WO2023051054A1 - Nano-graphite printing liquid and preparation method therefor, and organic light-emitting diode - Google Patents

Abstract

A nano-graphite printing liquid and an organic light-emitting diode prepared therefrom. The nano-graphite printing liquid comprises: 0.1-0.7% of a nano-graphite particle, 0.2-0.8% of a polymer dispersant, 2.5-4% of a viscosity modifier, and the balance of a substrate wetting agent. The nano-graphite printing liquid is not prone to agglomeration and precipitation, and has good system stability.

Description

纳米石墨打印液及其制备方法、有机发光二极管Nano-graphite printing liquid and preparation method thereof, organic light-emitting diode

本申请要求于2021年09月28日提交中国专利局，申请号为202111145219.7，申请名称为“纳米石墨打印液及其制备方法、有机发光二极管”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on September 28, 2021, with the application number 202111145219.7, and the application name is "Nanographite Printing Liquid and Its Preparation Method, Organic Light-Emitting Diode", the entire content of which is incorporated incorporated in this application.

技术领域technical field

本申请属于打印材料技术领域，尤其涉及一种纳米石墨打印液及其制备方法，以及一种有机发光二极管。The application belongs to the technical field of printing materials, and in particular relates to a nano-graphite printing liquid and a preparation method thereof, and an organic light-emitting diode.

背景技术Background technique

OLED显示器件通常包括基板、阳极、发光层和阴极，为了提高载离子注入水平，还会在电极和发光层之间设置空穴注入层、空穴传输层、电子注入层、电子传输层等。典型的OLED显示器件包括基板、阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层和阴极。为了提高OLED的发光性能，可用喷墨打印技术在阳极上喷涂自组层，利用纳米粒子的光学和电学效应提升OLED器件的综合性能。将金属纳米粒子制成喷涂液，有望实现纳米粒子的上述性能。但是，喷涂液中的金属纳米粒子易发生团聚、沉淀，这样不仅不能提升OLED的综合性能，还会影响OLED的空穴传输性能。OLED display devices usually include a substrate, an anode, a light-emitting layer, and a cathode. In order to increase the level of ion-carrying injection, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, etc. are arranged between the electrode and the light-emitting layer. A typical OLED display device includes a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode. In order to improve the luminous performance of OLED, inkjet printing technology can be used to spray a self-assembled layer on the anode, and the optical and electrical effects of nanoparticles can be used to improve the comprehensive performance of OLED devices. The above-mentioned properties of nanoparticles are expected to be realized by making metal nanoparticles into spraying liquid. However, the metal nanoparticles in the spraying liquid are prone to agglomeration and precipitation, which not only fails to improve the overall performance of the OLED, but also affects the hole transport performance of the OLED.

技术问题technical problem

本申请的目的在于提供一种纳米石墨打印液及其制备方法，以及一种有机发光二极管，旨在解决现有的喷涂液中的纳米粒子容易团聚、沉淀，影响OLED的空穴传输性能的问题。The purpose of this application is to provide a nano-graphite printing liquid and its preparation method, as well as an organic light-emitting diode, aiming to solve the problem that the nanoparticles in the existing spraying liquid are easy to agglomerate and precipitate, which affects the hole transport performance of OLED .

技术解决方案technical solution

为实现上述申请目的，本申请采用的技术方案如下：In order to realize the above-mentioned application purpose, the technical scheme adopted in this application is as follows:

本申请一方面提供一种纳米石墨打印液，以所述纳米石墨打印液的总质量为100%计，所述纳米石墨打印液包括如下质量百分含量的下列组分：On the one hand, the present application provides a nano-graphite printing liquid, based on the total mass of the nano-graphite printing liquid as 100%, the nano-graphite printing liquid includes the following components in the following mass percentages:

纳米石墨粒子      0.1~0.7%，Nano Graphite Particles 0.1~0.7%,

高分子分散剂      0.2~0.8%，polymer dispersant 0.2~0.8%,

粘度调节剂        2.5~4%，Viscosity modifiers 2.5~4%,

基材润湿剂余量。Substrate wetting agent balance.

可选的，所述纳米石墨粒子的粒径小于或等于50nm。Optionally, the particle size of the graphite nano particles is less than or equal to 50nm.

可选的，所述纳米石墨粒子的粒径为10~30nm。Optionally, the particle size of the graphite nano particles is 10-30 nm.

可选的，所述高分子分散剂吸附在所述纳米石墨粒子表面，形成高分子吸附层。Optionally, the polymer dispersant is adsorbed on the surface of the graphite nano particles to form a polymer adsorption layer.

可选的，所述高分子分散剂选自失水山梨醇油酸酯、硬脂酸单甘油酯、乙撑基双硬脂酰胺中的至少一种。Optionally, the polymer dispersant is at least one selected from sorbitan oleate, monoglyceride stearate, and ethylene bisstearamide.

可选的，所述基材润湿剂选自非离子型表面活性剂。Optionally, the substrate wetting agent is selected from nonionic surfactants.

可选的，所述基材润湿剂选自烷基酚醚表面活性剂、聚氧乙烯脂肪醇醚表面活性剂、聚氧乙烯聚氧丙烯嵌段共聚物表面活性剂、硅醇类表面活性剂中的至少一种。Optionally, the substrate wetting agent is selected from alkylphenol ether surfactants, polyoxyethylene fatty alcohol ether surfactants, polyoxyethylene polyoxypropylene block copolymer surfactants, silanol surfactants at least one of the agents.

可选的，还包括其他助剂。Optionally, other additives are also included.

本申请第二方面提供一种纳米石墨打印液的制备方法，包括以下步骤：The second aspect of the present application provides a method for preparing nano-graphite printing liquid, comprising the following steps:

取纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂，将纳米石墨粒子和基材润湿剂混合处理，得到纳米石墨溶液；Taking nano-graphite particles, polymer dispersant, viscosity regulator and substrate wetting agent, mixing the nano-graphite particles and substrate wetting agent to obtain nano-graphite solution;

在所述纳米石墨溶液中加入所述高分子分散剂和所述粘度调节剂后，对得到的混合物料进行机械搅拌，得到第一混合体系；After adding the polymer dispersant and the viscosity modifier into the nano-graphite solution, mechanically stir the obtained mixed material to obtain the first mixed system;

将所述第一混合体系进行超声震荡处理，得到纳米石墨打印液；Ultrasonic vibration treatment is performed on the first mixed system to obtain nano-graphite printing liquid;

其中，所述纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂在所述纳米石墨打印液中的质量百分含量如下：Wherein, the mass percentages of the nano-graphite particles, polymer dispersant, viscosity regulator and substrate wetting agent in the nano-graphite printing liquid are as follows:

纳米石墨粒子      0.1~0.7%，Nano Graphite Particles 0.1~0.7%,

高分子分散剂      0.2~0.8%，polymer dispersant 0.2~0.8%,

粘度调节剂        2.5~4%，Viscosity modifiers 2.5~4%,

基材润湿剂余量。Substrate wetting agent balance.

