CN109935720A - White light quanta point light emitting diode and preparation method thereof - Google Patents
White light quanta point light emitting diode and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of white light quanta point light emitting diodes and preparation method thereof, comprising: provides hearth electrode；Quantum dot performed thin film is prepared on hearth electrode, the quantum dot surface in the quantum dot performed thin film is connected with initial ligand；Quantum dot performed thin film, which is placed in, to be passed through gaseous displaced ligands and carry out the displacement of gas phase ligand in obturator, and the first layer quantum dot film of quantum dot surface combination displaced ligands is obtained, which, which can be connected to, lacks two quantum dots；The quantum dot film of N layer stackup is made using the preparation method of first layer quantum dot film, obtains the lamination that shines；Or the quantum dot film of N-1 layer stackup is made using the preparation method of first layer quantum dot film, an organic light emitting film is prepared on N-1 layers of quantum dot film, obtains the lamination that shines；Wherein, N is positive integer, 2≤N≤10；And shine that lamination is compound emits white light；Wherein, hearth electrode is anode, and top electrode is cathode；Or hearth electrode is cathode, top electrode is anode.
Description
Technical field
The invention belongs to technical field of flat panel display, and in particular to a kind of white light quanta point light emitting diode and its preparation side
Method.
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, the quantum spot white light device of mainstream is mainly by by redgreenblue (or more luminescent color) quantum dot
Mixing, preparation mixing quantum dot light emitting layer, to realize white light parts.But after different quantum dots mixing, between quantum dot compared with
Be easy to happen energy transmission, thus the white light parts based on the method preparation for mixing different colours quantum dot be easy to appear it is luminous
The case where color changes with the change of voltage.Meanwhile based on current solution manufacturing method, the wheat flour on quantum dot layer
When standby second layer quantum dot layer, the second layer can largely destroy the quantum dot film of first layer using solvent, to be not easy reality
The device architecture that existing multi-layer quantum point successively stacks.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, provide a kind of white light quanta point light emitting diode and
Preparation method, it is intended to it solves in existing white light quanta point light emitting diode preparation process, it cannot between multi-layer quantum point film
It successively stacks and forms the technical issues of shining lamination.
Another object of the present invention is to provide a kind of display screens containing above-mentioned white light quanta point light emitting diode.
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 preparation method of white light quanta point light emitting diode, includes the following steps:
Hearth electrode is provided；
Quantum dot performed thin film is prepared on the hearth electrode, the quantum dot surface connection in the quantum dot performed thin film
There is initial ligand；The quantum dot performed thin film, which is placed in, to be passed through gaseous displaced ligands in obturator, carried out gas phase and matched
Body displacement, obtains first layer quantum dot film of the quantum dot surface in conjunction with the displaced ligands, the displaced ligands can be connected to
Few two quantum dots；
The quantum dot film of N layer stackup is made using the preparation method of the first layer quantum dot film, obtains shining folded
Layer；Or
The quantum dot film of N-1 layer stackup is made using the preparation method of the first layer quantum dot film, at N-1 layers
An organic light emitting film is prepared on quantum dot film, obtains the lamination that shines；
Wherein, N is positive integer, 2≤N≤10；And the luminous lamination is compound emits white light；
Top electrode is prepared on the luminous lamination；
Wherein, the hearth electrode is anode, and the top electrode is cathode；Or the hearth electrode is cathode, the top electrode
For anode.
Correspondingly, a kind of white light quanta point light emitting diode, which is characterized in that the white light quanta point light emitting diode by
Above-mentioned preparation method is made.
In addition, a kind of display screen, including above-mentioned white light quanta point light emitting diode.
