WO2019129015A1 - 一种薄膜及其制备方法与qled器件 - Google Patents

一种薄膜及其制备方法与qled器件 Download PDF

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WO2019129015A1
WO2019129015A1 PCT/CN2018/123689 CN2018123689W WO2019129015A1 WO 2019129015 A1 WO2019129015 A1 WO 2019129015A1 CN 2018123689 W CN2018123689 W CN 2018123689W WO 2019129015 A1 WO2019129015 A1 WO 2019129015A1
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polymer material
film
quantum dots
film according
quantum
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French (fr)
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杨一行
程陆玲
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TCL Corp
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TCL Corp
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Priority claimed from CN201711435544.0A external-priority patent/CN109962170B/zh
Priority claimed from CN201711435542.1A external-priority patent/CN109962169B/zh
Priority claimed from CN201711435211.8A external-priority patent/CN109962128A/zh
Priority claimed from CN201711433458.6A external-priority patent/CN109962168B/zh
Priority claimed from CN201711431438.5A external-priority patent/CN109962167B/zh
Application filed by TCL Corp filed Critical TCL Corp
Publication of WO2019129015A1 publication Critical patent/WO2019129015A1/zh
Priority to US16/907,020 priority Critical patent/US12043777B2/en
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    • 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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Definitions

  • the invention relates to the field of quantum dots technology, in particular to a film and a preparation method thereof and a QLED device.
  • Quantum dots are special materials that are limited to the order of nanometers in three dimensions. This remarkable quantum confinement effect makes quantum dots have many unique nano properties: the emission wavelength is continuously adjustable, and the emission wavelength is narrow. Wide absorption spectrum, high luminous intensity, long fluorescence lifetime and good biocompatibility. These characteristics make quantum dots have broad application prospects in the fields of biomarkers, flat panel displays, solid state lighting, and photovoltaic solar energy.
  • quantum dots are usually formed separately to form a layer of light-emitting layer containing only quantum dot materials.
  • luminescent materials called guest materials
  • holes and electrons are first injected into the conduction band and valence band levels of the host material through respective transport layer materials and form excitons, at which time the excitons are not prone to recombination.
  • the excitons are transferred to the guest material by means of energy transfer, in which the excitons are combined to emit photons of corresponding wavelengths.
  • the guest organic molecule itself does not have the function of energy level binding, if a film is formed separately to form a light-emitting layer containing only the guest material, a very strong non-radiative energy transfer and concentration quenching will occur, so the subject-guest
  • the hybrid system is a more efficient way to achieve high luminous efficiency for OLEDs.
  • quantum dots have a core-shell structure
  • high-quality quantum dots themselves have very good energy level binding and corresponding exciton binding ability, so Direct use of pure quantum dot material as the light-emitting layer can achieve good device luminous efficiency, and the device structure is simpler and the exciton loss path is reduced.
  • quantum dots have limited ability to bind their own energy levels and excitons in such quantum dots due to the limitations of core-shell structure design.
  • These quantum dots can be in solution state (ie, quantum dot particles).
  • the inter-distance is relatively large) exhibits a high luminescence quantum yield, but in solid-state films (i.e., close packing between quantum dot particles), the luminous efficiency is significantly reduced due to strong non-radiative energy transfer and concentration quenching. Therefore, QLED devices based on such quantum dots will be very inefficient.
  • a film wherein the film comprises a polymer material and quantum dots dispersed in the polymer material, wherein the polymer material comprises at least one barrier polymer material, and the weight average of the barrier polymer material
  • the molecular weight is higher than 100,000.
  • a method for preparing a film comprising the steps of:
  • the polymer material comprises at least one barrier polymer material, and the barrier polymer material has a weight average molecular weight of more than 100,000.
  • a QLED device comprising a quantum dot luminescent layer, wherein the quantum dot luminescent layer is a thin film of the invention.
  • the film contains quantum dots and polymer materials, and the polymer material effectively separates the quantum dots and increases the mutual distance between the quantum dots, thereby reducing the interaction between the quantum dots and maximally suppressing the interaction between the quantum dots. No radiation energy transfer and concentration quenching, which can increase the quantum yield of quantum dots in the film. If the molecular weight of the barrier polymer material is too small to provide sufficient isolation effect, the weight average molecular weight of the barrier polymer material capable of effectively isolating the quantum dots is required to be 100,000 or more; the higher the molecular weight of the barrier polymer material, The better the isolation between the quantum dots, the higher the weight of the quantum dots that can be accommodated in the quantum dot film.
  • Figure 1 shows the structural formula of PVK in the present invention.
  • FIG. 2 is a structural formula of TFB in the present invention.
  • Figure 3 is a structural formula of poly-TPD in the present invention.
  • Figure 4 is a structural formula of the MEH-PPV in the present invention.
  • Figure 5 is a structural formula of a derivative of PVK in the present invention.
  • Figure 6 is a structural formula of another derivative of PVK in the present invention.
  • Figure 7 is a structural formula of another derivative of PVK in the present invention.
  • FIG. 8 is a flow chart of a method for preparing a film according to an embodiment of the present invention.
  • FIG. 9 is a schematic structural view of a quantum dot light emitting diode according to Embodiment 14 of the present invention.
  • the core-shell structure of some existing quantum dots has a limited ability to bind energy levels and excitons, and although it can exhibit a high luminescence quantum yield in a solution state (in which case the distance between quantum dot particles is large), However, in solid-state films (in which case the quantum dots are closely packed), the luminous efficiency is significantly reduced due to strong non-radiative energy transfer and concentration quenching.
  • Embodiments of the present invention provide a film, wherein the film includes a polymer material and quantum dots dispersed in the polymer material, wherein the polymer material includes at least one barrier polymer material, the barrier The weight average molecular weight of the polymer material is higher than 100,000.
  • the film contains quantum dots and a polymer material, and the polymer material is used to effectively separate the quantum dots and increase the mutual distance between the quantum dots, thereby reducing the interaction between the quantum dots and suppressing the quantum dots to the utmost extent.
  • the non-radiative energy transfer and concentration quenching achieve an increase in quantum yield of quantum dots in the film.
  • the molecular weight of the barrier polymer material is too small to provide sufficient isolation effect, the weight average molecular weight of the barrier polymer material capable of effectively isolating the quantum dots is required to be 100,000 or more; the higher the molecular weight of the barrier polymer material, The better the isolation between the quantum dots, the higher the weight of the quantum dots that can be accommodated in the quantum dot film.
  • the film of the embodiment of the present invention contains quantum dots and one or more barrier polymer materials, and the weight average molecular weight of the barrier polymer material is higher than 100,000 because the weight average molecular weight of the barrier polymer material is too small. Can not effectively isolate.
  • the higher the weight average molecular weight of the barrier polymer material the better the isolation effect between the quantum dots, and the higher the weight content of the quantum dots that can be accommodated in the film.
  • the quantum dots are oil soluble quantum dots or water soluble quantum dots.
  • the quantum dots are oil-soluble quantum dots
  • the surface ligand of the oil-soluble quantum dots is a thiol or a carboxylic acid.
  • the quantum dots are selected from one or more of Group II-VI quantum dots, III-V quantum dots, and IV-VI quantum dots. In some specific embodiments, the quantum dots are selected from the group consisting of a single quantum dot of group II-VI, group III-V, group IV-VI, and a core shell of group II-VI, group III-V, and group IV-VI. One or more of a type of quantum dot or a hybrid quantum dot.
  • the II-VI single quantum dots are selected from the group consisting of CdSe, CdS, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe
  • the III-V single quantum dot is selected from the group consisting of InP, GaP, GaAs, InAs, InAsP, GaAsP, InGaP, InGaAs, and InGaAsP;
  • the single quantum dot is selected from one of PbS, PbSe, PbTe, PbSeS, PbSeTe, and Pb
  • the quantum dots are selected from the group consisting of Group II-VI quantum dots.
  • the quantum dots are selected from Group II-VI quantum dots containing Te.
  • the Group II-VI quantum dots containing Te have a narrower band gap than the Group II-VI quantum dots containing Se, so when they are used to prepare luminescent quantum dots in the visible light band (green or red), they cannot grow thicker.
  • the shell layer prevents the luminescence wavelength from being excessively red-shifted, so the distance between the quantum dots will be very close, and the strong interaction in the solid film will be more prominent in the Te-containing II-VI quantum dots. Strong non-radiative energy transfer and concentration quenching in solid-state films result in a significant decrease in the luminous efficiency of Group II-VI quantum dots containing Te.
  • the quantum dots are selected from the group consisting of Group II-VI quantum dots containing Cd and Te. In some specific embodiments, the quantum dots are selected from the group consisting of CdTe, CdTeS, and one of core-shell quantum dots having CdTe or CdTeS as nuclei.
  • CdTe, CdTeS and other quantum dots containing Cd and Te have deeper conduction band energy levels than other Te-containing II-VI quantum dots, the binding effect on electrons is better, so the same method of avoiding the quenching of luminous efficiency will be CdTe, CdTeS, etc. produce better results.
  • the barrier polymer has a carrier mobility of 10 -8 cm 2 V -1 s -1 or more. Since a film containing a barrier polymer material and a quantum dot is used as a light-emitting layer in a QLED device application, it is necessary to consider charge transport in a barrier polymer material after charge injection into the film, so that carrier mobility of the polymer material is required to be blocked. Meet certain requirements (above 10 -8 cm 2 V -1 s -1 ).
  • the barrier polymer material has a weight average molecular weight of more than 200,000.