可选的，所述机械搅拌时间为30~60min。Optionally, the mechanical stirring time is 30-60 minutes.

可选的，在所述机械搅拌处理中，促进所述高分子分散剂在所述纳米石墨粒子表面的吸附。Optionally, during the mechanical stirring treatment, the adsorption of the polymer dispersant on the surface of the graphite nanoparticles is promoted.

可选的，所述超声震荡处理的波长为微米级波长，超声频率大于或等于20KHz，超声震荡处理的时间30~120min。Optionally, the wavelength of the ultrasonic vibration treatment is a micron-scale wavelength, the ultrasonic frequency is greater than or equal to 20KHz, and the time of the ultrasonic vibration treatment is 30 to 120 minutes.

可选的，所述机械搅拌时间为30~60min；所述超声震荡处理的波长为微米级波长，超声频率大于或等于20KHz，超声震荡处理的时间30~120min。Optionally, the mechanical stirring time is 30-60 min; the wavelength of the ultrasonic vibration treatment is a micron-scale wavelength, the ultrasonic frequency is greater than or equal to 20 KHz, and the ultrasonic vibration treatment time is 30-120 min.

本申请第三方面提供一种有机发光二极管，包括相对设置的阳极和阴极，在所述阳极和所述阴极之间层叠设置的有机发光层，在有机发光层和所述阳极之间层叠设置的纳米石墨层，所述纳米石墨层由本申请第一方面提供的所述纳米石墨打印液打印形成。The third aspect of the present application provides an organic light emitting diode, including an anode and a cathode disposed opposite to each other, an organic light-emitting layer is stacked between the anode and the cathode, and an organic light-emitting layer is stacked between the organic light-emitting layer and the anode A nano-graphite layer, the nano-graphite layer is formed by printing the nano-graphite printing solution provided in the first aspect of the present application.

可选的，所述有机发光二极管还包括层叠设置在所述阴极和所述有机发光层之间的电子注入层和电子传输层之间的至少一层。Optionally, the organic light emitting diode further includes at least one layer between an electron injection layer and an electron transport layer stacked between the cathode and the organic light emitting layer.

可选的，所述有机发光二极管还包括层叠设置在所述纳米石墨层和所述有机发光层之间的空穴注入层和空穴传输层之间的至少一层；所述有机发光二极管还包括层叠设置在所述阴极和所述有机发光层之间的电子注入层和电子传输层之间的至少一层。Optionally, the organic light emitting diode further includes at least one layer between the hole injection layer and the hole transport layer stacked between the nano graphite layer and the organic light emitting layer; the organic light emitting diode also It includes at least one layer between the electron injection layer and the electron transport layer stacked between the cathode and the organic light emitting layer.

本申请提供的纳米石墨打印液，高分子分散剂吸附在纳米石墨粒子表面形成高分子吸附层，保持纳米石墨粒子的稳定分散，并提高纳米石墨粒子的分散性；同时，高分子分散剂的吸附促使纳米石墨粒子表面形成电荷，从而提高纳米石墨粒子之间的反作用力，最终得到性能稳定的纳米石墨打印液。相较于金属纳米粒子形成的纳米粒子喷涂液，本申请提供的纳米石墨打印液纳米石墨离子分布均匀，不易发生团聚和沉淀，具有很好的体系稳定性。In the nano-graphite printing liquid provided by this application, the polymer dispersant is adsorbed on the surface of the nano-graphite particles to form a polymer adsorption layer, which keeps the stable dispersion of the nano-graphite particles and improves the dispersibility of the nano-graphite particles; at the same time, the adsorption of the polymer dispersant Prompting the formation of charges on the surface of nano-graphite particles, thereby increasing the reaction force between nano-graphite particles, and finally obtaining nano-graphite printing fluid with stable performance. Compared with the nano-particle spraying liquid formed of metal nanoparticles, the nano-graphite printing liquid provided by this application has uniform distribution of nano-graphite ions, is not prone to agglomeration and precipitation, and has good system stability.

本申请提供的纳米石墨打印液的制备方法，通过机械搅拌和超声震荡提高混合物料的分散均匀性，同时，高分子分散剂在纳米石墨粒子表面形成高分子吸附层，进一步提高纳米石墨粒子的分散性。经过物理分散和化学分散的双层作用，形成的纳米石墨喷打印液体系稳定性好，纳米石墨分布均匀，不易发生团聚和沉淀现象。The preparation method of the nano-graphite printing liquid provided by this application improves the dispersion uniformity of the mixed material through mechanical stirring and ultrasonic vibration. At the same time, the polymer dispersant forms a polymer adsorption layer on the surface of the nano-graphite particles to further improve the dispersion of the nano-graphite particles. sex. After the double-layer effect of physical dispersion and chemical dispersion, the formed nano-graphite jet printing liquid system has good stability, the distribution of nano-graphite is uniform, and it is not easy to agglomerate and precipitate.

本申请提供的有机发光二极管，在阳极表面打印第一方面提供的纳米石墨打印液，由于纳米石墨打印液的分散均匀性和稳定性增强，纳米石墨分布均匀，不易发生团聚和沉淀，可以降低甚至消除对OLED空穴传输性能的影响，不仅如此，纳米石墨的具有体积效应、量子隧道效应以及表面效应，纳米石墨表面的等离子基元可以在几纳米的尺度内上产生局部强烈电场，可加强电子的通过速率，进而加强激子的产生速率，可以大大提高OLED的发光效率。纳米石墨打印液中的基材润湿剂赋予打印液超级铺展性，可以降低水性体系表面张力，提高对基材的润湿能力，进而提高纳米石墨打印液与玻璃基板的附着能力。此外，纳米石墨打印液中不含金属纳米粒子，可以避免OLED内的激子碰撞金属纳米粒子产生的解离现象，进一步提高器件发光效率。The organic light-emitting diode provided by this application prints the nano-graphite printing liquid provided by the first aspect on the surface of the anode. Because the dispersion uniformity and stability of the nano-graphite printing liquid are enhanced, the nano-graphite is evenly distributed, and it is not easy to agglomerate and precipitate, which can reduce even Eliminate the impact on OLED hole transport performance, not only that, nano-graphite has volume effect, quantum tunneling effect and surface effect, the plasmon element on the surface of nano-graphite can generate local strong electric field on the scale of several nanometers, which can strengthen electrons The pass rate, and then enhance the exciton generation rate, can greatly improve the luminous efficiency of OLED. The substrate wetting agent in the nano-graphite printing liquid endows the printing liquid with super spreadability, which can reduce the surface tension of the water-based system, improve the wetting ability to the substrate, and then improve the adhesion between the nano-graphite printing liquid and the glass substrate. In addition, the nano-graphite printing liquid does not contain metal nanoparticles, which can avoid the dissociation phenomenon caused by the excitons in the OLED colliding with the metal nanoparticles, and further improve the luminous efficiency of the device.