The preparation method of white light quanta point light emitting diode provided by the invention shines lamination constantly preparing, using gas
Phase method carries out surface ligand displacement to every layer of quantum dot performed thin film, not only simple process, but also displaced ligands can be connected to less
Two quantum dots, so that crosslinked after quantum dot film forming, the film after being crosslinked not will receive topmost thin film solvent
Influence realize white-light emitting so as to prepare the luminous lamination of multi-layer quantum point thin film stack.Using vapor phase method pair
The surface in situ ligand exchange of quantum dot performed thin film is displaced ligands, carries out ligand displacement, gas phase relative to using solwution method
Ligand exchange in situ has solvent-free damage (overall performance for the quantum dot film that raising obtains), low in cost, simple process
Outstanding advantages of, the initial ligand of quantum dot surface in quantum dot performed thin film is replaced by displacement using ligand exchange in situ and is matched
Body, thus surface polarity and surface tension after changing quantum dot film forming, and then by the polarity of control quantum dot surface, it keeps away
Exempt from quantum dot light emitting layer from the influence of upper layer electronic functional material solution solvent, when quantum dot solution is formed by film-forming process
After quantum dot performed thin film, the arrangement of quantum dot and position are substantially stationary, carry out ligand with gaseous displaced ligands again at this time and set
The problem of solution sedimentation would not be occurred by changing, and quantum dot film forming procedure is not influenced by the ligand structure after exchanging.In addition, adopting
Ligand displacement is carried out with vapor phase method, ligand displacement degree is more abundant in gas phase atmosphere, and the selection of displaced ligands is not by solution ring
The limitation in border has preferable selection flexibility, scale and industrialized production may be implemented；And matched using distinctive conjugation
Body displacement makes the dissolubility, dispersibility and its conductive capability of the quantum dot in the quantum dot film of preparation reach better balance
State further increases the stability and carrier transport ability of quantum dot film, correspondingly improves luminous efficiency, improve it
Overall performance.
White light quanta point light emitting diode in white light quanta point light emitting diode and display screen provided by the invention by
Above-mentioned preparation method obtains, because containing the compound luminous lamination to emit white light, it can be achieved that white-light emitting, overcomes existing redgreenblue
When (or more luminescent color) quantum dot is mixed with mixing quantum dot light emitting layer, energy transmission is easy to happen between quantum dot
Problem, to reduce not influence of the same electric field to device luminescent color.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
On the one hand, the embodiment of the invention provides a kind of preparation method of white light quanta point light emitting diode, including it is as follows
Step:
S01: hearth electrode is provided；
S02: quantum dot performed thin film, the quantum dot surface in the quantum dot performed thin film are prepared on the hearth electrode
It is connected with initial ligand；The quantum dot performed thin film, which is placed in, to be passed through gaseous displaced ligands, carry out gas in obturator
The displacement of phase ligand, obtains first layer quantum dot film of the quantum dot surface in conjunction with the displaced ligands, the displaced ligands can connect
Connect at least two quantum dots；
S03: the quantum dot film of N layer stackup is made using the preparation method of the first layer quantum dot film, is sent out
Light lamination；Or
The quantum dot film of N-1 layer stackup is made using the preparation method of the first layer quantum dot film, at N-1 layers
An organic light emitting film is prepared on quantum dot film, obtains the lamination that shines；
Wherein, N is positive integer, 2≤N≤10；And the luminous lamination is compound emits white light；
S04: top electrode is prepared on the luminous lamination；
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 white light quanta point light emitting diode provided in an embodiment of the present invention shines lamination constantly preparing,
Surface ligand displacement is carried out to every layer of quantum dot performed thin film using vapor phase method, not only simple process, but also displaced ligands can connect
Connect at least two quantum dots, so that crosslink after quantum dot film forming, it is thin that the film after being crosslinked not will receive upper layer
The influence of membrane solvent realizes white light so as to prepare the luminous lamination of multi-layer quantum point thin film stack using solwution method
It shines.N is the integer more than or equal to 2 and less than or equal to 10, is specifically as follows 2,3,4,5,6,7,8,9 equivalences.It is further excellent
Selection of land, in the N layers of quantum dot film, 2≤N≤5；And the thickness of every layer of quantum dot film is preferably 2-80nm.
