WO2018035948A1 - 发光二极管装置、其制备方法和基于其的显示装置 - Google Patents

发光二极管装置、其制备方法和基于其的显示装置 Download PDF

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WO2018035948A1
WO2018035948A1 PCT/CN2016/102252 CN2016102252W WO2018035948A1 WO 2018035948 A1 WO2018035948 A1 WO 2018035948A1 CN 2016102252 W CN2016102252 W CN 2016102252W WO 2018035948 A1 WO2018035948 A1 WO 2018035948A1
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quantum dots
zns
energy transfer
range
shell
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French (fr)
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王允军
孔祥兴
王军佐
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苏州星烁纳米科技有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H10K50/121—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants for assisting energy transfer, e.g. sensitization
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

Definitions

  • the present invention relates to the field of display product manufacturing technology, and in particular to a light emitting diode device including a quantum dot and an energy transfer molecule, and a method of fabricating the same, including a display device of the light emitting secondary light device.
  • Quantum dots are nano-sized semiconductor nanocrystals with controlled surface chemical states and dimensionally dependent optical properties. Quantum dots can be photoluminescent and electroluminescent. In display device applications, quantum dots are no less inferior to organic light-emitting diodes (OLEDs), and have the following advantages: 1) lifetime, quantum dots composed of inorganic cores, with potential long life; 2) color purity, quantum dots generated There are many different types of colors, providing an improved super visual experience for end users; 3) flexibility, quantum dots are soluble in both water and non-aqueous solvents, which provides more for the production of display devices of all sizes choose and reduce production, handling and disposal costs.
  • OLEDs organic light-emitting diodes
  • a typical QLED structure consists of a transparent anode on which an organic hole transport layer is deposited, followed by a layer of colloidal quantum dots, an organic electron transport layer, and a metal cathode.
  • Two electroluminescent mechanisms have been proposed in QLEDs. The first mechanism is that electrons and hole carriers transported through the organic charge transport layer are directly injected into the quantum dots where they form an excited state capable of radiating recombination.
  • the second mechanism is a high-energy excited state formed in an organic molecule surrounded by a quantum dot film, which transfers the excited state energy to the quantum dot, and then causes the quantum dot to emit light.
  • quantum dot excited states are formed in the recombination of holes and electrons.
  • the holes are derived from organic or polymeric layers, and electrons are also derived from organic and polymeric layers.
  • This mechanism has two main problems. First, a portion of the holes and/or electrons formed by the organic and polymeric layers recombine directly and result in emission of the main matrix.
  • One way to overcome this problem is to create a hybrid organic/inorganic multilayer with an external quantum efficiency of 0.5% by sandwiching a single layer of quantum dots between the organic electron and the hole transport layer by a phase separation process. QLED structure.
  • the above sandwich structure will help balance carrier injection.
  • the second QLED is its low internal quantum efficiency, which is due to the existence of energy level barriers of quantum dots, especially when they are coated with an organic ligand, because of the low conductivity of semiconductor nanocrystals. This makes it more difficult for carriers to be injected into quantum dots, and thus the problem of low quantum efficiency deteriorates.
  • the thickness of the quantum dots is a single layer configuration (less than 10 nm). Increasing the thickness of the quantum dots results in a decrease in the brightness of the LEDs. This may be caused by the difficulty of implanting a carrier fluid into the quantum dot multilayer because the HOMO and LOMO of the quantum dots are much lower than those of organic semiconductors. In multi-layer quantum dot devices, it is currently the result of tunneling of quantum dots in an electric field. In order to increase the brightness of the LED, it is necessary to operate the LED at a high voltage, which results in high thermal efficiency and low stability of the device.
  • the quantum dots are encapsulated in a thin layer of surfactant such as oleic acid, oleylamine or trialkyloxonium.
  • surfactant such as oleic acid, oleylamine or trialkyloxonium.
  • the flexible alkyl chain on the nanoparticles makes it susceptible to deformation/damage under electric and heating conditions, thereby affecting the life of the device.
  • a stable quantum dot luminescent layer is necessary for QDLEDs.
  • QDLEDs In general, low-brightness and low external quantum efficiency QDLEDs come from two main reasons: very thin luminescent quantum dot single layer, and small defects in the luminescent layer can cause degradation of device performance (from hole or electron transport materials). Radiation generated in the process; lack of long-term thermal stability of the quantum dot structure. In order to improve the brightness of QLED, it has been reported that quantum dots are coated on the surface of the hole transporting material to form green and red quantum dots/donor hybrids. These devices have better electroluminescence properties, but are inevitably The ground shines from the subject.
  • hole transport materials and electron transport materials in applied organic light emitting diodes can also be used in green and red light emitting QLEDs because of their broadband system.
  • the energy of the excited state in the hole transporting material and the electron transporting layer can be efficiently injected into the QLED, and thus it is easy to obtain narrow photoluminescence from the quantum dot.
  • the development of new carrier transport materials is critical to the successful development of deep blue to violet LEDs.
  • current QLEDs include cadmium-containing quantum dots such as cadmium selenide, cadmium sulfide or core-shell structures of cadmium selenide/zinc selenide/zinc sulfide, cadmium sulfide/zinc sulfide.
  • cadmium-containing quantum dots such as cadmium selenide, cadmium sulfide or core-shell structures of cadmium selenide/zinc selenide/zinc sulfide, cadmium sulfide/zinc sulfide.
  • the present invention provides a light emitting diode device including quantum dots and energy transfer molecules, which can effectively enhance charge injection into the light emitting layer.
  • the anode and cathode are used for DC voltage to cause current to flow in the device and emit radiation in the form of ultraviolet, visible or near-infrared light to illuminate the device.
  • the luminescent layer includes quantum dots and energy transfer molecules, and the energy transfer molecules have high electron and/or hole carrier injection capability as a dispersion medium of the quantum dots, and are performed by click chemistry with the quantum dots. Cross-linking.
  • the invention provides a new charge injection method for QLED, and the energy transfer molecule has the functions of quantum dot dispersion solvent and energy transfer.
  • the QLED constructed by this method promotes the injection of charges in quantum dots from the energy transfer process of the energy transfer molecules mixed near the surface of the quantum dots to the quantum dot nucleus, especially the injection of electrons from the cathode vector sub-points.
  • the energy transfer molecule has high fluorescence quantum efficiency, reversible redox properties in a non-aqueous electrolyte, and a band gap wider than the quantum dots, thereby obtaining efficient electron and/or hole carrier injection. .
  • the quantum dot and the energy transfer molecule form a composite layer by click chemical crosslinking, wherein the energy transfer molecule comprises one of an ethynyl group or an azido functional group, and a ligand terminal group of the quantum dot Any one of an ethynyl group or an azide group is included; after the heat treatment, the quantum dot and the energy transfer molecule are crosslinked to form a composite layer.
  • the energy transfer molecules are molecules, oligomers or polymers, including at least one of the following groups of molecules or their derivatives:
  • the organometallic fluorescent emitter is hybridized with a wide three-line bandgap substrate to achieve high brightness LEDs.
  • a ligand with a long alkyl chain compound to bind to the surface of the quantum dot.
  • the energy transfer molecule is 2,7-bis(diphenylphosphonium oxide)-9,9-octylfluorene (PO8), and the presence of the PO8 can effectively enhance electron injection into the quantum dot/PO8 In the hybrid layer, and blocking the hole carrier from entering the hybrid layer, the current at the same applied voltage can be reduced.
  • the composite layer of the quantum dot and the PO8 is prepared by spin coating a mixed solution.
  • the substrate is a glass or a flexible substrate.
  • the anode material is a conductive metal oxide or a conductive polymer.
  • the cathode material includes any one of Al, Ca, Ba, Ca/Al, and Ag.
  • the hole transport layer comprises at least one of the group consisting of a tertiary aromatic amine, a thiophene oligomer, a thiophene polymer, a pyrrole oligomer, a vinyl benzene oligomer, a vinyl phenylene Polymer, vinyl carbazole oligomer, vinyl carbazole polymer, fluoro oligomer, fluoropolymer, ethynyl phenylene oligomer, ethynyl phenylene polymer, phenylene oligomer, phenylene Polymer, acetylene oligomer, acetylene polymer, phthalocyanine, phthalocyanine derivative, laverine and procalin derivatives.
  • a tertiary aromatic amine a thiophene oligomer, a thiophene polymer, a pyrrole oligomer, a vinyl benzene oligomer
  • the electron transport layer comprises at least one of the following groups of molecules: oxadiazoles, oxadiazole derivatives, oxazoles, oxazole derivatives, isoxazole, isoxazole derivatives , thiazole, thiazole derivatives, 1,2,3-triazole, 1,2,3-triazole derivatives, 1,3,5-triazines, 1,3,5-triazine derivatives, Quinoxaline, quinoxaline derivative, pyrrole oligomer, pyrrole polymer, vinyl benzene oligomer, vinyl benzene polymer, vinyl carbazole oligomer, vinyl carbazole polymer, fluorine Oligomer, fluoropolymer, ethynyl phenylene oligomer, ethynyl phenylene polymer, benzoic oligomer, phenylene polymer, thiophene oligomer, thiophene polymer, ace
  • the quantum dot comprises one of quantum dots of the following structure:
  • CdS/ZnS core/shell structure CdS/ZnSe/ZnS core/shell/shell structure or CdZnS/ZnSe/ZnS core/shell/shell structure quantum dots, having a size in the range of 1.5-10 nm;
  • PbS/ZnS core/shell structure quantum dots having a size in the range of 1.5-10 nm;
  • PbSe/ZnS core/shell structure quantum dots having a size in the range of 1.5-10 nm;
  • the quantum dot comprises at least one of the following quantum dots: a ZnSe/ZnSeS/ZnS quantum dot having an electroluminescence peak in the range of 380-450 nm and a cadmium or mercury content of less than 0.001% by mass; Luminescence peaks in the range of 480-900 nm, cadmium or mercury content less than 0.001% by mass of ZnTe/ZnSe/ZnS quantum dots, ZnTe/ZnTeSe/ZnSe quantum dots or ZnTe/ZnTeSe/ZnS quantum dots; electroluminescence peak at 500 CdSe/CdZnS/ZnS quantum dots or CdSe/CdZnSe/ZnSe/ZnS quantum dots with a cadmium or mercury content of less than 50% in the range of -700 nm.
