CN109962128A - A kind of film and preparation method thereof and QLED device - Google Patents
A kind of film and preparation method thereof and QLED device Download PDFInfo
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- CN109962128A CN109962128A CN201711435211.8A CN201711435211A CN109962128A CN 109962128 A CN109962128 A CN 109962128A CN 201711435211 A CN201711435211 A CN 201711435211A CN 109962128 A CN109962128 A CN 109962128A
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- 239000002096 quantum dot Substances 0.000 claims abstract description 247
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- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 41
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- 239000011258 core-shell material Substances 0.000 claims description 20
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- 229920002521 macromolecule Polymers 0.000 claims description 13
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- 239000000203 mixture Substances 0.000 claims description 10
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- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
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- 229910004611 CdZnTe Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention discloses a kind of film and preparation method thereof and QLED device, the film includes high molecular material and the quantum dot that is dispersed in the high molecular material, wherein the high molecular material includes at least one barrier high molecular material, and the weight average molecular weight of the barrier high molecular material is higher than 100,000.Compared with the film of existing pure quantum dot, contain quantum dot and high molecular material in film of the present invention, quantum dot is effectively isolated using high molecular material and increases the mutual distance between quantum dot, to reduce the radiationless energy transfer and concentration quenching between the interaction between quantum dot and utmostly inhibition quantum dot, reach the promotion of quantum dot light emitting quantum yield in film.Using this film with high photoluminescence quantum yield into QLED device, efficient QLED device can be achieved with.
Description
Technical field
The present invention relates to technology of quantum dots fields more particularly to a kind of film and preparation method thereof and QLED device.
Background technique
Quantum dot is a kind of special material for being limited in nanometer scale in three dimensions, this significant
Quantum confined effect makes quantum dot be provided with many unique nanometer properties: launch wavelength is continuously adjustable, emission wavelength is narrow, inhales
Receive spectral width, luminous intensity height, fluorescence lifetime length and good biocompatibility etc..These features mark quantum dot in biology
The fields such as note, FPD, solid-state lighting, photovoltaic solar all have broad application prospect.
In the application of typical electroluminance display, quantum dot is usually individually to form a film to form one layer only to include quantum
Point material luminescent layer, this in organic light emitting diode device (OLED), luminescent material (referred to as guest materials) be usually with
The case where a certain proportion of doping concentration is blended in barrier material and then forms a film is different.In barrier-object mixing material
In the situation for expecting luminescent layer, hole and electronics pass through conduction band and valence band energy that respectively transmission layer material is injected into barrier material first
In grade and exciton is formed, and exciton is not intended to occur compound at this time, but exciton transfer is arrived by way of energy transmission
In guest materials, the photon that composed emission goes out respective wavelength occurs for exciton in guest materials.Since in OLED, object is organic
Molecule itself and the function of not having energy level constraint can be sent out so if individually film forming formation contains only the luminescent layer of guest materials
Raw radiationless energy transfer and concentration quenching strongly, therefore barrier-object mixed system is one for OLED
Kind more effectively obtains the mode of high-luminous-efficiency.
It is general since quantum dot itself has core-shell structure but for light emitting diode with quantum dots (QLED)
For, the quantum dot itself of high quality will have very good energy level constraint and corresponding exciton confinement ability, so directly
The pure quanta point material of use, which is connect, as luminescent layer can be realized as good device light emitting efficiency, while device architecture is simpler
Single, exciton loss access is reduced.
But the limitation for thering are some quantum dots to design due to core-shell structure, cause in this kind of quantum dot for itself
Energy level and exciton confinement ability are very limited, although this kind of quantum dot can under solution state (i.e. distance between quantum dot particles
It is bigger) show higher photoluminescence quantum yield, but (i.e. between quantum dot particles tightly packed) in solid film can be by
Luminous efficiency is caused to significantly reduce in strong radiationless energy transfer and concentration quenching.Therefore the QLED based on this kind of quantum dot
Device efficiency will be very low.
Therefore for itself this kind of energy level and the limited quantum dot of exciton confinement ability, the design of corresponding QLED device and
Preparation method has much room for improvement.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of film and preparation method thereof and QLED
Device, it is intended to solve existing some quantum dots itself energy level and exciton confinement ability is insufficient, there are radiationless in solid film
Energy transfer and concentration quenching lead to the problem that luminous efficiency is low in QLED device.
Technical scheme is as follows:
A kind of film, wherein the film includes high molecular material and the quantum dot that is dispersed in the high molecular material, wherein
The high molecular material includes at least one barrier high molecular material, and the weight average molecular weight of the barrier high molecular material is higher than 10
Ten thousand, the high molecular material further includes that at least one charge transmission adjusts high molecular material, and the charge transmission adjusts macromolecule
The weight average molecular weight of material is lower than 100,000.
The film, wherein the high molecular material is adjusted by a kind of barrier high molecular material and a kind of transmission of charge
High molecular material composition, the charge transmission adjust high molecular material and account for the mass fraction of high molecular material lower than 10%.
The film, wherein the weight average molecular weight of the barrier high molecular material is between 10-30 ten thousand, the quantum
The mass fraction that point accounts for film is 0.5-25%.
The film, wherein the weight average molecular weight of the barrier high molecular material is between 30-50 ten thousand, the quantum
The mass fraction that point accounts for film is 0.5-60%.
The film, wherein the weight average molecular weight of the barrier high molecular material is between 50-150 ten thousand, the quantum
The mass fraction that point accounts for film is 0.5-90%.
The film, wherein the mass fraction that the quantum dot accounts for film is 0.5-20%.
The film, wherein the mass fraction that the quantum dot accounts for film is 2-10%.
The film, wherein the carrier mobility of the barrier high molecular material is 10-6 cm2V-1s-1Hereinafter, institute
It states charge transmission and adjusts high molecular material selected from conducting polymer, the charge transmission adjusts high molecular material and accounts for high molecular material
Mass fraction be 0.5-5%.
The film, wherein the conducting polymer is selected from polyacetylene, polyphenylene sulfide, polyaniline, polypyrrole and poly- thiophene
One of pheno.
The film, wherein the carrier mobility of the barrier high molecular material is 10-6 cm2V-1s-1More than, institute
It states charge transmission and adjusts high molecular material selected from non-conductive polymer, the charge transmission adjusts high molecular material and accounts for macromolecule material
The mass fraction of material is 5-10%.
The film, wherein the non-conductive polymer is selected from phenolic resin, polyethylene, dimethyl silicone polymer, gathers
One of styrene, polymethacrylates, polyacrylate and polycarbonate.
A kind of preparation method of film, wherein comprising steps of
Quantum dot and high molecular material are mixed in a dispersion medium；
Film is made in mixed solution, obtains the film；
Wherein the high molecular material includes at least one barrier high molecular material, the Weight-average molecular of the barrier high molecular material
Amount is higher than 100,000, and the high molecular material further includes that at least one charge transmission adjusts high molecular material, and the charge transmission is adjusted
The weight average molecular weight for saving high molecular material is lower than 100,000.