Use vapor phase method to the surface in situ ligand exchange of quantum dot performed thin film for displaced ligands, relative to using solution
Method carries out ligand displacement, and gas phase original position ligand exchange has the solvent-free damage (globality for the quantum dot film that raising obtains
Can), low in cost, simple process outstanding advantages of, using ligand exchange in situ by quantum dot surface in quantum dot performed thin film
Initial ligand be replaced into displaced ligands, so that surface polarity and surface tension after changing quantum dot film forming, and then pass through
The polarity for controlling quantum dot surface, avoids quantum dot light emitting layer from the influence of upper layer electronic functional material solution solvent, equivalent
After son point solution forms quantum dot performed thin film by film-forming process, the arrangement of quantum dot and position are substantially stationary, use again at this time
After gaseous displaced ligands, which carry out ligand displacement, the problem of solution sedimentation would not occurs, and quantum dot film forming procedure is not exchanged
Ligand structure influence.In addition, carrying out ligand displacement using vapor phase method, ligand displacement degree is more abundant in gas phase atmosphere, and
The selection of displaced ligands by the limitation of solution environmental, does not have preferable selection flexibility, scale and industrialization may be implemented
Production；And using distinctive conjugated ligand replace, make preparation quantum dot film in quantum dot dissolubility, dispersibility with
Its conductive capability reaches better equilibrium state, further increases the stability and carrier transport ability of quantum dot film,
Luminous efficiency is correspondingly improved, its overall performance is improved.
Specifically, it in above-mentioned steps S03, after one layer of quantum dot film of every preparation, needs logical to the quantum dot film
It crosses gas phase reaction and carries out ligand displacement, be then further continued for depositing another layer of quantum dot film, displaced ligands can connect two simultaneously
A or more than two quantum dots, after treatment obtain the luminous lamination that there is ligand to be crosslinked.Wherein, before the ligand displacement
Quantum dot surface contains initial ligand, and specifically, the initial ligand is organic ligand, including but not limited to tetradecene, 16
Alkene, octadecylene, octadecylamine, octadecenic acid, trioctylamine, trioctylphosphine oxide (TOPO), tri octyl phosphine, octadecylphosphonic acid, 9- 18
One of enamine, mercaptoundecylic acid are a variety of.
Preferably, the n-th layer in luminous lamination can be machine light-emitting film, i.e., prepare on N-1 layers of quantum dot film
One organic light emitting film.The n-th layer quantum dot film layer does not have to ligand exchange, therefore can be quantum dot light emitting material, can also
To be substituted for luminous organic material, and each layer less than N is quantum dot light emitting material, is since it is desired that carrying out ligand exchange.
Preferably, the structural formula of the displaced ligands is X1-R-X2, wherein X1And X2For that can be connected with quantum dot surface
The functional group of (as chelated), such as halogen atom ,-SH ,-COOH ,-NH2、-OH、-NO2、-SO3H, phosphino-, phosphate etc.；R is hydrocarbon
Base or alkyl derivative, selected from saturated alkane, the unsaturated alkane, fragrance containing any organo-functional group or without organo-functional group
One of hydrocarbon is a variety of, including but not limited to alkane, alkene, alkynes, aromatic hydrocarbon, cycloalkane, halogenated hydrocarbons, alcohol, ether, phenol, aldehyde,
One of ketone, carboxylic acid, ester, nitrogenous compound are a variety of.Specifically, the displaced ligands include but is not limited to 1,2- ethylene dithiol
Pungent two mercaptan of alcohol, 1,4- succinimide mercaptans, 1,6- ethanthiol, 1,8-, 1,4- dimercaptobenzene, 1,4- benzene dimethanethiol, sulfydryl second
Amine, mercaptopropylamine, thioacetic acid, 3- mercaptopropionic acid, 3- mercaptobutyric acid, 6- mercaptohexanoic acid, 1,2- ethylenediamine, 1,3- propane diamine,
1,4- butanediamine, 1,5- pentanediamine, 1,6- hexamethylene diamine, 4- mercaptobenzoic acid, mercapto glycerol, 1- Trimethylamine ethyl mercaptan, nitro
It is benzenethiol, sulfo group benzenethiol, mercaptophenylacetic acid, nitrobenzene-sulfonic acid, phenylenediamine, mercaptoaniline, nitroaniline, aniline sulfonic acid, right
Phthalic acid, to one of phenylenediacetic Acid, aminobenzoic acid, 4- (diphenylphosphino) benzoic acid or a variety of.