  • the molar ratio of the quantum dots to the energy transfer molecules in the composite layer of the quantum dots and the energy transfer molecules is between 100,000:1 and 1:100,000.
  • the light-emitting diode device has electroluminescence having a wavelength in the range of 380-900 nm when a direct current voltage of 0-30 V is applied between the anode and the cathode.
  • Another object of the present invention is to provide a method of fabricating a light emitting diode device comprising quantum dots and energy transfer molecules as described above, comprising the steps of:
  • a conductive layer is disposed on the anode layer
  • a light-emitting layer is then disposed on the hole transport layer.
  • the luminescent layer is a composite layer of the quantum dots and the energy transfer molecules, and the preparation of the composite layer is selected from one of the following three steps:
  • a cathode layer is disposed on the electron transport layer.
  • Another object of the present invention is to provide an electronic display device including the above-described light emitting diode device including quantum dots and energy transfer molecules capable of outputting visual information or tactile information, which is operated as an input information by an electric signal
  • the quantum dot light emitting diode device can be used for color display of monochrome, two-color, three-color, four-color or more colors, wherein the three-color display comprises a combination of blue-violet, green and red, or a combination of blue, green and red;
  • the four-color display includes a combination of purple blue, green, yellow, and red.
  • the electronic display device includes a color gamut covering a plurality of colors, more than the National Television Commission (CIE) based 19692 ° color gamut.
  • CIE National Television Commission
  • the present invention increases the ability of quantum dots to generate excitons by simply dispersing quantum dots in the main body of the energy transfer molecule, and the high electron and/or hole carrier injection capability of the energy transfer molecules,
  • the long alkyl chain possessed by the energy transfer molecule allows it to bind well to the ligand group on the surface of the quantum dot, which is more conducive to the energy transfer process between the quantum dot and the energy transfer molecule, thereby obtaining a high electroluminescence.
  • the luminous efficiency provides a new and effective method and idea for the injection of holes/electrons in quantum dots. Therefore, the present invention can improve the performance of quantum dot electroluminescent devices.
  • 1a, 1b, and 1c are schematic views showing the multilayer structure of the QLED device of the present invention.
  • Figure 2 shows the chromaticity values and colors of the 10 QLED device examples proposed by the present invention
  • Figure 3 shows an energy transfer molecule (2,7-bis(diphenylphosphonium oxide)-9,9-octylfluorene, PO8) and three quantum dot solutions (blue-violet ZnSe/ZnSeS/ZnS quantum) Absorption spectra and photoluminescence spectra of CdSe/CdZnS/ZnS quantum dots emitting green light and CdSe/CdZnS/ZnS quantum dots emitting red light;
  • Figure 4 shows the energy transfer process for a QLED in operation.
  • the hybrid layer comprises ZnSe/ZnSeS/ZnS quantum dots and is surrounded by energy transfer molecules PO8;
  • Figure 5 shows the energy transfer process of a QLED with a multilayer structure as shown in Figure 1c and a hybrid layer consisting of quantum dots and energy transfer molecules that facilitate electron and hole injection into the quantum.
  • 6a, 6b, 6c, 6d, and 6e show exemplary structures of molecular classes (a, b, c, d) and oligomers/polymers (e) of the energy transfer molecule of the present invention
  • Figures 7a and 7b show the synthesis of the energy transfer molecules (a) and (e) of the two examples of Figure 6;
  • Figure 8a and Figure 8b show scanning electron micrographs of quantum dots at two different magnifications in the present invention.
  • the size of ZnSe/ZnSeS/ZnS quantum dots with core/shell/shell structure is about 9 nm, photoluminescence
  • the peak wavelength is at 440 nm;
  • Figure 9 shows an energy level embodiment of the material used in the QLED of the present invention.
  • Figures 10a, 10b and 10c show the electroluminescent properties of a blue-violet QLED, which is partly composed of ZnSe/ZnSeS/ZnS quantum dots and an energy transfer molecule PO8;
  • Figure 11a and Figure 11b show the (a)J-V-I curve and (b) EQE and luminescence performance curves of the violet-emitting QLED, which are partially composed of ZnSe/ZnSeS/ZnS quantum dots and energy transfer molecules PO8;
  • Figure 12a and Figure 12b show the effect of the molar ratio of quantum dots to energy transfer molecule PO8 on device performance.
  • Figures (a) and (b) show the luminescence brightness and EQE of QLEDs constructed with ZnSe/ZnSeS/ZnS quantum dots, respectively. The effect of PO8 content.
  • Figure 13 shows the stability of the QLED device, cycled 1200 times at intermittent switching operating voltage 0-6v;
  • Figure 14 shows a stable curve of a violet-emitting ZnSe/ZnSeS/ZnS QLED device
  • Figure 15a, Figure 15b and Figure 15c show the electroluminescent properties of a green-emitting QLED consisting in part of a CdSe/CdZnS/ZnS quantum dot and an energy transfer molecule PO8;
  • Figures 16a and 16b show (a) J-V-I curves and (b) EQE and luminous efficiency curves for green-emitting QLEDs, which are partially composed of CdSe/CdZnS/ZnS quantum dots and energy transfer molecules PO8;
  • Figure 17a, Figure 17b and Figure 17c show the electroluminescent properties of a red-emitting QLED consisting in part of a CdSe/CdZnS/ZnS quantum dot and an energy transfer molecule PO8;
  • Figures 18a and 18b show (a) J-V-I curves and (b) EQE and luminescence performance curves for red-emitting QLEDs, which are partially composed of CdSe/CdZnS/ZnS quantum dots and energy transfer molecules PO8.
  • FIG. 1 is a schematic view showing a multilayer structure of a QLED device according to an embodiment of the present invention, including an anode, a hole transport layer, a quantum dot and an energy transfer molecule, and an electron transport layer, in order from bottom to top. And a cathode.
  • the electron transport layer is optional.
  • the anode is used to connect the positive electrode of the external power source.
  • the anode material is a conductive metal oxide or a conductive polymer, preferably indium tin oxide (ITO), and the thickness of the layer where the anode is located may be 10-1000 nm, preferably 100-400 nm.
  • the anode surface is also provided with a conductive layer capable of injecting holes.
  • the conductive layer is preferably a coating of poly 3,4-ethylenedioxythiophene:polystyrene sulfonate (PEDOT:PSS) in a molar ratio of 5:1, the PEDOT The PSS coating may have a thickness of from 5 to 100 nm, preferably from 10 to 50 nm.
  • the electrically conductive layer is disposed on the anode by spin coating.
  • the hole transport layer is used for injecting and transporting holes, mainly for transporting holes to the light-emitting layer, and the hole transport layer may be selected from one of the following groups: tert-arylamine, thiophene oligomerization , thiophene polymer, pyrrole oligomer, vinyl benzene oligomer, vinyl benzene polymer, vinyl carbazole oligomer, vinyl carbazole polymer, fluoro oligomer, fluoropolymer, Ethynyl phenylene oligomer, ethynyl phenylene polymer, phenylene oligomer, phenylene polymer, acetylene oligomer, acetylene polymer, phthalocyanine, phthalocyanine derivative, laverine and laverine derivative .
  • the hole transport layer is a vinyl carbazole polymer (PVK), and the hole transport layer is disposed on the conductive layer by spin coating, the hole transport layer
  • the thickness may be from 20 to 600 nm, preferably from 50 to 200 nm.
  • the anode injects holes into the conductive layer, and the conductive layer further injects holes into the hole transport layer and transports it to the light emitting layer.
  • the luminescent layer of the quantum dot and the energy transfer molecule is mainly used for luminescence, and luminescence is due to recombination of holes and electrons from holes and electron transport layers located above and below the luminescent layer.
  • the luminescent layer has three modes, as shown in Figure 1: a) the energy transfer molecule is donor type, which can promote electron injection into the quantum dot; b) the energy transfer molecule is the acceptor The type can promote the injection of holes into the quantum dots; c) the energy transfer molecules are donor-acceptor type, which can simultaneously promote the simultaneous injection of electrons and holes into the quantum dots.
  • the quantum dots are dispersed in the energy transfer molecules, and the energy transfer molecules are molecules, oligomers or polymers.
  • the energy transfer molecule is prone to generate electrons or/and holes, and the energy transfer molecule has a band gap wider than the quantum dot, and at the same time, the energy transfer molecule has a long alkyl chain which can be well
  • the surface of the quantum dots is combined and cross-linked by click chemistry. The above method leads to the injection of electron or/and hole vector sub-points, thereby solving the problem that excitons in the quantum dots are not easily injected.
  • the quantum dots comprise one of the following structured quantum dots:
  • CdS/ZnS core/shell structure CdS/ZnSe/ZnS core/shell/shell structure or CdZnS/ZnSe/ZnS core/shell/shell structure quantum dots, having a size in the range of 1.5-10 nm;
  • PbS/ZnS core/shell structure quantum dots having a size in the range of 1.5-10 nm;
  • PbSe/ZnS core/shell structure quantum dots having a size in the range of 1.5-10 nm;
  • the quantum dots comprise cadmium having an electroluminescence peak in the range of 380-450 nm.
  • ZnSe/ZnSeS/ZnS quantum dots with a mercury content of less than 0.001% by mass electroluminescence peaks in the range of 480-900 nm, cadmium or mercury content less than 0.001% by mass of ZnTe/ZnSe/ZnS quantum dots, ZnTe/ ZnTeSe/ZnSe quantum dots or ZnTe/ZnTeSe/ZnS quantum dots; CdSe/CdZnS/ZnS quantum dots or CdSe/CdZnSe/ZnSe/ZnS quantum with electroluminescence peaks in the range of 500-700 nm and cadmium or mercury content less than 50% point.