The preparation method of the film, wherein the high molecular material is by a kind of barrier high molecular material and a kind of electricity
Lotus transmission adjusts high molecular material composition, and the mass fraction that the charge transmission adjusting high molecular material accounts for high molecular material is lower than
10%。
The preparation method of the film, wherein the quantum dot is oil-soluble quantum dot, the oil-soluble quantum dot
Surface ligand is mercaptan or carboxylic acid.
The preparation method of the film, wherein the quantum dot is selected from CdTe, CdTeS and using CdTe or CdTeS as core
One of core-shell quanta dots.
The preparation method of the film, wherein in the film, the mass fraction of the quantum dot is 0.5-20%.
The preparation method of the film, wherein the mass fraction of the quantum dot is 2-10%.
A kind of QLED device, the QLED device includes quantum dot light emitting layer, which is characterized in that the quantum dot light emitting
Layer is film of the present invention.
The QLED device, wherein the film with a thickness of 10-80nm.
The utility model has the advantages that contain quantum dot and high molecular material in film of the present invention compared with the film of existing pure quantum dot,
Quantum dot is effectively isolated using high molecular material and increases the mutual distance between quantum dot, to reduce the phase between quantum dot
Radiationless energy transfer and concentration quenching between interaction and utmostly inhibition quantum dot, reach quantum dot light emitting in film
The promotion of quantum yield.If the molecular weight for obstructing high molecular material is too small, enough isolation effects can not be played, therefore it is required that energy
It is enough to realize the weight average molecular weight for being effectively isolated the barrier high molecular material of quantum dot 100,000 or more；Obstruct point of high molecular material
Son amount is higher, and the isolation effect mutual for quantum dot is better, thus the quantum that can be accommodated in quantum dot film
The weight content of point is higher.Using this film with high photoluminescence quantum yield into QLED device, it can be achieved with efficiently
The QLED device of rate.
Detailed description of the invention
Fig. 1 is the structural formula of PVK in the present invention.
Fig. 2 is the structural formula of TFB in the present invention.
Fig. 3 is the structural formula of poly-TPD in the present invention.
Fig. 4 is the structural formula of MEH-PPV in the present invention.
Fig. 5 is the structural formula of the derivative of PVK in the present invention.
Fig. 6 is the structural formula of another derivative of PVK in the present invention.
Fig. 7 is the structural formula of the another derivative of PVK in the present invention.
Fig. 8 is the structural schematic diagram of light emitting diode with quantum dots in the embodiment of the present invention 14.
Specific embodiment
The present invention provides a kind of film and preparation method thereof and QLED device, for make the purpose of the present invention, technical solution and
Effect is clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein
It is only used to explain the present invention, be not intended to limit the present invention.
The core-shell structure of existing certain quantum dots itself is very limited for energy level and exciton confinement ability, although can be
(distance is big between quantum dot particles at this time) shows higher photoluminescence quantum yield under solution state, but in solid film
It is (tightly packed between quantum dot particles at this time) luminous efficiency to be led to due to strong radiationless energy transfer and concentration quenching
It significantly reduces.This is because the core-shell structure when quantum dot cannot very well fetter electron cloud or exciton on energy level
When, electron cloud or exciton will diffuse more readily into quantum dot surface, at this time if the distance between quantum dot is close mutually
Effect is very strong (such as situation in solid film), then being diffused into the electron cloud on surface or exciton in quantum dot will occur
Strong interaction, so that strong radiationless energy transfer and concentration quenching occurs, so that the quantum in solid film
Point photoluminescence quantum yield significantly reduces.So that the QLED device efficiency using this solid film can also significantly reduce.
So itself this core-shell structure cannot be provided it is enough for the quantum dot of energy level and exciton confinement,
Use pure quanta point material that cannot obtain well as the scheme of quantum dot light emitting layer film in QLED device in the prior art
Effect.
Enough quantum dots for energy level and exciton confinement cannot be provided for itself this core-shell structure, in order to
Increase distance between quantum dot so that the interaction between quantum dot is reduced, utmostly to inhibit the nothing between quantum dot
Radiation energy transfer and concentration quenching need quantum dot and high molecular material being mixed with film, have using high molecular material
Effect isolation quantum dot simultaneously increases the mutual distance between quantum dot, to reduce the interaction between quantum dot and utmostly
Inhibit the radiationless energy transfer and concentration quenching between quantum dot, reaches the promotion of quantum dot film photoluminescence quantum yield.Benefit
With this quantum dot film with high photoluminescence quantum yield into QLED device, efficient QLED device can be achieved with.Cause
This, the present invention is mainly improved and is seen below:
The present invention provides a kind of film, wherein the film includes high molecular material and is dispersed in the high molecular material
Quantum dot, wherein the high molecular material includes at least one barrier high molecular material, the weight of the barrier high molecular material is equal
Molecular weight is higher than 100,000.
Compared with the existing film prepared using pure quantum dot, quantum dot and high molecular material are contained in film of the present invention,
Quantum dot is effectively isolated using high molecular material and increases the mutual distance between quantum dot, to reduce the phase between quantum dot
Radiationless energy transfer and concentration quenching between interaction and utmostly inhibition quantum dot, reach quantum dot light emitting in film
The promotion of quantum yield.If the molecular weight for obstructing high molecular material is too small, enough isolation effects can not be played, therefore it is required that energy
It is enough to realize the weight average molecular weight for being effectively isolated the barrier high molecular material of quantum dot 100,000 or more；Obstruct point of high molecular material
Son amount is higher, and the isolation effect mutual for quantum dot is better, thus the quantum that can be accommodated in quantum dot film
The weight content of point is higher.Using this film with high photoluminescence quantum yield into QLED device, it can be achieved with efficiently
The QLED device of rate.
Film of the present invention contains quantum dot and one or more kinds of barrier high molecular materials, obstructs the weight of high molecular material
Average molecular weight is higher than 100,000, if can not play effective this is because the weight average molecular weight of the barrier high molecular material is too small
Isolation effect.The weight average molecular weight of the barrier high molecular material is higher, and the isolation effect mutual for quantum dot is got over
Good, the weight content for the quantum dot that can be accommodated in the film is higher.
Preferably, the quantum dot is oil-soluble quantum dot or water-soluble quantum dot.
It is further preferred that the quantum dot is oil-soluble quantum dot, the surface ligand of the oil-soluble quantum dot is sulphur
Alcohol or carboxylic acid.
