CN109148698A - The mixed film and preparation method and QLED device of quantum dot and carrier crosslinking - Google Patents
The mixed film and preparation method and QLED device of quantum dot and carrier crosslinking Download PDFInfo
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- CN109148698A CN109148698A CN201710464477.9A CN201710464477A CN109148698A CN 109148698 A CN109148698 A CN 109148698A CN 201710464477 A CN201710464477 A CN 201710464477A CN 109148698 A CN109148698 A CN 109148698A
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
Abstract
The present invention discloses the mixed film and preparation method and QLED device of quantum dot and carrier crosslinking, and method obtains mixed liquor comprising steps of quantum dot and carrier are mixed in solvent；Mixed liquor is made to the mixed film containing quantum dot and carrier by solwution method；Before mixed film is completely dried, vacuumize process is carried out；HHIC processing is carried out in vacuum, so that crosslinking between quantum dot and carrier, obtains the mixed film of quantum dot and carrier crosslinking；Wherein, the carrier is one or both of polymer and small molecule.The present invention carries out vacuumize process (vacuumizing at a slow speed for conventional) in solution film forming process.In vacuum, before film is completely dried, HHIC crosslinking Treatment, the relative position of fixed solute are carried out.Increase energy required for mutually separating, uniform film can be prepared, reduce the requirement of pumping speed, effectively prevent the problem of traditional heating cross-linking method is unevenly distributed mixed film.
Description
Technical field
The present invention relates to the mixed film of LED technology field more particularly to a kind of quantum dot and carrier crosslinking and
Preparation method and QLED device.
Background technique
Colloid (Colloid) quantum dot is the nano material system based on liquid phase distribution.Colloidal Quantum Dots pass through different
Preparation process (spin coating, printing, transfer or coating etc.), prepares quantum dot multilayer or single thin film.Due to Colloidal Quantum Dots system
In, quantum dot disperses in a solvent, and solvent volatilizees after film forming, forms the solid film for there was only quantum dot accumulation.Between quantum dot
It is linked with faint Van der Waals force, under external influence (mechanical force, solvent etc.), film morphology is not able to maintain, therefore colloid amount
The application of son point is very limited.For example, in the preparation process of light emitting diode with quantum dots (QLED), due to quantum dot without
Method crosslinking, may be washed away, therefore limit the preparation process and material of QLED by the solvent of the preparation process on quantum dot layer
Selection, to constrain the property and application of QLED.
The problem of solution of quantum dot crosslinking at present mainly uses heat cross-linking method, the method is that heating may be broken
The property of bad crosslinking substance, especially some functional groups chemically react at high temperature.In addition, heat treatment and standing may
The case where being unevenly distributed mixed film, reason be different solutes surface can it is different, solvent volatilization or it is molten
When agent is stood, the solute of different surfaces energy tends to assemble.If after having deposited solution, solvent flashing quickly, it is possible to reduce molten
The time of matter aggregation, to prevent the generation of split-phase.Vacuum drying method can make solvent quickly volatilize, but take out to vacuum
Speed has high requirements, the solvent for boiling point less than 150 DEG C, needs that air pressure is dropped to 0.1pa from atmospheric pressure in 10min；For
High boiling solvent (boiling point > 200 DEG C), it is desirable that it is harsher, it needs that air pressure is dropped to 0.1pa from atmospheric pressure in 5min.If only used
Vacuum suction goes the requirement for meeting not split-phase, and the short time needs to reach capacity vacuum 10^-1Pa, the high requirements on the equipment.And at
It cannot be crosslinked after film, if carrying out other processing after film forming, such as heat, it can further split-phase.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide the mixing of a kind of quantum dot and carrier crosslinking
Film and preparation method and QLED device, it is intended to which solving existing heat cross-linking method makes the space object of quantum dot and carrier in film
The problem of reason is unevenly distributed.
Technical scheme is as follows:
A kind of preparation method of quantum dot and the mixed film of carrier crosslinking, wherein include:
Step A, quantum dot and carrier are mixed in solvent, obtain mixed liquor；
Step B, mixed liquor is made by solwution method by the mixed film containing quantum dot and carrier；
Step C, before mixed film is completely dried, vacuumize process is carried out；HHIC processing is carried out in vacuum, is obtained
The mixed film of quantum dot and carrier crosslinking.