  • the quantum dots emitting blue-violet light are preferably ZnSe/ZnSeS/ZnS quantum dots; the green-emitting quantum dots are preferably CdSe/CdZnS/ZnS quantum dots; and the red-emitting quantum dots are preferably CdSe/CdZnS/ ZnS quantum dots.
  • the energy transfer molecules are molecules, oligomers or polymers (molecule groups shown in Figure 6 or their derivatives, and (a)-(d) in Figure 6 represent Molecular structure, (e) represents oligomer/polymer structure).
  • the energy transfer molecule has one of an ethynyl group or an azido functional group, and the ligand terminal group of the quantum dot has either one of an ethynyl group or an azide group; After the heat treatment, the quantum dots and the energy transfer molecules are crosslinked to form a composite layer.
  • the energy transfer molecule is PO8.
  • the molar ratio of the quantum dots to the energy transfer molecules is between 100,000:1 and 1:100,000, and the preparation of the composite layer is selected from one of the following three steps:
  • the light-emitting layer is disposed on the hole transport layer by spin coating, and the light-emitting layer may have a thickness of 10 to 300 nm, preferably a thickness of 40 to 100 nm.
  • the electron transport layer is mainly used to function to transport electrons to the light-emitting layer, and the electron transport layer is selected from one of the group consisting of oxadiazoles, oxadiazole derivatives, oxazoles, and oxazoles.
  • isoxazole isoxazole derivatives, thiazoles, thiazole derivatives, 1,2,3-triazole, 1,2,3-triazole derivatives, 1,3,5-triazines, 1,3,5-triazine derivative, quinoxaline, quinoxaline derivative, pyrrole oligomer, pyrrole polymer, vinyl benzene oligomer, vinyl phenylene polymer, vinyl fluorene Oxazole oligomer, vinyl carbazole polymer, fluoro oligomer, fluoropolymer, ethynyl phenylene oligomer, ethynyl phenylene polymer, phenylene oligomer, phenylene polymer, thiophene oligomerization , thiophene polymer, acetylene oligomer, acetylene polymer, TiO 2 nanoparticles, ZnO nanoparticles, SnO nanoparticles
  • the cathode material is used to connect a negative electrode of an external power source.
  • the cathode material comprises any one or more of Al, Ca, Ba, Ca/Al, Ag, in a specific
  • the cathode material is Al.
  • the cathode material may have a thickness of 10 to 600 nm, preferably a thickness of 50 to 200 nm.
  • the cathode material is disposed on the electron transport layer by a vaporization method, and the cathode layer has a thickness of 200 nm.
  • the manufacturing process of the embodiment of the present invention involves a specific deposition process for the anode, the hole transport layer, the light emitting layer, the electron transport layer, and the cathode, which may include, but is not limited to, spin coating, spray coating, printing, and vacuum steaming.
  • a specific deposition process for the anode, the hole transport layer, the light emitting layer, the electron transport layer, and the cathode which may include, but is not limited to, spin coating, spray coating, printing, and vacuum steaming.
  • spin coating spray coating
  • printing printing
  • vacuum steaming One of the plating.
  • Fig. 2 shows chromaticity values and colors (white small circles) of ten examples of QLED devices proposed in the embodiment of the present invention. Chromaticity values and colors show four blue-violet QLEDs, three green QLEDs, and three red QLEDs in the CIE 19762° color gamut. The experimental results in the figure show that among the 10 devices, the color of 9 QLEDs exceeds the range of the NTSC standard color gamut (black triangle).
  • the main forming material of the anode is ITO
  • the main forming material of the conductive layer is PEDOT:PSS
  • the main forming material of the hole transport layer is PVK
  • the luminescent layer is ZnSe/ZnS core-shell quantum dot.
  • the main forming material of the composite layer and the cathode of PO8 is Al.
  • Figure 3 shows the energy transfer molecule PO8 and three quantum dot solutions (blue-violet ZnSe/ZnSeS/ZnS quantum dots, green-emitting CdSe/CdZnS/ZnS quantum dots, and red light) in a specific embodiment.
  • CdSe/CdZnS/ZnS The absorption spectrum and photoluminescence spectrum of quantum dots).
  • the absorption wavelength of PO8 is in the range of 270-330 nm, and its photoluminescence wavelength is in the range of 310-400 nm, all falling within the absorption spectrum range of three kinds of quantum dots. This large degree of spectral overlap is extremely large.
  • FIG. 4 shows the energy transfer process of a QLED in operation in a particular embodiment, in which the luminescent layer comprises ZnSe/ZnSeS/ZnS quantum dots and the energy transfer molecule PO8 is encapsulated.
  • the PO8 molecule can inject electrons from the cathode layer and transport it to similar quantum dots. The injected electron-hole pairs form an excited state, from which a photon is generated and emitted.
  • Figure 5 shows the energy transfer process of a QLED with an luminescent layer composed of quantum dots and a specific energy transfer molecule in a multi-layer structure as shown in Figure 1c.
  • the energy transfer molecules shown in the figure can simultaneously promote electrons. And holes are injected into the quantum dots.
  • FIG. 8 (a) and (b) of Fig. 8 respectively show scanning electron micrographs of quantum dots at high magnification and low magnification in the examples of the present invention.
  • the experimental results show that the size of ZnSe/ZnSeS/ZnS quantum dots with core/shell/shell structure is about 9 nm.
  • Figure 10 shows the electroluminescent properties of a blue-violet-emitting QLED in an embodiment of the invention, which is partially composed of ZnSe/ZnSeS/ZnS quantum dots and energy transfer molecules PO8.
  • (a) show an optical image of the bright blue-violet light of the device in operation.
  • (c) Corresponding electroluminescence spectrum, the results show that the QLED has an emission peak wavelength of about 440 nm and a very sharp half-width (14.6 nm).
  • Figure 11 shows (a) JVI curve, (b) EQE and luminous efficiency curves of a QLED composed of ZnSe/ZnSeS/ZnS quantum dots and an energy transfer molecule PO8 in a specific embodiment of the present invention.
  • the maximum EQE is 3.4%
  • the maximum luminous efficiency is 23 lm/W.
  • Figure 12 is a graph showing the effect of the molar ratio of quantum dots to the energy transfer molecule PO8 on device performance in a specific embodiment of the present invention
  • Figures (a) and (b) are QLEDs constructed with ZnSe/ZnSeS/ZnS quantum dots, respectively.
  • the luminescence brightness and the change of EQE with the content of PO8 it can be seen that in a certain molar ratio range (1:0-1:25), the luminescence brightness and EQE increase significantly with the increase of the molar ratio of quantum dots to PO8 molecules.
  • Figure 13 shows the stability of the QLED device in a specific embodiment of the present invention. It can be seen that the QLED brightness can still maintain good stability after the switching cycle of 1200 times under the intermittent operating voltage of 0-6v.
  • Figure 14 shows an embodiment of the present invention, the violet-ZnSe / ZnSeS / ZnS QLED means of stable curves, experimental results show that, under 10cd / 2 m emission luminance, half-life of 133 hours QLED 2
  • Figure 15 shows the electroluminescent properties of a green-emitting QLED in an embodiment of the invention, which is partially composed of CdSe/CdZnS/ZnS quantum dots and energy transfer molecules PO8.
  • Figure (a) shows the electroluminescence spectrum of the device operating at a voltage of 6-14 V, and (b) and (c) optical images showing the bright green light of the device in operation.
  • FIG. 16 shows (a) JVI curve, (b) EQE, and luminous efficiency curve of the green-emitting QLED in the embodiment of the present invention, which is partially composed of CdSe/CdZnS/ZnS quantum dots and energy transfer molecules PO8, which can be seen in the figure. Its maximum luminous brightness is 3800 cd/m 2 .
  • Figure 17 is a graph showing the electroluminescence properties of a red-emitting QLED in an embodiment of the present invention, which is partially composed of a CdSe/CdZnS/ZnS quantum dot and an energy transfer molecule PO8.
  • (a) represents the electroluminescence spectrum of the device operating at a voltage of 6-16 V
  • Figure 18 shows (a) JVI curve, (b) EQE and luminous efficiency curves of a red-emitting QLED in an embodiment of the present invention. It is partially composed of CdSe/CdZnS/ZnS quantum dots and energy transfer molecule PO8. As can be seen, the maximum luminance is 6300 cd/m 2 , the corresponding wavelength is 625 nm, the maximum EQE is 0.63%, and the corresponding luminance is 68 cd/m 2 .
  • the reaction was stirred at -70 °C for an additional 3 hours before quenching of 2 ml of degassed methanol.
  • the volatiles were removed under reduced pressure to leave an oily liquid.
  • ITO chips covered with a polymer Twelve pre-patterned ITO chips covered with a polymer were placed on a glass substrate and immersed in a 5% aqueous sodium hydroxide solution at 80 ° C for 5 min. The above procedure was repeated, and then the chip was washed with nano-pure water, 20% ethanolamine aqueous solution, and sonicated for 15 min, followed by washing and drying with sufficient nano-pure water. Finally, the ITO chip is loaded into the plasma cleaning chamber to clean the surface of the ITO coated device.
  • a pre-cleaned ITO coated device chip coated with a conductive layer was applied to a 200 ⁇ l molar ratio of 5:1 PEDOT:PSS aqueous solution at a rotational speed of 1750 rpm using a spin coating apparatus. Surface, rotation time 60s.
  • the device was then vacuum dried in a 180 ° C container for 20 min, cooled to room temperature, and further coated with another layer of hole transport layer polybutyl butyl-benzidine (molecular weight > 50,000) on the device, using 100 ⁇ l
  • the chlorobenzene dispersion of wt 0.05% polymer was spin-coated at a rotation speed of 2500 rpm and a rotation time of 60 s.