It is highly preferred that the displaced ligands are conjugated ligand, in conjugated ligand: X1And X2For 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, carbon-carbon double bond, carbon-carbon triple bond, fragrant ring group
At least one of.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 activity is consistent, can react with quantum dot；If both sides activity is inconsistent, need to control reactant dosage and reaction
Parameter, 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 sends out
Raw reaction.And R is undersaturated alkyl or alkyl derivative, i.e., with the organo units knot of conjugation (electron delocalization effect)
Structure, conjugation 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；
The organo units structure with conjugation includes but is not limited to double bond and the alternately arranged linear structure of singly-bound and/or ring
Shape structure, wherein further three bond structures can be also contained (particularly, it should be appreciated that organise by classics in this configuration
Theory, in the present case benzene ring structure be considered as three carbon-carbon single bonds and three carbon-carbon double bonds alternate connection ring-type it is total
One of yoke structure), wherein the cyclic structure, which can be orderly cyclic structure, is also possible to heterocycle structure；Specifically, institute
Stating the functional group contained in the organo units structure with conjugation includes but is not limited to phenyl ring ,-C=C- ,-C ≡ C- ,-C=
One of O- ,-N=N- ,-C ≡ N ,-C=N- or a variety of；Particularly, in the organo units structure with conjugation
Circular structure can be contained, wherein the ring structure includes but is not limited to benzene ring structure, luxuriant and rich with fragrance structure, naphthalene structure, indenes structure, pyrene knot
Gou, Benzyl structure, acenaphthene structure, acenaphthylene structure, fluorene structured, anthracene structure, fluoranthene structure, benzanthracene structure, benzofluoranthrene structure, benzo
Pyrene structure, indeno pyrene structure, dibenzanthracene structure, benzo structure, pyrrole structure, pyridine structure, pyridazine structure, furans knot
Structure, thiophene-structure, indole structure, porphine structure, porphyrin structure, thiazole structure, glyoxaline structure, pyrazine structure, pyrimidine structure, quinoline
Quinoline structure, isoquinoline structure, pteridine structure, acridine structure, oxazole structure, carbazole structure, triazole structure, benzofuran structure,
One of benzothiophene structure, benzothiazole structure, benzoxazoles structure, benzopyrrole structure, benzimidazole structure are more
Kind.
It is further preferred that displaced ligands described in the embodiment of the present invention comprise the following structure formula 1-4 it is any shown in change
At least one of object is closed,
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 be saturated or unsaturated
Alkyl, such as alkyl, alkylene, alkynes base, aryl, heteroaryl and its derivative.X1, X1 ', X2, X2 ', X3, X3 ' it is to live
Property 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.
Meanwhile the quantum dot in the quantum dot 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-。
Specifically, above-mentioned gas phase ligand displacement can carry out in obturator, and the quantum dot film is placed in can be closed
In device, it is described can obturator as reaction unit, on the one hand, can prevent water, oxygen enter, to ligand displacement cause shadow
It rings；Importantly, it is described can obturator closed environment, pressurization or vacuum environment can be formed, so that ligand be promoted to set
Change the progress of reaction.Theoretically, it as long as the airtight chamber for being able to achieve 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, and the embodiment of the present invention does not limit strictly.The embodiment of the present invention is logical
It crosses and is passed through gaseous displaced ligands, provide material base for ligand exchange.Further, by can be in obturator described in adjusting
Pressure, temperature, the partial pressure of displaced ligands, realize gas phase ligand displacement, make quantum dot surface in the quantum dot performed thin film
Initial surface ligand and the displaced ligands occur ligand exchange, finally obtain quantum dot surface in conjunction with the displaced ligands
Quantum dot film.
Further, described the step of being passed through gaseous displaced ligands includes: that the displaced ligands of liquid are evaporated or boiled
Obtain gaseous displaced ligands after rising processing, then be passed through it is described can be in obturator., it is liquid under most of displaced ligands room temperature
State, therefore by the available gaseous displaced ligands of the method, then be passed into and can carry out gas phase ligand and set in obturator
It changes.Described the step of being passed through gaseous displaced ligands also may include: by solid-state cementation ligand through distillation processing or successively through liquid
Change, obtain gaseous displaced ligands after evaporation process, then be passed through it is described can be in obturator.Aliquot replacement ligand, such as benzene two
Amine, mercaptoaniline, nitroaniline, aniline sulfonic acid room temperature are solid-state, therefore gaseous displaced ligands can be obtained by the method, then
The displacement of gas phase ligand can be carried out in obturator by being passed into.
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 displaced ligands 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 displaced ligands guarantees appropriate level of the displaced ligands 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 displaced ligands).Further preferably
, during gas phase ligand displacement, it is described can the internal pressure of obturator be 10-4~102Pa, the displaced ligands
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 initial surface ligand, the type of displaced ligands,
And it is described can the internal pressure of obturator, the partial pressure of displaced ligands and it is different, between 0.5-360min.