Still more preferably, the quantum dot is selected from II-VI group quantum dot, iii-v quantum dot and group IV-VI quantum
One of point is a variety of.Specifically, the quantum dot be selected from II-VI group, iii-v, group IV-VI single quantum dot and
One of II-VI group, iii-v, the core-shell type quantum point of group IV-VI or mixed type quantum dot are a variety of.As an example,
The single quantum dot of II-VI group be selected from CdSe, CdS, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS,
ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdSeSTe, ZnSeSTe and
One of CdZnSeSTe etc.；The single quantum dot of iii-v be selected from InP, GaP, GaAs, InAs, InAsP, GaAsP, InGaP,
One of InGaAs and InGaAsP etc.；The single quantum dot of group IV-VI be selected from PbS, PbSe, PbTe, PbSeS, PbSeTe and
One of PbSTe etc.；The core-shell type quantum point is selected from CdZnSe/ZnS, CdZnSeS/ZnS, CdTe/ZnS, CdZnSe/
One of ZnS, CdZnSeS/ZnS, CdTe/ZnS, CdTe/CdSe, CdTe/ZnTe, CdSe/CdS and CdSe/ZnS etc.；Institute
It states mixed type quantum dot and is selected from CdTe/CdS/ZnS etc..
Still further preferably, the quantum dot is selected from II-VI group quantum dot.
Again still further preferably, the quantum dot is selected from the II-VI group quantum dot containing Te.II-VI group quantum containing Te
Point has narrower band gap compared to the II-VI group quantum dot containing Se, therefore is preparing visible light wave range (green or red)
Luminescent quantum dot when, thicker shell cannot be grown, to avoid the excessive red shift of emission wavelength, therefore between the quantum dot
Distance can be very close, the strong phenomenon of interaction in solid film can be more prominent in the II-VI group quantum dot containing Te
Out, radiationless energy transfer and concentration quenching strong in solid film will lead to the effect of the II-VI group quantum dot light emitting containing Te
Rate significantly reduces.Therefore for the QLED device of the II-VI group quantum dot containing Te, to quantum in quantum dot light emitting layer film
What luminous efficiency was quenched between point effectively avoids becoming to be even more important.Most preferably, the quantum dot is selected from the II-VI containing Cd and Te
Race's quantum dot.As an example, in core-shell quanta dots of the quantum dot selected from CdTe, CdTeS and using CdTe or CdTeS as core
It is a kind of.The conduction level of other opposite II-VI group quantum dots containing Te of quantum dot due to CdTe, CdTeS etc. containing Cd, Te is more
It is deep, it is more preferable for the constraint effect of electronics, therefore the method for similarly luminous efficiency being avoided to be quenched can produce CdTe, CdTeS etc.
Raw more preferably effect.
Preferably, the carrier mobility of the barrier high molecular material is 10-8 cm2V-1s-1More than.Due to containing resistance
It is used as luminescent layer in the application of QLED device every the film of high molecular material and quantum dot, after film need to being injected into view of charge
Charge transmission in barrier high molecular material, so the carrier mobility of barrier high molecular material need to meet certain requirement
(10-8 cm2V-1s-1More than).
It is further preferred that the weight average molecular weight of the barrier high molecular material is higher than 200,000.Obstruct high molecular material
Weight average molecular weight is higher, and the isolation effect mutual for quantum dot is better.Weight average molecular weight is selected to be higher than 200,000 resistance
Every high molecular material, the isolation effect mutual to quantum dot can be further improved, measure in film to further be promoted
Son point photoluminescence quantum yield.
Still more preferably, the weight average molecular weight of the barrier high molecular material is higher than 300,000.
Still further preferably, the weight average molecular weight of the barrier high molecular material is higher than 500,000.
In a preferred embodiment, the barrier high molecular material is selected from the PVK that weight average molecular weight is higher than 500,000
The TFB of (poly- (9- vinyl carbazole)) and its derivative, weight average molecular weight higher than 500,000 and its derivative, weight average molecular weight are higher than
The 500000 poly- (2- methoxyl group -5-(2'- ethyl hexyl of MEH-PPV(of poly-TPD and its derivative, weight average molecular weight higher than 500,000
Oxygroup) -1,4- is to phenylacetylene)) and its derivative one kind.Wherein, the structural formula of the PVK is shown in Fig. 1, the structure of the TFB
Formula is shown in that Fig. 2, the structural formula of the poly-TPD are shown in that Fig. 3, the structural formula of the MEH-PPV are shown in Fig. 4.As an example, the TFB
Derivative can in Fig. 5-Fig. 7 any structural molecule.The present invention selects above-mentioned barrier high molecular material, can maximize
The isolation effect mutual to quantum dot is improved, promotes quantum dot light emitting quantum yield in film to maximize.
Preferably, the film is made of quantum dot and a kind of barrier high molecular material, and the quantum dot accounts for the matter of film
Amount score is 0.5-90%.In other words, a kind of specific high molecular material, the resistance are contained only in film described in the present embodiment
It is higher than 100,000 every the weight average molecular weight of high molecular material, the weight average molecular weight of the barrier high molecular material is higher, for quantum
The mutual isolation effect of point is better, and the weight content for the quantum dot that can be accommodated in the film is higher.
It is further preferred that it is described barrier high molecular material weight average molecular weight between 100,000-30 ten thousand, the quantum dot
The mass fraction for accounting for film is 0.5-30%.
It is further preferred that it is described barrier high molecular material weight average molecular weight between 300,000-50 ten thousand, the quantum dot
The mass fraction for accounting for film is 0.5-66%.
It is further preferred that it is described barrier high molecular material weight average molecular weight between 500,000-150 ten thousand, the quantum
The mass fraction that point accounts for film is 0.5-90%.
The molecular weight for obstructing high molecular material is higher, and the isolation effect mutual for quantum dot is better, thus
The weight content for the quantum dot that can be accommodated in quantum dot film is higher.
Still more preferably, it is 0.5-20% that the quantum dot, which accounts for the mass fraction of film,.
Still further preferably, it is 2-10% that the quantum dot, which accounts for the mass fraction of film,.
Still more preferably, the carrier mobility of the barrier high molecular material is 10-6 cm2V-1s-1More than, with
Further enhance the transmission of charge in the film.
Preferably, the film is made of quantum dot and high molecular material, and the high molecular material is by two kinds of barrier high scores
Sub- material composition.In other words, high molecular material of the present invention only includes two kinds of barrier high molecular materials, described two barrier high scores
The weight average molecular weight of sub- material is above 100,000, and the mass fraction that the quantum dot accounts for film is 0.5-90%.Described two barriers
The weight average molecular weight of high molecular material is higher, and the isolation effect mutual for quantum dot is better, can hold in the film
The weight content for the quantum dot received is higher.
Preferably, it is 0.5-90% that the quantum dot, which accounts for the mass fraction of film,.
It is further preferred that the mass fraction that the quantum dot accounts for film is 0.5-20%.
Still further preferably, it is 2-10% that the quantum dot, which accounts for the mass fraction of film,.