  • Selecting a barrier polymer material having a weight average molecular weight of more than 200,000 can further improve the isolation effect between the quantum dots, thereby further increasing the quantum yield of quantum dots in the film.
  • the barrier polymer material has a weight average molecular weight of more than 300,000.
  • the barrier polymer material has a weight average molecular weight of more than 500,000.
  • the barrier polymer material is selected from the group consisting of PVK (poly(9-vinylcarbazole)) having a weight average molecular weight of more than 500,000 and derivatives thereof, TFB having a weight average molecular weight of more than 500,000, and derivatives thereof.
  • PVK poly(9-vinylcarbazole)
  • TFB having a weight average molecular weight of more than 500,000
  • MEH-PPV poly(2-methoxy-5-(2'-ethylhexyloxy) having a weight average molecular weight of more than 500,000
  • One of -1,4-p-phenylacetylene is shown in FIG.
  • the structural formula of the poly-TPD is shown in FIG. 3
  • the structural formula of the MEH-PPV is shown in FIG. 4
  • the derivative of TFB can be selected from any of the structural molecules of Figures 5-7. Selecting the above-mentioned barrier polymer material can maximize the isolation effect between the quantum dots, thereby maximizing the quantum yield of quantum dots in the film.
  • the film is composed of quantum dots and a barrier polymer material, the quantum dots occupying a mass fraction of the film of 0.5-90%.
  • the quantum dots occupying a mass fraction of the film of 0.5-90%.
  • the weight average molecular weight of the barrier polymer material is higher than 100,000, and the weight average molecular weight of the barrier polymer material is higher. The better the isolation between the quantum dots, the higher the weight content of the quantum dots that can be accommodated in the film.
  • the barrier polymer material has a weight average molecular weight of between 100,000 and 300,000, and the quantum dot accounts for 0.5-30% by mass of the film.
  • the barrier polymer material has a weight average molecular weight of 300,000 to 500,000, and the quantum dot accounts for 0.5-66% of the mass fraction of the film.
  • the barrier polymer material has a weight average molecular weight of between 500,000 and 1.5 million, and the quantum dot accounts for 0.5 to 90% of the mass fraction of the film.
  • the quantum dots account for 0.5-20% of the mass fraction of the film.
  • the quantum dots account for 2-10% of the mass fraction of the film.
  • the barrier polymer has a carrier mobility of 10 -6 cm 2 V -1 s -1 or more to further enhance the transport of charge in the film.
  • the film is comprised of quantum dots and a polymeric material comprised of two barrier polymeric materials.
  • the polymer material of the embodiment of the present invention comprises only two kinds of barrier polymer materials, and the weight average molecular weight of the two barrier polymer materials is higher than 100,000, and the quantum dots account for 0.5 mass fraction of the film. 90%.
  • the weight average molecular weight of the barrier polymer material is between 500,000 and 1.5 million, and the quantum dot accounts for 0.5-90% of the mass fraction of the film. In some specific embodiments, the quantum dots account for 0.5-20% of the mass fraction of the film.
  • the quantum dots account for 2-10% of the mass fraction of the film.
  • the carrier mobility of the two barrier polymer materials is above 10 -6 cm 2 V -1 s -1 to further enhance the transport of charge in the film.
  • the polymer material further comprises at least one charge transport regulating polymer material, wherein the charge transport regulating polymer material has a weight average molecular weight of less than 100,000, and the charge transport regulating polymer material accounts for a high The mass fraction of molecular materials is less than 10%.
  • the polymer material of the embodiment of the present invention includes at least one barrier polymer material and at least one charge transport regulating polymer material, and the barrier polymer material has a weight average molecular weight of more than 100,000, and the charge transporting
  • the weight average molecular weight of the polymer material is adjusted to be less than 100,000, and the higher the weight average molecular weight of the barrier polymer material, the better the isolation effect between the quantum dots, and the weight of the quantum dots that can be accommodated in the film.
  • the addition of the charge transport regulating polymer material can adjust the charge transport performance of the film applied in the QLED device, and can ensure that the luminescence quantum yield of the film itself is not affected.
  • the polymer material needs to be a non-conductive polymer in order to effectively control and regulate the transport of charge in the film.
  • the polymer material is composed of a barrier polymer material and a charge transport modulation polymer material.
  • the polymer material of the embodiment of the present invention is only a barrier polymer material and a charge transport regulating polymer material, and the weight average molecular weight of the barrier polymer material is higher than 100,000, and the charge transfer regulation
  • the weight average molecular weight of the polymer material is less than 100,000, and the higher the weight average molecular weight of the barrier polymer material, the better the isolation effect between the quantum dots, and the weight content of the quantum dots which can be accommodated in the film. The higher.
  • the weight average molecular weight of the barrier polymer material is between 500,000 and 1.5 million, and the quantum dot accounts for 0.5-90% of the mass fraction of the film. In some specific embodiments, the quantum dots account for 0.5-20% of the mass fraction of the film.
  • the quantum dots account for 2-10% of the mass fraction of the film.
  • the barrier polymer has a carrier mobility of 10 -6 cm 2 V ⁇ 1 s ⁇ 1 or less
  • the charge transport regulating polymer material is selected from a conductive polymer to enhance the charge.
  • the charge transport regulating polymer material accounts for 0.5-5% by mass of the polymer material.
  • the conductive polymer is one selected from the group consisting of polyacetylene, polyphenylene sulfide, polyaniline, polypyrrole, and polythiophene.
  • the barrier polymer has a carrier mobility of 10 -6 cm 2 V -1 s -1 or more
  • the charge transport regulating polymer material is selected from a non-conductive polymer for effective control. And regulating the transport of charge in the film, the charge transport regulating polymer material occupies 5-10% of the mass fraction of the polymer material.
  • the non-conductive polymer is selected from the group consisting of phenolic resins, polyethylene, polydimethylsiloxane (PDMS), polystyrene, polymethacrylate, polyacrylate, and polycarbonate. One of the others.
  • the film is composed of quantum dots and a polymer material composed of two barrier polymer materials and a charge transport regulating polymer material.
  • the weight average molecular weight of the barrier polymer material is between 500,000 and 1.5 million, and the quantum dot accounts for 0.5-90% of the mass fraction of the film. In some specific embodiments, the quantum dots account for 0.5-20% of the mass fraction of the film. In some specific embodiments, the quantum dots account for 2-10% of the mass fraction of the film.
  • the carrier mobility of the two barrier polymer materials is less than 10 -6 cm 2 V -1 s -1
  • the charge transport regulating polymer material is selected from the group consisting of conductive polymers, thereby The charge transport in the film is enhanced, and the charge transfer regulating polymer material accounts for 0.5-5% by mass of the polymer material.
  • the conductive polymer is selected from the group consisting of polyacetylene, polyphenylene sulfide, polyaniline, polypyrrole, and polythiophene.
  • the carrier mobility of the two barrier polymer materials is above 10 -6 cm 2 V -1 s -1
  • the charge transport regulating polymer material is selected from the group consisting of non-conductive polymers.
  • the charge transport regulating polymer material accounts for 5-10% of the mass fraction of the polymer material.
  • the non-conductive polymer is selected from the group consisting of phenolic resin, polyethylene, polydimethylsiloxane, polystyrene, polymethacrylate, polyacrylate, and polycarbonate.
  • Embodiments of the present invention also provide a flow chart of a method for preparing a film, as shown in FIG. 8, which includes the steps of:
  • the polymer material comprises at least one barrier polymer material, and the barrier polymer material has a weight average molecular weight of more than 100,000.
  • the dispersion medium is selected from the group consisting of organic solvents.
  • the organic solvent is selected from a non-polar organic solvent.
  • the non-polar organic solvent may be selected from the group consisting of chloroform, toluene, chlorobenzene, n-hexane, and n-octane.
  • TOP trioctylphosphine
  • TBP tributylphosphine
  • ODE octadecene
  • OA oleic acid
  • ODA octadecylamine
  • TOA trioctylamine
  • OAm oleylamine
  • the mixed solution is formed into a film by a solution method to obtain the film.
  • the solution method is selected from the group consisting of a spin coating method, a printing method, a knife coating method, a immersion pulling method, a immersion method, a spray coating method, a roll coating method, a casting method, a slit coating method, and One of strip coating methods and the like.
  • Embodiments of the present invention also provide a QLED device comprising a quantum dot luminescent layer, wherein the quantum dot luminescent layer is a thin film of the present invention.
  • Embodiments of the present invention apply a film having a high luminescence quantum yield to a QLED device, enabling a highly efficient QLED device.
  • the film has a thickness of 10-80 nm.
  • 0.5 mL of the quantum dot solution prepared in the step 1) is separately added to the above PVK chlorobenzene solution and thoroughly mixed, thereby sequentially forming PVK/QD weight concentrations of 40/1, 30/1, 20/1, 10/1, 8/1, 4/1, 2/1, 1/1, 0.5/1, 0.3/1, 0.1/1 mg/mL chlorobenzene solution;
  • the above chlorobenzene solution is formed into a film by spin coating in an inert atmosphere, and annealed at 120 ° C for 15 minutes to prepare a film having a weight percentage of different quantum dots.
  • the luminescence quantum yield of each film in Example 1 is shown in Table 1 below, and different ratios of barrier polymer materials were added to the film compared to the film formed from the pure quantum dot material (last row) (in this case, PVK) can significantly improve the luminescence quantum yield of the film, which is greatly increased from 3% of pure film to 53%, which is close to the quantum yield of quantum dots in solution, indicating the isolation effect of PVK polymer on quantum dots in the film. good.
