WO2020252953A1 - 电致发光器件及其制备方法、电子设备 - Google Patents

电致发光器件及其制备方法、电子设备 Download PDF

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WO2020252953A1
WO2020252953A1 PCT/CN2019/106372 CN2019106372W WO2020252953A1 WO 2020252953 A1 WO2020252953 A1 WO 2020252953A1 CN 2019106372 W CN2019106372 W CN 2019106372W WO 2020252953 A1 WO2020252953 A1 WO 2020252953A1
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layer
electrode
graphene oxide
electroluminescent device
functional structure
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PCT/CN2019/106372
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French (fr)
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汪亚民
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武汉华星光电半导体显示技术有限公司
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Priority to US16/613,436 priority Critical patent/US11245084B2/en
Publication of WO2020252953A1 publication Critical patent/WO2020252953A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom

Definitions

  • the invention relates to the field of display technology, in particular to an electroluminescent device, a preparation method thereof, and electronic equipment.
  • Electroluminescence display equipment is a type of self-luminous display device, which generates excitons through the transfer and recombination of carriers between various functional layers, and emits light by relying on organic compounds or metal complexes with high quantum efficiency. It has the characteristics of self-luminescence, high brightness, high efficiency, high contrast, and high responsiveness.
  • the graphene oxide In the oxidized state of graphene oxide, the sp2 hybrid conjugation of the graphene itself will be destroyed, resulting in the lack of freely moving ⁇ electrons in the graphene oxide. Therefore, in the oxidized state, the graphene oxide is almost insulative and has energy bands. The gap is very wide, about 3.5 eV or more.
  • Ionic bond is a very strong ion pair. Conjugated ions have less anion and cation effects due to the presence of conjugation. Therefore, how to combine ionic compounds with conjugated ions with graphene oxide to make graphene oxide change from oxidation to reduction, so that it can generate freely moving ⁇ electrons in the conjugated region to regulate graphene oxide
  • the insulation performance and electrical conductivity are the problems that need to be solved at present.
  • the present invention provides an electroluminescent device, a preparation method thereof, and an electronic device, which are used to prepare a functional structure layer by doping a dopant material with conjugated ions into a graphene oxide material.
  • the ability of the functional structure layer, especially the hole injection layer to inject carriers, is enhanced, thereby enhancing the photoelectric performance of the electroluminescent device.
  • the present invention provides an electroluminescent device comprising a first electrode and a second electrode; and a functional structure layer, which is arranged between the first electrode and the second electrode;
  • the functional structure layer has a doped material and a graphene oxide material, and the doped material has conjugated ions.
  • the functional structure layer includes a hole injection layer, the materials used include the doping material and the graphene oxide material, and the doping material includes conjugated ions;
  • a hole injection layer is provided on the first electrode; a hole transport layer is provided on the hole injection layer; a light emitting layer is provided on the hole transport layer; an electron transport layer is provided on the light emitting layer
  • the electron injection layer is arranged on the electron transport layer; the second electrode is arranged on the electron injection layer.
  • the material used for the hole transport layer includes tetraphenyl diphenyl diamine compounds, bifendate, N,N′-bis(1-naphthyl)-N,N′- At least one of diphenyl-1,1'-biphenyl-4-4'-diamine.
  • the doping material is N,N dimethyl dinitrite nitrate; the weight ratio of the doping material to the graphene oxide material is 1:1 to 1:99.
  • the structural formula of the N,N dimethyl diphosphite nitrate includes at least one of the following structural formulas:
  • the present invention also provides a preparation method for preparing the electroluminescent device, including the following steps: providing a conductive glass with the first electrode on the surface; forming the functional structure layer on the conductive glass There is one side of the first electrode, the functional structure layer has a doped material and a graphene oxide material, and the doped material has conjugated ions; the second electrode is formed by a vacuum evaporation method on the The functional structure layer is away from the side of the first electrode.
  • the step of providing the conductive glass includes washing the conductive glass with deionized water, then rinsing the conductive glass with warm water for 30 minutes to 50 minutes, and then drying, The temperature of the warm water is maintained at 15° C.-35° C.; then the conductive glass is cleaned with a plasma cleaner for 6 minutes to 15 minutes.
  • the step of forming the functional structure layer includes providing a doping material and a graphene oxide material, dissolving the doping material in deionized water to obtain a doping material solution,
  • the graphene oxide material is dissolved in deionized water and subjected to ultrasonic vibration to obtain a graphene oxide solution;
  • the doping material solution is doped into the graphene oxide solution, and ultrasonic dispersion is performed for 2 hours to 4 hours, and at the same time
  • the temperature is adjusted to 30-50°C to obtain a mixed solution.