Still more preferably, the carrier mobility of described two barrier high molecular materials is 10-6 cm2V-1s-1With
On, to further enhance the transmission of charge in the film.
Preferably, the high molecular material further includes that at least one charge transmission adjusts high molecular material, and the charge passes
The defeated weight average molecular weight for adjusting high molecular material is lower than 100,000, and the charge transmission adjusts high molecular material and accounts for high molecular material
Mass fraction is lower than 10%.In other words, high molecular material of the present invention includes at least one barrier high molecular material and at least one
Charge transmission adjusts high molecular material, and the weight average molecular weight of the barrier high molecular material is higher than 100,000, and the charge transmission is adjusted
The weight average molecular weight for saving high molecular material is lower than 100,000, and the weight average molecular weight of the barrier high molecular material is higher, for quantum
The mutual isolation effect of point is better, and the weight content for the quantum dot that can be accommodated in the film is higher.The charge
The addition that transmission adjusts high molecular material can adjust film and apply the charge transport properties in QLED device, and can guarantee
The photoluminescence quantum yield of film itself is unaffected.
When the carrier mobility for obstructing high molecular material is excessively high (10-6 cm2V-1s-1More than), it needs in the film
Charge transmission is added and adjusts high molecular material, it need to be non-conductive high score that the charge transmission under this situation, which adjusts high molecular material,
Son, effectively to control and adjust the transmission of charge in the film.
It is further preferred that the high molecular material adjusts high score by a kind of barrier high molecular material and a kind of transmission of charge
Sub- material composition.In other words, high molecular material of the present invention is only that a kind of barrier high molecular material and a kind of transmission of charge are adjusted
High molecular material, the weight average molecular weight of the barrier high molecular material are higher than 100,000, and the charge transmission adjusts high molecular material
Weight average molecular weight be lower than 100,000, it is described barrier high molecular material weight average molecular weight it is higher, it is mutual for quantum dot
Isolation effect is better, and the weight content for the quantum dot that can be accommodated in the film is higher.
Preferably, it is 0.5-90% that the quantum dot, which accounts for the mass fraction of film,.
It is further preferred that the mass fraction that the quantum dot accounts for film is 0.5-20%.
Still further preferably, it is 2-10% that the quantum dot, which accounts for the mass fraction of film,.
In a preferred embodiment, the carrier mobility of the barrier high molecular material is 10-6 cm2V-1s-1
Hereinafter, the charge transmission adjusts high molecular material and is selected from conducting polymer, thus enhance the transmission of charge in the film, it is described
It is 0.5-5% that charge transmission, which adjusts high molecular material and accounts for the mass fraction of high molecular material,.As an example, the conducting polymer
Selected from one of polyacetylene, polyphenylene sulfide, polyaniline, polypyrrole and polythiophene etc..
In a preferred embodiment, the carrier mobility of the barrier high molecular material is 10-6 cm2V-1s-1
More than, the charge transmission adjusts high molecular material and is selected from non-conductive polymer, effectively to control and adjust charge in film
In transmission, it is 5-10% that charge transmission, which adjusts high molecular material and accounts for the mass fraction of high molecular material,.As an example, institute
It states non-conductive polymer and is selected from phenolic resin, polyethylene, dimethyl silicone polymer (PDMS), polystyrene, polymethylacrylic acid
One of ester, polyacrylate and polycarbonate etc..
Preferably, the film is made of quantum dot and high molecular material, and the high molecular material is by two kinds of barrier high scores
Sub- material and a kind of transmission of charge adjust high molecular material composition.
Preferably, it is 0.5-90% that the quantum dot, which accounts for the mass fraction of film,.
It is further preferred that the mass fraction that the quantum dot accounts for film is 0.5-20%.
Still further preferably, it is 2-10% that the quantum dot, which accounts for the mass fraction of film,.
In a preferred embodiment, the carrier mobility of described two barrier high molecular materials is 10-6
cm2V-1s-1Hereinafter, the charge transmission adjusts high molecular material and is selected from conducting polymer, to enhance the biography of charge in the film
Defeated, it is 0.5-5% that the charge transmission, which adjusts high molecular material and accounts for the mass fraction of high molecular material,.As an example, the conduction
Macromolecule is selected from one of polyacetylene, polyphenylene sulfide, polyaniline, polypyrrole and polythiophene.
In a preferred embodiment, the carrier mobility of described two barrier high molecular materials is 10-6
cm2V-1s-1More than, the charge transmission adjusts high molecular material and is selected from non-conductive polymer, effectively to control and adjust charge
Transmission in the film, it is 5-10% that the charge transmission, which adjusts high molecular material and accounts for the mass fraction of high molecular material,.As act
Example, the non-conductive polymer are selected from phenolic resin, polyethylene, dimethyl silicone polymer, polystyrene, polymethylacrylic acid
One of ester, polyacrylate and polycarbonate.
The present invention also provides a kind of preparation methods of film, wherein comprising steps of
Quantum dot and high molecular material are mixed in a dispersion medium；
Film is made in mixed solution, obtains the film；
Wherein the high molecular material includes at least one barrier high molecular material, the Weight-average molecular of the barrier high molecular material
Amount is higher than 100,000.
Preferably, the decentralized medium is selected from organic solvent.It is further preferred that the organic solvent has selected from nonpolarity
Solvent, as an example, the non-polar organic solvent can be selected from chloroform, toluene, chlorobenzene, n-hexane, normal octane, decahydro
Naphthalene, tridecane, n-octyl, tri octyl phosphine (TOP), tributylphosphine (TBP), octadecylene (ODE), oleic acid (OA), octadecyl
One of amine (ODA), trioctylamine (TOA) and oleyl amine (OAm) etc..
Preferably, mixed solution is made by film using solwution method, obtains the film.As an example, described molten
Liquid method is selected from spin-coating method, print process, knife coating, dip-coating method, infusion method, spray coating method, roll coating process, casting method, slit and applies
One of cloth method and strip rubbing method etc..
The present invention also provides a kind of QLED device, the QLED device includes quantum dot light emitting layer, wherein the quantum
Point luminescent layer is film of the present invention.Film with high photoluminescence quantum yield is applied in QLED device by the present invention, energy
Enough realize efficient QLED device.
Preferably, the film with a thickness of 10-80nm.
Below by embodiment, the present invention is described in detail.