  • the apparatus was then dried in a vacuum vessel at 160 ° C for 40 min.
  • the device is cooled and a quantum dot luminescent layer and energy transfer molecules are spin coated thereon.
  • the process of preparing a mixture of quantum dots and energy transfer molecules is to dissolve the quantum dots purified in n-hexane/toluene, change the concentration to adjust the absorbance at 400 nm to about 1.0, and then add 0.01% by mass of energy to the solution. Transfer molecules.
  • the process of spin-coating the mixed solution on the surface of the device sheet was as follows: 100 ⁇ L of the solution was added to the surface of the chip, and spin-coated at a rotation speed of 2000 rpm for 60 seconds, and then the chip was dried under a vacuum of 140 ° C for 30 minutes, and cooled. To normal temperature. Then, a cathode layer of a 200 nm-thick aluminum layer was vapor-deposited by a method of thermal evaporation in a vacuum of 2 ⁇ 10 -6 Torr. The device was then closed, wrapped in epoxy resin and irradiated with a UV lamp for 10 min.
  • the electrical and optical properties of QLED are tested in a system powered by the KEITHLEY Series 2400 Multi-Source Meter (with LabTracer 2.0 software), an Ossila OLED/OPV test platform, a NEWPORT 2835C multi-function optical source, and a calibration NEWPORT
  • the construction of the green CdSe/CdSeS/ZnS QLED was similar to that of the four-violet QLEDs in the above examples, except that the green CdSe/CdSeS/ZnS quantum dots modified with surface ligands replaced the ZnSe/ZnSeS/ZnS quantum dots.
  • red-light CdSe/CdSeS/ZnS QLED was similar to that of the purple-emitting QLED of Example 4 above, except that the ZnSe/ZnSeS/ZnS quantum dots were replaced with red CdSe/CdSeS/ZnS quantum dots modified with surface ligands.
  • the maximum EQE is 3.4%, the maximum luminance is 38 cd/m 2 , and the emission peak is 440 nm.
  • the storage time is greater than 3 months.
  • the device When tested in air and in the surrounding environment, the device has a half-life of more than 130 hours.
  • Electroluminescence in the cyan-red range (480-700 nm) wavelength of visible light.
  • the green light QLED has a maximum brightness of 3000 cd/m 2 and an emission peak at 525 nm.
  • the maximum brightness of the red QLED is 6300 cd/m 2 and the emission peak is 625 nm.
  • the maximum luminous efficiency was 4.57 lm/W, and the luminance of the light was 41.4 cd/m 2 .
  • the red QLED's turn-on voltage is as low as 1.9V, and the green QLED's turn-on voltage is as low as 2.2V.
  • the shelf life is greater than 6 months.
  • the device has a half-life of more than 130 hours in air and in the surrounding environment.

Abstract

提供了一种发光二极管装置及其制备方法和电子显示设备，所述发光二极管装置包括衬底、阳极、空穴传输层、发光层、电子传输层以及阴极，发光层由量子点和能量转移分子结合而成，能量转移分子与量子点通过点击化学进行交联。能量转移分子作为量子点的分散介质具有高电子/空穴载流子注入能力，可促进能量转移分子中的激子产生，实现从能量转移分子到荧光量子点之间的有效能量转移。在一定的电压下，该装置可以在380-900nm的波长范围内发光，最大发射峰值从紫外到深红光范围。

Description

发光二极管装置、其制备方法和基于其的显示装置 技术领域
本发明涉及显示产品制造技术领域，尤其涉及一种包括量子点和能量转移分子的发光二极管装置及其制备方法，包含该发光二级光装置的显示装置。
背景技术
量子点是纳米尺寸的半导体纳米晶体，具有可控的表面化学状态和取决于尺寸的光学性质。量子点可以光致发光和电致发光。在显示装置应用中，量子点毫不逊色于有机发光二极管(OLED)，并且具有以下优点：1)寿命，量子点由无机核组成，具有潜在的长寿命；2)颜色纯度，量子点产生的颜色种类非常多，为终端用户提供了改进的超级视觉体验；3)灵活性，量子点在水和非水溶剂中均可溶，这为制备各式各样大小的显示装置提供了更多的选择，并且减少了生产、操作和处理成本。
一个典型的QLED结构由一个透明的阳极，其上沉积了一层有机空穴传输层，接着再沉积一层胶体量子点单层，一个有机电子传输层，以及一个金属阴极。QLED中已经有两种电致发光机理被提出。第一种机理为，通过有机电荷传输层传输的电子和空穴载体，被直接注入到量子点中，这里他们可以形成能够辐射重组的激发态。第二种机理为，包覆在量子点膜片周围的有机分子中形成的高能激发态，将激发态能量共振转移给量子点，然后使得量子点发光。
尽管在设备装配和高质量量子点合成上有所进步，但QLED的机理还是一样的：量子点激发态在空穴和电子的重新复合中形成。空穴来自有机或者高分子层，电子也来自有机和高分子层。这个机理有两个主要问题。第一，有机和聚合层形成的一部分空穴和/或电子，直接重组并导致主矩阵的发射。克服这个问题的一种方法是，通过一个相分离过程来使量子点单层夹在有机电子和空穴传输层之间，来建立一个具有外量子效率0.5％的杂化的有机/无机多层QLED结构。假定薄量子点层有助于减轻低量子点载流子迁移率的影响，那么上述夹层结构将有助于平衡载流子注入。然而，在高亮条件下，即使这些装置也可以展示出明显的从有机基质中发射的性能。第二种QLED的主要缺点是其出现低内量子效率，这源自量子点的能级壁垒的存在，尤其是当他们包覆了一层有机配体的时候，由于半导体纳米晶体具有低导电性，使得载流子更难注入到量子点，因而低量子效率的问题恶化了。
在最好的QLED中，量子点的厚度为单层配置(小于10nm)。增加量子点的厚度，导致LED亮度的降低。这可能是由载流体难以注入到量子点多层中去引起的，因为量子点的HOMO和LOMO远远低于有机半导体。在多层量子点装置中，目前就是电场中量子点的隧道效应的结果。为了提高LED的亮度，需要高电压运行LED，这会导致设备的高热效应和低稳定性。此外，量子点包裹在一种薄层表面活性剂中，比如油酸，油胺或者三烷基氧瞵。纳米颗粒上的柔性烷基链使其容易在电场和加热的情况下变形/损伤，从而影响装置的寿命，一种稳定的量子点发光层对QDLED而言是必要的。
总的来说，低亮度和低外量子效率的QDLED来自两个主要原因：非常薄的发光量子点单层，发光层中很小的缺陷都会引起装置的性能下降(从空穴或者电子传输材料中产生的辐射)；缺乏长期热稳定的量子点结构。为了提高QLED的亮度，目前已经报道了在空穴传输材料的表面包覆量子点，形成绿色和红色的量子点/供体杂化体，这些装置具有较好的电致发光性能，但是不可避免地从主体发光。
典型的，应用的有机发光二极管中的空穴传输材料和电子传输材料也可以应用在绿色和红色发光QLED中，因为他们的宽带系。空穴传输材料和电子传输层中的激发态的能量可以有效地注入到QLED中，因而从量子点中获得窄的光致发光是容易的。然而，对蓝光发光二 极管而言，尤其是对紫光发光二极管(400-440nm)，宽带隙的有机p-型(用于空穴注入)和n-型(用于电子注入)半导体，都是OLED和QLED所需要的，发展新型的载体传输材料对深蓝到紫光LED的成功开发非常关键。