  • the weight percentage of the dopant material is 0.1wt%-50wt%; coating the mixed solution on the conductive glass has the The hole injection layer is formed on the surface of the first electrode.
  • the step of forming the functional structure layer further includes after forming the hole injection layer, fixing the conductive glass on the mask plate and transferring it to the vacuum evaporation chamber In the room, use a molecular pump to vacuum the vacuum evaporation chamber until the vacuum degree of the vacuum evaporation chamber is lower than 4.0 ⁇ 10 -4 -6.5 ⁇ 10 -4 Pa;
  • the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer are sequentially formed on the hole transport layer.
  • the invention also provides an electronic device with the electroluminescent device.
  • the difference in conductivity can be obtained according to the redox characteristics of the graphene oxide, and then according to the characteristics of the conjugated ion compound, the ion with the conjugated ion
  • the compound is doped into graphene oxide so that conjugated ions containing aromatic rings can be grafted on the surface of the graphene oxide through ⁇ - ⁇ stacking, and the graphene oxide is negatively charged after hydrolysis, so the ionic compound
  • the cations in the ionic compound will form an electrostatic interaction with it, thereby further reducing the anion and cation forces of the ionic compound.
  • conjugated ion compound doped graphene oxide may also be applied to the hole input layer, which is bound to open up the application prospect of conjugated ion compound doped graphene oxide.
  • Fig. 1 is a structural diagram of an electroluminescent device according to an embodiment of the invention.
  • FIG. 2 is the electroluminescence spectra of the electroluminescence devices of method examples 1-5 and comparative example 1 of the present invention.
  • Fig. 3 is a graph showing the relationship between brightness and voltage of the electroluminescent devices of method examples 1-5 and comparative example 1 of the present invention.
  • Electroluminescent device 100 electronic equipment;
  • 3a hole injection layer 3b hole transport layer;
  • 3c light-emitting layer 3d electron transport layer
  • the electroluminescent device 10 of the present invention includes a first electrode 2, a functional structure layer 3, and a second electrode 4.
  • the first electrode 2 is arranged on one side of the conductive glass 1, and the first electrode 2 is an anode.
  • the functional structure layer 3 includes a hole injection layer 3a, a hole transport layer 3b, and a light emitting layer 3c. Wherein the hole injection layer 3a is provided on the first electrode 2; the hole transport layer 3b is provided on the hole injection layer 3a; the light emitting layer 3c is provided on the hole transport layer 3b Above, the second electrode 4 is directly disposed on the light-emitting layer 3c, and the second electrode 4 is a cathode.
  • the functional structure layer 3 has a doped material and a graphene oxide material, and the doped material has conjugated ions.
  • the hole injection layer 3a uses the dopant material and the graphene oxide material, and in the hole injection layer 3a, the weight of the dopant material and the graphene oxide material The ratio is 1:1-1:99.
  • an ionic compound with conjugated ions is doped into graphene oxide, so that conjugated ions containing aromatic rings can be grafted on the surface of the graphene oxide through ⁇ - ⁇ stacking.
  • the graphene oxide is negatively charged after hydrolysis, so the cations in the ionic compound will form an electrostatic interaction with it, thereby further reducing the anion and cation forces of the ionic compound. Therefore, after doping, the voltage of the electroluminescent device is affected. Below, anions and cations will accelerate the directional movement, because the doped conjugated ions enhance the ability of the hole injection layer 3a to inject carriers, thereby enhancing the photoelectric performance of the electroluminescent device.
  • the doping material is N,N dimethyl dinitrite nitrate, and its structural formula includes at least one of the following structural formulas:
  • the structural formula of the graphene oxide is as follows:
  • the material used for the hole transport layer 3b includes tetraphenyl diphenyl diamine compounds, biphenyl diester, N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1 At least one of'-biphenyl-4-4'-diamine.
  • the functional structure layer 3 may also be provided with an electron transport layer 3d and an electron injection layer 3e; the electron transport layer 3d is provided on the light-emitting layer 3c; the electron injection layer 3e is provided on the electron On the transport layer 3d; the second electrode 4 is provided on the electron injection layer 3e.
  • an electron blocking layer (not shown in the figure) may be further provided in the functional structure layer 3, which is provided between the first electrode 2 and the second electrode 4.
  • the functional structure layer 3 which is provided between the first electrode 2 and the second electrode 4.
  • it may be provided between the light emitting layer 3c and the hole transport layer 3b, so that when a current is applied between the anode and the cathode, the electron blocking layer prevents electrons from leaking in the organic light emitting layer 3c.
  • a hole blocking layer (not shown in the figure) may be further provided in the functional structure layer 3, which is provided between the first electrode 2 and the second electrode 4.