The preparation method of the quantum dot and the mixed film of carrier crosslinking, wherein the carrier is polymer and small
One or both of molecule.
The preparation method of the quantum dot and the mixed film of carrier crosslinking, wherein the polymer is the first p-type half
One of conductor material, the first n-type semiconductor, first insulator material, first luminescent material are a variety of；Described small point
Son be one of the second p-type semiconductor material, the second n-type semiconductor, second insulator material, the second luminescent material or
It is a variety of.
The preparation method of the quantum dot and the mixed film of carrier crosslinking, wherein first p-type semiconductor material
For one of PVK, TFB, poly-TPD, P3HT or a variety of, first n-type semiconductor is OXD-7, and described first absolutely
Edge body material is one of PMMA, PVP, PEN, PET or a variety of, and first luminescent material is MEH-PPV.
The preparation method of the quantum dot and the mixed film of carrier crosslinking, wherein second p-type semiconductor material
For one of NPB, CBP, TCTA or a variety of, second n-type semiconductor is one of Bphen, Alq, Liq or more
Kind, the second insulator material is UGH1, and second luminescent material is one or both of Irppy3, Firpic.
The preparation method of the quantum dot and the mixed film of carrier crosslinking, wherein in the step A, the solvent
For toluene, benzene, chlorobenzene, dimethylbenzene, chloroform, acetone, normal octane, isooctane, hexamethylene, n-hexane, pentane, isopentane, N,
Dinethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, hexamethyl phosphoramide, positive fourth
One of ether, methyl phenyl ethers anisole, phenetole, acetophenone, aniline, diphenyl ether are a variety of.
The preparation method of the quantum dot and the mixed film of carrier crosslinking, wherein the step C is specifically included:
Before mixed film is completely dried, vacuumize process is carried out；HHIC processing is carried out in vacuum, is passed through H2, and make H2Transformation
At H plasma, crosslinking Treatment is carried out to the mixed film containing quantum dot and carrier by H plasma, obtains quantum dot and carrier
The mixed film of crosslinking.
The preparation method of the quantum dot and the mixed film of carrier crosslinking, wherein the energy of the H plasma is 1 ~
100eV, the time of the crosslinking Treatment are 0.5 ~ 30min.
A kind of mixed film of quantum dot and carrier crosslinking, wherein the mixed film that the quantum dot is crosslinked with carrier is adopted
It is prepared with as above any preparation method；Quantum dot is uniformly distributed with carrier in the mixed film；Wherein, described
Carrier is one or both of polymer and small molecule.
A kind of QLED device, wherein the mixing that the QLED device, which includes quantum dot as described above, to be crosslinked with carrier is thin
Film.
The utility model has the advantages that the present invention in solution film forming process, carries out vacuumize process (vacuumizing at a slow speed for conventional).?
In vacuum, film be completely dried before (still in liquid, and not formed solid film), carry out HHIC crosslinking Treatment, Gu
Determine the relative position of solute.Increase energy required for mutually separating, uniform film can be prepared, reduce the requirement of pumping speed.Separately
Outer not need to heat because of HHIC cross-linking process, cannot provide effective kinetic energy makes mixed film split-phase, effectively prevents hot place
The case where reason and standing may all be such that mixed film is unevenly distributed.The mixed film of different quantum dots, can be different face
The quantum dot of color is mixed into a polymer or the carrier of small molecule, and the physical space distribution of fixing them.
Detailed description of the invention
Fig. 1 is the process of the preparation method preferred embodiment of the mixed film of a kind of quantum dot of the present invention and carrier crosslinking
Figure.
Fig. 2 is the vacuum degree and the change curve of time under vacuumized conditions at a slow speed.
Fig. 3 is the SEM figure of mixed film made from comparative example 1.
Fig. 4 is the SEM figure of mixed film made from embodiment 1.
Fig. 5 is the SEM figure of mixed film made from embodiment 2.