  • PVK has a large weight average molecular weight (1.1 million), and it can be seen that the weight percentage of QD has an improvement in luminous efficiency in a wide range of 2-90%.
  • 0.5 mL of the quantum dot solution prepared in the step 1) is separately added to the above PVK chlorobenzene solution and thoroughly mixed, thereby sequentially forming PVK/QD weight concentrations of 40/1, 30/1, 20/1, 10/1, 8/1, 4/1, 2/1, 1/1, 0.5/1, 0.3/1, 0.1/1 mg/mL chlorobenzene solution;
  • the above chlorobenzene solution is formed into a film by spin coating in an inert atmosphere, and annealed at 120 ° C for 15 minutes to prepare a film having a weight percentage of different quantum dots.
  • the luminescence quantum yield of each film in Example 3 is shown in Table 2 below, and different ratios of barrier polymer materials were added to the film compared to the film formed from the pure quantum dot material (last row) (in this case, PVK) can significantly improve the luminescence quantum yield of the film, which is greatly increased from 3% of pure film to 52%, which is close to the quantum yield of quantum dots in solution, indicating the isolation effect of PVK polymer on quantum dots in the film. good.
  • PVK has a large weight average molecular weight (500,000), and it can be seen that the weight percentage of QD has an improvement in luminous efficiency in a wide range of 2-66%.
  • TFB/QD weight concentrations 40/1, 30/1, 20/1, 10 /1, 8/1, 4/1, 2/1, 1/1, 0.5/1, 0.3/1, 0.1/1 mg/mL in toluene solution;
  • the above toluene solution is formed into a film by spin coating in an inert atmosphere, and annealed at 110 ° C for 15 minutes to prepare a film having a weight percentage of different quantum dots.
  • the luminescence quantum yield of each film in Example 5 is shown in Table 3 below, and different ratios of barrier polymer materials were added to the film compared to the film formed from the pure quantum dot material (last row) (in this case, TFB) can significantly improve the luminescence quantum yield of the film, which is greatly increased from 3% of pure quantum dot film to 48%, which is close to the quantum yield of quantum dots in solution, indicating that TFB polymer is in the film for quantum dots.
  • the isolation is good.
  • TFB has a weight average molecular weight of 200,000, and it can be seen that the weight percentage of QD has an improvement in luminous efficiency in the range of 2 to 30%.
  • the QD weight percentage which can function to improve the efficiency is larger.
  • TFB/QD weight concentrations 40/1, 30/1, 20/1, 10 /1, 8/1, 4/1, 2/1, 1/1, 0.5/1, 0.3/1, 0.1/1 mg/mL in toluene solution;
  • the above toluene solution is formed into a film by spin coating in an inert atmosphere, and annealed at 110 ° C for 15 minutes to prepare a film having a weight percentage of different quantum dots.
  • the luminescence quantum yield of each film in Example 7 is shown in Table 4 below. Compared with the film formed from the pure quantum dot material (the last row), different ratios of barrier polymers having a molecular weight of only 50,000 were added to the film. When the material (in this case, TFB), the luminescence quantum yield of the film hardly improved, indicating that the low molecular weight TFB polymer has poor isolation effect on the quantum dots in the film.
  • the preparation method of the film of the embodiment comprises the following steps:
  • TFB weight average molecular weight: ⁇ 200,000
  • the above toluene solution is formed into a film by spin coating in an inert atmosphere and annealed at 110 ° C for 15 minutes to prepare a film having a weight percentage of different quantum dots;
  • the preparation method of the film of the embodiment comprises the following steps:
  • 0.5 mL of the quantum dot solution prepared in the step 1) is separately added to the above PVK/polythiophene chlorobenzene solution and thoroughly mixed, thereby sequentially forming PVK/QD weight concentrations of 40/1, 30/1, 20 /1, 10/1, 8/1, 4/1mg/mL of chlorobenzene solution, at this time, the weight percentage of the charge transport regulating polymer material polythiophene in the polymer material is less than 5%;
  • a film having a different weight percentage of quantum dots can be prepared by forming a film of the above chlorobenzene solution by spin coating in an inert atmosphere and annealing at 120 ° C for 15 minutes.
  • the charge transfer regulating polymer material is mainly used to improve the charge transport of the thin film in the QLED device, it has little effect on the luminescence quantum yield of the film itself, so its effect on the quantum yield of the quantum dot film luminescence is improved. 2 similar.
  • the preparation method of the film of the embodiment (composed of a quantum dot, a barrier polymer material PVK and a barrier polymer material TFB) comprises the following steps:
  • 0.5 mL of the quantum dot solution prepared in the step 1) was separately added to the above PVK/TFB chlorobenzene solution and thoroughly mixed, thereby sequentially forming a PVK/TFB/QD weight concentration of 20/20/1, 15/. 15/1, 10/10/1, 5/5/1, 4/4/1, 2/2/1, 1/1/1, 0.5/0.5/1, 0.3/0.2/1, 0.2/0.1/ 1 mg/mL chlorobenzene solution;
  • a film having a different weight percentage of quantum dots can be prepared by forming a film of the above chlorobenzene solution by spin coating in an inert atmosphere and annealing at 120 ° C for 15 minutes.
  • the luminescence quantum yield of each film in Example 11 is shown in Table 5 below, and different ratios of barrier polymer materials were added to the film as compared with the film formed from the pure quantum dot material (last row) (in this case, PVK+TFB) can significantly improve the luminescence quantum yield of the film, which is greatly increased from 3% of pure quantum dot film to 50%, which is close to the quantum yield of quantum dots in solution, indicating that PVK+TFB barrier polymer material is The isolation effect on the quantum dots in the film is good.
  • PVK and TFB have weight average molecular weights of -1.1 million and 20,000,000, respectively, and it can be seen that the weight percentage of QD has an improvement in luminous efficiency in a wide range of 2-70%.
  • the preparation method of the film of the embodiment comprises the following steps:
  • TFB weight average molecular weight is : ⁇ 200,000
  • poly-TPD weight average molecular weight: ⁇ 120,000
  • PMMA are each fully soluble in 0.5mL of toluene
  • the quantum dot solution prepared in the step 1) was separately added to the above TFB/poly-TPD/PMMA toluene solution and thoroughly mixed, thereby sequentially forming a TFB+poly-TPD/QD weight concentration of 40/1. , 30/1, 20/1, 10/1, 8/1, 4/1 mg/mL toluene solution, at this time, the weight percentage of the charge transport regulating polymer material PMMA in the polymer material is in the range of 5-10% ;
  • a film having a different weight percentage of quantum dots can be prepared by forming a film of the above toluene solution by spin coating in an inert atmosphere and annealing at 110 ° C for 15 minutes.
  • the charge transfer regulating polymer material is mainly to improve the charge transport of the thin film application in the QLED device, it has little effect on the luminescence quantum yield of the film itself, so the effect of improving the quantum yield of the film luminescence is similar to that of the fourth embodiment. .
  • the quantum dot light emitting diode of this embodiment includes an ITO substrate 11, a bottom electrode 12, a PEDOT: PSS hole injection layer 13, a poly-TPD hole transport layer 14, and a quantum dot in this order from bottom to top.
  • the light-emitting layer 15, the ZnO electron transport layer 16, and the Al top electrode 17.
  • the quantum dot light-emitting layer 15 is prepared by preparing a CdTe/CdZnS quantum dot (the luminescence peak of the solution is 631 nm, the half-value width is 30 nm, and the luminescence quantum yield is 56%), the weight concentration is 1 mg/mL, and the PVK weight concentration is It was a 20 mg/mL toluene solution, spin-coated at 3000 rpm for 60 seconds, and annealed at 110 ° C for 15 minutes in an inert atmosphere.
  • Example 14 a QLED device using a film of a barrier polymer material PVK as a quantum dot light-emitting layer was used, and the external quantum efficiency was 3.1%, and the electroluminescence peak wavelength was 633 nm.
  • a QLED device using a pure quantum dot material as a quantum dot light-emitting layer has an outer quantum dot efficiency of 0.5% and an electroluminescence peak wavelength of 642 nm.
  • the efficiency of the QLED device using the quantum dot film containing PVK as the quantum dot light-emitting layer is significantly improved compared to the device in which the pure quantum dot without PVK is added as the light-emitting layer; and the wavelength of the light-emitting peak is red relative to the wavelength in the solution.
  • the degree of shift is also greatly reduced, further indicating that PVK has an effective weakening effect on the interaction between quantum dots.
  • Charge Transfer Modulation Polymer Improves Efficiency of Quantum Dot Light-Emitting Diode Devices 1
  • Example 14 A similar device structure and preparation in Example 14 was employed, wherein the quantum dot luminescent layer was prepared by preparing a CdTe/CdZnS quantum dot (the luminescence peak of the solution was 631 nm, the half width was 30 nm, and the luminescence quantum yield was 56%).
  • a chlorobenzene solution having a weight concentration of 1 mg/mL, a PVK weight concentration of 20 mg/mL, and a polythiophene concentration of 0.8 mg/mL, spin-coated at 3000 rpm for 60 seconds, and annealed at 110 ° C in an inert atmosphere. minute.
  • a QLED device using a film containing PVK and polythiophene as a quantum dot light-emitting layer has an external quantum efficiency of 5.1% and an electroluminescence peak wavelength of 633 nm.
  • Example 14 a QLED device using only a film of a barrier polymer material PVK as a quantum dot light-emitting layer was used, and the external quantum efficiency was 3.1%, and the electroluminescence peak wavelength was 633 nm. .