  • the hole blocking layer can be arranged between the electron transport layer 3d and the light-emitting layer 3c, so that when a current is applied between the anode and the cathode, the hole blocking layer can confine carriers and excitons in the light-emitting layer.
  • layer 3c In layer 3c.
  • the absolute value of the difference between the HOMO energy level or the valence band energy level of the p-type semiconductor material of the layer 3a or the hole transport layer 3b or the hole injection layer 3a or the electron blocking layer is less than 0.5 eV, preferably Less than 0.2eV.
  • the anode material may be conductive metal or metal oxide or conductive polymer, for example, aluminum copper, gold, silver, magnesium, iron, cobalt, nickel, molybdenum, palladium, platinum, indium tin oxide, aluminum doped zinc oxide, etc. .
  • Other suitable anode materials are known, and those of ordinary skill in the art can easily select and use them.
  • the anode material can be deposited using any suitable technology, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) deposition methods, and the like.
  • the anode is patterned and structured.
  • the patterned indium tin oxide conductive glass 1 is commercially available and can be used to prepare the device of the present invention.
  • the cathode may be conductive metal or metal oxide or metal alloy or conductive polymer.
  • all materials that can be used as the cathode of the electroluminescent device 10 can be used as the cathode material of the electroluminescent device 10 of the present invention, such as aluminum, gold, silver, calcium, barium, magnesium, lithium fluoride and Aluminum, magnesium-silver alloy, barium fluoride and aluminum, copper, iron, cobalt, nickel, molybdenum, palladium, platinum, indium tin oxide, etc.
  • the cathode can easily inject electrons into the electron injection layer 3e or the electron transport layer 3d or directly into the light emitting layer 3c.
  • the work function of the cathode and the LUMO energy of the luminous body in the light-emitting layer 3c or the electron injection layer 3e or the electron transport layer 3d or the n-type semiconductor material of the hole blocking layer The absolute value of the difference in energy level or conduction band energy level is less than 0.5 eV, preferably less than 0.2 eV.
  • the cathode material can be deposited using any suitable technology, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) deposition methods, and the like.
  • the light-emitting layer 3c is an organic light-emitting layer, which is doped with an organic light-emitting material, and the organic light-emitting material is selected from a singlet light-emitting body, a triplet light-emitting body or a thermally activated delayed fluorescence light-emitting material (TADF).
  • TADF thermally activated delayed fluorescence light-emitting material
  • the present invention also provides a preparation method for preparing the electroluminescent device 10, including the following steps:
  • the step of providing a conductive glass 1 with the first electrode 2 on the surface includes washing the conductive glass 1 with deionized water, and then using Rinse the conductive glass 1 with warm water, the rinse time is 30 minutes-50 minutes, dry after rinsing, and the temperature of the warm water is maintained at 15°C-35°C; then the conductive glass 1 is cleaned with a plasma cleaner , The cleaning time is 6 minutes -15 minutes.
  • the surface work function of the first electrode 2 can be increased to 4 eV-8 eV or more, and the interface contact between the first electrode 2 and the subsequent functional structure layer 3 is improved.
  • the functional structure layer 3 is formed on the side of the conductive glass 1 with the first electrode 2.
  • the 3 steps of forming the functional structure layer include the following steps:
  • the concentration of the graphene oxide material is 0.5 mg/ml.
  • the concentration of the graphene oxide can be adjusted by the method of ultraviolet light reduction.
  • the doping material solution is doped into the graphene oxide solution, and ultrasonic dispersion is carried out for 2 hours to 4 hours, while the temperature is adjusted to 30-50°C to obtain a mixed solution.
  • the weight percentage of the dopant material is 10 wt%.
  • the mixed solution is applied to the surface of the conductive glass 1 having the first electrode 2 to form the hole injection layer 3a.
  • the conductive glass 1 is fixed on the mask plate and transferred to a vacuum evaporation chamber, and a molecular pump is used to evacuate the vacuum evaporation chamber until the vacuum
  • the vacuum degree of the evaporation chamber is lower than 4.0 ⁇ 10 -4 -6.5 ⁇ 10 -4 Pa; tetraphenyl diphenyl diamine compound and biphenyl are evaporated on the hole transport layer 3b by a vacuum evaporation method
  • One or two mixed solutions of diester, N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine or Three mixed solutions are formed on the hole injection layer 3a to form the hole transport layer 3b.
  • the light emitting layer 3c, the electron transport layer 3d, and the electron injection layer are sequentially formed.
  • the material used for the light-emitting layer 3c can be tris(8-hydroxyquinoline) aluminum, and the material used for the electron injection layer is lithium fluoride.