Specific embodiment
The present invention provides the mixed film and preparation method and QLED device of a kind of quantum dot and carrier crosslinking, to make this hair
Bright purpose, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that herein
Described specific embodiment is only used to explain the present invention, is not intended to limit the present invention.
HHIC(Hyperthermal hydrogen induced cross-linking) technology is to pass through H2As starting
Then reactant makes H2It is transformed into H plasma, then to be suitble to the H plasma of energy to open C-H, H-O, S-H, the chemistry such as H-N
Key.These chemical bonds opened are re-engaged later, so that chemical substance is crosslinked together.The method time-consuming is short, and condition is wanted
Low (room temperature) is asked, does not have particular/special requirement to reactant, and new substance will not be generated.
Specifically, in HHIC reactor, ion source is accelerated by electron cyclotron, makes plasma using electron cyclotron resonace
Ionization.Microwave is injected into the corresponding electron cyclotron resonace of frequency of certain volume.The volume includes low-pressure gas such as hydrogen, helium
Gas etc..The alternating electric field of microwave is set as synchronous with the gyration period of gas free electron, and increases its vertical kinetic energy.Then,
When the gas collisions in the free electron and volume of electrification, if their kinetic energy is greater than the ionization energy of atom or molecule,
They will cause to ionize.Particle after ionization obtains certain kinetic energy by electric field acceleration, obtains the particle of kinetic energy by touching
It hits, transfers energy to uncharged particle.By adjusting the size of electric field, the kinetic energy of particle is controlled.There is certain kinetic energy
Particle such as H2As starting reactant, it is crosslinked aimed thin film.In general, having bond energy such as the following table 1 of H key.
Table 1
| Chemical bond | H-H | H-C | N-H | O-H | Si-H | P-H | S-H |
| Bond energy (eV) | 18.9 | 18 | 16.9 | 20.2 | 13.9 | 13.8 | 15.8 |
Therefore with the H of certain energy2, H key can be opened.Form the free radical of protium and other groups, the reaction being related to
It is as follows:
-C-H → -C•+ H•• (1)；
-N-H → -N•+ H•• (2)；
-O-H → -O•+ H•• (3)；
-Si-H → -Si•+ H•• (4)；
-P-H → -P•+ H•• (5)；
-S-H → -S•+ H•• (6)；
=C-H → =C•+ H•• (7)。
Above-mentioned free radical can be combined with each other, so that substance be made to be linked to together.In organic matter ,-c h bond is largely to deposit
, and the bond energy of the bond energy of-C-H and H-H key is very close to therefore ,-C-H is most likely to occur cross-linking reaction.And pass through
Adjusting electric field can control reaction energy, to targetedly open different chemical bonds.Use H2It, will not as reactant
Generate new by-product.And the H generated2, pass back through air-flow and take away.
After free radical is formed, it can spread in the film:
•C- C- C-……- C- C- C-H → H-C- C- C-……- C- C- C• (8)
Free radical is very big in the surface concentration of film at the beginning, and by diffusion, free radical can be handed in this way to film internal migration
Connection reaction occurs inside film, so that entire film be made to be crosslinked.
Simultaneously with this, free radical can be reacted to each other between very active, different free radical, free radical and it is non-from
Proton exchange, such as following formula (9) can be occurred by base:
-X•+H-R- → -X-H+•R- (9)；
Wherein H-R- is alkane group, and X is other factors, therefore the reaction of this proton exchange, can expand the substance of crosslinking
Range.
Contain various organic ligands on the surface of quantum dot, the present invention can make organic ligand and other by HHIC method
The crosslinking of organic/inorganic group, the reaction equation being related to is mainly formula (1) and (8), this is because containing in polymer or small molecule
A large amount of unsaturated carbon bond, HHIC method open the-C-H of quantum dot surface organic ligands, then carbon radicals and the free base weight of H
It is new to combine, so that polymer or small molecule be made to be linked to together with quantum dot.
Fig. 1 is a kind of process of the preparation method preferred embodiment of the mixed film of quantum dot and carrier crosslinking of the invention
Figure, as shown, itself comprising steps of
Step S100, quantum dot and carrier are mixed in solvent, obtain mixed liquor；
Carrier of the present invention can be one of polymer and small molecule or a variety of.