Embodiment 1
The preparation method of the film of the present embodiment difference quantum dot weight percent, comprising the following steps:
1) the CdTe/CdZnS core-shell quanta dots for, weighing 20 mg are substantially soluble in 10 mL chlorobenzenes, and forming concentration is 2 mg/mL's
Quantum dot solution, the glow peak of this quantum dot solution are 631 nm, and half-peak breadth is 30 nm, photoluminescence quantum yield 56%；
2) 40 mg, 30 mg, 20 mg, 10 mg, 8 mg, 4 mg, 2 mg, 1 mg, 0.5 mg, 0.3 mg, 0.1, are weighed respectively
PVK (the weight average molecular weight are as follows: ten thousand) ~ 110 are respectively substantially soluble in the chlorobenzene of 0.5 mL of mg；
3) it, is separately added into prepared 0.5 mL of quantum dot solution in step 1) in above-mentioned PVK chlorobenzene solution and sufficiently mixes
It closes, so that sequentially forming PVK/QD weight concentration is 40/1,30/1,20/1,10/1,8/1,4/1,2/1,1/1,0.5/1,0.3/
1, the chlorobenzene solution of 0.1/1 mg/mL；
4) above-mentioned chlorobenzene solution is formed a film in an inert atmosphere by the method for spin coating, and is annealed 15 minutes at 120 DEG C, i.e.,
The film with different quantum dot weight percent can be prepared.
Embodiment 2
Obstruct promotion effect of the addition for thin-film light emitting quantum yield of high molecular material
The photoluminescence quantum yield of each film is as shown in table 1 below in embodiment 1, is formed by film compared to by pure quanta point material
(last line), the barrier high molecular material (being PVK in this example) that different proportion is added in the film can significantly improve film
Photoluminescence quantum yield, be significantly increased from the 3% of pure film to 53%, produced substantially close to the luminescent quantum of quantum dot in the solution
Rate illustrates that PVK macromolecule is good for the isolation effect of quantum dot in the film.PVK has very big Weight-average molecular in this
It measures (1,100,000), it can be seen that a wide range of interior improvement result that has luminous efficiency of the weight percent of QD in 2-90%.
The photoluminescence quantum yield of table 1, film
Embodiment 3
The preparation method of the film of the present embodiment difference quantum dot weight percent, comprising the following steps:
1) the CdTe/CdZnS core-shell quanta dots for, weighing 20 mg are substantially soluble in 10 mL chlorobenzenes, and forming concentration is 2 mg/mL's
Quantum dot solution, the glow peak of this quantum dot solution are 631 nm, and half-peak breadth is 30 nm, photoluminescence quantum yield 56%；
2) 40 mg, 30 mg, 20 mg, 10 mg, 8 mg, 4 mg, 2 mg, 1 mg, 0.5 mg, 0.3 mg, 0.1, are weighed respectively
PVK (the weight average molecular weight are as follows: ten thousand) ~ 50 are respectively substantially soluble in the chlorobenzene of 0.5 mL of mg；
3) it, is separately added into prepared 0.5 mL of quantum dot solution in step 1) in above-mentioned PVK chlorobenzene solution and sufficiently mixes
It closes, so that sequentially forming PVK/QD weight concentration is 40/1,30/1,20/1,10/1,8/1,4/1,2/1,1/1,0.5/1,0.3/
1, the chlorobenzene solution of 0.1/1 mg/mL；
4) above-mentioned chlorobenzene solution is formed a film in an inert atmosphere by the method for spin coating, and is annealed 15 minutes at 120 DEG C, i.e.,
The film with different quantum dot weight percent can be prepared.
Embodiment 4
Obstruct promotion effect of the addition for thin-film light emitting quantum yield of high molecular material
The photoluminescence quantum yield of each film is as shown in table 2 below in embodiment 3, is formed by film compared to by pure quanta point material
(last line), the barrier high molecular material (being PVK in this example) that different proportion is added in the film can significantly improve film
Photoluminescence quantum yield, be significantly increased from the 3% of pure film to 52%, produced substantially close to the luminescent quantum of quantum dot in the solution
Rate illustrates that PVK macromolecule is good for the isolation effect of quantum dot in the film.PVK has biggish Weight-average molecular in this example
It measures (500,000), it can be seen that a wide range of interior improvement result that has luminous efficiency of the weight percent of QD in 2-66%.
The photoluminescence quantum yield of table 2, film
Embodiment 5
The preparation method of the film of the present embodiment difference quantum dot weight percent, comprising the following steps:
1) the CdTe/CdS core-shell quanta dots for, weighing 20 mg are substantially soluble in 10 mL toluene, form the amount that concentration is 2 mg/mL
Son point solution, the glow peak of this quantum dot solution are 628 nm, and half-peak breadth is 32 nm, photoluminescence quantum yield 54%；
2) 40 mg, 30 mg, 20 mg, 10 mg, 8 mg, 4 mg, 2 mg, 1 mg, 0.5 mg, 0.3 mg, 0.1, are weighed respectively
TFB (the weight average molecular weight are as follows: ten thousand) ~ 20 are respectively substantially soluble in the toluene of 0.5 mL of mg；
3) it, is separately added into prepared 0.5 mL of quantum dot solution in step (1) in above-mentioned TFB toluene solution and sufficiently mixes
It closes, so that sequentially forming TFB/QD weight concentration is 40/1,30/1,20/1,10/1,8/1,4/1,2/1,1/1,0.5/1,0.3/
1, the toluene solution of 0.1/1 mg/mL；
4) above-mentioned toluene solution is formed a film in an inert atmosphere by the method for spin coating, and is annealed 15 minutes at 110 DEG C, i.e.,
The film with different quantum dot weight percent can be prepared.
Embodiment 6
Obstruct promotion effect of the addition for thin-film light emitting quantum yield of high molecular material
The photoluminescence quantum yield of each film is as shown in table 3 below in embodiment 5, is formed by film compared to by pure quanta point material
(last line), the barrier high molecular material (being TFB in this example) that different proportion is added in the film can significantly improve film
Photoluminescence quantum yield, be significantly increased from the 3% of pure quantum dot film to 48%, substantially close to the luminous quantity of quantum dot in the solution
Sub- yield illustrates that TFB macromolecule is good for the isolation effect of quantum dot in the film.The Weight-average molecular that TFB has in this
Amount is 200,000, it can be seen that the weight percent of QD has the improvement result of luminous efficiency in the range of 2-30%.Compared to
Embodiment 2 and embodiment 4, it can be seen that when obstructing the increase of high molecular weight average molecular weight, can play the role of improving efficiency
QD weight percentage ranges it is bigger.
The photoluminescence quantum yield of table 3, film
Embodiment 7
The preparation method of the film of the present embodiment difference quantum dot weight percent, comprising the following steps:
1) the CdTe/CdS core-shell quanta dots for, weighing 20 mg are substantially soluble in 10 mL toluene, form the amount that concentration is 2 mg/mL
Son point solution, the glow peak of this quantum dot solution are 628 nm, and half-peak breadth is 32 nm, photoluminescence quantum yield 54%；
2) 40 mg, 30 mg, 20 mg, 10 mg, 8 mg, 4 mg, 2 mg, 1 mg, 0.5 mg, 0.3 mg, 0.1, are weighed respectively
TFB (the weight average molecular weight are as follows: ten thousand) 5 are respectively substantially soluble in the toluene of 0.5 mL of mg；
3) it, is separately added into prepared 0.5 mL of quantum dot solution in step (1) in above-mentioned TFB toluene solution and sufficiently mixes
It closes, so that sequentially forming TFB/QD weight concentration is 40/1,30/1,20/1,10/1,8/1,4/1,2/1,1/1,0.5/1,0.3/
1, the toluene solution of 0.1/1 mg/mL；
4) above-mentioned toluene solution is formed a film in an inert atmosphere by the method for spin coating, and is annealed 15 minutes at 110 DEG C, i.e.,
The film with different quantum dot weight percent can be prepared.