  • the organic material used in the hole transport layer 3b and the evaporation rate of tris(8-hydroxyquinoline) aluminum are controlled at The evaporation rate of the lithium fluoride is controlled at
  • the second electrode 4 is vapor-deposited on the functional structure layer 3.
  • the material of the second electrode 4 is aluminum, and the vapor deposition rate is controlled at Finally, the electroluminescent device 10 is formed.
  • the difference between this method example and method example 1 is that: in the mixed solution, the weight percentage of the doping material is 20 wt%.
  • the difference between this method example and method example 1 is that: in the mixed solution, the weight percentage of the doping material is 30 wt%.
  • the difference between this method example and method example 1 is that: in the mixed solution, the weight percentage of the doping material is 40 wt%.
  • the difference between this method example and method example 1 is that: in the mixed solution, the weight percentage of the doping material is 50 wt%.
  • the difference between this comparative example 1 and method example 1 is that the graphene oxide solution is not doped with dopant materials with conjugated ions, and the hole injection layer 3a is directly made of the graphene oxide solution.
  • the weight percentage of the dopant material in the mixed solution may also be 0.1 wt%, 1 wt%, or the like.
  • the present invention selects the electroluminescent devices prepared in method examples 1-5 and tests their electroluminescent performance.
  • the electroluminescent devices prepared in this comparative example 1 and method examples 1-5 have the peak position of the electroluminescence spectrum at about 500 nm, indicating that the concentration of the graphene oxide itself has an impact on the
  • the light-emitting layer 3c is tris(8-quinolinolato) aluminum and the electroluminescence peak does not have much influence.
  • the concentration of conjugated ions in the mixed solution affects the hole injection capability, that is, in the mixed solution, the concentration of the doping material affects the void Hole injection capability, within the range of the weight percentage of the doping material being less than or equal to 20wt%, as the concentration of the doping material increases, the luminescence capability of the electroluminescent device will also