Correspondingly, it the embodiment of the invention provides a kind of white light quanta point light emitting diode, is made by above-mentioned preparation method.
The white light quanta point light emitting diode of the embodiment of the present invention is because containing the hair by multi-layer quantum point thin film stack
Light lamination overcomes existing redgreenblue (or more luminescent color) quantum dot to be mixed with combined amount, it can be achieved that white-light emitting
When son point luminescent layer, the problem of being easy to happen energy transmission between quantum dot, thus reduce not same electric field to device luminescent color
Influence.
In the embodiment of the present invention, the white light quanta point light emitting diode can be eurymeric white light quanta point light-emitting diodes
Pipe, or transoid white light quanta point light emitting diode.As a kind of implementation situation, the white light quanta point light emitting diode
For eurymeric white light quanta point light emitting diode, i.e., the described hearth electrode is anode, and the top electrode is cathode.Implement as another kind
Situation, the white light quanta point light emitting diode are transoid white light quanta point light emitting diode, 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 white light quanta point light emitting diode further includes function
Decorative layer, the functionalized modification layer include hole injection layer, hole transmission layer, electron injecting layer, in electron transfer layer at least
It is a kind of.The hole injection layer, hole transmission layer are arranged between anode and luminous lamination, and the electron injecting layer, electronics pass
Defeated layer is arranged luminous between lamination and cathode.
Substrate in the white light quanta point light emitting diode is rigid substrate or flexible substrate, and the rigid substrate includes
But one of it is not limited to glass, metal foil or a variety of；The flexible substrate includes but is not limited to poly terephthalic acid second two
Alcohol ester (PET), polyethylene terephthalate (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), one of polyvinylpyrrolidone (PVP), textile fabric or 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.
It is further preferred that white light quanta point light emitting diode described in the embodiment of the present invention further includes interface-modifying layer, institute
Interface-modifying layer is stated as at least one layer in electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer.
The packaged type of the white light quanta point light emitting diode can be partial encapsulation, full encapsulation or not encapsulate, this hair
Bright embodiment does not limit strictly.
It preferably, further include that functionalized modification layer is set between lamination and electrode luminous, e.g., when hearth electrode is anode, top
It further include at least one layer in deposition of hole implanted layer and hole transmission layer before preparing luminous lamination when electrode is cathode；
It further include in the deposition electron transfer layer on lamination that shines, at least one layer in electron injecting layer before preparing top electrode.Work as bottom
It further include deposition electron transfer layer, electron injecting layer before preparing luminous lamination when electrode is cathode, top electrode is anode
In at least one layer；It further include shining on lamination in deposition of hole implanted layer and hole transmission layer before preparing top electrode
At least one 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 film, can be realized, wherein the chemical method includes but is not limited to chemical gaseous phase with chemical method or physical method
One of sedimentation, successive ionic layer adsorption and reaction method, anodizing, strike, coprecipitation are a variety of；Institute
Stating physical method includes but is not limited to physical coating method or solution processing method, wherein solution processing method include but is not limited to spin-coating method,
Print process, knife coating, dip-coating method, infusion method, spray coating method, roll coating process, casting method, slit coating method, strip rubbing method；
Physical coating method includes but is not limited to thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering method, multi-arc ion plating film
One of method, physical vaporous deposition, atomic layer deposition method, pulsed laser deposition are a variety of.
The hole injection layer is selected from the organic material with Hole injection capacity.Prepare the hole of the hole injection layer
Including but not limited to poly- (3,4- the ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS) of injection material, CuPc
(CuPc), tetra- cyanogen quinone of 2,3,5,6- tetra- fluoro- 7,7', 8,8'--bismethane (F4-TCNQ), six cyano -1 2,3,6,7,10,11-,
One of six azepine benzophenanthrene (HATCN) of 4,5,8,9,12-, transition metal oxide, transition metal chalcogenide compound are more
Kind.Wherein, the transition metal oxide includes but is not limited to MoO3、VO2、WO3、CrO3, at least one of CuO；The gold
Belonging to chalcogenide compound includes but is not limited to MoS2、MoSe2、WS2、WSe2, at least one of CuS.