  • Example 14 A similar device structure and preparation in Example 14 was employed, wherein the quantum dot luminescent layer was prepared by preparing a CdTe/CdZnS quantum dot (the luminescence peak of the solution was 628 nm, the half width was 32 nm, and the luminescence quantum yield was 54%). a chlorobenzene solution having a weight concentration of 1 mg/mL, a TFB weight concentration of 30 mg/mL, and a PMMA weight concentration of 2.5 mg/mL, spin-coated at 3000 rpm for 60 seconds, and annealed at 110 ° C for 15 minutes in an inert atmosphere. . At the same time, a quantum dot solution containing no PMMA was prepared for comparison and film formation was carried out by the same method.
  • a QLED device using a film containing TFB and PMMA as a quantum dot light-emitting layer had an external quantum efficiency of 4.3% and an electroluminescence peak wavelength of 631 nm.
  • the QLED device using a thin film containing a polymer material TFB only as a quantum dot light-emitting layer has an external quantum efficiency of 2.7% and an electroluminescence peak wavelength of 634 nm. .
  • the effective inhibition of the interaction between the quantum dots by the barrier polymer material improves the luminous efficiency of the film, thereby increasing the luminous efficiency of the corresponding QLED device; and the smaller red shift of the electroluminescence peak further indicates the barrier.
  • the effective inhibition of polymer materials on the interaction between quantum dots improves the luminous efficiency of the film, thereby increasing the luminous efficiency of the corresponding QLED device; and the smaller red shift of the electroluminescence peak further indicates the barrier.
  • an embodiment of the present invention provides a film and a method for fabricating the same, and a QLED device, wherein the film contains quantum dots and a polymer material, and the polymer material is used to effectively separate quantum dots and increase mutual interaction between quantum dots.
  • the distance thereby reducing the interaction between the quantum dots and maximally suppressing the non-radiative energy transfer and concentration quenching between the quantum dots, thereby achieving an increase in quantum yield of quantum dots in the film.
  • the weight average molecular weight of the barrier polymer material capable of effectively isolating the quantum dots is required to be 100,000 or more; the higher the molecular weight of the barrier polymer material, The better the isolation between the quantum dots, the higher the weight of the quantum dots that can be accommodated in the quantum dot film.

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Abstract

一种薄膜及其制备方法与QLED器件，所述薄膜包括高分子材料和分散在所述高分子材料中的量子点，其中所述高分子材料包括至少一种阻隔高分子材料，所述阻隔高分子材料的重均分子量高于10万。薄膜中含有量子点与高分子材料，利用高分子材料有效隔离量子点并增大量子点之间的相互距离，从而减少量子点之间的相互作用并最大程度抑制量子点之间的无辐射能量转移和浓度淬灭，达到薄膜中量子点发光量子产率的提升。

Description

一种薄膜及其制备方法与QLED器件 技术领域
本发明涉及量子点技术领域，尤其涉及一种薄膜及其制备方法与QLED器件。
背景技术
量子点是一种在三个维度尺寸上均被限制在纳米数量级的特殊材料，这种显著的量子限域效应使得量子点具有了诸多独特的纳米性质：发射波长连续可调、发光波长窄、吸收光谱宽、发光强度高、荧光寿命长以及生物相容性好等。这些特点使得量子点在生物标记、平板显示、固态照明、光伏太阳能等领域均具有广泛的应用前景。
在典型的电致发光显示应用中，量子点通常是单独成膜从而形成一层仅包含量子点材料的发光层，这与有机发光二极管器件(OLED)中，发光材料(称为客体材料)通常是以一定比例的掺杂浓度混合在主体材料中然后成膜的情况是不相同的。在主体-客体混合材料发光层的情形中，空穴和电子首先通过各自传输层材料注入到主体材料的导带和价带能级上并形成激子，此时激子并不倾向于发生复合，而是通过能量传递的方式将激子转移到客体材料中，在客体材料中激子发生复合发射出相应波长的光子。由于在OLED中，客体有机分子本身并不具有能级束缚的功能，因此如果单独成膜形成仅含客体材料的发光层，会发生非常强烈的无辐射能量转移和浓度淬灭，因此主体-客体的混合体系对于OLED来说是一种更有效的获得高发光效率的方式。
但对于量子点发光二极管(QLED)来说，由于量子点自身具有核壳结构，因此一般来说，高质量的量子点自身就会具有非常良好的能级束缚及相应的激子束缚能力，所以直接采用纯的量子点材料作为发光层就能够实现很好的器件发光效率，同时器件结构更简单、激子损失途径减少。
但是有一些量子点由于核壳结构设计的局限性，导致在这类量子点中对于自身的能级和激子束缚能力很有限，这类量子点虽然能够在溶液状态下(即量子点粒子之间距离比较大)展现出较高的发光量子产率，但在固态薄膜中(即量子点粒子之间紧密堆积)会由于强烈的无辐射能量转移和浓度淬灭导致发光效率显著 降低。因此基于这类量子点的QLED器件效率就会很低。
因此对于这类自身能级和激子束缚能力有限的量子点，其相应QLED器件的设计和制备方案有待改进。
发明内容
一种薄膜，其中，所述薄膜包括高分子材料和分散在所述高分子材料中的量子点，其中所述高分子材料包括至少一种阻隔高分子材料，所述阻隔高分子材料的重均分子量高于10万。
一种薄膜的制备方法，其中，包括步骤：
将量子点和高分子材料混合在分散介质中；
将混合后的溶液制成薄膜，得到所述薄膜；
其中所述高分子材料包括至少一种阻隔高分子材料，所述阻隔高分子材料的重均分子量高于10万。
一种QLED器件，所述QLED器件包括量子点发光层，其中，所述量子点发光层为本发明所述薄膜。