附图说明Description of drawings

为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或现有技术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申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present application, the accompanying drawings that need to be used in the descriptions of the embodiments or the prior art will be briefly introduced below. Obviously, the accompanying drawings in the following description are only for the present application For some embodiments, those of ordinary skill in the art can also obtain other drawings based on these drawings without paying creative efforts.

图1是本申请实施例提供的高分子分散剂吸附在纳米石墨粒子表面的示意图；Fig. 1 is the schematic diagram that the macromolecule dispersant that the embodiment of the present application provides is adsorbed on the surface of nano-graphite particles;

图2是本申请实施例提供的纳米石墨打印液的制备工艺流程示意图；Fig. 2 is a schematic diagram of the preparation process of the nano-graphite printing solution provided in the embodiment of the present application;

图3是本申请实施例提供的有机发光二极管器件的结构示意图。Fig. 3 is a schematic structural diagram of an organic light emitting diode device provided by an embodiment of the present application.

本发明的实施方式Embodiments of the present invention

为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。In order to make the technical problems, technical solutions and beneficial effects to be solved in the present application clearer, the present application will be further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present application, and are not intended to limit the present application.

本申请中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。In this application, the term "and/or" describes the association relationship of associated objects, indicating that there may be three relationships, for example, A and/or B may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural. The character "/" generally indicates that the contextual objects are an "or" relationship.

本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项（个）或复数项（个）的任意组合。例如，“ a,b,或c中的至少一项（个）”，或，“a,b,和c中的至少一项（个）”，均可以表示：a, b, c, a-b（即a和b）, a-c, b-c, 或a-b-c，其中a,b,c分别可以是单个，也可以是多个。In this application, "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one (one) of a, b, or c", or "at least one (one) of a, b, and c" can mean: a, b, c, a-b ( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

应理解，在本申请的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实施例的实施过程构成任何限定。It should be understood that in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the order of execution, and some or all steps may be executed in parallel or sequentially, and the execution order of each process shall be based on its functions and The internal logic is determined and should not constitute any limitation to the implementation process of the embodiment of the present application.

在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。Terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of this application and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

术语“第一”、“第二”仅用于描述目的，用来将目的如物质彼此区分开，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。例如，在不脱离本申请实施例范围的情况下，第一XX也可以被称为第二XX，类似地，第二XX也可以被称为第一XX 。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。The terms "first" and "second" are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX can also be called the second XX, and similarly, the second XX can also be called the first XX. Thus, a feature defined as "first" and "second" may explicitly or implicitly include one or more of these features.

术语“OLED”为“Organic Electroluminescence Display”的缩写，表示有机发光二极管，又称有机电激光显示、有机发光半导体。The term "OLED" is "Organic The abbreviation of "Electroluminescence Display" means organic light-emitting diode, also known as organic electric laser display and organic light-emitting semiconductor.

以纳米金、纳米银、纳米铜、纳米铝等金属纳米粒子制作的喷涂液，金属纳米粒子易发生团聚、沉淀，这样不仅不能提升OLED的综合性能，还会影响OLED的空穴传输。此外，金属纳米粒子还会使OLED产生的激子解离，从而影响OLED的光耦合效率。有鉴于此，本申请实施例开发一种全新的纳米石墨打印液，以改善喷涂液的分散稳定性，使其能够满足喷墨打印的需求，并能够用作OLED的阳极表面，提高OLED器件的综合性能。具体的，Spraying liquids made of metal nanoparticles such as nano-gold, nano-silver, nano-copper, and nano-aluminum are prone to agglomeration and precipitation. This will not only fail to improve the overall performance of OLEDs, but also affect the hole transport of OLEDs. In addition, metal nanoparticles can also dissociate the excitons generated by OLEDs, thereby affecting the light coupling efficiency of OLEDs. In view of this, the embodiment of the present application develops a brand-new nano-graphite printing liquid to improve the dispersion stability of the spray liquid, so that it can meet the needs of inkjet printing, and can be used as the anode surface of OLED to improve the performance of OLED devices. Comprehensive performance. specific,

第一方面，本申请实施例提供一种纳米石墨打印液，包括纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂。In the first aspect, the embodiment of the present application provides a nano-graphite printing liquid, including nano-graphite particles, a polymer dispersant, a viscosity regulator and a substrate wetting agent.

本申请实施例提供的纳米石墨打印液，高分子分散剂吸附在纳米石墨粒子表面形成高分子吸附层，保持纳米石墨粒子的稳定分散，并提高纳米石墨粒子的分散性；同时，高分子分散剂的吸附促使纳米石墨粒子表面形成电荷，从而提高纳米石墨粒子之间的反作用力，最终得到性能稳定的纳米石墨打印液。相较于金属纳米粒子形成的纳米粒子喷涂液，本申请提供的纳米石墨打印液纳米石墨离子分布均匀，不易发生团聚和沉淀，具有很好的体系稳定性。In the nano-graphite printing solution provided in the embodiments of the present application, the polymer dispersant is adsorbed on the surface of the nano-graphite particles to form a polymer adsorption layer, which keeps the stable dispersion of the nano-graphite particles and improves the dispersibility of the nano-graphite particles; at the same time, the polymer dispersant The adsorption promotes the formation of charges on the surface of nano-graphite particles, thereby increasing the reaction force between nano-graphite particles, and finally obtaining nano-graphite printing fluid with stable performance. Compared with the nano-particle spraying liquid formed of metal nanoparticles, the nano-graphite printing liquid provided by this application has uniform distribution of nano-graphite ions, is not prone to agglomeration and precipitation, and has good system stability.

本申请实施例中，纳米石墨粒子作为纳米石墨打印液的功能性粒子，具有体积效应、量子隧道效应以及表面效应。本申请实施例将纳米石墨粒子分散在高分子分散剂、粘度调节剂和基材润湿剂中，形成稳定分散的纳米石墨打印液，用于形成在OLED阳极朝向发光层的一侧表面，形成纳米石墨自组装层，用于提高OLED的发光效率。In the embodiment of the present application, as the functional particles of the nano-graphite printing liquid, the nano-graphite particles have volume effect, quantum tunneling effect and surface effect. In the embodiment of the present application, nano-graphite particles are dispersed in a polymer dispersant, a viscosity modifier and a substrate wetting agent to form a stable dispersed nano-graphite printing solution, which is used to form on the surface of the OLED anode facing the light-emitting layer to form Nano-graphite self-assembled layer is used to improve the luminous efficiency of OLED.