Specifically, the polymer can be the first p-type semiconductor material, the first n-type semiconductor, first insulator
One of material, first luminescent material etc. are a variety of.For example, first p-type semiconductor material can be but be not limited to PVK
Poly- 3 hexyl thiophene of (polyvinylcarbazole), TFB, poly-TPD, P3HT() one of or it is a variety of.First n-type semiconductor
Material can be but be not limited to OXD-7.The first insulator material can be but be not limited to PMMA(poly-methyl methacrylate
Ester), PVP(polyvinylpyrrolidone), PEN(polyethylene naphthalate) and, PET(polyethylene terephthalate) in
It is one or more.First luminescent material can be but be not limited to MEH-PPV(red-luminescing material-photovoltaic material).Preferably,
The polymer is PVP.
Specifically, the small molecule is the second p-type semiconductor material, the second n-type semiconductor, second insulator material
One of material, second luminescent material are a variety of.For example, second p-type semiconductor material can be but be not limited to NPB,
One of CBP, TCTA or a variety of.Second n-type semiconductor can be but be not limited to Bphen(phenanthrolene),
One of Alq, Liq or a variety of.The second insulator material can be but be not limited to UGH1.Second luminescent material can
Think but be not limited to Ir(ppy) 3(tri- (2- phenylpyridine) close iridium), bis- (4,6- difluorophenyl pyridinato-N, the C2) pyridines of Firpic(
Formyl close iridium) one of or it is a variety of.Preferably, the small molecule is NPB.
Specifically, the solvent can be but be not limited to butanol, toluene, benzene, chlorobenzene, dimethylbenzene, chloroform, acetone, just pungent
Alkane, isooctane, hexamethylene, n-hexane, pentane, isopentane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- first
Base pyrrolidones, dimethyl sulfoxide, hexamethyl phosphoramide, n-butyl ether, methyl phenyl ethers anisole, phenetole, acetophenone, aniline, in diphenyl ether
It is one or more.Preferably, the solvent is butanol.
Specifically, the quantum dot (QD) can be but be not limited to red light quantum point, green light quantum point, blue light quantum point and
Gold-tinted quantum dot and one of infrared light quantum dot and ultraviolet light quantum dot or a variety of.For example, the quantum dot can be
Red light quantum point, green light quantum point or blue light quantum can also be the mixed of red light quantum point, green light quantum point and blue light quantum point
Close quantum dot.I.e. the present invention a kind of quantum dot of color can be mixed with the carrier of polymer or small molecule, can also be by
The quantum dot of different colours is mixed with polymer support or small molecule carrier.
Step S200, mixed liquor is made by solwution method by the mixed film containing quantum dot and carrier；
Mixed liquor is made one layer of mixed film, is dried in vacuo after film forming by the step S200 specifically, mixed liquor described in spin coating
Or (heating temperature is 0 ~ 120 DEG C, such as 120 DEG C) makes solvent volatilize by way of heating, formation contains only quantum dot and carrier
Amount mixed film.
Step S300, before mixed film is completely dried, vacuumize process is carried out；It is carried out at HHIC in vacuum
Reason obtains the mixed film of quantum dot and carrier crosslinking.
The step S300 is specifically included: before mixed film is completely dried, carrying out vacuumize process (at a slow speed for routine
It vacuumizes)；In vacuum, film be completely dried before (still in liquid, and not formed solid film), carry out at HHIC
Reason, is passed through H2, and make H2It is transformed into H plasma, crosslinking Treatment is carried out to mixed film by H plasma, so that quantum dot and load
It is crosslinked between body, obtains the mixed film of quantum dot and carrier crosslinking.Preferably, the energy for controlling the H plasma is 1
The energy of ~ 100eV, preferred H plasma are 1 ~ 10eV, such as 2eV, 3eV or 10eV.Preferably, the crosslinking Treatment is controlled
Time be 0.5 ~ 30min, time of preferred crosslinking Treatment is 0.5 ~ 10min, such as 0.5min, 1min or 2min.