有益效果：薄膜中含有量子点与高分子材料，利用高分子材料有效隔离量子点并增大量子点之间的相互距离，从而减少量子点之间的相互作用并最大程度抑制量子点之间的无辐射能量转移和浓度淬灭，达到薄膜中量子点发光量子产率的提升。阻隔高分子材料的分子量若过小，无法起到足够的隔离效果，因此要求能够实现有效隔离量子点的阻隔高分子材料的重均分子量在10万以上；阻隔高分子材料的分子量越高，对于量子点相互之间的隔离效果就越好，因而在量子点薄膜中所能容纳的量子点的重量含量就越高。
附图说明
图1为本发明中PVK的结构式。
图2为本发明中TFB的结构式。
图3为本发明中poly-TPD的结构式。
图4为本发明中MEH-PPV的结构式。
图5为本发明中PVK的衍生物的结构式。
图6为本发明中PVK的另一衍生物的结构式。
图7为本发明中PVK的又一衍生物的结构式。
图8为本发明的实施方式提供的一种薄膜的制备方法的流程图。
图9为本发明实施例14中量子点发光二极管的结构示意图。
具体实施方式
为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的实施方式和具体实施例仅仅用以解释本发明，并不用于限定本发明。
现有某些量子点自身的核壳结构对于能级和激子束缚能力很有限，其虽然能够在溶液状态下(此时量子点粒子之间距离大)展现出较高的发光量子产率，但在固态薄膜中(此时量子点粒子之间紧密堆积)会由于强烈的无辐射能量转移和浓度淬灭导致发光效率显著降低。这是因为当量子点的核壳结构在能级上不能很好对电子云或者激子进行束缚时，电子云或者激子就会更容易扩散到量子点表面，此时如果量子点之间的距离很近相互作用很强(例如固态薄膜中的情形)，那么量子点中扩散到表面的电子云或者激子就会发生强烈的相互作用，从而发生强烈的无辐射能量转移和浓度淬灭，使得在固态薄膜中的量子点发光量子产率显著降低。因而使得使用这种固态薄膜的QLED器件效率也会显著降低。
所以对于这种自身核壳结构不能提供足够的对于能级和激子束缚的量子点来说，现有技术中使用纯量子点材料作为QLED器件中量子点发光层薄膜的方案不能获得很好的效果。
对于这种自身核壳结构不能提供足够的对于能级和激子束缚的量子点，为了能够增大量子点之间距离从而减少量子点之间的相互作用，以便最大程度抑制量子点之间的无辐射能量转移和浓度淬灭，需要将量子点与高分子材料混合制备薄膜，利用高分子材料有效隔离量子点并增大量子点之间的相互距离，从而减少量子点之间的相互作用并最大程度抑制量子点之间的无辐射能量转移和浓度淬灭，达到量子点薄膜发光量子产率的提升。利用这种具有高发光量子产率的量子点薄膜到QLED器件中，就能实现高效率的QLED器件。因此，本发明主要改进见下文：
本发明的实施方式提供一种薄膜，其中，所述薄膜包括高分子材料和分散在所述高分子材料中的量子点，其中所述高分子材料包括至少一种阻隔高分子材 料，所述阻隔高分子材料的重均分子量高于10万。
本发明的实施方式薄膜中含有量子点与高分子材料，利用高分子材料有效隔离量子点并增大量子点之间的相互距离，从而减少量子点之间的相互作用并最大程度抑制量子点之间的无辐射能量转移和浓度淬灭，达到薄膜中量子点发光量子产率的提升。阻隔高分子材料的分子量若过小，无法起到足够的隔离效果，因此要求能够实现有效隔离量子点的阻隔高分子材料的重均分子量在10万以上；阻隔高分子材料的分子量越高，对于量子点相互之间的隔离效果就越好，因而在量子点薄膜中所能容纳的量子点的重量含量就越高。利用这种具有高发光量子产率的薄膜到QLED器件中，就能实现高效率的QLED器件。
本发明的实施方式薄膜含有量子点与一种或一种以上阻隔高分子材料，阻隔高分子材料的重均分子量高于10万，这是因为所述阻隔高分子材料的重均分子量若过小，无法起到有效的隔离效果。所述阻隔高分子材料的重均分子量越高，对于量子点相互之间的隔离效果就越好，在薄膜中所能容纳的量子点的重量含量就越高。
在一些实施方式中，所述量子点为油溶性量子点或水溶性量子点。
在一些具体的实施方式中，所述量子点为油溶性量子点，所述油溶性量子点的表面配体为硫醇或羧酸。
在一些具体的实施方式中，所述量子点选自II-VI族量子点、III-V族量子点和IV-VI族量子点中的一种或多种。在一些具体的实施方式中，所述量子点选自II-VI族、III-V族、IV-VI族的单一量子点及II-VI族、III-V族、IV-VI族的核壳型量子点或混合型量子点中的一种或多种。在一些具体的实施方式中，II-VI族单一量子点选自CdSe、CdS、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe、CdZnSTe、CdSeSTe、ZnSeSTe和CdZnSeSTe等中的一种；III-V族单一量子点选自InP、GaP、GaAs、InAs、InAsP、GaAsP、InGaP、InGaAs和InGaAsP等中的一种；IV-VI族单一量子点选自PbS、PbSe、PbTe、PbSeS、PbSeTe和PbSTe等中的一种；所述核壳型量子点选自CdZnSe/ZnS、CdZnSeS/ZnS、CdTe/ZnS、CdZnSe/ZnS、CdZnSeS/ZnS、CdTe/ZnS、CdTe/CdSe、CdTe/ZnTe、CdSe/CdS和CdSe/ZnS等中的一种；所述混合型量子点选自CdTe/CdS/ZnS等。
在一些具体的实施方式中，所述量子点选自II-VI族量子点。
在一些具体的实施方式中，所述量子点选自含Te的II-VI族量子点。含Te的II-VI族量子点相比于含Se的II-VI族量子点具有更窄的能带隙，因此在制备可见光波段(绿色或红色)的发光量子点时，不能生长较厚的壳层，以避免发光波长过分红移，因此所述的量子点之间的距离会非常接近，在固态膜中的相互作用强的现象会在含Te的II-VI族量子点中更为突出，在固态薄膜中强烈的无辐射能量转移和浓度淬灭会导致含Te的II-VI族量子点发光效率显著降低。因此对于含Te的II-VI族量子点的QLED器件来说，对量子点发光层薄膜中量子点间发光效率淬灭的有效避免变得尤其重要。在一些具体的实施方式中，所述量子点选自含Cd和Te的II-VI族量子点。在一些具体的实施方式中，所述量子点选自CdTe、CdTeS及以CdTe或CdTeS为核的核壳量子点中的一种。由于CdTe、CdTeS等含Cd、Te的量子点相对其他含Te的II-VI族量子点的导带能级更深，对于电子的束缚效果更好，因此同样的避免发光效率淬灭的办法会对CdTe、CdTeS等产生更佳的效果。
在一些实施方式中，所述阻隔高分子材料的载流子迁移率在10 -8cm 2V -1s -1以上。由于含有阻隔高分子材料和量子点的薄膜在QLED器件应用中作为发光层，需考虑到电荷注入到薄膜后在阻隔高分子材料中的电荷传输，所以阻隔高分子材料的载流子迁移率需满足一定的要求(在10 -8cm 2V -1s -1以上)。
在一些具体的实施方式中，所述阻隔高分子材料的重均分子量高于20万。阻隔高分子材料的重均分子量越高，对于量子点相互之间的隔离效果就越好。选择重均分子量高于20万的阻隔高分子材料，可以进一步提高对量子点相互之间的隔离效果，从而进一步提升薄膜中量子点发光量子产率。
在一些具体的实施方式中，所述阻隔高分子材料的重均分子量高于30万。
在一些具体的实施方式中，所述阻隔高分子材料的重均分子量高于50万。
在一些实施方式中，所述阻隔高分子材料选自重均分子量高于50万的PVK(聚(9-乙烯基咔唑))及其衍生物、重均分子量高于50万的TFB及其衍生物、重均分子量高于50万的poly-TPD及其衍生物、重均分子量高于50万的MEH-PPV(聚(2-甲氧基-5-(2'-乙基己氧基)-1,4-对苯乙炔))及其衍生物的一种。其中，所述PVK的结构式见图1，所述TFB的结构式见图2，所述poly-TPD的结构式见图3，所述MEH-PPV的结构式见图4。在一些具体的实施方式中，所述TFB的衍生物可以选自图5-图7中任一种结构分子。选择上述阻隔高分子 材料，可以最大化提高对量子点相互之间的隔离效果，从而最大化提升薄膜中量子点发光量子产率。
在一些实施方式中，所述薄膜由量子点和一种阻隔高分子材料组成，所述量子点占薄膜的质量分数为0.5-90％。换句话说，本实施方式中所述薄膜中仅含一种特定的高分子材料，所述阻隔高分子材料的重均分子量高于10万，所述阻隔高分子材料的重均分子量越高，对于量子点相互之间的隔离效果就越好，在薄膜中所能容纳的量子点的重量含量就越高。
在一些具体的实施方式中，所述阻隔高分子材料的重均分子量在10万-30万之间，所述量子点占薄膜的质量分数为0.5-30％。
在一些具体的实施方式中，所述阻隔高分子材料的重均分子量在30万-50万之间，所述量子点占薄膜的质量分数为0.5-66％。
在一些具体的实施方式中，所述阻隔高分子材料的重均分子量在50万-150万之间，所述量子点占薄膜的质量分数为0.5-90％。
阻隔高分子材料的分子量越高，对于量子点相互之间的隔离效果就越好，因而在量子点薄膜中所能容纳的量子点的重量含量就越高。
在一些具体的实施方式中，所述量子点占薄膜的质量分数为0.5-20％。
在一些具体的实施方式中，所述量子点占薄膜的质量分数为2-10％。
在一些具体的实施方式中，所述阻隔高分子材料的载流子迁移率在10 -6cm 2V -1s -1以上，以进一步增强电荷在薄膜中的传输。
在一些实施方式中，所述薄膜由量子点和高分子材料组成，所述高分子材料由两种阻隔高分子材料组成。换句话说，本发明实施方式高分子材料只包括两种阻隔高分子材料，所述两种阻隔高分子材料的重均分子量均高于10万，所述量子点占薄膜的质量分数为0.5-90％。所述两种阻隔高分子材料的重均分子量越高，对于量子点相互之间的隔离效果就越好，在薄膜中所能容纳的量子点的重量含量就越高。