在一些实施例中，以纳米石墨打印液的总质量为100%计，纳米石墨粒子的质量百分含量为0.1~0.7%。在这种情况下，纳米石墨打印液形成稳定的悬浊液。若纳米石墨打印液中纳米石墨粒子的含量过低，则不能显著发挥纳米石墨粒子的性能。示例性的，当将纳米石墨打印液用于形成在OLED阳极朝向发光层的一侧表面，形成纳米石墨自组装层时，若纳米石墨打印液中纳米石墨粒子的含量过低，低于0.1%，则不能有效提高OLED的发光效率。若纳米石墨打印液中纳米石墨粒子的含量过高，纳米石墨粒子容易沉降，不容易形成稳定的悬浊液体系，且容易造成打印喷头的堵塞。示例性的，以纳米石墨打印液的总质量为100%计，纳米石墨粒子的质量百分含量为0.1%、0.2%、0.3%、0.4%、0.5%、0.6%、0.7%等具体含量。In some embodiments, based on 100% of the total mass of the graphite nano-printing liquid, the mass percentage of the graphite nano-particles is 0.1-0.7%. In this case, nano-graphite printing fluid forms a stable suspension. If the content of nano-graphite particles in the nano-graphite printing liquid is too low, the performance of the nano-graphite particles cannot be significantly exerted. Exemplarily, when the nano-graphite printing liquid is used to form the surface of the OLED anode facing the light-emitting layer to form a nano-graphite self-assembled layer, if the content of nano-graphite particles in the nano-graphite printing liquid is too low, less than 0.1% , the luminous efficiency of the OLED cannot be effectively improved. If the content of nano-graphite particles in the nano-graphite printing liquid is too high, the nano-graphite particles are easy to settle, it is not easy to form a stable suspension system, and it is easy to cause blockage of the printing nozzle. Exemplarily, based on the total mass of the nanographite printing liquid as 100%, the mass percentage of the nanographite particles is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% and other specific contents.

在一些实施例中，纳米石墨粒子的粒径小于或等于50nm。粒径小于或等于50nm的纳米石墨粒子，具有较好的体积效应、量子隧道效应以及表面效应，从而使得纳米石墨打印液用于OLED时，能够提高OLED的发光效率。石墨粒子的粒径越小，越容易形成稳定的分散体系。若纳米石墨粒子的粒径过大，由于重力效应纳米石墨打印液中的纳米石墨粒子容易发生团聚而沉淀，导致纳米石墨打印液不稳定。特别的，当将纳米石墨打印液用于形成在OLED阳极朝向发光层的一侧表面，形成纳米石墨自组装层时，纳米石墨粒子的粒径过大，还会影响空穴传输效果。在一些实施例中，纳米石墨粒子的粒径为10~30nm。此时，得到的纳米石墨打印液在高分子分散剂、粘度调节剂和基材润湿剂的分散体系中具有优异的分散稳定性。In some embodiments, the particle size of the graphite nanoparticles is less than or equal to 50 nm. Nano-graphite particles with a particle size less than or equal to 50nm have good volume effect, quantum tunneling effect and surface effect, so that when nano-graphite printing liquid is used in OLED, it can improve the luminous efficiency of OLED. The smaller the particle size of graphite particles, the easier it is to form a stable dispersion system. If the particle size of the nano-graphite particles is too large, the nano-graphite particles in the nano-graphite printing liquid are prone to agglomeration and precipitation due to the gravitational effect, resulting in the instability of the nano-graphite printing liquid. In particular, when the nano-graphite printing solution is used to form a nano-graphite self-assembled layer on the surface of the OLED anode facing the light-emitting layer, the particle size of the nano-graphite particles is too large, which will also affect the hole transport effect. In some embodiments, the diameter of the graphite nano-particles is 10-30 nm. At this time, the obtained nano-graphite printing liquid has excellent dispersion stability in the dispersion system of the polymer dispersant, the viscosity modifier and the substrate wetting agent.

本申请实施例中，高分子分散剂用于保持纳米石墨粒子在纳米石墨打印液中的分散均匀性。具体的，参考图1，一方面，高分子分散剂吸附在纳米石墨粒子（2）表面，形成高分子吸附层（3），保持纳米石墨粒子的稳定分散；另一方面，高分子分散剂的吸附促使纳米石墨粒子表面电荷（1）增加，纳米石墨粒子（2）之间的反作用力提高，进一步提高纳米石墨打印液的分散稳定性。In the embodiment of the present application, the polymer dispersant is used to maintain the dispersion uniformity of the graphite nano particles in the graphite nano printing liquid. Specifically, referring to Figure 1, on the one hand, the polymer dispersant is adsorbed on the surface of the graphite nanoparticle (2) to form a polymer adsorption layer (3) to maintain the stable dispersion of the graphite nanoparticle; on the other hand, the polymer dispersant The adsorption promotes the increase of the surface charge (1) of the nano-graphite particles, and the increase of the reaction force between the nano-graphite particles (2), which further improves the dispersion stability of the nano-graphite printing liquid.

可选的，高分子分散剂选自失水山梨醇油酸酯、硬脂酸单甘油酯、乙撑基双硬脂酰胺中的至少一种。这些高分子分散剂能够吸附在纳米石墨粒子表面，防止纳米石墨粒子的团聚，提高纳米石墨打印液的分散稳定性。Optionally, the polymer dispersant is at least one selected from sorbitan oleate, monoglyceride stearate, and ethylene bisstearamide. These polymer dispersants can be adsorbed on the surface of nano-graphite particles, prevent the agglomeration of nano-graphite particles, and improve the dispersion stability of nano-graphite printing liquid.

在一些实施例中，以纳米石墨打印液的总质量为100%计，高分子分散剂的质量百分含量为0.2~0.8%。示例性的，以纳米石墨打印液的总质量为100%计，高分子分散剂的质量百分含量为0.2%、0.3%、0.4%、0.5%、0.6%、0.7%、0.8%等具体含量。In some embodiments, based on 100% of the total mass of the graphite nano-printing liquid, the mass percentage of the polymer dispersant is 0.2-0.8%. Exemplarily, based on the total mass of the nano-graphite printing liquid as 100%, the mass percentage of the polymer dispersant is 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, etc. .

本申请实施例中，添加粘度调节剂来调节纳米石墨打印液的粘度，使得纳米石墨打印液能够满足打印要求。示例性的，粘度调节剂可以选择氧化聚乙烯蜡、亚乙基双硬脂酸酰胺等，但不限于此。In the embodiment of the present application, a viscosity regulator is added to adjust the viscosity of the nano-graphite printing liquid, so that the nano-graphite printing liquid can meet the printing requirements. Exemplarily, the viscosity modifier can be selected from oxidized polyethylene wax, ethylene bis stearic acid amide, etc., but not limited thereto.

在一些实施例中，以纳米石墨打印液的总质量为100%计，粘度调节剂的质量百分含量为2.5~4%。示例性的，以纳米石墨打印液的总质量为100%计，粘度调节剂的质量百分含量为2.5%、2.8%、3.0%、3.2%、3.4%、3.5%、3.8%、4.0%等具体含量。In some embodiments, based on 100% of the total mass of the graphite nano-printing liquid, the mass percentage of the viscosity modifier is 2.5-4%. Exemplarily, based on the total mass of the nano-graphite printing liquid as 100%, the mass percentage of the viscosity modifier is 2.5%, 2.8%, 3.0%, 3.2%, 3.4%, 3.5%, 3.8%, 4.0%, etc. Specific content.