为了提高QLED的长期稳定性，量子点的交联已经被报道。1，7-二胺庚烷被用于交联绿色和红色量子点LED中的量子点。然而，发射层中的量子点仍然是单层结构，导致低亮度和低外量子效率(EQE)。在相II中，我们为蓝/紫光量子点发展了一种新型的供体-受体宿主。根据密度泛函理论，这些新的供体受体材料具有大带隙。这些供体受体材料包括功能乙炔烯，其可以经过与量子点表面包覆的叠氮烷基含硫配体通过点击化学交联。
在另一方面，当前的QLED包括含镉量子点，如硒化镉、硫化镉或者核壳结构的硒化镉/硒化锌/硫化锌、硫化镉/硫化锌。这些镉材料内在的毒性、处理和处置这些镉材料的高成本、以及基于镉的材料对环境会造成破坏的关注，限制了QLED的发展和应用包括需要全生命周期管理的大规模商业化和工业化生产。发展下一代的环境友好的QLED，较少含有或者其他有毒重金属，对发展量子点应用以及量子点技术向产品的商业化具有重要作用。
发明内容
针对现有QLED显示装置存在的上述问题，本发明提供了一种包括量子点和能量转移分子的发光二极管装置，能够有效地提升电荷注入到发光层中。
本发明的目的在于提供一种包括量子点和能量转移分子的发光二极管装置，包括：
a)空穴传输层，用于注入和传输空穴；
b)发光层，与所述空穴传输层接触；
c)电子传输层，与所述发光层接触，用于注入和传输电子到所述发光层；
d)阳极和阴极，用于直流电压，使电流在装置中流动，并以紫外线、可见光或者近红外光的形式发出辐射，使装置发光。
所述发光层包括量子点与能量转移分子，所述能量转移分子作为所述量子点的分散介质具有高的电子和/或空穴载流子注入能力，且与所述量子点通过点击化学进行交联。
本发明为QLED中提供了一种新的电荷注入方法，能量转移分子兼具量子点分散溶剂和能量转移的作用。通过该方法构建的QLED，从混合在量子点表面附近的能量转移分子到量子点核的能量转移过程，促进了量子点中电荷的注入，尤其是电子从阴极向量子点的注入。
优选地，所述能量转移分子具有高荧光量子效率、在非水电解质中可逆的氧化还原性质、以及比所述量子点宽的带隙，从而获得高效的电子和/或空穴载流子注入。
优选地，所述量子点与所述能量转移分子通过点击化学交联形成复合层，其中所述能量转移分子包括乙炔基或者叠氮基官能团中的一种，所述量子点的配体末端基包括乙炔基或者叠氮基两者中任何一个；经过热处理后，所述量子点和所述能量转移分子完成交联形成复合层。
优选地，所述能量转移分子为分子类、低聚物类或者聚合物类，包括以下分子组或者他们的衍生物中的至少一种：
Figure PCTCN2016102252-appb-000001
Figure PCTCN2016102252-appb-000002
其中R1，R2，R3为-(CH2)x-(CH＝CH)y-(CH2)z-R；R为以下基团中的一种-H，-Cl，-Br，-I，-OH，-OCH3，-OC2H5，-CHO，-COOCH3，-COOH，-CONH2，-COCl，-COBr，-COI，-NH2，-N+(CH3)3，-C(CH3)3，-CH＝CH2，-CCH，-C6H5，-C5H5，-N3，-OCN，-NCO，-CN，-NC，-NO2，-C5H4N，-SH，-S-S-H，-SOCH3，-RSO2H，-SCN，-NCS，-CSH，-PH2，瞵酰基，磷酸基，鸟嘌呤基，胞嘧啶基，腺嘌呤基，胸腺嘧啶基。具有上述结构的能量转移分子具有两个官能团位点，P＝O官能团有利于电子向量子点的注入、杂环氮官能团有利于空穴的注入。
有机金属荧光发射体与宽的三线带隙基底进行杂化，实现了高亮度LED。我们试图制备一个具有长烷基链化合物，来结合量子点表面的配体。优选地，所述能量转移分子为2，7-双(二苯基氧化瞵)-9，9-辛基芴(PO8)，所述PO8的存在，能够有效地提升电子注入到量子点/PO8杂化层中，并且阻挡空穴载体进入到杂化层，如此可以减少在同样外加电压下的电流。
优选地，所述量子点与所述PO8的复合层通过旋涂混合溶液的方法制备出来。
优选地，所述衬底为玻璃或者柔性衬底。
优选地，所述阳极材料为导电金属氧化物或者导电聚合物。
优选地，所述阴极材料包括Al、Ca、Ba、Ca/Al、Ag中的任意一种。
优选地，所述空穴传输层包括以下组的分子中的至少一种：叔芳胺、噻吩低聚物、噻吩聚合物、吡咯低聚物、乙烯基苯撑低聚物、乙烯基苯撑聚合物、乙烯基咔唑低聚物、乙烯基咔唑聚合物、氟低聚物、氟聚合物、乙炔基苯撑低聚物、乙炔基苯撑聚合物、苯撑低聚物、苯撑聚合物、乙炔低聚物、乙炔聚合物、酞菁、酞菁衍生物、紫菜碱和紫菜碱衍生物。
优选地，所述电子传输层包括以下组的分子中的至少一种：恶二唑类、噁二唑类衍生物、恶唑类、恶唑类衍生物、异恶唑、异恶唑衍生物、噻唑、噻唑衍生物、1，2，3-三唑、1，2，3-三唑衍生物、1，3，5-三嗪类、1，3，5-三嗪类化合物衍生物、喹喔啉、喹喔啉衍生物、吡咯低聚物、吡咯聚合物、乙烯基苯撑低聚物、乙烯基苯撑聚合物、乙烯基咔唑低聚物、乙烯基咔唑聚合物、氟低聚物、氟聚合物、乙炔基苯撑低聚物、乙炔基苯撑聚合物、苯撑低聚物、苯撑聚合物、噻吩低聚物、噻吩聚合物、乙炔低聚物、乙炔聚合物、TiO2纳米颗粒、ZnO纳米颗粒、SnO纳米颗粒、金纳米颗粒和银纳米颗粒。
优选地，所述量子点包括以下结构的量子点中的一种：
a)ZnSe/ZnSeS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
b)ZnTe/ZnSe/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
c)ZnTe/ZnTeS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
d)CdSe/CdZnS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
e)CdSe/CdZnSe/ZnSe/ZnS核/壳/壳/壳结构量子点，尺寸在1.5-9nm范围内；
f)CdTe/CdZnS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
g)CdS/ZnS核/壳结构、CdS/ZnSe/ZnS核/壳/壳结构或者CdZnS/ZnSe/ZnS核/壳/壳结构量子点，尺寸在1.5-10nm范围内；
h)CdTe/Inp/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
i)InP/ZnS核/壳结构量子点，尺寸在1.5-9nm范围内；
j)锰掺杂ZnSe：Mn2+/ZnS核/壳结构量子点，ZnSe/ZnS：Mn2+/ZnS核/壳/壳结构量子点或者ZnS：Mn2+/ZnS核/壳结构量子点，尺寸在1.5-9nm范围内；
k)铜掺杂ZnS：Cu2+/ZnS核/壳结构量子点或者ZnSe：Cu2+/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
l)ZnSe/InP/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
m)PbS/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
n)PbSe/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
o)CuInS2量子点和核/壳结构的CuInS2/ZnS量子点，尺寸在1.5-10nm范围内；
p)CuS/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
q)AgInS2量子点和AgInS2/ZnS核壳结构量子点，尺寸在1.5-10nm范围内
优选地，所述量子点包括以下量子点中的至少一种：具有电致发光峰值在380-450nm范围内，镉或者汞含量低于0.001％质量分数的ZnSe/ZnSeS/ZnS量子点；电致发光峰值在480-900nm范围内，镉或者汞含量低于0.001％质量分数的ZnTe/ZnSe/ZnS量子点、ZnTe/ZnTeSe/ZnSe量子点或者ZnTe/ZnTeSe/ZnS量子点；电致发光峰值在500-700nm范围内，镉或者汞含量低于50％的CdSe/CdZnS/ZnS量子点或者CdSe/CdZnSe/ZnSe/ZnS量子点。
优选地，所述量子点与所述能量转移分子的复合层中所述量子点与所述能量转移分子的摩尔比在100000∶1和1∶100000之间。
优选地，当在阴阳极之间加上0-30V的直流电压时，所述发光二极管装置具有波长在380-900nm范围内的电致发光。
本发明的另一个目的在于提供一种如上所述的包括量子点和能量转移分子的发光二极管装置的制备方法，包括以下步骤：
提供一衬底，在所述衬底上设置阳极层；
优选地，在所述阳极层上设置一层导电层；
接着在所述导电层上设置空穴传输层；
然后在所述空穴传输层上设置发光层。所述发光层为所述量子点与所述能量转移分子构成的复合层，所述复合层的制备选自以下三个步骤中的一个：
a)将所述量子点的溶液与所述能量转移分子的溶液混合；
b)将所述量子点的粉末溶解到所述能量转移分子的溶液；
c)将所述能量转移分子的固体或者浆料溶解到所述量子点的溶液中；
随后将电子传输层设置于所述发光层上；
最后将阴极层设置于所述电子传输层上。
本发明的另一个目的在于提供一种包括如上所述的包括量子点和能量转移分子的发光二极管装置的电子显示装置，能够输出视觉信息或者触觉信息，通过电信号作为输入信息来运转，所述量子点发光二极管装置可用于单色、双色、三色、四色或者更多颜色的彩色显示，其中，三色显示包括蓝紫色、绿色和红色的结合，或者蓝色、绿色和红色的结合；四色显示包括紫蓝色、绿色、黄色和红色的结合。
所述电子显示装置，包括一个覆盖多种颜色的色域，多于国家电视系统委员会基于国际照明委员会(CIE)的19762°色域。
本发明的有益效果：本发明通过将量子点简单分散在能量转移分子主体中，能量转移分子高的电子和/或空穴载流子注入能力，增加了量子点产生激子的能力，同时由于能量转移分子具备的长烷基链，使得其能很好的和量子点表面的配体基团结合，更加有利于量子点和能量转移分子之间的能量转移过程，从而获得了高的电致发光效率，为目前量子点空穴/电子的注入提供了一种新的、有效的方法和思路，因此，本发明可以提升量子点电致发光器件的性能。更进一步的，基于本发明对无镉量子点或者低镉量子点应用的良好实验结果，对发展下一代环境友好的QLED、量子点应用以及量子点技术相关产品的商业化具有重要意义。
