CN109148701A - 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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- CN109148701A CN109148701A CN201710465120.2A CN201710465120A CN109148701A CN 109148701 A CN109148701 A CN 109148701A CN 201710465120 A CN201710465120 A CN 201710465120A CN 109148701 A CN109148701 A CN 109148701A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
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；Crosslinking Treatment is carried out to the mixed film containing quantum dot and carrier by HHIC technology, so that crosslinking between quantum dot and carrier, obtains the mixed film of quantum dot and carrier crosslinking.The present invention can make independent quantum dot crosslinked together with carrier using HHIC technology, obtain the mixed film of quantum dot and carrier crosslinking.In addition, HHIC cross-linking method of the present invention does not need crosslinked group, crosslinked group can be greatly reduced, quantum dot is quenched, improve the luminous efficiency of quantum dot.Further, since generating a large amount of free radical in HHIC cross-linking process, free radical can be moved on impurity, and quantum dot is quenched in passivation impurity, to further increase the luminous efficiency of quantum dot.
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 solution of quantum dot crosslinking at present mainly uses chemical method, i.e., chemistry is added in quantum dot preparation process
Crosslinked group reacts crosslinked group, to be crosslinked quantum dot by heat treatment or light processing after film forming.The method is asked
Topic is that crosslinked group is usually the very strong group of chemical activity, such as: the-CH=groups such as O and-OH, these crosslinked groups can the amount of making
Son point is quenched, to influence the luminous efficiency and electron mobility of quantum dot.Secondly in the mixed film containing quantum dot and carrier
In, general carrier discord quantum dot crosslinking, i.e., only carrier is crosslinked, because of the crosslinking group of carrier.
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 crosslinked group in existing cross-linking method is quenched quantum dot, influences quantum
Point luminous efficiency；And crosslinking is easy to happen in the mixed film containing quantum dot and carrier, between carrier, and carrier and quantum dot
Between the problem of being difficult to happen crosslinking.
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, crosslinking Treatment is carried out to the mixed film containing quantum dot and carrier by HHIC technology, so that quantum dot and carrier
Between crosslink, obtain quantum dot and carrier crosslinking mixed film.
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: will
Mixed film containing quantum dot and carrier is placed in HHIC reactor, is passed through H2, and make H2Be transformed into H plasma, by H etc. from
Son carries out crosslinking Treatment to the mixed film containing quantum dot and carrier, so that crosslinking between quantum dot and carrier, the amount of obtaining
The mixed film of son point and carrier 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 1 ~ 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.
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 carries out crosslinking Treatment to the mixed film comprising quantum dot and carrier using HHIC technology,
So that independent quantum dot is crosslinked together with carrier in mixed film, the mixed film of quantum dot and carrier crosslinking is obtained.Separately
Outside, HHIC cross-linking method of the present invention does not need crosslinked group, can greatly reduce crosslinked group and quantum dot is quenched, to mention
The luminous efficiency of high quantum dot.Further, since generating a large amount of free radical in HHIC cross-linking process, free radical can move to miscellaneous
In matter, quantum dot is quenched in passivation impurity, to further increase the luminous efficiency of quantum dot.
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 be respectively in embodiment 1 QD and TFB crosslinking mixed film ultraviolet spectrogram and QD and TFB it is uncrosslinked
The comparative result figure of the ultraviolet spectrogram of mixed film.
Fig. 3 be embodiment 3 in green light QD, blue light QD, feux rouges QD, OXD-7 and Liq crosslinking mixed film luminescent spectrum
Figure.
Fig. 4 be respectively in embodiment 4 HHIC method prepare QD and PVC crosslinking mixed film luminescent spectrum test and
The comparative result figure of the luminescent spectrum test of the mixed film for QD and the PVC crosslinking that in reference examples 5 prepared by Chemical Crosslinking Methods.
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 this proton is handed over
The reaction changed can expand the species range of crosslinking.
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.Quantum dot of the present invention is distributed to polymer
Or in small molecule, the distance between quantum dot can be increased, to improve the luminous efficiency of quantum dot.
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), 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 TFB.