Embodiment 8
Cross promotion Contrast on effect of the addition for thin-film light emitting quantum yield of the barrier high molecular material of small-molecular-weight
The photoluminescence quantum yield of each film is as shown in table 4 below in embodiment 7, is formed by film compared to by pure quanta point material
(last line), when the molecular weight of addition different proportion is only 50,000 barrier high molecular material (being TFB in this example) in the film
The photoluminescence quantum yield of film almost without improvement, illustrate the TFB macromolecule of low molecular weight in the film for quantum dot every
From ineffective.
The photoluminescence quantum yield of table 4, film
Embodiment 9
The present embodiment film (is transmitted by quantum dot, a kind of barrier high molecular material TFB and a kind of charge and adjusts high molecular material
PMMA composition) preparation method, comprising the following steps:
1) the CdTeS/CdS core-shell quanta dots for, weighing 20 mg are substantially soluble in 10 mL toluene, and forming concentration is 2 mg/mL's
Quantum dot solution, the glow peak of this quantum dot solution are 605 nm, and half-peak breadth is 29 nm, photoluminescence quantum yield 56%；
2), weigh respectively 40/3 mg, 30/2 mg, 20/2 mg, 10/1 mg, 8/0.5 mg, 4/0.2 mg TFB (divide equally again
~ 20 ten thousand) son amount are as follows:/PMMA is respectively substantially soluble in the toluene of 0.5 mL；
3) it, is separately added into prepared 0.5 mL of quantum dot solution in step 1) in above-mentioned TFB/PMMA toluene solution and fills
Divide mixing, so that it is molten to sequentially form the toluene that TFB/QD weight concentration is 40/1,30/1,20/1,10/1,8/1,4/1 mg/mL
Liquid, at this time charge transmission adjust weight percent of the high molecular material PMMA in high molecular material within the scope of 5-10%；
4) above-mentioned toluene solution is formed a film in an inert atmosphere by the method for spin coating, and is annealed 15 minutes at 110 DEG C, i.e.,
The film with different quantum dot weight percent can be prepared；
5) charge in QLED device is applied to pass since the addition that charge transmits adjusting high molecular material mainly improves film
It is defeated, the photoluminescence quantum yield of film itself is influenced less, therefore it is for the promotion effect and reality of thin-film light emitting quantum yield
It is similar to apply example 6.
Embodiment 10
The present embodiment film (transmits adjusting high molecular material by quantum dot, a kind of barrier high molecular material PVK and a kind of charge to gather
Thiophene composition) preparation method, comprising the following steps:
1) the CdTe/CdZnS core-shell quanta dots for, weighing 20 mg are substantially soluble in 10 mL chlorobenzenes, and forming concentration is 2 mg/mL's
Quantum dot solution, the glow peak of this quantum dot solution are 631 nm, and half-peak breadth is 30 nm, photoluminescence quantum yield 56%；
2) 40/1.5 mg, 30/1.0 mg, 20/1.0 mg, 10/0.5 mg, 8/0.3 mg, 4/0.2 mg, 2/, are weighed respectively
~ 110 ten thousand) PVK (weight average molecular weight are as follows:/polythiophene is respectively substantially soluble in of 0.1 mg, 1/0.03 mg, 0.5/0.01 mg
In the chlorobenzene of 0.5 mL；
3) prepared 0.5 mL of quantum dot solution, is separately added into step 1) in above-mentioned PVK/ polythiophene chlorobenzene solution simultaneously
It is sufficiently mixed, to sequentially form the chlorobenzene that PVK/QD weight concentration is 40/1,30/1,20/1,10/1,8/1,4/1 mg/mL
Solution, at this time charge transmission adjust weight percent of the high molecular material polythiophene in high molecular material below 5%；
4) above-mentioned chlorobenzene solution is formed a film in an inert atmosphere by the method for spin coating, and is annealed 15 minutes at 120 DEG C, i.e.,
The film with different quantum dot weight percent can be prepared.
The charge in QLED device is applied since the addition that charge transmits adjusting high molecular material mainly improves film
Transmission influences less the photoluminescence quantum yield of film itself, therefore its promotion for quantum dot film photoluminescence quantum yield
Effect is similar to Example 2.
Embodiment 11
The preparation side of the present embodiment film (being made of quantum dot, barrier high molecular material PVK and barrier high molecular material TFB)
Method, comprising the following steps:
1) it is 2 mg/mL's that the CdTe/CdZnS core-shell quanta dots for, weighing 20 mg, which are substantially soluble in 10 mL chlorobenzenes and form concentration,
Quantum dot solution, the glow peak of this quantum dot solution are 631 nm, and half-peak breadth is 30 nm, photoluminescence quantum yield 56%；
2) 20/20 mg, 15/15 mg, 10/10 mg, 5/5 mg, 4/4 mg, 2/2 mg, 1/1 mg, 0.5/0.5, are weighed respectively
~ 110 ten thousand) PVK (weight average molecular weight are as follows:/TFB (weight average molecular weight are as follows: ~ 20 ten thousand) of mg, 0.3/0.2 mg, 0.2/0.1 mg
Respectively it is substantially soluble in the chlorobenzene of 0.5 mL；
3) it, is separately added into prepared 0.5 mL of quantum dot solution in step (1) in above-mentioned PVK/TFB chlorobenzene solution and fills
Divide mixing, so that sequentially forming PVK/TFB/QD weight concentration is 20/20/1,15/15/1,10/10/1,5/5/1,4/4/1,2/
2/1, the chlorobenzene solution of 1/1/1,0.5/0.5/1,0.3/0.2/1,0.2/0.1/1 mg/mL；
4) above-mentioned chlorobenzene solution is formed a film in an inert atmosphere by the method for spin coating, and is annealed 15 minutes at 120 DEG C, i.e.,
The film with different quantum dot weight percent can be prepared.