附图说明
图1a、图1b、图1c显示了本发明的QLED装置的多层结构示意图；
图2显示了本发明提出的10个QLED装置示例的色度值和颜色；
图3显示了一种能量转移分子(2，7-双(二苯基氧化瞵)-9，9-辛基芴，PO8)和三种量子点溶液(发蓝紫光的ZnSe/ZnSeS/ZnS量子点，发绿光的CdSe/CdZnS/ZnS量子点，以及发红光的CdSe/CdZnS/ZnS量子点)的吸收光谱和光致发光光谱；
图4显示了运行中的QLED的能量转移过程。杂化层包括ZnSe/ZnSeS/ZnS量子点，以及包裹着能量转移分子PO8；
图5显示了运行中的具有如图1c所示的多层结构，以及由量子点和能量转移分子组成的杂化层的QLED的能量转移过程，能量转移分子可以促进电子和空穴注入到量子点中；
图6a、图6b、图6c、图6d、图6e显示了本发明中能量转移分子的分子类(a，b，c，d)和低聚物/聚合物类(e)的示例结构；
图7a和图7b显示了图6中两个示例的能量转移分子(a)和(e)的合成方法；
图8a和图8b显示了本发明中量子点在两个不同的倍率下的扫描电子显微镜图，具有核/壳/壳结构的ZnSe/ZnSeS/ZnS量子点的尺度大小在9nm左右，光致发光峰波长在440nm；
图9显示了本发明的QLED中所用的材料的能级实施例；
图10a、图10b和图10c显示了发蓝紫色QLED的电致发光性能，其部分由ZnSe/ZnSeS/ZnS量子点和能量转移分子PO8组成；
图11a和图11b显示了发紫光的QLED的(a)J-V-I曲线和(b)EQE和发光效能曲线，其部分由ZnSe/ZnSeS/ZnS量子点和能量转移分子PO8组成；
图12a和图12b显示了量子点与能量转移分子PO8的摩尔比对装置性能的影响，图(a)和(b)分别为以ZnSe/ZnSeS/ZnS量子点构建的QLED的发光亮度和EQE随PO8含量的影响。
图13显示了QLED装置的稳定性，在间歇开关运行电压0-6v下循环1200次；
图14显示了发紫光的ZnSe/ZnSeS/ZnS的QLED装置稳定的曲线；
图15a、图15b和图15c显示了一种发绿光的QLED的电致发光性能，其部分由CdSe/CdZnS/ZnS量子点和能量转移分子PO8组成；
图16a和图16b显示了发绿光的QLED的(a)J-V-I曲线和(b)EQE和发光效率曲线，其部分由CdSe/CdZnS/ZnS量子点和能量转移分子PO8组成；
图17a、图17b和图17c显示了发红光的QLED的电致发光性能，其部分由CdSe/CdZnS/ZnS量子点和能量转移分子PO8组成；
图18a和图18b显示了发红光的QLED的(a)J-V-I曲线和(b)EQE和发光效能曲线，其部分由CdSe/CdZnS/ZnS量子点和能量转移分子PO8组成。
具体实施方式
下面将结合本发明实施方式，对本发明实施例中的技术方案进行详细地描述，显然，所描述的实施方式仅仅是本发明一部分实施方式，而不是全部实施方式。基于本发明中的实施方式，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施方式，都属于本发明保护范围。
图1说明了本发明实施例中的QLED装置的多层结构的示意图，从下往上依次包括一个阳极，一个空穴传输层，一个量子点和能量转移分子的发光层，一个电子传输层，以及一个阴极。电子传输层是可选择的。
所述阳极用于连接外电源的正极，在一个具体的实施例中，阳极材料为导电金属氧化物或者导电聚合物，优选为铟锡氧化物(ITO)，所述阳极所在层的厚度可以为10-1000nm，优选为100-400nm。
在一个优选的实施例中，为了提高空穴的注入效率，所述阳极表面还设置有能够注入空穴的导电层。在一个具体的实施例中，所述导电层优选为摩尔比为5∶1的聚3，4-乙撑二氧噻吩：聚苯乙烯磺酸盐(PEDOT：PSS)的涂层，所述PEDOT：PSS涂层的厚度可以为5-100nm，优选厚度为10-50nm，在一个具体的实施例中导电层通过旋涂的方式设置在所述阳极上。
所述空穴传输层用于注入和传输空穴，主要起传输空穴到发光层的作用，所述空穴传输层可以选自以下组的分子中的一种：叔芳胺、噻吩低聚物、噻吩聚合物、吡咯低聚物、乙烯基苯撑低聚物、乙烯基苯撑聚合物、乙烯基咔唑低聚物、乙烯基咔唑聚合物、氟低聚物、氟聚合物、乙炔基苯撑低聚物、乙炔基苯撑聚合物、苯撑低聚物、苯撑聚合物、乙炔低聚物、乙炔聚合物、酞菁、酞菁衍生物、紫菜碱和紫菜碱衍生物。在一个具体的实施例中，所述空穴传输层为乙烯基咔唑聚合物(PVK)，所述空穴传输层通过旋涂的方式设置在所述导电层上，所述空穴传输层的厚度可以为20-600nm，优选厚度为50-200nm。
在一个具体实施例中，阳极将空穴注入导电层，导电层进一步将空穴注入空穴传输层并传输给发光层。
所述量子点和能量转移分子的发光层主要用于发光，发光是由于来自位于所述发光层上下的空穴和电子传输层中空穴和电子的复合。根据能量转移分子能量转移的结构和功能，发光层具有三个模式，如图1中所示：a)能量转移分子为供体型，能够促进电子注入到量子点；b)能量转移分子为受体型，能够促进空穴注入到量子点；c)能量转移分子为供体-受体型，能够同时促进电子和空穴同时注入到量子点。所述量子点分散在所述能量转移分子中，所述能量转移分子为分子类、低聚物类或者聚合物类。所述能量转移分子易于产生电子或/和空穴，且所述能量转移分子具有比所述量子点宽的带隙，同时，所述能量转移分子具备的长烷基链可以很好的和所述量子点表面进行结合，通过点击化学进行交联，以上方式导致了电子或/和空穴向量子点的注入，从而解决了量子点中激子不易被注入的难题。在一个优选的实施例中，所述量子点包括以下结构的量子点中的一种：
a)ZnSe/ZnSeS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
b)ZnTe/ZnSe/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
c)ZnTe/ZnTeS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
d)CdSe/CdZnS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
e)CdSe/CdZnSe/ZnSe/ZnS核/壳/壳/壳结构量子点，尺寸在1.5-9nm范围内；
f)CdTe/CdZnS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
g)CdS/ZnS核/壳结构、CdS/ZnSe/ZnS核/壳/壳结构或者CdZnS/ZnSe/ZnS核/壳/壳结构量子点，尺寸在1.5-10nm范围内；
h)CdTe/InP/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
i)InP/ZnS核/壳结构量子点，尺寸在1.5-9nm范围内；
j)锰掺杂ZnSe：Mn2+/ZnS核/壳结构量子点，ZnSe/ZnS：Mn2+/ZnS核/壳/壳结构量子点或者ZnS：Mn2+/ZnS核/壳结构量子点，尺寸在1.5-9nm范围内；
k)铜掺杂ZnS：Cu2+/ZnS核/壳结构量子点或者ZnSe：Cu2+/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
l)ZnSe/InP/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
m)PbS/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
n)PbSe/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
o)CuInS2量子点和核/壳结构的CuInS2/ZnS量子点，尺寸在1.5-10nm范围内；
p)CuS/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
q)AgInS2量子点和AgInS2/ZnS核壳结构量子点，尺寸在1.5-10nm范围内。
在一个优选的实施例中，所述量子点包括具有电致发光峰值在380-450nm范围内，镉 或者汞含量低于0.001％质量分数的ZnSe/ZnSeS/ZnS量子点；电致发光峰值在480-900nm范围内，镉或者汞含量低于0.001％质量分数的ZnTe/ZnSe/ZnS量子点、ZnTe/ZnTeSe/ZnSe量子点或者ZnTe/ZnTeSe/ZnS量子点；电致发光峰值在500-700nm范围内，镉或者汞含量低于50％的CdSe/CdZnS/ZnS量子点或者CdSe/CdZnSe/ZnSe/ZnS量子点。在一个具体的实施例中，发蓝紫色光的量子点优选ZnSe/ZnSeS/ZnS量子点；发绿光的量子点优选CdSe/CdZnS/ZnS量子点；发红光的量子点优选CdSe/CdZnS/ZnS量子点。
在一个优选的实施例中，所述能量转移分子为分子类、低聚物类或者聚合物类(图6所示的分子组或者他们的衍生物，图6中(a)-(d)代表分子类结构、(e)代表低聚物/聚合物类结构)。在一个优选的实施例中，所述能量转移分子具有包括乙炔基或者叠氮基官能团中的一种，所述量子点的配体末端基具有包括乙炔基或者叠氮基两者中任何一个；经过热处理后，所述量子点和所述能量转移分子完成交联形成复合层。在一个具体的实施例中，所述能量转移分子为PO8。在一个优选的实施例中，所述量子点与所述能量转移分子的摩尔比在100000∶1和1∶100000之间，复合层的制备选自以下三个步骤中的一个：
a)将所述量子点的溶液与所述能量转移分子的溶液混合；
b)将所述量子点的粉末溶解到所述能量转移分子的溶液；
c)将所述能量转移分子的固体或者浆料溶解到所述量子点的溶液中。
在一个具体的实施例中，所述发光层通过旋涂方式设置在所述空穴传输层上，所述发光层的厚度可以为10-300nm，优选厚度为40-100nm。