increase, but in the When the weight percentage of the doping material reaches more than 20wt%, it will bring about the problem of excess conjugated ions, that is, after the voltage is 7.5V, the brightness of the electroluminescent device begins to decrease, because the electroluminescent device The rapid increase in current density may be caused by the enhancement of hole injection capability, but the level of electron injection has not been improved, which leads to an increase in non-radiative recombination in the electroluminescent device, so that its brightness decreases.
  • the present invention also provides an electronic device 100 having the electroluminescent device 10 described above.
  • the main design point of the present invention is the electroluminescent device 10, and other structures will not be repeated.
  • the electronic device 100 of the present invention includes all electronic devices 100 having the electroluminescent device 10 of the present invention, including display devices, lighting devices, light sources, sensors, and so on.

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Abstract

一种电致发光器件及其制备方法、电子设备，电致发光器件，包括第一电极和第二电极；以及功能结构层，设于所述第一电极和所述第二电极之间；所述功能结构层中具有掺杂材料和氧化石墨烯材料，所述掺杂材料中具有共轭离子。

Description

电致发光器件及其制备方法、电子设备 技术领域
本发明涉及显示技术领域，具体为一种电致发光器件及其制备方法、电子设备。
背景技术
电致发光显示设备是一类自发光型的显示装置，通过载流子在各个功能层间的转移、复合产生激子，依靠高量子效率的有机化合物或金属配合物发光。其具有自发光、高亮度、高效率、高对比度、高响应性等特点。
氧化石墨烯在氧化状态下，石墨烯本身的sp2杂化共轭会被破坏，导致氧化石墨烯中缺少了自由移动的π电子，所以在氧化状态下，氧化石墨烯几乎处于绝缘，同时能带间隙很宽，大约3.5eV以上。
离子键是非常强烈的一种离子对，共轭离子因为共轭的存在，其阴阳离子的作用效果减小。因此，怎样通过带有共轭离子的离子化合物与氧化石墨烯结合，以使氧化石墨烯从氧化变成还原状态，使之在共轭区域产生自由移动的π电子，以此来调节氧化石墨烯的绝缘性能和导电性能是目前需要解决的问题。
技术问题
为解决上述技术问题：本发明提供一种电致发光器件及其制备方法、电子设备，通过将具有共轭离子的掺杂材料掺杂于氧化石墨烯材料中，用于制备功能结构层，以增强功能结构层，特别是空穴注入层的注入载流子的能力，从而增强致发光器件的光电性能。
技术解决方案
解决上述问题的技术方案是：本发明提供一种电致发光器件，包括第一电极和第二电极；以及功能结构层，设于所述第一电极和所述第二电极之间；所述功能结构层中具有掺杂材料和氧化石墨烯材料，所述掺杂材料中具有共轭离子。
在本发明一实施例中，所述功能结构层包括空穴注入层，其所用材料中具有所述掺杂材料和所述氧化石墨烯材料，所述掺杂材料中具有共轭离子；所述空穴注入层设于所述第一电极上；空穴传输层，设于所述空穴注入层上；发光层，设于所述空穴传输层上；电子传输层，设于所述发光层上；电子注入层，设于所述电子传输层上；所述第二电极设于所述电子注入层上。
在本发明一实施例中，所述空穴传输层所用材料包括四苯基联苯二胺类化合物、联苯双酯、N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺中的至少一种。
在本发明一实施例中，所述掺杂材料为N，N二甲基二亚定硝酸盐；所述掺杂材料与所述氧化石墨烯材料的重量比为1：1-1:99。
在本发明一实施例中，所述N，N二甲基二亚定硝酸盐的结构式包括以下结构式的至少一种：
Figure PCTCN2019106372-appb-000001
本发明还提供了一种制备方法，用以制备所述的电致发光器件，包括以下步骤：提供一导电玻璃，其表面具有所述第一电极；形成所述功能结构层于所述导电玻璃具有所述第一电极的一面，所述功能结构层中具有掺杂材料和氧化石墨烯材料，所述掺杂材料中具有共轭离子；通过真空蒸镀法形成所述第二电极于所述功能结构层远离所述第一电极的一侧。