Embodiment 12
Obstruct promotion effect of the addition for thin-film light emitting quantum yield of high molecular material
The photoluminescence quantum yield of each film is as shown in table 5 below in embodiment 11, thin compared to being formed by by pure quanta point material
Film (last line), the barrier high molecular material (being PVK+TFB in this example) that different proportion is added in the film can significantly change
The photoluminescence quantum yield of kind film, is significantly increased from the 3% of pure quantum dot film to 50%, in the solution substantially close to quantum dot
Photoluminescence quantum yield illustrates that PVK+TFB barrier high molecular material is good for the isolation effect of quantum dot in the film.In this example
PVK and TFB is respectively provided with weight average molecular weight ~ 1,100,000 and ~ 20 ten thousand, it can be seen that big model of the weight percent of QD in 2-70%
Enclose the interior improvement result for having luminous efficiency.
The photoluminescence quantum yield of table 5, film
Embodiment 13
The present embodiment film is (by quantum dot, barrier high molecular material TFB, barrier high molecular material poly-TPD and a kind of charge
Transmission adjust high molecular material PMMA composition) preparation method, comprising the following steps:
1) the CdTeS/CdS core-shell quanta dots for, weighing 20 mg are substantially soluble in the amount for forming that concentration is 2 mg/mL in 10 mL toluene
Son point solution, the glow peak of this quantum dot solution are 605 nm, and half-peak breadth is 29 nm, photoluminescence quantum yield 56%；
2) 30/10/3 mg, 20/10/2 mg, 15/5/2 mg, 6/4/1 mg, 5/3/0.5 mg, 3/1/0.2 mg, are weighed respectively
~ 12 ten thousand) ~ 20 ten thousand) TFB (weight average molecular weight are as follows:/poly-TPD (weight average molecular weight are as follows:/PMMA is respectively substantially soluble in
In the toluene of 0.5 mL；
3) the prepared quantum dot solution in step 1), is separately added into above-mentioned TFB/poly-TPD/PMMA toluene solution
0.5 mL is simultaneously sufficiently mixed, so that sequentially forming TFB+poly-TPD/QD weight concentration is 40/1,30/1,20/1,10/1,8/
1, the toluene solution of 4/1 mg/mL, at this time charge transmission adjust weight percent of the high molecular material PMMA in high molecular material
Than within the scope of 5-10%；
4) above-mentioned toluene solution is formed a film in an inert atmosphere by the method for spin coating, and is annealed 15 minutes at 110 DEG C, i.e.,
The film with different quantum dot weight percent can be prepared.
The charge in QLED device is applied since the addition that charge transmits adjusting high molecular material mainly improves film
Transmission influences less the photoluminescence quantum yield of film itself, thus its for thin-film light emitting quantum yield promotion effect with
Embodiment 4 is similar.
Embodiment 14
The present embodiment light emitting diode with quantum dots, as shown in figure 8, successively include: from bottom to top ITO substrate 11, hearth electrode 12,
PEDOT:PSS hole injection layer 13, poly-TPD hole transmission layer 14, quantum dot light emitting layer 15, ZnO electron transfer layer 16 and Al
Top electrode 17.
Wherein, quantum dot light emitting layer 15 the preparation method comprises the following steps: preparing CdTe/CdZnS quantum dot, (glow peak of solution is
631 nm, half-peak breadth are 30 nm, photoluminescence quantum yield 56%) weight concentration is that 1 mg/mL, PVK weight concentration is 20 mg/
The toluene solution of mL was annealed 15 minutes at 110 DEG C in an inert atmosphere with revolving speed spin-coating film 60 seconds of 3000 rpm.
Embodiment 15
Improved efficiency of the above-mentioned film for light emitting diode with quantum dots device
QLED device of the film as quantum dot light emitting layer in embodiment 14 using the high molecular material PVK containing barrier, it is outer to measure
Sub- efficiencies are 3.1%, a length of 633 nm of electroluminescent spike.
As a comparison, the QLED device using pure quanta point material as quantum dot light emitting layer, outer quantum point efficiency knot
Fruit is 0.5%, a length of 642 nm of electroluminescent spike.
It can be seen that using contain the quantum dot film of PVK as quantum dot light emitting layer QLED device efficiency compared to
The pure quantum dot for not adding PVK will be significantly improved as the device of luminescent layer；Glow peak wavelength is relative to solution medium wave simultaneously
Long red shift degree also greatly reduces, and further illustrates that PVK plays effective weaken for the interaction between quantum dot and imitates
Fruit.
Embodiment 16
Charge transmission adjusts macromolecule for the improved efficiency 1 of light emitting diode with quantum dots device
Using device architecture and preparation similar in embodiment 14, wherein quantum dot light emitting layer the preparation method comprises the following steps: prepare
CdTe/CdZnS quantum dot (glow peak of solution is 631 nm, and half-peak breadth is 30 nm, photoluminescence quantum yield 56%) weight is dense
Degree is the chlorobenzene solution that 1 mg/mL, PVK weight concentration is 20 mg/mL, polythiophene weight concentration is 0.8 mg/mL, with 3000
The revolving speed spin-coating film of rpm 60 seconds is annealed 15 minutes at 110 DEG C in an inert atmosphere.
Using QLED device of the film as quantum dot light emitting layer for containing PVK and polythiophene, external quantum efficiency result
It is 5.1%, a length of 633 nm of electroluminescent spike.
And the QLED device in embodiment 14 using the film containing only barrier high molecular material PVK as quantum dot light emitting layer
Part, external quantum efficiency result are 3.1%, a length of 633 nm of electroluminescent spike.
It can be seen that although suitable polythiophene is added in the quantum dot film containing PVK for the amount of quantum dot film
Sub- yield does not influence (embodiment 10), but the higher charge mobility of polythiophene can be in quantum point luminescent layer
Charge transmission and corresponding charge balance, thus can further promote the luminous efficiency of quantum dot QLED device.
Embodiment 17
Charge transmission adjusts macromolecule for the improved efficiency 2 of light emitting diode with quantum dots device
Using device architecture and preparation similar in embodiment 14, wherein quantum dot light emitting layer the preparation method comprises the following steps: prepare
CdTe/CdZnS quantum dot (glow peak of solution is 628 nm, and half-peak breadth is 32 nm, photoluminescence quantum yield 54%) weight is dense
Degree is that 1 mg/mL, TFB weight concentration is the chlorobenzene solution that 30 mg/mL, PMMA weight concentrations are 2.5 mg/mL, with 3000
The revolving speed spin-coating film of rpm 60 seconds is annealed 15 minutes at 110 DEG C in an inert atmosphere.Meanwhile preparing the quantum for being free of PMMA
Point solution forms a film as a comparison and using same procedure.
Using QLED device of the film as quantum dot light emitting layer for containing TFB and PMMA, external quantum efficiency result is
4.3%, a length of 631 nm of electroluminescent spike.
And QLED device of the film containing only barrier high molecular material TFB as quantum dot light emitting layer is used, outer quantum
Efficiencies are 2.7%, a length of 634 nm of electroluminescent spike.