本申请实施例中，基材润湿剂作为纳米石墨打印液的主要分散溶剂，用于分散纳米石墨粒子，并提高纳米石墨打印液的铺展性，降低纳米石墨打印液的表面张力，提高纳米石墨打印液对基材的润湿能力，进而提高纳米石墨打印液与玻璃基板的附着能力。In the embodiment of this application, the substrate wetting agent is used as the main dispersing solvent of the nano-graphite printing liquid to disperse the nano-graphite particles, improve the spreadability of the nano-graphite printing liquid, reduce the surface tension of the nano-graphite printing liquid, and improve the The wetting ability of the printing liquid to the substrate, thereby improving the adhesion of the nano-graphite printing liquid to the glass substrate.

在一些实施例中，基材润湿剂选自非离子型表面活性剂。通过非离子型表面活性剂可以有效提高纳米石墨打印液与玻璃基板的附着能力，使得纳米石墨打印液形成在OLED阳极表面如阳极玻璃基板上时，纳米石墨打印液在阳极表面具有较好的铺展性，纳米石墨离子自组装形成自组装层。In some embodiments, the substrate wetting agent is selected from nonionic surfactants. The adhesion of nano-graphite printing liquid to glass substrate can be effectively improved by non-ionic surfactant, so that when nano-graphite printing liquid is formed on the OLED anode surface such as an anode glass substrate, nano-graphite printing liquid has better spread on the anode surface properties, nano-graphite ions self-assemble to form a self-assembled layer.

本申请实施例中，基材润湿剂作为纳米石墨打印液的基体成分。即纳米石墨打印液，除去纳米石墨粒子、高分子分散剂、粘度调节剂和其他可能存在的助剂，剩余的成分为基材润湿剂。在一些实施例中，基材润湿剂选自烷基酚醚表面活性剂、聚氧乙烯脂肪醇醚表面活性剂、聚氧乙烯聚氧丙烯嵌段共聚物表面活性剂、硅醇类表面活性剂中的至少一种。上述基材润湿剂对纳米石墨粒子具有一定的分散性，更重要的是，有利于纳米石墨粒子在基板上的铺展。In the embodiment of the present application, the substrate wetting agent is used as the matrix component of the nano-graphite printing liquid. That is, nano-graphite printing liquid, remove nano-graphite particles, polymer dispersant, viscosity modifier and other possible additives, and the remaining ingredients are substrate wetting agents. In some embodiments, the substrate wetting agent is selected from alkylphenol ether surfactants, polyoxyethylene fatty alcohol ether surfactants, polyoxyethylene polyoxypropylene block copolymer surfactants, silanol surfactants at least one of the agents. The substrate wetting agent mentioned above has certain dispersibility to the graphite nano-particles, and more importantly, it is beneficial to the spreading of the graphite nano-particles on the substrate.

在一些实施例中，纳米石墨打印液由纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂组成。在一些实施例中，纳米石墨打印液包括纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂，此外，还可以根据实际需要添加其他助剂。In some embodiments, the nano-graphite printing fluid consists of nano-graphite particles, a polymer dispersant, a viscosity modifier and a substrate wetting agent. In some embodiments, the nano-graphite printing liquid includes nano-graphite particles, a polymer dispersant, a viscosity regulator and a substrate wetting agent, and other additives can also be added according to actual needs.

本申请实施例中，以纳米石墨打印液的总质量为100%计，基材润湿剂的含量为纳米石墨打印液除基材润湿剂以外的其他组分含量之和的余量。示例性的，当纳米石墨打印液由纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂组成时，以纳米石墨打印液的总质量为100%计，基材润湿剂的含量为纳米石墨粒子、高分子分散剂、粘度调节剂质量百分含量之和的余量；当纳米石墨打印液包括纳米石墨粒子、高分子分散剂、粘度调节剂、基材润湿剂和其他助剂时，以纳米石墨打印液的总质量为100%计，基材润湿剂的含量为纳米石墨粒子、高分子分散剂、粘度调节剂和其他助剂质量百分含量之和的余量。In the examples of the present application, based on the total mass of the nano-graphite printing liquid as 100%, the content of the substrate wetting agent is the balance of the sum of the contents of other components of the nano-graphite printing liquid except the substrate wetting agent. Exemplarily, when the nano-graphite printing liquid is composed of nano-graphite particles, a polymer dispersant, a viscosity modifier and a substrate wetting agent, the total mass of the nano-graphite printing liquid is 100%, and the amount of the substrate wetting agent The content is the balance of the sum of the mass percentages of nano-graphite particles, polymer dispersants, and viscosity modifiers; when the nano-graphite printing liquid includes nano-graphite particles, polymer dispersants, viscosity modifiers, substrate wetting agents and other For additives, based on the total mass of nano-graphite printing liquid as 100%, the content of substrate wetting agent is the balance of the sum of the mass percentages of nano-graphite particles, polymer dispersants, viscosity modifiers and other additives .

将本申请实施例含有纳米石墨粒子的纳米石墨打印液形成在OLED阳极朝向申请层的一侧表面时，纳米石墨粒子发生自组装形成自组装层，可以改善OLED的发光效率。When the nano-graphite printing solution containing nano-graphite particles in the embodiment of the present application is formed on the surface of the OLED anode facing the application layer, the nano-graphite particles self-assemble to form a self-assembled layer, which can improve the luminous efficiency of the OLED.

本申请实施例提供的纳米石墨打印液，可以通过下述方法制备得到。The nano-graphite printing solution provided in the examples of this application can be prepared by the following method.

第二方面，如图2所示，本申请实施例提供一种纳米石墨打印液的制备方法，包括以下步骤：In the second aspect, as shown in Figure 2, the embodiment of the present application provides a method for preparing nano-graphite printing liquid, comprising the following steps:

S01. 取纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂，将纳米石墨粒子和基材润湿剂混合处理，得到纳米石墨溶液。S01. Take nano-graphite particles, polymer dispersant, viscosity modifier and substrate wetting agent, and mix the nano-graphite particles and substrate wetting agent to obtain nano-graphite solution.

该步骤中，纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂的选择如上文所述，为了节约篇幅，此处不再赘述。In this step, the selection of graphite nano-particles, polymer dispersant, viscosity regulator and substrate wetting agent is as described above, and will not be repeated here to save space.

本申请实施例中，将纳米石墨粒子和基材润湿剂混合，使纳米石墨粒子初步分散在基材润湿剂中。在一些实施例中，将纳米石墨粒子和基材润湿剂混合，进行搅拌处理，促进纳米石墨粒子在基材润湿剂中的分散。In the embodiment of the present application, the nano-graphite particles are mixed with the substrate wetting agent, so that the nano-graphite particles are preliminarily dispersed in the substrate wetting agent. In some embodiments, the nano-graphite particles and the substrate wetting agent are mixed and stirred to promote the dispersion of the nano-graphite particles in the substrate wetting agent.

S02. 在纳米石墨溶液中加入高分子分散剂和粘度调节剂后，对得到的混合物料进行机械搅拌，得到第一混合体系。S02. After adding a polymer dispersant and a viscosity modifier to the nano-graphite solution, mechanically stir the obtained mixed material to obtain the first mixed system.