所述阻隔高分子材料的重均分子量在50万-150万之间，所述量子点占薄膜的质量分数为0.5-90％。在一些具体的实施方式中，所述量子点占薄膜的质量分数为0.5-20％。
在一些具体的实施方式中，所述量子点占薄膜的质量分数为2-10％。
在一些具体的实施方式中，所述两种阻隔高分子材料的载流子迁移率均在 10 -6cm 2V -1s -1以上，以进一步增强电荷在薄膜中的传输。
在一些实施方式中，所述高分子材料还包括至少一种电荷传输调节高分子材料，所述电荷传输调节高分子材料的重均分子量低于10万，所述电荷传输调节高分子材料占高分子材料的质量分数低于10％。换句话说，本发明的实施方式高分子材料包括至少一种阻隔高分子材料和至少一种电荷传输调节高分子材料，所述阻隔高分子材料的重均分子量高于10万，所述电荷传输调节高分子材料的重均分子量低于10万，所述阻隔高分子材料的重均分子量越高，对于量子点相互之间的隔离效果就越好，在薄膜中所能容纳的量子点的重量含量就越高。所述电荷传输调节高分子材料的加入能够调节薄膜应用在QLED器件中的电荷传输性能，并能够保证薄膜本身的发光量子产率不受影响。
当阻隔高分子材料的载流子迁移率过高时(在10 -6cm 2V -1s -1以上)，需要在薄膜中加入电荷传输调节高分子材料，这种情形下的电荷传输调节高分子材料需为非导电高分子，以便有效控制和调节电荷在薄膜中的传输。
在一些具体的实施方式中，所述高分子材料由一种阻隔高分子材料和一种电荷传输调节高分子材料组成。换句话说，本发明的实施方式高分子材料仅为一种阻隔高分子材料和一种电荷传输调节高分子材料，所述阻隔高分子材料的重均分子量高于10万，所述电荷传输调节高分子材料的重均分子量低于10万，所述阻隔高分子材料的重均分子量越高，对于量子点相互之间的隔离效果就越好，在薄膜中所能容纳的量子点的重量含量就越高。
所述阻隔高分子材料的重均分子量在50万-150万之间，所述量子点占薄膜的质量分数为0.5-90％。在一些具体的实施方式中，所述量子点占薄膜的质量分数为0.5-20％。
在一些具体的实施方式中，所述量子点占薄膜的质量分数为2-10％。
在一些实施方式中，所述阻隔高分子材料的载流子迁移率在10 -6cm 2V -1s -1以下，所述电荷传输调节高分子材料选自导电高分子，从而增强电荷在薄膜中的传输，所述电荷传输调节高分子材料占高分子材料的质量分数为0.5-5％。在一些具体的实施方式中，所述导电高分子选自聚乙炔、聚苯硫醚、聚苯胺、聚吡咯和聚噻吩等中的一种。
在一些实施方式中，所述阻隔高分子材料的载流子迁移率在10 -6cm 2V -1s -1以上，所述电荷传输调节高分子材料选自非导电高分子，以便有效控制和调节电荷 在薄膜中的传输，所述电荷传输调节高分子材料占高分子材料的质量分数为5-10％。在一些具体的实施方式中，所述非导电高分子选自酚醛树脂、聚乙烯、聚二甲基硅氧烷(PDMS)、聚苯乙烯、聚甲基丙烯酸酯、聚丙烯酸酯和聚碳酸酯等中的一种。
在一些实施方式中，所述薄膜由量子点和高分子材料组成，所述高分子材料由两种阻隔高分子材料和一种电荷传输调节高分子材料组成。
所述阻隔高分子材料的重均分子量在50万-150万之间，所述量子点占薄膜的质量分数为0.5-90％。在一些具体的实施方式中，所述量子点占薄膜的质量分数为0.5-20％。在一些具体的实施方式中，所述量子点占薄膜的质量分数为2-10％。
在一些实施方式中，所述两种阻隔高分子材料的载流子迁移率均在10 -6cm 2V -1s -1以下，所述电荷传输调节高分子材料选自导电高分子，从而增强电荷在薄膜中的传输，所述电荷传输调节高分子材料占高分子材料的质量分数为0.5-5％。在一些具体的实施方式中，所述导电高分子选自聚乙炔、聚苯硫醚、聚苯胺、聚吡咯和聚噻吩中的一种。
在一些实施方式中，所述两种阻隔高分子材料的载流子迁移率均在10 -6cm 2V -1s -1以上，所述电荷传输调节高分子材料选自非导电高分子，以便有效控制和调节电荷在薄膜中的传输，所述电荷传输调节高分子材料占高分子材料的质量分数为5-10％。在一些具体的实施方式中，所述非导电高分子选自酚醛树脂、聚乙烯、聚二甲基硅氧烷、聚苯乙烯、聚甲基丙烯酸酯、聚丙烯酸酯和聚碳酸酯中的一种。
本发明的实施方式还提供一种薄膜的制备方法的流程图，如图8所示，其包括步骤：
S10、将量子点和高分子材料混合在分散介质中；
S20、将混合后的溶液制成薄膜，得到所述薄膜；
其中所述高分子材料包括至少一种阻隔高分子材料，所述阻隔高分子材料的重均分子量高于10万。
在一些实施方式中，所述分散介质选自有机溶剂。在一些具体的实施方式中，所述有机溶剂选自非极性有机溶剂，在一些具体的实施方式中，所述非极性有机溶剂可以选自氯仿、甲苯、氯苯、正己烷、正辛烷、十氢萘、十三烷、正辛基苯、 三辛基膦(TOP)、三丁基膦(TBP)、十八烯(ODE)、油酸(OA)、十八烷基胺(ODA)、三辛胺(TOA)和油胺(OAm)等中的一种。
在一些实施方式中，采用溶液法将混合后的溶液制成薄膜，得到所述薄膜。在一些具体的实施方式中，所述溶液法选自旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法和条状涂布法等中的一种。
本发明的实施方式还提供一种QLED器件，所述QLED器件包括量子点发光层，其中，所述量子点发光层为本发明所述薄膜。本发明的实施方式将具有高发光量子产率的薄膜应用到QLED器件中，能够实现高效率的QLED器件。
在一些实施方式中，所述薄膜的厚度为10-80nm。
下面通过实施例对本发明的实施方式进行详细说明。
实施例1
本实施例不同量子点重量百分比的薄膜的制备方法，包括以下步骤：
1)、称取20mg的CdTe/CdZnS核壳量子点充分溶于10mL氯苯中，形成浓度为2mg/mL的量子点溶液，此量子点溶液的发光峰为631nm，半峰宽为30nm，发光量子产率为56％；
2)、分别称取40mg、30mg、20mg、10mg、8mg、4mg、2mg、1mg、0.5mg、0.3mg、0.1mg的PVK(重均分子量为：～110万)各自充分溶于0.5mL的氯苯中；
3)、在上述PVK氯苯溶液中分别加入在步骤1)中所配制的量子点溶液0.5mL并充分混合，从而依次形成PVK/QD重量浓度为40/1、30/1、20/1、10/1、8/1、4/1、2/1、1/1、0.5/1、0.3/1、0.1/1mg/mL的氯苯溶液；
4)、在惰性气氛中将上述氯苯溶液通过旋涂的方法成膜，并在120℃下退火15分钟，即可制备得到具有不同量子点重量百分比的薄膜。
实施例2
阻隔高分子材料的加入对于薄膜发光量子产率的提升效果
实施例1中各薄膜的发光量子产率如下表1所示，相比于由纯量子点材料所形成的薄膜(最后一行)，在薄膜中加入不同比例的阻隔高分子材料(此例中为PVK)可以显著改善薄膜的发光量子产率，从纯薄膜的3％大幅增加到53％，基本接近量子点在溶液中的发光量子产率，说明PVK高分子在薄膜中对于量子点 的隔离效果良好。此例中PVK具有很大的重均分子量(110万)，可以看到，QD的重量百分比在2-90％的大范围内均有发光效率的改善作用。
表1、薄膜的发光量子产率
Figure PCTCN2018123689-appb-000001
实施例3
本实施例不同量子点重量百分比的薄膜的制备方法，包括以下步骤：
1)、称取20mg的CdTe/CdZnS核壳量子点充分溶于10mL氯苯中，形成浓度为2mg/mL的量子点溶液，此量子点溶液的发光峰为631nm，半峰宽为30nm，发光量子产率为56％；
2)、分别称取40mg、30mg、20mg、10mg、8mg、4mg、2mg、1mg、0.5mg、0.3mg、0.1mg的PVK(重均分子量为：～50万)各自充分溶于0.5mL的氯苯中；
3)、在上述PVK氯苯溶液中分别加入在步骤1)中所配制的量子点溶液0.5mL并充分混合，从而依次形成PVK/QD重量浓度为40/1、30/1、20/1、10/1、8/1、4/1、2/1、1/1、0.5/1、0.3/1、0.1/1mg/mL的氯苯溶液；
4)、在惰性气氛中将上述氯苯溶液通过旋涂的方法成膜，并在120℃下退火 15分钟，即可制备得到具有不同量子点重量百分比的薄膜。
实施例4
阻隔高分子材料的加入对于薄膜发光量子产率的提升效果
实施例3中各薄膜的发光量子产率如下表2所示，相比于由纯量子点材料所形成的薄膜(最后一行)，在薄膜中加入不同比例的阻隔高分子材料(此例中为PVK)可以显著改善薄膜的发光量子产率，从纯薄膜的3％大幅增加到52％，基本接近量子点在溶液中的发光量子产率，说明PVK高分子在薄膜中对于量子点的隔离效果良好。此例中PVK具有较大的重均分子量(50万)，可以看到，QD的重量百分比在2-66％的大范围内均有发光效率的改善作用。
表2、薄膜的发光量子产率
Figure PCTCN2018123689-appb-000002
实施例5
本实施例不同量子点重量百分比的薄膜的制备方法，包括以下步骤：
1)、称取20mg的CdTe/CdS核壳量子点充分溶于10mL甲苯中，形成浓度为2mg/mL的量子点溶液，此量子点溶液的发光峰为628nm，半峰宽为32nm， 发光量子产率为54％；
2)、分别称取40mg、30mg、20mg、10mg、8mg、4mg、2mg、1mg、0.5mg、0.3mg、0.1mg的TFB(重均分子量为：～20万)各自充分溶于0.5mL的甲苯中；
3)、在上述TFB甲苯溶液中分别加入在步骤1)中所配制的量子点溶液0.5mL并充分混合，从而依次形成TFB/QD重量浓度为40/1、30/1、20/1、10/1、8/1、4/1、2/1、1/1、0.5/1、0.3/1、0.1/1mg/mL的甲苯溶液；