所述电子传输层主要用于起传输电子到发光层的作用，所述电子传输层选自以下组分子中的一种：恶二唑类、噁二唑类衍生物、恶唑类、恶唑类衍生物、异恶唑、异恶唑衍生物、噻唑、噻唑衍生物、1，2，3-三唑、1，2，3-三唑衍生物、1，3，5-三嗪类、1，3，5-三嗪类化合物衍生物、喹喔啉、喹喔啉衍生物、吡咯低聚物、吡咯聚合物、乙烯基苯撑低聚物、乙烯基苯撑聚合物、乙烯基咔唑低聚物、乙烯基咔唑聚合物、氟低聚物、氟聚合物、乙炔基苯撑低聚物、乙炔基苯撑聚合物、苯撑低聚物、苯撑聚合物、噻吩低聚物、噻吩聚合物、乙炔低聚物、乙炔聚合物、TiO2纳米颗粒、ZnO纳米颗粒、SnO纳米颗粒、金纳米颗粒和银纳米颗粒。所述电子传输层的厚度可以为20-600nm，优选为50-200nm，所述电子传输层是可选择的。在一个具体的实施例中，所述电子传输层通过旋涂方式设置在所述发光层上。
所述阴极材料用于连接外电源的负极，在一个优选的实施例中，所述阴极材料包括Al、Ca、Ba、Ca/Al、Ag中的任意一种或一种以上，在一个具体的实施例中，所述阴极材料为Al。所述阴极材料厚度可以为10-600nm，优选厚度为50-200nm。在一个具体的实施例中，所述阴极材料通过蒸渡方式设置于所述电子传输层上，所述阴极层厚度为200nm。
应理解的是，本发明实施例的制造过程涉及对上述阳极、空穴传输层、发光层、电子传输层、阴极的具体地沉积工艺可以包括但不限于旋涂、喷涂、印刷、以及真空蒸镀中的一种。
图2显示了本发明实施例中提出的10个QLED装置示例的色度值和颜色(白色小圈)。色度值和颜色在CIE 19762°色域显示了4个蓝紫色QLED，三个绿色QLED以及三个红色QLED。图中实验结果表明，在10个装置中，9个QLED的颜色超出了NTSC标准色域的范围(黑色三角)。
在一个更加具体的实施例中，阳极的主要形成材料为ITO、导电层的主要形成材料为PEDOT：PSS、空穴传输层的主要形成材料为PVK、发光层为ZnSe/ZnS核壳结构量子点和PO8的复合层、阴极的主要形成材料为Al。在本发明具体的实施例中的发光二极管装置的能级结构如图9所示。
图3显示了在一个具体的实施例中能量转移分子PO8和三种量子点溶液(发蓝紫光的ZnSe/ZnSeS/ZnS量子点，发绿光的CdSe/CdZnS/ZnS量子点，以及发红光的CdSe/CdZnS/ZnS 量子点)的吸收光谱和光致发光光谱。PO8的吸收波长在270-330nm范围内，并且其光致发光波长在310-400nm范围内，全部落入了三种量子点的吸收光谱范围内，这种较大的光谱重叠程度，极大的增加了能量转移分子与量子点之间能量转移的概率，为装置的量子产率提供了可靠的保证。图4显示了一个具体的实施例中运行中的QLED的能量转移过程，图中发光层包括ZnSe/ZnSeS/ZnS量子点，以及包裹着能量转移分子PO8。当QLED运行时，PO8分子可以从阴极层中注入电子，并将其传输给相近的量子点。所注入的电子-空穴对形成了一个激发态，一个光子由此产生并且发射出去。
图5显示了运行中的具有如图1c所示的多层结构，由量子点和一个具体的能量转移分子组成发光层的QLED的能量转移过程，图中所示的能量转移分子可以同时促进电子和空穴注入到量子点中。
图7中(a)和(b)分别显示了图6中两个示例的能量转移分子(a)和(e)的合成方法。
图8中(a)和(b)分别显示了本发明的实施例中量子点在高倍率和低倍率下的扫描电子显微镜图。实验结果表明，具有核/壳/壳结构的ZnSe/ZnSeS/ZnS量子点的尺度大小在9nm左右。
图10显示了本发明的实施例中发蓝紫色光的QLED的电致发光性能，其部分由ZnSe/ZnSeS/ZnS量子点和能量转移分子PO8组成。(a)、(b)显示了运行中的设备的明亮蓝紫色光的光学图像。(c)为其对应的电致发光光谱，图中结果表明，QLED的发射峰值波长在440nm左右，且具有非常尖锐的半峰宽(14.6nm)。
图11显示了在本发明具体的实施例中发紫光的，其部分由ZnSe/ZnSeS/ZnS量子点和能量转移分子PO8组成的QLED的(a)J-V-I曲线、(b)EQE和发光效率曲线。从图中可见，在发光亮度为38cd/m2时，最大EQE为3.4％，最大发光效率为23lm/W。
图12显示了本发明具体的实施例中，量子点与能量转移分子PO8的摩尔比对装置性能的影响，图(a)和(b)分别为以ZnSe/ZnSeS/ZnS量子点构建的QLED的发光亮度和EQE随PO8含量的变化，图中可见，在一定摩尔比范围内(1∶0-1∶25)，发光亮度和EQE随着量子点与PO8分子摩尔比的增加而明显增加。
图13显示了本发明具体的实施例中QLED装置的稳定性，图中可见，在间歇运行电压0-6v下，开关循环1200次后，QLED的亮度依然能保持很好的稳定性。
图14显示了本发明实施例中发紫光的ZnSe/ZnSeS/ZnS的QLED装置稳定的曲线，实验结果表明，在10cd/m2发光亮度下，QLED的半衰期为133小时2
图15显示了本发明实施例中发绿色的QLED的电致发光性能，其部分由CdSe/CdZnS/ZnS量子点和能量转移分子PO8组成。图(a)表示装置在6-14V电压下运行时的电致发光光谱，以及(b)和(c)显示了运行中的设备的明亮绿光的光学图像。
图16显示了本发明实施例中发绿光的QLED的(a)J-V-I曲线、(b)EQE和发光效率曲线，其部分由CdSe/CdZnS/ZnS量子点和能量转移分子PO8组成，图中可见，其最大发光亮度3800cd/m2。
图17显示了本发明实施例中发红光QLED的电致发光性能，其部分由CdSe/CdZnS/ZnS量子点和能量转移分子PO8组成。(a)代表了装置在6-16V电压下运行时的电致发光光谱，以及(b)和(c)显示了运行中的设备的明亮红光的光学图像。
图18显示了本发明实施例中发红光的QLED的(a)J-V-I曲线、(b)EQE和发光效率曲线。其部分由CdSe/CdZnS/ZnS量子点和能量转移分子PO8组成。图中可见，最大发光亮度为6300cd/m2，对应波长在625nm处，最大EQE为0.63％，对应发光亮度为68cd/m2处。
实施例1
P8分子的合成：
氩气氛围下，将3.29g(6mmol)2，7-二溴-9，9-二辛基芴溶解到80ml无水四氢呋喃中，并降温到-78℃(干冰-丙酮浴)。缓慢逐滴加入5.1ml正丁基锂(2.5M在己烷中；12.75mmol)，得到浓稠明亮的黄色溶液。在-70℃下持续搅拌20min，然后提升反应混合物的温度至0℃。再将温度升至常温，加入2.8g(12.75mmol)氯化二苯基瞵。在2ml脱气甲醇的淬灭之前，将反应物在-70℃搅拌额外的3小时。减压去除挥发物，剩下油性液体。将粗制的材料纯化，通过二氧化硅的柱色谱法(Rf＝0.29)，以氯仿/正己烷(2∶8)作为流动相，最后得到3.50g(77％)化学纯的P8。
实施例2
PO8分子的合成：
将3.03g(4mmol)P8，50ml二氯甲烷和10ml 30％的过氧化氢溶液混合，常温下混合搅拌过夜。将有机层分离，并依次水洗和盐水洗。将产物进行蒸发干燥，得到白色固体，通过将其在甲苯/正己烷中重结晶而进一步纯化，最后得到2.7g(85％)的化学纯PO8。
实施例3
预图案化的ITO片的预处理和清洁：
在玻璃基底上设置12个表面覆盖有聚合物的预图案化的ITO芯片，浸入到80℃的5％的氢氧化钠水溶液中5min。重复上述步骤，然后将芯片用纳米纯水、20％乙醇胺水溶液清洗，并超声15min，接着用充足的纳米纯水清洗和干燥。最后，将ITO芯片负载到等离子清洗室，将ITO包覆的设备表面清洁干净。
实施例4
通过高质量的ZnSe/ZnSeS/ZnS量子点，构建紫光QLED：
预清洁的ITO涂层的设备芯片，涂上一层导电层，实验过程为：利用旋涂仪器，在旋转速度为1750rpm，将200微升摩尔比率5∶1的PEDOT∶PSS水溶液涂覆到其表面，旋转时间60s。接着将装置在180℃的容器中真空干燥20min，降温到常温，在装置上进一步涂覆另一层空穴传输层聚4-丁基苯-联苯胺(分子量＞50,000)，通过运用100微升wt 0.05％聚合物的氯苯分散液进行旋涂，旋转速度为2500rpm，旋转时间60s。然后将装置在160℃的真空容器中干燥40min。将装置冷却，并在其上旋涂量子点发光层和能量转移分子。制备量子点和能量转移分子的混合物的过程为，将溶解在正己烷/甲苯中纯化的量子点，改变浓度使其在400nm的吸收度调整到约1.0，然后在溶液加入0.01％质量分数的能量转移分子。混合溶液旋涂在装置片的表面的过程为：加入100微升溶液到芯片表面，并在旋转速度2000rpm速度下，旋涂60秒，接着将芯片在140℃的真空下干燥30分钟，并降温到常温。然后通过在2×10-6托的真空中热蒸镀的方法，蒸镀200nm厚度铝层的阴极层。然后将装置封闭，包裹在环氧树脂中，并在一个UV灯的辐射下10min。QLED的电学和光学性质，在以KEITHLEY系列2400多功能源表(附带LabTracer 2.0软件)为能量源的系统中测试，一个Ossila OLED/OPV测试平台，一个NEWPORT 2835C多功能光学源，与一个校准NEWPORT 818光学检测探针，计量仪的输出由LabView 8.2软件收集，测试了发光面积1.5mm×3mm＝4.5×10-6m2的QLED。
实施例5
通过高质量的CdSe/CdSeS/ZnS量子点，构建绿光QLED：
绿光CdSe/CdSeS/ZnS QLED的构建与上述实施例中4发紫光的QLED相似，除了用表面配体修饰的绿光CdSe/CdSeS/ZnS量子点取代ZnSe/ZnSeS/ZnS量子点。
实施例6
通过高质量的CdSe/CdSeS/ZnS量子点，构建红光QLED：
红光CdSe/CdSeS/ZnS QLED的构建与上述实施例4中发紫光的QLED相似，除了用表面配体修饰的红光CdSe/CdSeS/ZnS量子点取代ZnSe/ZnSeS/ZnS量子点。
测试结果：
基于无镉，表面修饰有配体的ZnSe/ZnSeS/ZnS量子点和能量转移分子的QLED的装置性能，可以总结为如下：
1)在紫外-紫光范围380nm-450nm的电致发光波长(图10)。
2)最大发光亮度620cd/m2(图11)。
3)最大发光效率23.22lm/W(图11)。
4)最大EQE为3.4％，最大发光亮度为38cd/m2，发射峰值为440nm。
5)发射峰具有尖锐的线宽度(半峰宽＝14.6nm)(图10)。
6)打开电压只有2.8V(图10)。
7)保存时间大于3个月。
8)当在空气和周围环境下测试时，设备半衰期大于130小时。