该步骤中，在纳米石墨溶液中加入高分子分散剂和粘度调节剂，高分子分散剂用于提高纳米石墨粒子在液相体系中的分散性，粘度调节剂用于调节液相体系的粘度。In this step, a polymer dispersant and a viscosity regulator are added to the nano-graphite solution, the polymer dispersant is used to improve the dispersibility of the nano-graphite particles in the liquid phase system, and the viscosity modifier is used to adjust the viscosity of the liquid phase system.

本申请实施例中，在纳米石墨溶液中加入高分子分散剂和粘度调节剂后，进行机械搅拌处理。通过机械搅拌对混合物料进行物理分散，促使纳米石墨粒子与高分子分散剂均匀分散，并一定程度促进高分子分散剂在纳米石墨粒子表面的吸附。在一些实施例中，机械搅拌时间为30~60min。该搅拌条件下，能够较好的实现纳米石墨粒子与高分子分散剂的物理分散。In the examples of the present application, after adding a polymer dispersant and a viscosity regulator to the nano-graphite solution, mechanical stirring is performed. The mixed material is physically dispersed by mechanical stirring, which promotes the uniform dispersion of the nano-graphite particles and the polymer dispersant, and promotes the adsorption of the polymer dispersant on the surface of the nano-graphite particles to a certain extent. In some embodiments, the mechanical stirring time is 30-60 minutes. Under this stirring condition, the physical dispersion of the graphite nano particles and the polymer dispersant can be better realized.

S03. 将第一混合体系进行超声震荡处理，得到纳米石墨打印液。S03. Ultrasonic vibration treatment is performed on the first mixed system to obtain nano-graphite printing liquid.

该步骤中，在通过机械搅拌对混合物料进行物理分散的基础上，进一步进行超声震荡处理，进一步促进纳米石墨粒子与高分子分散剂均匀分散，并提高高分子分散剂在纳米石墨粒子表面的吸附效果，在纳米石墨粒子表面形成高分子吸附层。在此条件下，纳米石墨打印液中的纳米石墨粒子在物理分散（机械搅拌和超声震荡处理）和化学分散（高分子分散剂）的双层作用下，纳米石墨粒子的表面能被削弱，并且在纳米石墨粒子表面形成高分子吸附层，纳米粒子表面的电荷增加，提高纳米粒子间的反作用力，从而制备出性能稳定的纳米石墨打印液。In this step, on the basis of physically dispersing the mixed material by mechanical stirring, ultrasonic vibration treatment is further carried out to further promote the uniform dispersion of nano-graphite particles and polymer dispersant, and improve the adsorption of polymer dispersant on the surface of nano-graphite particles As a result, a polymer adsorption layer is formed on the surface of nano-graphite particles. Under this condition, the nano-graphite particles in the nano-graphite printing liquid are under the double-layer action of physical dispersion (mechanical stirring and ultrasonic vibration treatment) and chemical dispersion (polymer dispersant), the surface energy of the nano-graphite particles is weakened, and A polymer adsorption layer is formed on the surface of the nano-graphite particles, the charge on the surface of the nanoparticles is increased, and the reaction force between the nanoparticles is improved, thereby preparing a nano-graphite printing fluid with stable performance.

在一些实施例中，超声震荡处理的波长为微米级波长，超声频率大于或等于20KHz，超声震荡处理的时间30~120min。该条件下，有利于高分子分散剂在纳米石墨粒子表面充分结合并形成高分子吸附层，进而提高纳米石墨打印液的分散稳定性能。In some embodiments, the wavelength of the ultrasonic vibration treatment is a micron-scale wavelength, the ultrasonic frequency is greater than or equal to 20 KHz, and the time of the ultrasonic vibration treatment is 30 to 120 minutes. Under this condition, it is beneficial for the polymer dispersant to be fully combined on the surface of the nano-graphite particles to form a polymer adsorption layer, thereby improving the dispersion stability of the nano-graphite printing solution.

在一些实施例中，机械搅拌时间为30~60min；超声震荡处理的波长为微米级波长，超声频率大于或等于20KHz，超声震荡处理的时间30~120min。In some embodiments, the mechanical stirring time is 30-60 minutes; the wavelength of the ultrasonic oscillation treatment is a micron-scale wavelength, the ultrasonic frequency is greater than or equal to 20KHz, and the ultrasonic oscillation treatment time is 30-120 minutes.

本申请实施例提供的纳米石墨打印液的制备方法，通过机械搅拌和超声震荡提高混合物料的分散均匀性，同时，高分子分散剂在纳米石墨粒子表面形成高分子吸附层，进一步提高纳米石墨粒子的分散性。经过物理分散和化学分散的双层作用，形成的纳米石墨喷打印液体系稳定性好，纳米石墨分布均匀，不易发生团聚和沉淀现象。The preparation method of the nano-graphite printing solution provided in the embodiment of the present application improves the dispersion uniformity of the mixed material through mechanical stirring and ultrasonic vibration. At the same time, the polymer dispersant forms a polymer adsorption layer on the surface of the nano-graphite particles to further improve the of dispersion. After the double-layer effect of physical dispersion and chemical dispersion, the formed nano-graphite jet printing liquid system has good stability, the distribution of nano-graphite is uniform, and it is not easy to agglomerate and precipitate.

本申请实施例第三方面提供一种有机发光二极管，包括相对设置的阳极和阴极，在阳极和阴极之间层叠设置的有机发光层，在有机发光层和阳极之间层叠设置的纳米石墨层，纳米石墨层由本申请第一方面提供的纳米石墨打印液打印形成。The third aspect of the embodiment of the present application provides an organic light-emitting diode, including an anode and a cathode disposed opposite to each other, an organic light-emitting layer stacked between the anode and the cathode, and a nano-graphite layer stacked between the organic light-emitting layer and the anode, The nano-graphite layer is formed by printing the nano-graphite printing solution provided in the first aspect of the present application.