Existing heat cross-linking method, heating may destroy the property of crosslinking substance, and especially some functional groups are at high temperature
It chemically reacts.There may be split-phase problems, especially quantum dot and polymer for liquid phase presoma, due to their surface energy
The case where difference, quantum dot and polymer are unevenly distributed in mixed film after heating.The present invention carries out the prior art
It improves, is in place of improved core: in solution film forming process, carrying out vacuumize process (vacuumizing at a slow speed for conventional).
In vacuum, film be completely dried before (still in liquid, and not formed solid film), carry out HHIC crosslinking Treatment,
The relative position of fixed solute.Increase energy required for mutually separating, uniform film can be prepared, reduce the requirement of pumping speed.
It then can be still phase separation structure in two alternate respective crosslinkings if after solution is completely dried film forming, then carrying out hydrogenation crosslinking.HHIC exists
During vacuumizing, under relatively high vacuum degree, it is crosslinked solute, it is mobile to increase solute for the relative position of fixed solute
Degree of difficulty.In addition because HHIC cross-linking process does not need to heat, cannot provide effective kinetic energy makes mixed film split-phase, effectively
It avoids heat treatment and stands the case where may all mixed film being made to be unevenly distributed.The mixed film of different quantum dots, can
The quantum dot of different colours is mixed into a polymer or the carrier of small molecule, and the physical space of fixing them point
Cloth.
The mixed film of a kind of quantum dot of the invention and carrier crosslinking, wherein the quantum dot is mixed with carrier crosslinking
Film is closed to be prepared using as above any preparation method.The present invention is crosslinked in resulting mixed film through HHIC method
Quantum dot is uniformly distributed with carrier.Preferably, the quantum dot and carrier crosslinking mixed film with a thickness of 10-100nm, such as
40nm, 50nm or 100nm.
A kind of QLED device of the invention, wherein the QLED device includes any quantum dot and carrier as above
The mixed film of crosslinking.The quantum dot and the mixed film of carrier crosslinking can be used as the functional layer of QLED device, the function
Layer includes luminescent layer, electron transfer layer, electron injecting layer, hole transmission layer, hole injection layer.The quantum dot and carrier are crosslinked
Functional layer of the mixed film as QLED device, the stability of QLED device can be effectively improved, and can ensure that QLED device
Electrical properties.
Below by embodiment, the present invention is described in detail.Following comparative examples 1 and embodiment 1-3 are in such as Fig. 2
Shown in the reaction that carries out under vacuumized conditions at a slow speed.
Fig. 2 (horizontal axis is time min, the longitudinal axis is air pressure Pa) is vacuum degree and time under common vacuumized conditions at a slow speed
Change curve, pressure drops to the pumping speed that 1Pa or less needs 5min from 10^5Pa, drops to 0.1Pa and need 10min or more.
Comparative example 1
10mg QD and 10mgPVP are mixed into 1ml butanol solvent, mixed liquor is obtained；It is thin that one layer of mixing is made in mixed liquor
Film carries out vacuumize process, is completely dried film, obtains mixed film.
Electronic Speculum (SEM) test is scanned to mixed film made from the present embodiment, test result is shown in Fig. 3, can from Fig. 3
Know, QD and PVP split-phase are serious.
Embodiment 1
10mg QD and 10mgPVP are mixed into 1ml butanol solvent, obtain mixed liquor.Mixed liquor described in spin coating, by mixed liquor system
At one layer of mixed film containing QD and PVP, before film is completely dried, vacuumize process is carried out；A point in vacuum
(in vacuum, before film is completely dried) carries out HHIC processing, is passed through H2, and make H2Be transformed into H plasma, adjust H etc. from
Sub- energy is 10eV, crosslinking Treatment 1min, obtains the mixed film of QD and PVP crosslinking.Continue to be vacuum-treated, keeps film complete
White drying can form the mixed film of 40nm.
Electronic Speculum (SEM) test is scanned to mixed film made from the present embodiment, test result is shown in Fig. 4, can from Fig. 4
Know, two-phase is evenly distributed in mixed film.And conventional heating methods is used to be crosslinked, most of PVP can gather film after split-phase
Upper layer.
