acid, 4- (diphenylphosphino) benzene first
At least one of acid；Or
The displaced ligands be octylame, propylamine, cetylamine, 4- sulfydryl methyl phenyl ethers anisole, in 1- hydroxy-3-methoxy-propane at least
It is a kind of；Or
The displaced ligands be selected from 2- mercaptobenzoic acid, 4- mercaptobenzoic acid, 4-aminobenzoic acid, 4-HBA, to sulphur
Yl benzoic acid, paranitrobenzoic acid, 4- mercaptoaniline, 4- hydroxyanilines, 4- cyano-aniline, 4- sulfydryl styrene acid, 4- hydroxyl
Styrene acid, 2- (4- hydroxy phenyl) pyridine, the chloro- 5- cyano thiazole of 2-, 2- Amino 3 cyano thiophene, 3- amino -5- sulfydryl -
At least one of 1,2,4- triazole.
6. the preparation method of transoid QLED device as described in any one in claim 1-5, which is characterized in that by the quantum dot
The method that displaced ligands in performed thin film and the displaced ligands solution carry out ligand exchange in situ are as follows: the quantum dot is pre-
Made membrane, which is immersed in the displaced ligands solution, carries out ligand exchange in situ.
7. the preparation method of transoid QLED device as described in any one in claim 1-5, which is characterized in that the hole transport
When the material of layer is highly polar organic material, in the displaced ligands of the displaced ligands solution, X2 is low pole or nonpolar official
It can roll into a ball, the low pole or non-polar functional group are selected from-CO- ,-COOR ,-NO2、-O-、-O-CH3、-CH3At least one of.
8. the preparation method of eurymeric QLED device as described in any one in claim 1-5, which is characterized in that the hole transport
When the material of layer is low pole organic material, in the displaced ligands of the displaced ligands solution, X2 is highly polar functional group, described
Highly polar functional group is selected from-COOH ,-OH ,-CN ,-NHCO-CH3、-NH2,-SH, at least one of-CHO.
9. the preparation method of eurymeric QLED device as described in any one in claim 1-5, which is characterized in that the hole transport
When the material of layer is inorganic compound, in the displaced ligands of the displaced ligands solution, X2 is low pole or non-polar functional group,
The low pole or non-polar functional group are selected from-CO- ,-COOR ,-NO2、-O-、-O-CH3、-CH3At least one of.
10. a kind of transoid QLED device, special including cathode, quantum dot light emitting layer, hole functional layer and anode that stacking combines
Sign is, wherein the transoid QLED device is prepared by any one of claim 1-9 the method.
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