本申请实施例提供的有机发光二极管，在阳极表面打印第一方面提供的纳米石墨打印液，由于纳米石墨打印液的分散均匀性和稳定性增强，纳米石墨分布均匀，不易发生团聚和沉淀，可以降低甚至消除对OLED空穴传输性能的影响，不仅如此，纳米石墨的具有体积效应、量子隧道效应以及表面效应，纳米石墨表面的等离子基元可以在几纳米的尺度内上产生局部强烈电场，可加强电子的通过速率，进而加强激子的产生速率，可以大大提高OLED的发光效率。纳米石墨打印液中的基材润湿剂赋予打印液超级铺展性，可以降低水性体系表面张力，提高对基材的润湿能力，进而提高纳米石墨打印液与玻璃基板的附着能力。此外，纳米石墨打印液中不含金属纳米粒子，可以避免OLED内的激子碰撞金属纳米粒子产生的解离现象，进一步提高器件发光效率。The organic light-emitting diode provided in the embodiment of the present application prints the nano-graphite printing liquid provided in the first aspect on the surface of the anode. Due to the enhanced dispersion uniformity and stability of the nano-graphite printing liquid, the distribution of nano-graphite is uniform, and it is not easy to agglomerate and precipitate. Reduce or even eliminate the impact on OLED hole transport performance, not only that, nano-graphite has volume effect, quantum tunneling effect and surface effect, and the plasmon element on the surface of nano-graphite can generate local strong electric field on the scale of several nanometers, which can Enhancing the passage rate of electrons, and then enhancing the generation rate of excitons, can greatly improve the luminous efficiency of OLEDs. The substrate wetting agent in the nano-graphite printing liquid endows the printing liquid with super spreadability, which can reduce the surface tension of the water-based system, improve the wetting ability to the substrate, and then improve the adhesion between the nano-graphite printing liquid and the glass substrate. In addition, the nano-graphite printing liquid does not contain metal nanoparticles, which can avoid the dissociation phenomenon caused by the excitons in the OLED colliding with the metal nanoparticles, and further improve the luminous efficiency of the device.

在一些实施例中，有机发光二极管还包括层叠设置在阴极和有机发光层之间的电子注入层和电子传输层之间的至少一层。示例性的，有机发光二极管还包括层叠设置在阴极和有机发光层之间的电子传输层；或，有机发光二极管还包括层叠设置在阴极和有机发光层之间的电子注入层和电子传输层。当然，阴极和有机发光层之间也可以设置一层同时具有电子注入和电子传输功能的材料层。In some embodiments, the organic light emitting diode further includes at least one layer between the electron injection layer and the electron transport layer stacked between the cathode and the organic light emitting layer. Exemplarily, the organic light emitting diode further includes an electron transport layer stacked between the cathode and the organic light emitting layer; or, the organic light emitting diode further includes an electron injection layer and an electron transport layer stacked between the cathode and the organic light emitting layer. Certainly, a material layer having both electron injection and electron transport functions can also be arranged between the cathode and the organic light-emitting layer.

在一些实施例中，有机发光二极管还包括层叠设置在纳米石墨层和有机发光层之间的空穴注入层和空穴传输层之间的至少一层。示例性的，有机发光二极管还包括层叠设置在纳米石墨层和有机发光层之间的空穴传输层；或，有机发光二极管还包括层叠设置在纳米石墨层和有机发光层之间的空穴注入层和空穴传输层。当然，纳米石墨层和有机发光层之间也可以设置一层同时具有空穴注入和空穴传输功能的材料层。In some embodiments, the organic light emitting diode further includes at least one layer between the hole injection layer and the hole transport layer stacked between the nano graphite layer and the organic light emitting layer. Exemplarily, the organic light emitting diode further includes a hole transport layer stacked between the nano-graphite layer and the organic light-emitting layer; or, the organic light-emitting diode further includes a hole injection layer stacked between the nano-graphite layer and the organic light-emitting layer layer and hole transport layer. Certainly, a material layer having both hole injection and hole transport functions can also be arranged between the nano-graphite layer and the organic light-emitting layer.

在一些实施例中，有机发光二极管还包括层叠设置在纳米石墨层和有机发光层之间的空穴注入层和空穴传输层，以及层叠设置在阴极和有机发光层之间的电子注入层和电子传输层。In some embodiments, the organic light emitting diode further includes a hole injection layer and a hole transport layer stacked between the graphite nano layer and the organic light emitting layer, and an electron injection layer and a hole transport layer stacked between the cathode and the organic light emitting layer. electron transport layer.

本申请实施例中，有机发光二极管还可以包括衬底，阳极或阴极设置在衬底上。In the embodiment of the present application, the organic light emitting diode may further include a substrate, and the anode or the cathode is disposed on the substrate.

本申请实施例提供的有机发光二极管根据分为正置结构有机发光二极管和倒置结构有机发光二极管。The organic light emitting diodes provided in the embodiments of the present application are divided into organic light emitting diodes with an upright structure and organic light emitting diodes with an inverted structure.

在一种实施方式中，正置结构有机发光二极管包括相对设置的阳极和阴极，设置在阳极和阴极之间的有机发光层，以及设置在阳极和有机发光层之间的纳米石墨层，且阳极设置在衬底上。进一步的，阴极和有机发光层之间可以设置电子注入层、电子传输层中的至少一层；在纳米石墨层和有机发光层之间可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层。在一些正置结构有机发光二极管的实施例中，有机发光二极管包括衬底，设置在衬底表面的阳极，设置在阳极表面的纳米石墨层，设置在纳米石墨层表面的空穴注入层，设置在空穴注入层表面的空穴传输层，设置在空穴传输层表面的有机发光层，设置在有机发光层表面的电子传输层，设置在电子传输层表面的电子注入层，以及设置在电子注入层表面的阴极。In one embodiment, the organic light-emitting diode with a positive structure includes an anode and a cathode arranged oppositely, an organic light-emitting layer arranged between the anode and the cathode, and a nano-graphite layer arranged between the anode and the organic light-emitting layer, and the anode set on the substrate. Further, at least one of an electron injection layer and an electron transport layer can be set between the cathode and the organic light emitting layer; a hole transport layer, a hole injection layer and an electron blocking layer can be set between the nano graphite layer and the organic light emitting layer and other hole functional layers. In some embodiments of organic light-emitting diodes with a positive structure, the organic light-emitting diode includes a substrate, an anode disposed on the surface of the substrate, a nano-graphite layer disposed on the surface of the anode, a hole injection layer disposed on the surface of the nano-graphite layer, and The hole transport layer on the surface of the hole injection layer, the organic light-emitting layer on the surface of the hole transport layer, the electron transport layer on the surface of the organic light-emitting layer, the electron injection layer on the surface of the electron transport layer, and the electron transport layer on the surface of the electron transport layer. Inject the cathode on the surface of the layer.

在一种实施方式中，倒置结构有机发光二极管包括相对设置的阳极和阴极，设置在阳极和阴极之间的有机发光层，以及设置在阳极和有机发光层之间的纳米石墨层，且阴极设置在衬底上。进一步的，阴极和有机发光层之间可以设置电子注入层、电子传输层中的至少一层；在纳米石墨层和有机发光层之间可以设置空穴传输层、空穴注入层和电子阻挡层等空穴功能层。在一些倒置结构有机发光二极管的实施例中，发光二极管包括衬底，设置在衬底表面的阴极，设置在阴极表面的电子注入层，设置在电子注入层表面的电子传输层，设置在电子传输层表面的有机发光层，设置在有机发光层表面的空穴传输层，设置在空穴传输层表面的空穴注入层，设置在空穴注入层表面的阳极。In one embodiment, an organic light emitting diode with an inverted structure includes an anode and a cathode arranged oppositely, an organic light-emitting layer arranged between the anode and the cathode, and a nano-graphite layer arranged between the anode and the organic light-emitting layer, and the cathode is arranged on the substrate. Further, at least one of an electron injection layer and an electron transport layer can be set between the cathode and the organic light emitting layer; a hole transport layer, a hole injection layer and an electron blocking layer can be set between the nano graphite layer and the organic light emitting layer and other hole functional layers. In some embodiments of an organic light emitting diode with an inverted structure, the light emitting diode includes a substrate, a cathode disposed on the surface of the substrate, an electron injection layer disposed on the surface of the cathode, an electron transport layer disposed on the surface of the electron injection layer, and an electron transport layer disposed on the surface of the electron transport layer. The organic light-emitting layer on the surface of the layer, the hole transport layer on the surface of the organic light-emitting layer, the hole injection layer on the surface of the hole transport layer, and the anode on the surface of the hole injection layer.