9)在循环打开和关闭1200次后，设备仍然稳定，显示出发射强度没有明显变化(小于5％的偏差)。
10)三个代表性的发光颜色，1976CIE L*a*b色域，色度值(0.242，0.051)，(0.235，0.075)，以及(0.224，0.097)(图2)。
基于CdSe/ZnS量子点和能量转移分子的QLED，可以总结为如下：
11)在可见光的青-红范围(480-700nm)波长内的电致发光。
12)绿光QLED的最大亮度达3000cd/m2，发射峰值在525nm。
13)红光QLED的最大亮度达6300cd/m2，发射峰值在625nm。
14)最大发光效率4.57lm/W，发光亮度在41.4cd/m2处。
15)红光QLED的打开电压低至1.9V，绿光QLED的打开电压低至2.2V。
16)最大EQE为0.7％，发光亮度在41.4cd/m2处。
17)发射峰具有尖锐的线宽(半峰宽＝24nm)。
18)保存寿命大于6个月。
19)在空气和周围环境中，设备半衰期大于130小时。
20)在循环打开和关闭520次后，设备仍然稳定，并显示出发射强度没有明显变化(小于5％的偏差)。
21)三个代表性的绿光发光颜色，1976CIE L*a*b色域，色度值(0.102，0.558)，(0.092，0.560)，以及(0.088，0.562)。
22)三个代表性的红光发光颜色，1976CIE L*a*b色域，色度值(0.478，0.521)，(0.482，0.524)，以及(0.484，0.525)。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。

Claims (15)

  1. 一种发光二极管装置，包括：
    a)空穴传输层，用于注入和传输空穴；
    b)发光层，与所述空穴传输层接触；
    c)电子传输层，与所述发光层接触，用于注入和传输电子到所述发光层；
    d)阳极和阴极，用于通直流电压，使电流在装置中流动，并以紫外线、可见光或者近红外光的形式发出辐射，使装置发光，
    其特征在于：所述发光层包括量子点与能量转移分子，所述能量转移分子作为所述量子点的分散介质具有高效的电子和/或空穴载流子注入能力，且与所述量子点通过点击化学进行交联。
  2. 根据权利要求1所述的发光二极管装置，其特征在于：当在所述阴极与所述阳极之间加上0-30V的直流电压时，所述发光二极管装置具有波长在380-900nm范围内的电致发光。
  3. 根据权利要求1所述的发光二极管装置，其特征在于：所述能量转移分子具有高荧光量子效率、在非水电解质中可逆的氧化还原性质以及比所述量子点宽的带隙，从而获得高效的电子和/或空穴载流子注入能力。
  4. 根据权利要求1所述的发光二极管装置，其特征在于：所述量子点与所述能量转移分子经过热处理之后通过点击化学交联形成复合层，其中所述能量转移分子包括乙炔基或者叠氮基官能团，所述量子点的配体末端基包括乙炔基或者叠氮基。
  5. 根据权利要求1所述的发光二极管装置，其特征在于：所述能量转移分子为分子类、低聚物类或者聚合物类，包括以下分子组或者他们的衍生物中的至少一种：
    Figure PCTCN2016102252-appb-100001
    其中R1，R2，R3为-(CH2)x-(CH＝CH)y-(CH2)z-R；R为以下基团中的一种-H，-Cl，-Br，-I，-OH，-OCH3，-OC2H5，-CHO，-COOCH3，-COOH，-CONH2，-COCl，-COBr，-COl，-NH2，-N+(CH3)3，-C(CH3)3，-CH＝CH2，-CCH，-C6H5，-C5H5，-N3，-OCN，-NCO，-CN，-NC，-NO2，-C5H4N，-SH，-S-S-H，-SOCH3，-RSO2H，-SCN，-NCS，-CSH，-PH2，膦酰基，磷酸基，鸟嘌呤基，胞嘧啶基，腺嘌呤基，胸腺嘧啶基。
  6. 根据权利要求1所述的发光二极管装置，其特征在于：所述电子传输层包括以下组的分子中的至少一种：恶二唑类、噁二唑类衍生物、恶唑类、恶唑类衍生物、异恶唑、异恶唑衍生物、噻唑、噻唑衍生物、1，2，3-三唑、1，2，3-三唑衍生物、1，3，5-三嗪类、1，3，5-三嗪类化合物衍生物、喹喔啉、喹喔啉衍生物、吡咯低聚物、吡咯聚合物、乙烯基苯撑低聚物、乙烯基苯撑聚合物、乙烯基咔唑低聚物、乙烯基咔唑聚合物、氟低聚 物、氟聚合物、乙炔基苯撑低聚物、乙炔基苯撑聚合物、苯撑低聚物、苯撑聚合物、噻吩低聚物、噻吩聚合物、乙炔低聚物、乙炔聚合物、TiO2纳米颗粒、ZnO纳米颗粒、SnO纳米颗粒、金纳米颗粒和银纳米颗粒。
  7. 根据权利要求1所述的发光二极管装置，其特征在于：所述空穴传输层包括以下组的分子中的至少一种：叔芳胺、噻吩低聚物、噻吩聚合物、吡咯低聚物、乙烯基苯撑低聚物、乙烯基苯撑聚合物、乙烯基咔唑低聚物、乙烯基咔唑聚合物、氟低聚物、氟聚合物、乙炔基苯撑低聚物、乙炔基苯撑聚合物、苯撑低聚物、苯撑聚合物、乙炔低聚物、乙炔聚合物、酞菁、酞菁衍生物、紫菜碱和紫菜碱衍生物。
  8. 根据权利要求1所述的发光二极管装置，其特征在于：所述量子点包括以下结构的量子点中的一种：
    a)ZnSe/ZnSeS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
    b)ZnTe/ZnSe/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
    c)ZnTe/ZnTeS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
    d)CdSe/CdZnS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
    e)CdSe/CdZnSe/ZnSe/ZnS核/壳/壳/壳结构量子点，尺寸在1.5-9nm范围内；
    f)CdTe/CdZnS/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
    g)CdS/ZnS核/壳结构、CdS/ZnSe/ZnS核/壳/壳结构或者CdZnS/ZnSe/ZnS核/壳/壳结构量子点，尺寸在1.5-10nm范围内；
    h)CdTe/InP/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
    i)InP/ZnS核/壳结构量子点，尺寸在1.5-9nm范围内；
    j)锰掺杂ZnSe：Mn2+/ZnS核/壳结构量子点，ZnSe/ZnS：Mn2+/ZnS核/壳/壳结构量子点或者ZnS：Mn2+/ZnS核/壳结构量子点，尺寸在1.5-9nm范围内；
    k)铜掺杂ZnS：Cu2+/ZnS核/壳结构量子点或者ZnSe：Cu2+/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
    l)ZnSe/InP/ZnS核/壳/壳结构量子点，尺寸在1.5-9nm范围内；
    m)PbS/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
    n)PbSe/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
    o)CuInS2量子点和核/壳结构的CuInS2/ZnS量子点，尺寸在1.5-10nm范围内；
    p)CuS/ZnS核/壳结构量子点，尺寸在1.5-10nm范围内；
    q)AgInS2量子点和AgInS2/ZnS核壳结构量子点，尺寸在1.5-10nm范围内。
  9. 根据权利要求8所述的发光二极管装置，其特征在于：所述量子点包括以下量子点中的至少一种：具有电致发光峰值在380-450nm范围内，镉或者汞含量低于0.001％质量分数的ZnSe/ZnSeS/ZnS量子点；电致发光峰值在480-900nm范围内，镉或者汞含量低于0.001％质量分数的ZnTe/ZnSe/ZnS量子点、ZnTe/ZnTeSe/ZnSe量子点或者ZnTe/ZnTeSe/ZnS量子点；电致发光峰值在500-700nm范围内，镉或者汞含量低于50％的CdSe/CdZnS/ZnS量子点或者CdSe/CdZnSe/ZnSe/ZnS量子点。
  10. 根据权利要求1所述的发光二极管装置，其特征在于：所述发光层中所述量子点与所述能量转移分子的摩尔比在100000∶1和1∶100000之间。
  11. 一种发光二极管装置的制备方法，其特征在于；所述制备方法包括以下步骤：
    提供一衬底，在所述衬底上设置阳极层；
    接着在所述阳极层上设置空穴传输层；
    然后在所述空穴传输层上设置发光层，所述发光层为量子点与能量转移分子构成的复合层；
    随后将电子传输层设置于所述发光层上；
    最后将阴极层设置于所述电子传输层上。
  12. 如权利要求11所述的发光二极管装置的制备方法，其特征在于：所述复合层的制备选自以下三个步骤中的一个：
    a)将所述量子点的溶液与所述能量转移分子的溶液混合；
    b)将所述量子点的粉末溶解到所述能量转移分子的溶液；
    c)将所述能量转移分子的固体或者浆料溶解到所述量子点的溶液中。
  13. 一种电子显示装置，其特征在于：所述电子显示装置用于输出视觉信息或者触觉信息，通过电信号作为输入信息来运转，所述电子显示装置包括权利要求1-10中任一项所述的发光二极管装置，所述发光二极管装置用于至少一种颜色的彩色显示。
  14. 如权利要求13所述的电子显示装置，其特征在于：所述发光二极管装置用于三色显示，所述三色包括蓝紫色、绿色和红色的结合，或者蓝色、绿色和红色的结合。
  15. 如权利要求13所述的电子显示装置，其特征在于：所述发光二极管装置用于四色显示，所述四色包括紫蓝色、绿色、黄色和红色的结合。
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CN111416053A (zh) * 2020-05-11 2020-07-14 京东方科技集团股份有限公司 一种量子点发光器件及其制备方法、显示面板、显示装置
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