4)、在惰性气氛中将上述甲苯溶液通过旋涂的方法成膜，并在110℃下退火15分钟，即可制备得到具有不同量子点重量百分比的薄膜。
实施例6
阻隔高分子材料的加入对于薄膜发光量子产率的提升效果
实施例5中各薄膜的发光量子产率如下表3所示，相比于由纯量子点材料所形成的薄膜(最后一行)，在薄膜中加入不同比例的阻隔高分子材料(此例中为TFB)可以显著改善薄膜的发光量子产率，从纯量子点薄膜的3％大幅增加到48％，基本接近量子点在溶液中的发光量子产率，说明TFB高分子在薄膜中对于量子点的隔离效果良好。此例中TFB具有的重均分子量为20万，可以看到，QD的重量百分比在2-30％的范围内均有发光效率的改善作用。相比于实施例2和实施例4，可以看到，当阻隔高分子的重均分子量增大时，能够起到改善效率作用的QD重量百分比范围更大。
表3、薄膜的发光量子产率
Figure PCTCN2018123689-appb-000003
Figure PCTCN2018123689-appb-000004
实施例7
本实施例不同量子点重量百分比的薄膜的制备方法，包括以下步骤：
1)、称取20mg的CdTe/CdS核壳量子点充分溶于10mL甲苯中，形成浓度为2mg/mL的量子点溶液，此量子点溶液的发光峰为628nm，半峰宽为32nm，发光量子产率为54％；
2)、分别称取40mg、30mg、20mg、10mg、8mg、4mg、2mg、1mg、0.5mg、0.3mg、0.1mg的TFB(重均分子量为：5万)各自充分溶于0.5mL的甲苯中；
3)、在上述TFB甲苯溶液中分别加入在步骤1)中所配制的量子点溶液0.5mL并充分混合，从而依次形成TFB/QD重量浓度为40/1、30/1、20/1、10/1、8/1、4/1、2/1、1/1、0.5/1、0.3/1、0.1/1mg/mL的甲苯溶液；
4)、在惰性气氛中将上述甲苯溶液通过旋涂的方法成膜，并在110℃下退火15分钟，即可制备得到具有不同量子点重量百分比的薄膜。
实施例8
过小分子量的阻隔高分子材料的加入对于薄膜发光量子产率的提升效果对比
实施例7中各薄膜的发光量子产率如下表4所示，相比于由纯量子点材料所形成的薄膜(最后一行)，在薄膜中加入不同比例的分子量仅为5万的阻隔高分子材料(此例中为TFB)时薄膜的发光量子产率几乎没有改善，说明低分子量的TFB高分子在薄膜中对于量子点的隔离效果不佳。
表4、薄膜的发光量子产率
Figure PCTCN2018123689-appb-000005
Figure PCTCN2018123689-appb-000006
实施例9
本实施例薄膜(由量子点、一种阻隔高分子材料TFB和一种电荷传输调节高分子材料PMMA组成)的制备方法，包括以下步骤：
1)、称取20mg的CdTeS/CdS核壳量子点充分溶于10mL甲苯中，形成浓度为2mg/mL的量子点溶液，此量子点溶液的发光峰为605nm，半峰宽为29nm，发光量子产率为56％；
2)、分别称取40/3mg、30/2mg、20/2mg、10/1mg、8/0.5mg、4/0.2mg的TFB(重均分子量为：～20万)/PMMA各自充分溶于0.5mL的甲苯中；
3)、在上述TFB/PMMA甲苯溶液中分别加入在步骤1)中所配制的量子点溶液0.5mL并充分混合，从而依次形成TFB/QD重量浓度为40/1、30/1、20/1、10/1、8/1、4/1mg/mL的甲苯溶液，此时电荷传输调节高分子材料PMMA在高分子材料中的重量百分比在5-10％范围内；
4)、在惰性气氛中将上述甲苯溶液通过旋涂的方法成膜并在110℃下退火15分钟，即可制备得到具有不同量子点重量百分比的薄膜；
5)由于电荷传输调节高分子材料的加入主要是改善薄膜应用在QLED器件中的电荷传输，对薄膜本身的发光量子产率影响不大，因此其对于薄膜发光量子产率的提升效果与实施例6类似。
实施例10
本实施例薄膜(由量子点、一种阻隔高分子材料PVK和一种电荷传输调节高分子材料聚噻吩组成)的制备方法，包括以下步骤：
1)、称取20mg的CdTe/CdZnS核壳量子点充分溶于10mL氯苯中，形成浓度为2mg/mL的量子点溶液，此量子点溶液的发光峰为631nm，半峰宽为30nm，发光量子产率为56％；
2)、分别称取40/1.5mg、30/1.0mg、20/1.0mg、10/0.5mg、8/0.3mg、4/0.2mg、2/0.1mg、1/0.03mg、0.5/0.01mg的PVK(重均分子量为：～110万)/聚噻吩各自充分溶于0.5mL的氯苯中；
3)、在上述PVK/聚噻吩氯苯溶液中分别加入在步骤1)中所配制的量子点溶液0.5mL并充分混合，从而依次形成PVK/QD重量浓度为40/1、30/1、20/1、10/1、8/1、4/1mg/mL的氯苯溶液，此时电荷传输调节高分子材料聚噻吩在高分子材料中的重量百分比在5％以下；
4)、在惰性气氛中将上述氯苯溶液通过旋涂的方法成膜并在120℃下退火15分钟，即可制备得到具有不同量子点重量百分比的薄膜。
由于电荷传输调节高分子材料的加入主要是改善薄膜应用在QLED器件中的电荷传输，对薄膜本身的发光量子产率影响不大，因此其对于量子点薄膜发光量子产率的提升效果与实施例2类似。
实施例11
本实施例薄膜(由量子点、阻隔高分子材料PVK和阻隔高分子材料TFB组成)的制备方法，包括以下步骤：
1)、称取20mg的CdTe/CdZnS核壳量子点充分溶于10mL氯苯中形成浓度为2mg/mL的量子点溶液，此量子点溶液的发光峰为631nm，半峰宽为30nm，发光量子产率为56％；
2)、分别称取20/20mg、15/15mg、10/10mg、5/5mg、4/4mg、2/2mg、1/1mg、0.5/0.5mg、0.3/0.2mg、0.2/0.1mg的PVK(重均分子量为：～110万)/TFB(重均分子量为：～20万)各自充分溶于0.5mL的氯苯中；
3)、在上述PVK/TFB氯苯溶液中分别加入在步骤1)中所配制的量子点溶液0.5mL并充分混合，从而依次形成PVK/TFB/QD重量浓度为20/20/1、15/15/1、10/10/1、5/5/1、4/4/1、2/2/1、1/1/1、0.5/0.5/1、0.3/0.2/1、0.2/0.1/1mg/mL的氯 苯溶液；
4)、在惰性气氛中将上述氯苯溶液通过旋涂的方法成膜并在120℃下退火15分钟，即可制备得到具有不同量子点重量百分比的薄膜。
实施例12
阻隔高分子材料的加入对于薄膜发光量子产率的提升效果
实施例11中各薄膜的发光量子产率如下表5所示，相比于由纯量子点材料所形成的薄膜(最后一行)，在薄膜中加入不同比例的阻隔高分子材料(此例中为PVK+TFB)可以显著改善薄膜的发光量子产率，从纯量子点薄膜的3％大幅增加到50％，基本接近量子点在溶液中的发光量子产率，说明PVK+TFB阻隔高分子材料在薄膜中对于量子点的隔离效果良好。此例中PVK和TFB分别具有重均分子量～110万和～20万，可以看到，QD的重量百分比在2-70％的大范围内均有发光效率的改善作用。
表5、薄膜的发光量子产率
Figure PCTCN2018123689-appb-000007
实施例13
本实施例薄膜(由量子点、阻隔高分子材料TFB、阻隔高分子材料poly-TPD 和一种电荷传输调节高分子材料PMMA组成)的制备方法，包括以下步骤：
1)、称取20mg的CdTeS/CdS核壳量子点充分溶于10mL甲苯中形成浓度为2mg/mL的量子点溶液，此量子点溶液的发光峰为605nm，半峰宽为29nm，发光量子产率为56％；
2)、分别称取30/10/3mg、20/10/2mg、15/5/2mg、6/4/1mg、5/3/0.5mg、3/1/0.2mg的TFB(重均分子量为：～20万)/poly-TPD(重均分子量为：～12万)/PMMA各自充分溶于0.5mL的甲苯中；
3)、在上述TFB/poly-TPD/PMMA甲苯溶液中分别加入在步骤1)中所配制的量子点溶液0.5mL并充分混合，从而依次形成TFB+poly-TPD/QD重量浓度为40/1、30/1、20/1、10/1、8/1、4/1mg/mL的甲苯溶液，此时电荷传输调节高分子材料PMMA在高分子材料中的重量百分比在5-10％范围内；
4)、在惰性气氛中将上述甲苯溶液通过旋涂的方法成膜并在110℃下退火15分钟，即可制备得到具有不同量子点重量百分比的薄膜。
由于电荷传输调节高分子材料的加入主要是改善薄膜应用在QLED器件中的电荷传输，对薄膜本身的发光量子产率影响不大，因此其对于薄膜发光量子产率的提升效果与实施例4类似。
实施例14
本实施例量子点发光二极管，如图9所示，自下而上依次包括：ITO衬底11、底电极12、PEDOT：PSS空穴注入层13、poly-TPD空穴传输层14、量子点发光层15、ZnO电子传输层16及Al顶电极17。
其中，量子点发光层15的制备方法为：配制CdTe/CdZnS量子点(溶液的发光峰为631nm，半峰宽为30nm，发光量子产率为56％)重量浓度为1mg/mL、PVK重量浓度为20mg/mL的甲苯溶液，以3000rpm的转速旋涂成膜60秒，在惰性气氛中110℃下退火15分钟。
实施例15
上述薄膜对于量子点发光二极管器件的效率提升
实施例14中采用含阻隔高分子材料PVK的薄膜作为量子点发光层的QLED器件，其外量子效率结果为3.1％，电致发光峰波长为633nm。
作为对比，采用纯量子点材料作为量子点发光层的QLED器件，其外量子 点效率结果为0.5％，电致发光峰波长为642nm。