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 toluene, benzene, chlorobenzene, dimethylbenzene, chloroform, acetone, normal octane, different
Octane, hexamethylene, n-hexane, pentane, isopentane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methylpyrrole
One of alkanone, dimethyl sulfoxide, hexamethyl phosphoramide, n-butyl ether, methyl phenyl ethers anisole, phenetole, acetophenone, aniline, diphenyl ether
Or it is a variety of.Preferably, described is chlorobenzene.
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
Mixed film.
Step S300, crosslinking Treatment is carried out to the mixed film containing quantum dot and carrier by HHIC technology, so that quantum
It is crosslinked between point and carrier, obtains the mixed film of quantum dot and carrier crosslinking.
The step S300 is specifically included: the mixed film containing quantum dot and carrier being placed in HHIC reactor, 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, so that
It is crosslinked between quantum dot and carrier, obtains the mixed film of quantum dot and carrier crosslinking.Preferably, control described H etc. from
The energy of son is 1 ~ 100eV, and the energy of preferred H plasma is 10eV.Preferably, the time for controlling the crosslinking Treatment is
1 ~ 30min, the time of preferred crosslinking Treatment are 10min.
In the prior art, multi-component crosslinking needs different crosslinking agent or crosslinking functionality, has an impact to quantum dot,
Such as the presence of crosslinked group-CH=O ,-OH, quantum dot is quenched, seriously affects the luminous efficiency of quantum dot.The present invention is to existing
Technology is improved, and is in place of improved core: using HHIC technology to the mixed film comprising quantum dot and carrier into
Row crosslinking Treatment forms quantum dot and carrier crosslinking so that independent quantum dot and carrier are crosslinked together in mixed film
Mixed film.The present invention does not need crosslinking agent or crosslinking functionality using HHIC technology, is conducive to multicomponent mixing and keeps group
Performance.In addition, general carrier is difficult to be crosslinked with quantum dot in the mixed film of quantum dot and carrier, i.e., only handed between carrier
Connection, because of the crosslinking group of carrier.The present invention can be crosslinked quantum dot and carrier using HHIC technology, particular by HHIC skill
Art makes organic ligand and the crosslinking of other organic/inorganic groups of quantum dot surface.In addition, the present invention utilizes HHIC technology, it is not required to
Crosslinking agent or crosslinking functionality are wanted, quantum dot can be greatly reduced and be quenched, to improve the luminous efficiency of quantum dot.And due to
A large amount of free radical is generated in HHIC cross-linking process, free radical can move on impurity, and quantum dot is quenched in passivation impurity,
To further increase the luminous efficiency of quantum dot.
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 resulting mixed film through HHIC method and exists
Better than the quantum dot of traditional heating crosslinking and the mixed film of carrier in stability, and its electrical properties does not change, can
Expand application and the selection range of solwution method.Preferably, the quantum dot is with the mixed film of carrier crosslinking 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.
Embodiment 1
The preparation step for the mixed film that QD and TFB is crosslinked is as follows:
10mg QD and 10mgTFB are mixed into 1ml chlorobenzene solvent, obtain mixed liquor.Mixed liquor described in spin coating, by mixed liquor system
At one layer of mixed film, vacuum drying makes solvent volatilize after film forming, forms the mixed film of 40nm.The mixed film is put into
In HHIC reactor, it is passed through H2, and make H2It is transformed into H plasma, adjusting H plasma energy is 10eV, and crosslinking Treatment 10min is obtained
To the mixed film of QD and TFB crosslinking.
Mixed film and QD and TFB uncrosslinked mixed film point to the QD made from the present embodiment and TFB crosslinking
Not carry out infrared test, test result is shown in Fig. 2, and wave crest is TFB wave crest at 450nm in figure, and wave crest is QD wave crest at 530nm.Knot
There is no variation, QD and TFB to be crosslinked successfully for luminescent spectrum after fruit shows HHIC crosslinking.
Embodiment 2
The preparation step for the mixed film that QD and NPB is crosslinked is as follows:
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 makes solvent volatilize after film forming, forms the mixed film of 50nm at 120 DEG C.The mixed film is put into
In HHIC reactor, it is passed through H2, and make H2It is transformed into H plasma, adjusting H plasma energy is 10eV, and crosslinking Treatment 10min is obtained
To the mixed film of QD and NPB crosslinking.