在本发明一实施例中，在所述的提供所述导电玻璃的步骤中，包括用去离子水清洗所述导电玻璃，再用温水润洗所述导电玻璃30分钟-50分钟后烘干，所述温水的温度保持在15℃-35℃；然后用等离子体清洗器清洗所述导电玻璃6分钟-15分钟。
在本发明一实施例中，在所述的形成所述功能结构层步骤中包括 提供掺杂材料和氧化石墨烯材料，将所述掺杂材料溶解至去离子水中得到掺杂材料溶液，将所述氧化石墨烯材料溶解至去离子水中并进行超声波震荡得到氧化石墨烯溶液；将所述掺杂材料溶液掺杂至所述氧化石墨烯溶液中，并进行超声分散2小时-4小时,同时将温度调至30-50℃，得到混合溶液，在所述混合溶液中，所述掺杂材料的重量百分比为0.1wt％-50wt％；将所述混合溶液涂布于所述导电玻璃具有所述第一电极的表面形成所述空穴注入层。
在本发明一实施例中，在所述的形成所述功能结构层步骤中还包括在形成所述空穴注入层之后，将所述导电玻璃固定在掩模板上，并转移到真空蒸镀腔室内，使用分子泵对所述真空蒸镀腔室抽真空，直至所述真空蒸镀腔室的真空度低于4.0×10 -4-6.5×10 -4Pa；通过真空蒸镀法在所述空穴传输层上依次形成所述空穴传输层、所述发光层、所述电子传输层、所述电子注入层。
本发明还提供了一种电子设备，具有所述的电致发光器件。
有益效果
本发明的电致发光器件及其制备方法、电子设备，根据其氧化石墨烯的氧化还原特性，可以得到其导电性的差异，然后根据共轭离子化合物的特点，将带有共轭离子的离子化合物掺杂于氧化石墨烯中，使得含有芳香环的共轭离子可以通过π-π堆叠作用接枝在所述氧化石墨烯的表面，而所述氧化石墨烯在水解后带负电，所以离子化合物中的阳离子会与其形成静电作用，从而使得离子化合物的阴阳离子作用力进一步减小，所以掺杂之后，在所述电致发光器件的电压作用下， 阴阳离子会加速定向移动，原因在于掺杂的共轭离子增强了所述空穴注入层的注入载流子的能力，从而增强了电致发光器件的光电性能。根据本发明的研究，共轭离子化合物掺杂氧化石墨烯也有可能应用到空穴输入层中，这势必开拓了共轭离子化合物掺杂氧化石墨烯应用前景。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
下面结合附图和实施例对本发明作进一步解释。
图1是本发明实施例的电致发光器件结构图。
图2为本发明方法示例1-5与对比例1的电致发光器件的电致发光光谱图。
图3为本发明方法示例1-5与对比例1的电致发光器件的亮度与电压关系图。
10电致发光器件；                 100电子设备；
1导电玻璃；                      2第一电极；
3功能结构层；                    4第二电极；
3a空穴注入层；                   3b空穴传输层；
3c发光层；                       3d电子传输层；
3e电子注入层。
本发明的实施方式
下面详细描述本发明的实施方式，所述实施方式的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施方式是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
以下实施例的说明是参考附加的图式，用以例示本发明可用以实施的特定实施例。本发明所提到的方向用语，例如「上」、「下」、「前」、「后」、「左」、「右」、「顶」、「底」等，仅是参考附加图式的方向。因此，使用的方向用语是用以说明及理解本发明，而非用以限制本发明。
如图1所示，在本发明一实施例中，本发明的电致发光器件10，包括第一电极2、功能结构层3、第二电极4。
所述第一电极2设置在导电玻璃1的一面，所述第一电极2为阳极。所述功能结构层3包括空穴注入层3a、空穴传输层3b、发光层3c。其中所述空穴注入层3a设于所述第一电极2上；所述空穴传输层3b设于所述空穴注入层3a上；所述发光层3c设于所述空穴传输层3b上，所述第二电极4直接设置于所述发光层3c上，所述第二电极4为阴极。
所述功能结构层3中具有掺杂材料和氧化石墨烯材料，所述掺杂材料中具有共轭离子。具体的讲，所述空穴注入层3a所用材料即采用所述掺杂材料和所述氧化石墨烯材料，在所述空穴注入层3a中， 所述掺杂材料和氧化石墨烯材料的重量比为1:1-1:99。本实施例中，将带有共轭离子的离子化合物掺杂于氧化石墨烯中，使得含有芳香环的共轭离子可以通过π-π堆叠作用接枝在所述氧化石墨烯的表面，而所述氧化石墨烯在水解后带负电，所以离子化合物中的阳离子会与其形成静电作用，从而使得离子化合物的阴阳离子作用力进一步减小，所以掺杂之后，在所述电致发光器件的电压作用下，阴阳离子会加速定向移动，原因在于掺杂的共轭离子增强了所述空穴注入层3a的注入载流子的能力，从而增强了电致发光器件的光电性能。
为了更加清楚地说明所述掺杂材料，本实施例中，所述掺杂材料选用N，N二甲基二亚定硝酸盐，其结构式包括以下结构式的至少一种：
Figure PCTCN2019106372-appb-000002
Figure PCTCN2019106372-appb-000003
所述氧化石墨烯的结构式如下：
Figure PCTCN2019106372-appb-000004
所述空穴传输层3b所用材料包括四苯基联苯二胺类化合物、联苯双酯、N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺中的至少一种。