It can be seen that although suitable PMMA is added in the quantum dot film containing TFB for the quantum of quantum dot film
Yield does not influence (embodiment 9), but the lower charge mobility of PMMA can be to the charge in quantum point luminescent layer
Transmission and corresponding charge balance, thus can further promote the luminous efficiency of quantum dot QLED device.
The interaction between quantum dot is carried out after effectively inhibiting using barrier high molecular material, improves the hair of film
Light efficiency, therefore also promote the luminous efficiency of corresponding QLED device；Smaller electroluminescent peak red shift simultaneously also further illustrates
Barrier high molecular material is for the effective inhibition that interacts between quantum dot.
In conclusion a kind of film provided by the invention and preparation method thereof and QLED device, with existing pure quantum dot
Film is compared, and quantum dot and high molecular material are contained in film of the present invention, quantum dot is effectively isolated using high molecular material and increases
Mutual distance between big quantum dot, to reduce the interaction between quantum dot and utmostly inhibit between quantum dot
Radiationless energy transfer and concentration quenching reach the promotion of quantum dot light emitting quantum yield in film.Obstruct high molecular material
If molecular weight is too small, enough isolation effects can not be played, therefore it is required that can be realized the barrier high score for being effectively isolated quantum dot
The weight average molecular weight of sub- material is 100,000 or more；The molecular weight for obstructing high molecular material is higher, mutual for quantum dot
Isolation effect is better, thus the weight content for the quantum dot that can be accommodated in quantum dot film is higher.Utilize this tool
There is the film of high photoluminescence quantum yield into QLED device, can be realized efficient QLED device.
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 (22)
1. a kind of film, which is characterized in that the film includes high molecular material and the amount that is dispersed in the high molecular material
Sub-, wherein the high molecular material includes at least one barrier high molecular material, the barrier high molecular material is divided equally again
Son amount is higher than 100,000, and the high molecular material further includes that at least one charge transmission adjusts high molecular material, the charge transmission
The weight average molecular weight for adjusting high molecular material is lower than 100,000.
2. film according to claim 1, which is characterized in that the charge transmission adjusts high molecular material and accounts for macromolecule material
The mass fraction of material is lower than 10%.
3. film according to claim 1, which is characterized in that the high molecular material by a kind of barrier high molecular material and
A kind of charge transmission adjusting high molecular material composition.
4. film according to claim 1-3, which is characterized in that the mass fraction that the quantum dot accounts for film is
0.5-20%。
5. film according to claim 4, which is characterized in that the mass fraction that the quantum dot accounts for film is 2-10%.
6. film according to claim 1-3, which is characterized in that the barrier high molecular material be selected from PVK and
Its derivative, TFB and its derivative, poly-TPD and its derivative and one of MEH-PPV and its derivative or a variety of.
7. film according to claim 1-3, which is characterized in that the quantum dot be selected from CdTe, CdTeS and with
CdTe or CdTeS is one of the core-shell quanta dots of core.
8. film according to claim 1-3, which is characterized in that the carrier of the barrier high molecular material moves
Shifting rate is 10-6 cm2V-1s-1Hereinafter, the charge transmission, which adjusts high molecular material, is selected from conducting polymer, the charge transmission
Adjusting high molecular material and accounting for the mass fraction of high molecular material is 0.5-5%.
9. film according to claim 8, which is characterized in that the conducting polymer is selected from polyacetylene, polyphenylene sulfide, gathers
One of aniline, polypyrrole and polythiophene.
10. film according to claim 1-3, which is characterized in that the carrier of the barrier high molecular material
Mobility is 10-6 cm2V-1s-1More than, the charge transmission adjusts high molecular material and is selected from non-conductive polymer, and the charge passes
The defeated high molecular material that adjusts accounts for the mass fraction of high molecular material as 5-10%.
11. film according to claim 10, which is characterized in that the non-conductive polymer is selected from phenolic resin, poly- second
One of alkene, dimethyl silicone polymer, polystyrene, polymethacrylates, polyacrylate and polycarbonate.
12. a kind of preparation method of film, which is characterized in that comprising steps of
Quantum dot and high molecular material are mixed in a dispersion medium；
Film is made in mixed solution, obtains the film；
Wherein the high molecular material includes at least one barrier high molecular material, the Weight-average molecular of the barrier high molecular material
Amount is higher than 100,000, and the high molecular material further includes that at least one charge transmission adjusts high molecular material, and the charge transmission is adjusted
The weight average molecular weight for saving high molecular material is lower than 100,000.
13. the preparation method of film according to claim 12, which is characterized in that the high molecular material is by a kind of barrier
High molecular material and a kind of transmission of charge adjust high molecular material composition, and the charge transmission adjusts high molecular material and accounts for macromolecule
The mass fraction of material is lower than 10%.
14. the preparation method of film according to claim 12, which is characterized in that the quantum dot is oil-soluble quantum
Point, the surface ligand of the oil-soluble quantum dot are mercaptan or carboxylic acid.
15. the preparation method of film according to claim 12, which is characterized in that the quantum dot is selected from CdTe, CdTeS
And using CdTe or CdTeS as one of core-shell quanta dots of core.
16. the preparation method of film according to claim 12, which is characterized in that in the film, the quantum dot
Mass fraction is 0.5-20%.
17. the preparation method of film according to claim 16, which is characterized in that the mass fraction of the quantum dot is 2-
10%。
18. the preparation method of the described in any item films of 2-17 according to claim 1, which is characterized in that the barrier macromolecule
The carrier mobility of material is 10-6 cm2V-1s-1Hereinafter, it is conducting polymer that the charge transmission, which adjusts high molecular material,
The conducting polymer is selected from one of polyacetylene, polyphenylene sulfide, polyaniline, polypyrrole and polythiophene.
19. the preparation method of the described in any item films of 2-17 according to claim 1, which is characterized in that the barrier macromolecule
The carrier mobility of material is 10-6 cm2V-1s-1More than, it is non-conductive high score that the charge transmission, which adjusts high molecular material,
Son, the non-conductive polymer are selected from phenolic resin, polyethylene, dimethyl silicone polymer, polystyrene, polymethylacrylic acid
One of ester, polyacrylate and polycarbonate.
20. the preparation method of film according to claim 12, which is characterized in that the barrier high molecular material is selected from
Two kinds in PVK and its derivative, TFB and its derivative, poly-TPD and its derivative and MEH-PPV and its derivative.
21. a kind of QLED device, the QLED device includes quantum dot light emitting layer, which is characterized in that the quantum dot light emitting layer
For any one of the claim 1-11 film.
22. QLED device according to claim 21, which is characterized in that the film with a thickness of 10-80nm.
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| PCT/CN2018/123689 WO2019129015A1 (en) | 2017-12-26 | 2018-12-26 | Thin film and fabrication method therefor and qled device |
| US16/907,020 US12043777B2 (en) | 2017-12-26 | 2020-06-19 | Thin film and fabrication method therefor and QLED device |
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