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.Mixed liquor is made one layer of mixed film, so that solvent is volatilized at 120 DEG C after film forming by mixed liquor described in spin coating,
Form the mixed film of 100nm.The mixed film is put into HHIC reactor, H is passed through2, and make H2It is transformed into H plasma,
Adjusting H plasma energy be 10eV, crosslinking Treatment 20min, obtain green light QD, blue light QD, feux rouges QD, OXD-7 and Liq crosslinking
Mixed film.
Luminescent spectrum is carried out to the mixed film of the green light QD obtained, blue light QD, feux rouges QD, OXD-7 and Liq crosslinking
Test, test result are shown in Fig. 3.
Embodiment 4
The step of preparing the mixed film that QD and PVC is crosslinked using HHIC method is as follows:
20mg QD and 5mg PVC are mixed into 1ml chlorobenzene solvent, mixed liquor is obtained.Mixed liquor described in spin coating, by mixed liquor
One layer of mixed film containing QD and PVC is made, vacuum drying makes solvent volatilize after film forming, forms the mixed containing QD and PVC of 50nm
Close film.The mixed film containing QD and PVC is put into HHIC reactor, H is passed through2, and make H2It is transformed into H plasma, adjusts
Section H plasma energy is 10eV, crosslinking Treatment 10min, obtains the mixed film of QD and PVC crosslinking.
Reference examples 5
The step of preparing the mixed film that QD and PVC is crosslinked using traditional chemical cross-linking method is as follows:
20mg QD is mixed with 5mg PVC, is crosslinked using suitable triazole dimercapto amine salt (FSH), mechanism of crosslinking is amine
Attack carbon chlorine polar bond carries out substitution reaction in conjunction with sulfydryl, obtains the mixed film of QD and PVC crosslinking.
The mixed film of QD and PVC crosslinking prepared by embodiment 4HHIC method and 5 traditional chemical cross-linking method of reference examples
Luminescent spectrum test is done respectively, and test result is shown in Fig. 4, the strong light of the mixed film of QD and the PVC crosslinking of HHIC method preparation
Mixed film luminous intensity of the degree much larger than QD and the PVC crosslinking of Chemical Crosslinking Methods preparation.This is because traditional chemistry is handed over
Linked method needs to add triazole dimercapto amine salt (FSH) crosslinking agent, and mechanism of crosslinking is amine attack carbon chlorine polar bond in conjunction with sulfydryl
Carry out substitution reaction.Amino in this reaction influences the characteristics of luminescence of quantum dot, and unreacted triazole dimercapto amine salt is to quench
Go out quantum dot light emitting the main reason for.In conclusion a kind of quantum dot provided by the invention and carrier crosslinking mixed film and
Preparation method and QLED device.The present invention carries out at crosslinking the mixed film comprising quantum dot and carrier using HHIC technology
Reason obtains the mixed film of quantum dot and carrier crosslinking so that independent quantum dot is crosslinked together with carrier in mixed film.
In the mixed film of quantum dot and carrier, general carrier is difficult to be crosslinked with quantum dot, i.e., is only crosslinked between carrier, because of carrier
Crosslinking group.The present invention can be crosslinked quantum dot and carrier using HHIC technology, make quantum dot particular by HHIC technology
The organic ligand on surface and other organic/inorganic groups are crosslinked.In addition, the present invention utilize HHIC technology, do not need crosslinking agent or
Crosslinking functionality can greatly reduce quantum dot and be quenched, to improve the luminous efficiency of quantum dot.And due to HHIC cross-linking process
Middle to generate a large amount of free radical, free radical can move on impurity, and quantum dot is quenched in passivation impurity, to further mention
The luminous efficiency of high quantum dot.The film that film by the crosslinking of HHIC method is crosslinked in stability better than traditional heating, and
And its electrical properties does not change.HHIC can expand application and the selection range of solwution method.
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, crosslinking Treatment is carried out to the mixed film containing quantum dot and carrier by HHIC technology, so that quantum dot and carrier
Between crosslink, obtain quantum dot and carrier crosslinking mixed film.
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: the mixed film containing quantum dot and carrier being placed in HHIC reactor, H is passed through2, and make H2It is transformed into H
Plasma carries out crosslinking Treatment to the mixed film containing quantum dot and carrier by H plasma, so that between quantum dot and carrier
It crosslinks, obtains 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 1 ~ 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.
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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