The hole transmission layer is selected from the organic material with cavity transmission ability, and including but not limited to poly- (9,9- bis- is pungent
Base fluorenes-CO-N- (4- butyl phenyl) diphenylamines) (TFB), polyvinylcarbazole (PVK), it is poly- (bis- (4- the butyl phenyl)-N of N, N',
Bis- (phenyl) benzidine of N'-) (poly-TPD), poly- (double-N of 9,9- dioctyl fluorene -co-, N- phenyl -1,4- phenylenediamine) (PFB),
4,4 ', 4 "-three (carbazole -9- base) triphenylamines (TCTA), 4,4'- bis- (9- carbazole) biphenyl (CBP), N, N '-diphenyl-N, N ' -
Two (3- aminomethyl phenyl) -1,1 '-biphenyl -4,4 '-diamines (TPD), N, N '-diphenyl-N, N '-(1- naphthalene) -1,1 '-biphenyl -
At least one of 4,4 '-diamines (NPB), doped graphene, undoped graphene, C60.It is described as another embodiment
Hole transmission layer 4 is selected from the inorganic material with cavity transmission ability, including but not limited to doped or non-doped MoO3、VO2、
WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2, at least one of CuS.
The electron transfer layer be selected from electronic transmission performance material, it is however preferred to have electronic transmission performance it is inorganic
Material or organic material, the inorganic material include but is not limited to N-shaped ZnO, TiO2、SnO2、Ta2O3、AlZnO、ZnSnO、
InSnO、Ca、Ba、CsF、LiF、Cs2CO3At least one of；The organic material includes being not limited to Alq3、TPBi、BCP、
At least one of BPhen, PBD, TAZ, OXD-7,3TPYMB, BP4mPy, TmPyPB, BmPyPhB, TQB.
And the embodiment of the invention also provides a kind of display screens, including above-mentioned white light quanta point light emitting diode.
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 white light quanta point light emitting diode, comprising the following steps:
PEDOT hole injection layer, TFB hole transmission layer, first layer CdSe red light quantum point are successively printed on ito anode
Performed thin film；
The first layer CdSe red light quantum point performed thin film of above-mentioned preparation is transferred in vacuum chamber, 1,2- second two is passed through
Mercaptan gases, wherein chamber interior pressure is 5Pa, the partial pressure of 1,2- dithioglycol gas is 1Pa, and chamber interior temperature is 25
DEG C, the processing time is 30min, and after treatment is taken out, the first layer CdSe red light quantum point film after obtaining ligand displacement；
It is pre- in the transposed first layer CdSe red light quantum point film prints second layer CdSe green light quantum point of ligand
Then second layer CdSe green light quantum point film is transferred in vacuum chamber, is passed through 1,2- dithioglycol gas by made membrane,
Wherein chamber interior pressure is 5Pa, the partial pressure of 1,2- dithioglycol gas is 1Pa, and chamber interior temperature is 25 DEG C, handles the time
For 30min, after treatment is taken out, the second layer CdSe green light quantum point film after obtaining ligand displacement；
In the transposed second layer CdSe green light quantum point luminescent layer prints third layer CdSe blue light quantum point of ligand
Then third layer CdSe basket light quanta point film is transferred in vacuum chamber, is passed through 1,2- dithioglycol gas by performed thin film
Body, wherein chamber interior pressure is 5Pa, the partial pressure of 1,2- dithioglycol gas is 1Pa, and chamber interior temperature is 25 DEG C, processing
Time is 30min, and after treatment is taken out, the third layer CdSe blue light quantum point film after obtaining ligand displacement；This three layers are not
Quantum dot film with color is the luminous lamination formed in white light quanta point light emitting diode；
The printing ZnO electron transfer layer on above-mentioned third layer CdSe blue light quantum point light-emitting film, last evaporating Al cathode,
Obtain white light quanta point light emitting diode.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of white light quanta point light emitting diode, which comprises the steps of:
Hearth electrode is provided；
Quantum dot performed thin film is prepared on the hearth electrode, the quantum dot surface in the quantum dot performed thin film is connected with just
Beginning ligand；The quantum dot performed thin film, which is placed in, to be passed through gaseous displaced ligands in obturator, carried out gas phase ligand and set
It changes, obtains first layer quantum dot film of the quantum dot surface in conjunction with the displaced ligands, the displaced ligands can be connected to few two
A quantum dot；
The quantum dot film of N layer stackup is made using the preparation method of the first layer quantum dot film, obtains the lamination that shines；Or
The quantum dot film of N-1 layer stackup is made using the preparation method of the first layer quantum dot film, in N-1 layers of quantum
An organic light emitting film is prepared on point film, obtains the lamination that shines；
Wherein, N is positive integer, 2≤N≤10；And the luminous lamination is compound emits white light；
Top electrode is prepared on the luminous lamination；
Wherein, the hearth electrode is anode, and the top electrode is cathode；Or the hearth electrode is cathode, the top electrode is sun
Pole.