可以看到，采用含有PVK的量子点薄膜作为量子点发光层的QLED器件效率相比于没有添加PVK的纯量子点作为发光层的器件要显著提高；同时发光峰波长相对于溶液中波长的红移程度也大大减少，进一步说明PVK对于量子点间的相互作用起到了有效的减弱效果。
实施例16
电荷传输调节高分子对于量子点发光二极管器件的效率提升1
采用实施例14中类似的器件结构和制备，其中，量子点发光层的制备方法为：配制CdTe/CdZnS量子点(溶液的发光峰为631nm，半峰宽为30nm，发光量子产率为56％)重量浓度为1mg/mL、PVK重量浓度为20mg/mL、聚噻吩重量浓度为0.8mg/mL的氯苯溶液，以3000rpm的转速旋涂成膜60秒，在惰性气氛中110℃下退火15分钟。
采用含有PVK和聚噻吩的薄膜作为量子点发光层的QLED器件，其外量子效率结果为5.1％，电致发光峰波长为633nm。
而实施例14中采用只含阻隔高分子材料PVK的薄膜作为量子点发光层的QLED器件，其外量子效率结果为3.1％，电致发光峰波长为633nm。。
可以看到，虽然在含有PVK的量子点薄膜中加入适量的聚噻吩对于量子点膜的量子产率没有影响(实施例10)，但聚噻吩较高的电荷迁移率可以用以调节量子点发光层中的电荷传输以及相应的电荷平衡，因而可以进一步提升量子点QLED器件的发光效率。
实施例17
电荷传输调节高分子对于量子点发光二极管器件的效率提升2
采用实施例14中类似的器件结构和制备，其中，量子点发光层的制备方法为：配制CdTe/CdZnS量子点(溶液的发光峰为628nm，半峰宽为32nm，发光量子产率为54％)重量浓度为1mg/mL、TFB重量浓度为30mg/mL、PMMA重量浓度为2.5mg/mL的氯苯溶液，以3000rpm的转速旋涂成膜60秒，在惰性气氛中110℃下退火15分钟。同时，配制不含PMMA的量子点溶液作为对比并采用相同方法成膜。
采用含有TFB和PMMA的薄膜作为量子点发光层的QLED器件，其外量子 效率结果为4.3％，电致发光峰波长为631nm。
而采用只含阻隔高分子材料TFB的薄膜作为量子点发光层的QLED器件，其外量子效率结果为2.7％，电致发光峰波长为634nm。。
可以看到，虽然在含有TFB的量子点薄膜中加入适量的PMMA对于量子点膜的量子产率没有影响(实施例9)，但PMMA较低的电荷迁移率可以用以调节量子点发光层中的电荷传输以及相应的电荷平衡，因而可以进一步提升量子点QLED器件的发光效率。
采用阻隔高分子材料对量子点之间的相互作用进行有效抑制后，提升了薄膜的发光效率，因此也提升相应QLED器件的发光效率；同时更小的电致发光峰红移也进一步说明了阻隔高分子材料对于量子点间相互作用的有效抑制。
综上所述，本发明的实施方式提供的一种薄膜及其制备方法与QLED器件，薄膜中含有量子点与高分子材料，利用高分子材料有效隔离量子点并增大量子点之间的相互距离，从而减少量子点之间的相互作用并最大程度抑制量子点之间的无辐射能量转移和浓度淬灭，达到薄膜中量子点发光量子产率的提升。阻隔高分子材料的分子量若过小，无法起到足够的隔离效果，因此要求能够实现有效隔离量子点的阻隔高分子材料的重均分子量在10万以上；阻隔高分子材料的分子量越高，对于量子点相互之间的隔离效果就越好，因而在量子点薄膜中所能容纳的量子点的重量含量就越高。利用这种具有高发光量子产率的薄膜到QLED器件中，能够实现高效率的QLED器件。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (31)

  1. 一种薄膜，其特征在于，所述薄膜包括高分子材料和分散在所述高分子材料中的量子点，其中所述高分子材料包括至少一种阻隔高分子材料，所述阻隔高分子材料的重均分子量高于10万。
  2. 根据权利要求1所述的薄膜，其特征在于，所述量子点为油溶性量子点，所述油溶性量子点的表面配体为硫醇或羧酸。
  3. 根据权利要求2所述的薄膜，其特征在于，所述量子点选自II-VI族量子点、III-V族量子点和IV-VI族量子点中的一种或多种。
  4. 根据权利要求3所述的薄膜，其特征在于，所述量子点选自含Te的II-VI族量子点。
  5. 根据权利要求4所述的薄膜，其特征在于，所述量子点选自含Cd和Te的II-VI族量子点。
  6. 根据权利要求1-5任一项所述的薄膜，其特征在于，所述阻隔高分子材料的载流子迁移率在10 -8cm 2V -1s -1以上。
  7. 根据权利要求6所述的薄膜，其特征在于，所述阻隔高分子材料的重均分子量高于20万。
  8. 根据权利要求7所述的薄膜，其特征在于，所述阻隔高分子材料的重均分子量高于50万。
  9. 根据权利要求1所述的薄膜，其特征在于，所述阻隔高分子材料选自PVK及其衍生物、TFB及其衍生物、poly-TPD及其衍生物和MEH-PPV及其衍生物中的一种或多种。
  10. 根据权利要求1所述的薄膜，其特征在于，所述薄膜由量子点和一种阻隔高分子材料组成，所述量子点占薄膜的质量分数为0.5-90％。
  11. 根据权利要求10所述的薄膜，其特征在于，所述阻隔高分子材料的重均分子量在10-30万之间，所述量子点占薄膜的质量分数为0.5-30％；
    或者，所述阻隔高分子材料的重均分子量在30-50万之间，所述量子点占薄膜的质量分数为0.5-66％；
    或者，所述阻隔高分子材料的重均分子量在50-150万之间，所述量子点占薄膜的质量分数为0.5-90％。
  12. 根据权利要求11所述的薄膜，其特征在于，所述量子点占薄膜的质量分数 为0.5-20％；
    和/或，所述阻隔高分子材料的载流子迁移率在10 -6cm 2V -1s -1以上。
  13. 根据权利要求1所述的薄膜，其特征在于，所述薄膜由高分子材料和分散在所述高分子材料中的量子点组成，所述高分子材料由两种阻隔高分子材料组成。
  14. 根据权利要求13所述的薄膜，其特征在于，
    所述两种阻隔高分子材料的重均分子量均高于10万；和/或，
    所述量子点占薄膜的质量分数为0.5-20％；和/或，
    所述两种阻隔高分子材料的载流子迁移率均在10 -6cm 2V -1s -1以上。
  15. 根据权利要求1所述的薄膜，其特征在于，所述高分子材料还包括至少一种电荷传输调节高分子材料，所述电荷传输调节高分子材料的重均分子量低于10万。
  16. 根据权利要求15所述的薄膜，其特征在于，所述电荷传输调节高分子材料占高分子材料的质量分数低于10％。
  17. 根据权利要求16所述的薄膜，其特征在于，所述高分子材料由一种阻隔高分子材料和一种电荷传输调节高分子材料组成。
  18. 根据权利要求15-17任一项所述的薄膜，其特征在于，所述阻隔高分子材料的载流子迁移率在10 -6cm 2V -1s -1以下，所述电荷传输调节高分子材料选自导电高分子，所述电荷传输调节高分子材料占高分子材料的质量分数为0.5-5％。
  19. 根据权利要求15-17任一项所述的薄膜，其特征在于，所述阻隔高分子材料的载流子迁移率在10 -6cm 2V -1s -1以上，所述电荷传输调节高分子材料选自非导电高分子，所述电荷传输调节高分子材料占高分子材料的质量分数为5-10％。
  20. 根据权利要求1所述的薄膜，其特征在于，所述高分子材料由两种阻隔高分子材料和一种电荷传输调节高分子材料组成，所述电荷传输调节高分子材料的重均分子量低于10万，所述电荷传输调节高分子材料占高分子材料的质量分数低于10％。
  21. 根据权利要求20所述的薄膜，其特征在于，所述两种阻隔高分子材料的载流子迁移率均在10 -6cm 2V -1s -1以下，所述电荷传输调节高分子材料选自导电高分子，所述电荷传输调节高分子材料占高分子材料的质量分数为0.5-5％。
  22. 根据权利要求20所述的薄膜，其特征在于，所述两种阻隔高分子材料的载 流子迁移率均在10 -6cm 2V -1s -1以上，所述电荷传输调节高分子材料选自非导电高分子，所述电荷传输调节高分子材料占高分子材料的质量分数为5-10％。
  23. 根据权利要求18或21所述的薄膜，其特征在于，所述导电高分子选自聚乙炔、聚苯硫醚、聚苯胺、聚吡咯和聚噻吩中的一种。
  24. 根据权利要求19或22所述的薄膜，其特征在于，所述非导电高分子选自酚醛树脂、聚乙烯、聚二甲基硅氧烷、聚苯乙烯、聚甲基丙烯酸酯、聚丙烯酸酯和聚碳酸酯中的一种。
  25. 根据权利要求17所述的薄膜，其特征在于，所述阻隔高分子材料为TFB，所述电荷传输调节高分子材料为PMMA。
  26. 一种薄膜的制备方法，其特征在于，包括步骤：
    将量子点和高分子材料混合在分散介质中；
    将混合后的溶液制成薄膜，得到所述薄膜；
    其中所述高分子材料包括至少一种阻隔高分子材料，所述阻隔高分子材料的重均分子量高于10万。
  27. 根据权利要求26所述的薄膜的制备方法，其特征在于，所述量子点为油溶性量子点，所述油溶性量子点的表面配体为硫醇或羧酸。
  28. 根据权利要求27所述的薄膜的制备方法，其特征在于，所述量子点选自含Cd和Te的II-VI族量子点。
  29. 根据权利要求26所述的薄膜的制备方法，其特征在于，所述薄膜中，所述量子点的质量分数为0.5-20％。
  30. 根据权利要求26至29任一项所述的薄膜的制备方法，其特征在于，所述阻隔高分子材料选自PVK及其衍生物、TFB及其衍生物、poly-TPD及其衍生物和MEH-PPV及其衍生物中的一种或多种。
  31. 一种QLED器件，所述QLED器件包括量子点发光层，其特征在于，所述量子点发光层为权利要求1-25任一项所述薄膜。
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