本实施例中，所述功能结构层3还可以设置电子传输层3d、电子注入层3e；所述电子传输层3d设于所述发光层3c上；所述电子注入层3e设于所述电子传输层3d上；所述第二电极4设于所述电子注入层3e上。
本实施例中，所述功能结构层3中还可以设置电子阻挡层(图未示)，设于所述第一电极2和所述第二电极4之间。例如可以设置在发光层3c和所述空穴传输层3b之间，使得当电流施加至阳极和阴极之间时，所述电子阻挡层防止电子在有机发光层3c中泄漏。
本实施例中，所述功能结构层3中还可以设置空穴阻挡层(图未示)，设于所述第一电极2和所述第二电极4之间。例如可以设置在所述电子传输层3d和所述发光层3c之间，使得当电流施加至阳极和阴极之间时，所述空穴阻挡层能够将载流子和激子限制在所述发光层3c中。
由于所述阳极可以容易地注入空穴到空穴注入层3a或空穴传输层3b或发光层3c中，所述阳极的功函数和所述发光层3c中的发光体或所述空穴注入层3a或所述空穴传输层3b或所述空穴注入层3a或所述电子阻挡层的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV，最好是小于0.2eV。
所述阳极材料可选用导电金属或金属氧化物或导电聚合物，例如选择铝铜、金、银、镁、铁、钴、镍、钼、钯、铂、氧化铟锡、铝掺杂氧化锌等。其他合适的阳极材料是已知的，本领域普通技术人员可容易地选择使用。所述阳极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包含射频磁控溅射、真空热蒸法、电子束(e-beam)沉积方法等。所述阳极是图案结构化的。图案化的氧化铟锡导电玻璃1可在市场上买到，并且可以用来制备本发明的器件。
所述阴极可选用导电金属或金属氧化物或金属合金或导电聚合物。原则上，所有可用作所述电致发光器件10的阴极的材料都可能作为本发明电致发光器件10的阴极材料，例如：铝、金、银、钙、钡、镁、氟化锂和铝、镁银合金、氟化钡和铝、铜、铁、钴、镍、钼、钯、铂、氧化铟锡等。所述阴极可以容易地注入电子到电子注入层 3e或电子传输层3d或直接到发光层3c中。在一个实施例中，所述阴极的功函数和所述发光层3c中发光体或所述电子注入层3e或所述电子传输层3d或所述空穴阻挡层的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV，最好是小于0.2eV。阴极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包含射频磁控溅射、真空热蒸法、电子束(e-beam)沉积方法等。
所述发光层3c为有机发光层，其中掺杂有机发光材料，有机发光材料选自单重态发光体、三重态发光体或者热激活延迟荧光发光材料(TADF)。
方法示例1
本发明还提供了一种制备方法，用以制备所述的电致发光器件10，包括以下步骤：
提供一表面具有所述第一电极2的导电玻璃1；具体的，在提供一表面具有所述第一电极2的导电玻璃1步骤中，包括用去离子水清洗所述导电玻璃1，再用温水润洗所述导电玻璃1，润洗时间为30分钟-50分钟，润洗后烘干，所述温水的温度保持在15℃-35℃；然后用等离子体清洗器清洗所述导电玻璃1，清洗时间为6分钟-15分钟。可以增加所述第一电极2的表面功函数至4eV-8eV以上，并提高了所述第一电极2与后续所述功能结构层3之间的界面接触。
形成所述功能结构层3于所述导电玻璃1具有所述第一电极2的一面。
具体的，在所述的形成所述功能结构层3步骤中包括以下步骤：
提供所述掺杂材料和所述氧化石墨烯材料，将所述掺杂材料溶解至去离子水中得到掺杂材料溶液；将所述氧化石墨烯材料溶解至去离子水中并进行超声波震荡得到氧化石墨烯溶液，本实施例中，所述氧化石墨烯材料的浓度为0.5mg/ml，在制备所述氧化石墨烯溶液过程中，可以通过紫外光还原的方法调节所述氧化石墨烯的浓度。
将所述掺杂材料溶液掺杂至所述氧化石墨烯溶液中，并进行超声分散2小时-4小时,同时将温度调至30-50℃，得到混合溶液，在所述混合溶液中，所述掺杂材料的重量百分比为10wt％。将所述混合溶液涂布于所述导电玻璃1具有所述第一电极2的表面形成所述空穴注入层3a。
在形成所述空穴注入层3a之后，将所述导电玻璃1固定在掩模板上，并转移到真空蒸镀腔室内，使用分子泵对所述真空蒸镀腔室抽真空，直至所述真空蒸镀腔室的真空度低于4.0×10 -4-6.5×10 -4Pa；通过真空蒸镀法在所述空穴传输层3b上蒸镀四苯基联苯二胺类化合物、联苯双酯、N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺中的一种或者两种混合溶液或者三种混合溶液于所述空穴注入层3a上，形成所述空穴传输层3b。
在形成所述空穴传输层3b后，依次形成所述发光层3c、所述电子传输层3d、所述电子注入层。所述发光层3c所用材料可以选择三(8-羟基喹啉)铝，所述电子注入层所用材料为氟化锂。所述空穴传输层3b的所用有机材料以及三(8-羟基喹啉)铝的蒸镀速率控制在
Figure PCTCN2019106372-appb-000005
所述氟化锂的蒸镀速率控制在
Figure PCTCN2019106372-appb-000006
当形成所述功能结构层3后，再在所述功能结构层3上蒸镀所述第二电极4，本示例中，所述第二电极4所用材料为铝，蒸镀速率控制在
Figure PCTCN2019106372-appb-000007
最终形成所述的电致发光器件10。
方法示例2
本方法示例与方法示例1的区别在于：在所述混合溶液中，所述掺杂材料的重量百分比为20wt％。
方法示例3
本方法示例与方法示例1的区别在于：在所述混合溶液中，所述掺杂材料的重量百分比为30wt％。
方法示例4