2. preparation method as described in claim 1, which is characterized in that the general structure of the displaced ligands is X1-R-X2,
Middle X1And X2For the functional group being connected with quantum dot surface, R is alkyl or alkyl derivative.
3. preparation method as claimed in claim 2, which is characterized in that the X in the displaced ligands1For halogen atom ,-SH ,-
COOH、-NH2、-OH、-NO2、-SO3H, at least one of phosphino-, phosphate；And/or
X in the displaced ligands2For halogen atom ,-SH ,-COOH ,-NH2、-OH、-NO2、-SO3H, phosphino-, in phosphate
It is at least one.
4. preparation method as claimed in claim 3, which is characterized in that the displaced ligands include 1,2- dithioglycol, Isosorbide-5-Nitrae-
Pungent two mercaptan of succinimide mercaptans, 1,6- ethanthiol, 1,8-, 1,4- dimercaptobenzene, 1,4- benzene dimethanethiol, mercaptoethylmaine, sulfydryl
Propylamine, thioacetic acid, 3- mercaptopropionic acid, 3- mercaptobutyric acid, 6- mercaptohexanoic acid, 1,2- ethylenediamine, 1,3- propane diamine, 1,4- fourth two
Amine, 1,5- pentanediamine, 1,6- hexamethylene diamine, 4- mercaptobenzoic acid, mercapto glycerol, 1- Trimethylamine ethyl mercaptan, nitrobenzenethiol, sulphur
Base benzenethiol, mercaptophenylacetic acid, nitrobenzene-sulfonic acid, phenylenediamine, mercaptoaniline, nitroaniline, aniline sulfonic acid, terephthalic acid (TPA),
To at least one of phenylenediacetic Acid, aminobenzoic acid, 4- (diphenylphosphino) benzoic acid.
5. the preparation method of quantum dot film as claimed in claim 2, which is characterized in that described to be passed through gaseous displaced ligands
The step of include: by the displaced ligands of liquid evaporated or boiling processing after obtain gaseous displaced ligands, then be passed through described
It can be in obturator；Or
Solid-state cementation ligand is obtained into gaseous displaced ligands after liquefaction, evaporation process through distillation processing or successively, then is passed through
It is described can be in obturator.
6. preparation method as described in claim 1, which is characterized in that
In the quantum dot film of the N layer stackup, 2≤N≤5；And/or
Every layer of quantum dot film with a thickness of 2-80nm.
7. preparation method as described in any one in claim 1-5, which is characterized in that it is described can the stagnation pressure in obturator be 10-5~103Pa, the partial pressure of the displaced ligands are 10-4~102Pa。
8. preparation method as claimed in claim 7, 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.
9. a kind of white light quanta point light emitting diode, which is characterized in that the white light quanta point light emitting diode is by claim
The described in any item preparation methods of 1-8 are made.
10. a kind of display screen, which is characterized in that the white light quanta point hair including the preparation of any one of claim 1-8 the method
Optical diode or white light quanta point light emitting diode as claimed in claim 9.
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| CN201711354834.2A CN109935720A (en) | 2017-12-15 | 2017-12-15 | White light quanta point light emitting diode and preparation method thereof |
| PCT/CN2018/121251 WO2019114829A1 (en) | 2017-12-15 | 2018-12-14 | Quantum dot film and preparation method therefor, and preparation method for quantum dot light-emitting diode |
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| CN201711354834.2A CN109935720A (en) | 2017-12-15 | 2017-12-15 | White light quanta point light emitting diode and preparation method thereof |
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| CN115207182A (en) * | 2022-09-15 | 2022-10-18 | 南昌凯捷半导体科技有限公司 | Red light mini LED with P-surface thin film conducting layer and preparation method thereof |
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