Embodiment 2
20mg QD and 5mgNPB are mixed into 1ml chlorobenzene solvent, obtain mixed liquor.Mixed liquor described in spin coating, mixed liquor is made
One layer of mixed film carries out vacuumize process before film is completely dried；B point (vacuum in vacuum
In, before film is completely dried) HHIC processing is carried out, it is passed through H2, and make H2It is transformed into H plasma, adjusting H plasma energy is
3eV, crosslinking Treatment 0.5min obtain the mixed film of QD and NPB crosslinking.Continue to be vacuum-treated, be completely dried film,
The mixed film of 50nm can be formed.
Electronic Speculum (SEM) test is scanned to mixed film made from the present embodiment, test result is shown in Fig. 5, can from Fig. 5
Know, two-phase distribution is very uniform in mixed film.And conventional heating methods is used to be crosslinked, it is gathered after most of NPB meeting split-phase thin
Film upper layer.
Embodiment 3
The preparation step for the mixed film that green light QD, blue light QD, feux rouges QD, OXD-7 and Liq are crosslinked is as follows:
25mg green light QD, 10mg blue light QD, 2mg feux rouges QD, 10mg OXD-7 and 15mg Liq are mixed into 1ml chlorobenzene solvent,
Obtain mixed liquor.One layer of mixed film is made in mixed liquor by mixed liquor described in spin coating, before film is completely dried, take out true
Vacancy reason；Respectively in the 1st minute vacuumized, the 3rd minute, progress HHIC processing in the 5th minute, it is passed through H2, and make H2It is transformed into H
Plasma, respectively adjust H plasma energy be 10eV, 5eV, 2eV, crosslinking Treatment 2min, 1.5min, 1min, obtain green light QD,
The mixed film that blue light QD, feux rouges QD, OXD-7 and Liq are crosslinked.Continue to be vacuum-treated, be completely dried film, can be formed
The mixed film of 100nm.
In the present embodiment HHIC cross-linking process, green light QD, blue light QD, feux rouges QD, OXD-7 are evenly distributed on Liq and mix
It in film, and is crosslinked with conventional heating methods, most of OXD-7 and Liq can gather film upper layer after split-phase.
Comparative example 1, under such pumping speed, 20min rear film split-phase such as Fig. 3.It can be in A point 10^1Pa or B point 10^0Pa
HHIC technique is added.Vacuum time is short at this time, and solute is mobile few, solvent portion volatilization.Each solute can be fixed after HHIC crosslinking
Physical location, or increase the mobile steric hindrance of solute；When further vacuum, it can still guarantee not split-phase.
The time that the present invention can be carried out by adjusting HHIC treatment process, the time of crosslinking Treatment and plasma energy
Amount, to obtain the mixed film of different uniformity coefficients, such as embodiment 1(Fig. 4) two-phase distribution uniform, and embodiment 2(Fig. 5)
Two-phase distribution is very uniform.
In conclusion the mixed film and preparation method and QLED device of a kind of quantum dot provided by the invention and carrier crosslinking
Part.In solution film forming process, vacuumize process (vacuumizing at a slow speed for conventional) is carried out.In vacuum, film is complete
(still in liquid, and not formed solid film) before white drying, HHIC crosslinking Treatment, the relative position of fixed solute are carried out.Increase
Add energy required for mutually separating, uniform film can be prepared, reduce the requirement of pumping speed.After if solution is completely dried film forming,
Hydrogenation crosslinking is carried out again, then can be still phase separation structure in two alternate respective crosslinkings.HHIC is during vacuumizing, opposite
Under higher vacuum degree, it is crosslinked solute, the relative position of fixed solute increases the mobile degree of difficulty of solute.In addition because of HHIC
Cross-linking process does not need to heat, and cannot provide effective kinetic energy makes mixed film split-phase, effectively prevents being heat-treated and stand all
The case where mixed film may being made to be unevenly distributed.The mixed film of different quantum dots, can be the quantum dot of different colours
It is mixed into a polymer or the carrier of small molecule, and the physical space distribution of fixing them.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. the preparation method of a kind of quantum dot and the mixed film of carrier crosslinking characterized by comprising
Step A, quantum dot and carrier are mixed in solvent, obtain mixed liquor；
Step B, mixed liquor is made by solwution method by the mixed film containing quantum dot and carrier；
Step C, before mixed film is completely dried, vacuumize process is carried out；HHIC processing is carried out in vacuum, is obtained
The mixed film of quantum dot and carrier crosslinking.