本方法示例与方法示例1的区别在于：在所述混合溶液中，所述掺杂材料的重量百分比为40wt％。
方法示例5
本方法示例与方法示例1的区别在于：在所述混合溶液中，所述掺杂材料的重量百分比为50wt％。
对比例1
本对比例1与方法示例1的区别在于：在所述氧化石墨烯溶液中，不掺杂具有共轭离子的掺杂材料，直接使用氧化石墨烯溶液制作空穴注入层3a。
当然在其他的方法示例中，所述混合溶液中的所述掺杂材料的重量百分比还可以为0.1wt％、1wt％等。为了方便比较性能，本发明选择方法示例1-5所制得的电致发光器件并对其电致发光性能进行 检测。
如图2所示，本对比例1和方法示例1-5所制得的电致发光器件，其电致发光光谱的波峰位置都在500nm左右，说明所述氧化石墨烯本身的浓度对所述发光层3c为三(8-羟基喹啉)铝的电致发光峰没有太大的影响。
如图3所示，其他功能层保持不变，判断出在所述混合溶液中，共轭离子的浓度影响空穴注入能力，即在所述混合溶液中，所述掺杂材料的浓度影响空穴注入能力，在所述掺杂材料的重量百分比小于等于20wt％的范围内，随着所述掺杂材料的浓度的增加，所述电致发光器件的发光能力也会提高，但是在所述掺杂材料的重量百分比达到20wt％以上时，则会带来共轭离子过剩的问题，即在电压在7.5V以后，所述电致发光器件的亮度开始下降，因为所述电致发光器件的电流密度快速增加，可能是空穴注入能力增强引起的，但是电子注入水平没有得到提高，导致所述电致发光器件中的非辐射复合增加，以使其亮度下降。
参见图1所示，本发明还提供了一种电子设备100，具有所述的电致发光器件10。本发明的主要设计要点在于电致发光器件10，至于其他结构就不再一一赘述。本发明的所述电子设备100，包括具有本发明的电致发光器件10所有电子设备100，包括显示设备、照明设备、光源、传感器等等。
以上仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应 包含在本发明的保护范围之内。

Claims (10)

  1. 一种电致发光器件，其包括
    第一电极和第二电极；以及
    功能结构层，设于所述第一电极和所述第二电极之间；
    所述功能结构层中具有掺杂材料和氧化石墨烯材料，所述掺杂材料中具有共轭离子。
  2. 根据权利要求1所述的电致发光器件，其中，所述功能结构层包括空穴注入层，其所用材料中具有所述掺杂材料和所述氧化石墨烯材料，所述掺杂材料中具有共轭离子；所述空穴注入层设于所述第一电极上；
    空穴传输层，设于所述空穴注入层上；
    发光层，设于所述空穴传输层上；
    电子传输层，设于所述发光层上；
    电子注入层，设于所述电子传输层上；
    所述第二电极设于所述电子注入层上。
  3. 根据权利要求1所述的电致发光器件，其中，所述空穴传输层所用材料包括四苯基联苯二胺类化合物、联苯双酯、N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺中的至少一种。
  4. 根据权利要求1所述的电致发光器件，其中，所述掺杂材料为N，N二甲基二亚定硝酸盐；所述掺杂材料与所述氧化石墨烯材料的重量比为1：1-1:99。
  5. 根据权利要求4所述的电致发光器件，其中，所述N，N二甲基二亚定硝酸盐的结构式包括以下结构式的至少一种：
    Figure PCTCN2019106372-appb-100001
  6. 一种制备方法，用以制备权利要求1所述的电致发光器件，其包括以下步骤：
    提供一导电玻璃，其表面具有所述第一电极；
    形成所述功能结构层于所述导电玻璃具有所述第一电极的一面，所述功能结构层中具有掺杂材料和氧化石墨烯材料，所述掺杂材料中具有共轭离子；
    通过真空蒸镀法形成所述第二电极于所述功能结构层远离所述第一电极的一侧。
  7. 根据权利要求6所述的制备方法，其中，在所述的提供所述导电玻璃的步骤中，包括
    用去离子水清洗所述导电玻璃，再用温水润洗所述导电玻璃30分钟 -50分钟后烘干，所述温水的温度保持在15℃-35℃；
    然后用等离子体清洗器清洗所述导电玻璃6分钟-15分钟。
  8. 根据权利要求6所述的制备方法，其中，在所述的形成所述功能结构层步骤中包括
    提供所述掺杂材料和所述氧化石墨烯材料，将所述掺杂材料溶解至去离子水中得到掺杂材料溶液，将所述氧化石墨烯材料溶解至去离子水中并进行超声波震荡得到氧化石墨烯溶液；
    将所述掺杂材料溶液掺杂至所述氧化石墨烯溶液中，并进行超声分散2小时-4小时,同时将温度调至30-50℃，得到混合溶液，在所述混合溶液中，所述掺杂材料的重量百分比为0.1wt％-50wt％；
    将所述混合溶液涂布于所述导电玻璃具有所述第一电极的表面形成所述空穴注入层。
  9. 根据权利要求1所述的制备方法，其中，在所述的形成所述功能结构层步骤中还包括
    在形成所述空穴注入层之后，将所述导电玻璃固定在掩模板上，并转移到真空蒸镀腔室内，使用分子泵对所述真空蒸镀腔室抽真空，直至所述真空蒸镀腔室的真空度低于4.0×10 -4-6.5×10 -4Pa；
    通过真空蒸镀法在所述空穴传输层上依次形成所述空穴传输层、所述发光层、所述电子传输层、所述电子注入层。
  10. 一种电子设备，其具有如权利要求1所述的电致发光器件。
PCT/CN2019/106372 2019-06-20 2019-09-18 电致发光器件及其制备方法、电子设备 WO2020252953A1 (zh)

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