2. the preparation method of quantum dot according to claim 1 and the mixed film of carrier crosslinking, which is characterized in that described
Carrier is one or both of polymer and small molecule.
3. the preparation method of quantum dot according to claim 2 and the mixed film of carrier crosslinking, which is characterized in that described
Polymer is the first p-type semiconductor material, the first n-type semiconductor, first insulator material, one in the first luminescent material
Kind is a variety of；The small molecule is the second p-type semiconductor material, the second n-type semiconductor, second insulator material, second
One of luminescent material is a variety of.
4. the preparation method of quantum dot according to claim 3 and the mixed film of carrier crosslinking, which is characterized in that described
First p-type semiconductor material is one of PVK, TFB, poly-TPD, P3HT or a variety of, first n-type semiconductor
For OXD-7, the first insulator material is one of PMMA, PVP, PEN, PET or a variety of, and first luminescent material is
MEH-PPV。
5. the preparation method of quantum dot according to claim 3 and the mixed film of carrier crosslinking, which is characterized in that described
Second p-type semiconductor material is one of NPB, CBP, TCTA or a variety of, second n-type semiconductor be Bphen,
One of Alq, Liq or a variety of, the second insulator material be UGH1, second luminescent material be Irppy3,
One or both of Firpic.
6. the preparation method of quantum dot according to claim 1 and the mixed film of carrier crosslinking, which is characterized in that described
In step A, the solvent be toluene, benzene, chlorobenzene, dimethylbenzene, chloroform, acetone, normal octane, isooctane, hexamethylene, n-hexane,
Pentane, isopentane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, six
One of methyl phosphamide, n-butyl ether, methyl phenyl ethers anisole, phenetole, acetophenone, aniline, diphenyl ether are a variety of.
7. the preparation method of quantum dot according to claim 1 and the mixed film of carrier crosslinking, which is characterized in that described
Step C is specifically included: before mixed film is completely dried, carrying out vacuumize process；HHIC processing is carried out in vacuum,
It is passed through H2, and make H2It is transformed into H plasma, crosslinking Treatment is carried out to the mixed film containing quantum dot and carrier by H plasma,
Obtain the mixed film of quantum dot and carrier crosslinking.
8. the preparation method of quantum dot according to claim 7 and the mixed film of carrier crosslinking, which is characterized in that described
The energy of H plasma is 1 ~ 100eV, and the time of the crosslinking Treatment is 0.5 ~ 30min.
9. the mixed film of a kind of quantum dot and carrier crosslinking, which is characterized in that the quantum dot and the mixing that carrier is crosslinked are thin
Film is prepared using the preparation method as described in claim 1 ~ 8 is any；Quantum dot and carrier are uniform in the mixed film
Distribution.
10. a kind of QLED device, which is characterized in that the QLED device includes quantum dot and carrier as claimed in claim 9
The mixed film of crosslinking.
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| CN112289939A (en) * | 2019-07-23 | 2021-01-29 | 夏普株式会社 | QLED fabricated by phase-separated emission layer patterning |
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| JP2003335053A (en) * | 2002-05-23 | 2003-11-25 | Fuji Photo Film Co Ltd | Sheet for inkjet recording |
| CN106229426A (en) * | 2016-09-18 | 2016-12-14 | Tcl集团股份有限公司 | The method of one brood lac chain quantum dot film and quantum dot film |
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| JP2003335053A (en) * | 2002-05-23 | 2003-11-25 | Fuji Photo Film Co Ltd | Sheet for inkjet recording |
| CN106229426A (en) * | 2016-09-18 | 2016-12-14 | Tcl集团股份有限公司 | The method of one brood lac chain quantum dot film and quantum dot film |
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| CN112289939A (en) * | 2019-07-23 | 2021-01-29 | 夏普株式会社 | QLED fabricated by phase-separated emission layer patterning |
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