在一些实施例中，若干个本申请实施例提供的有机发光二极管，可以组成有机发光器件。示例性的，如图3所示，有机发光器件包括阳极ITO玻璃1，设置在阳极ITO玻璃1上的若干有机发光二极管，有机发光二极管之间通过隔离柱2隔离，有机发光二极管1通过封装层3进行封装处理。有机发光二极管包括设置在ITO玻璃1上的纳米石墨自组装层4，设置在纳米石墨自组装层上的OLED器件层5，以及设置在OLED器件层5背离纳米石墨自组装层4自装置一侧的阴极层6。In some embodiments, several organic light emitting diodes provided in the embodiments of the present application may form an organic light emitting device. Exemplarily, as shown in FIG. 3 , the organic light-emitting device includes an anode ITO glass 1, a number of organic light-emitting diodes arranged on the anode ITO glass 1, the organic light-emitting diodes are separated by spacers 2, and the organic light-emitting diodes 1 pass through the encapsulation layer 3 for encapsulation. The organic light emitting diode comprises a nano-graphite self-assembled layer 4 arranged on the ITO glass 1, an OLED device layer 5 arranged on the nano-graphite self-assembled layer, and an OLED device layer 5 arranged on the side away from the nano-graphite self-assembled layer 4 from the device The cathode layer 6.

上述实施例中，衬底主要起到支撑有机发光二极管的作用，可选择刚性衬底如玻璃，或柔性衬底。In the above embodiments, the substrate is mainly used to support the organic light emitting diode, and a rigid substrate such as glass or a flexible substrate can be selected.

阳极可以采用常见的阳极材料和厚度，本申请实施例不作限定。例如，阳极材料可以为氧化铟锡（ITO）、掺氟氧化锡（FTO）、锑掺杂氧化锡（ATO）、铝掺杂氧化锌（AZO）中的一种或多种。在正置结构的有机发光二极管的一些实施例中，阳极设置在基本上作为一个整体，形成阳极基板，示例性的，如ITO基板。Common anode materials and thicknesses can be used for the anode, which are not limited in this embodiment of the present application. For example, the anode material may be one or more of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), and aluminum-doped zinc oxide (AZO). In some embodiments of the organic light emitting diode with a vertical structure, the anode is arranged substantially as a whole to form an anode substrate, for example, an ITO substrate.

纳米石墨层由本申请第一方面提供的纳米石墨打印液打印形成。纳米石墨打印液的情形如上文所述，为了节约篇幅，此处不再赘述。The nano-graphite layer is formed by printing the nano-graphite printing solution provided in the first aspect of the present application. The situation of the nano-graphite printing liquid is as described above, in order to save space, it will not be repeated here.

空穴注入层的材料可采用本领域常规的空穴注入材料，包括但不限于导电聚合物-聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸（PEDOT:PSS）。The material of the hole injection layer can be conventional hole injection materials in the field, including but not limited to conductive polymer-poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS).

空穴传输层的材料可采用具有空穴传输能力的有机材料，包括但不限于咔唑类、有机胺类和丁二烯类化合物，示例性的空穴传输层的材料可采用，N,N’-二苯基-N,N’-(1-萘基)-1,1’-联苯-4,4’-二胺（NPB）、聚乙烯咔唑（PVK）、聚噻吩（TPH）和4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]（TAPC）。The material of the hole transport layer can be an organic material with hole transport ability, including but not limited to carbazoles, organic amines and butadiene compounds. The material of the exemplary hole transport layer can be used, N,N '-Diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), polyvinylcarbazole (PVK), polythiophene (TPH) and 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (TAPC).

有机发光层中的发光材料可以采用常见的有机发光材料。The light-emitting material in the organic light-emitting layer can be a common organic light-emitting material.

电子传输层的材料包括具有电子传输能力的带隙大于发光材料带隙的氧化物半导体纳米颗粒材料，包括但不限于1,2.4—***衍生物（TAZ）、1,3.4—噁二唑类化合物（OXD）、2-(4-联苯基)-5-苯基恶二唑（PBD）中的一种或多种。在一些实施例中，金属氧化物纳米材料采用醇类溶剂分散后采用溶液法沉积。Materials for the electron transport layer include oxide semiconductor nanoparticle materials with electron transport capability and a band gap greater than that of the luminescent material, including but not limited to 1,2.4-triazole derivatives (TAZ), 1,3.4-oxadiazoles One or more of compound (OXD), 2-(4-biphenyl)-5-phenyloxadiazole (PBD). In some embodiments, the metal oxide nanomaterials are dispersed in an alcohol solvent and then deposited by a solution method.

电子注入层的材料可以选择常规的电子注入材料，包括但不限于MgP、MgF ₂。电子注入层可以通过。 The material of the electron injection layer can be selected from conventional electron injection materials, including but not limited to MgP and MgF ₂ . The electron injection layer can pass through.

本申请实施例中，阴极可以采用常见的阴极材料和厚度，本申请实施例不作限定。在一些实施例中，阴极的材料金属阴极材料，如金属合金。示例性的，阴极为锂铝合金，其中锂占合金重量的0.6%。金属氧化物可以是掺杂或非掺杂金属氧化物，示例性的，如ITO。在倒置结构的有机发光二极管的一些实施例中，阴极设置在基本上作为一个整体，形成阴极基板，示例性的，如ITO基板。In the embodiment of the present application, the common cathode material and thickness can be used for the cathode, which is not limited in the embodiment of the present application. In some embodiments, the material of the cathode is a metal cathode material, such as a metal alloy. Exemplarily, the cathode is a lithium aluminum alloy, wherein lithium accounts for 0.6% by weight of the alloy. The metal oxide can be doped or non-doped metal oxide, for example, ITO. In some embodiments of the organic light emitting diode with an inverted structure, the cathode is arranged substantially as a whole to form a cathode substrate, for example, an ITO substrate.

在一些实施例中，有机发光二极管还可以包括封装结构，封装结构的封装材料包树脂。示例性的，环氧树脂。用于封装的树脂原料包括其单体、预聚物、聚合物、引发剂及其他添加剂。In some embodiments, the organic light emitting diode may further include an encapsulation structure, and the encapsulation material of the encapsulation structure is covered with resin. Exemplary, epoxy resin. The resin raw materials used for encapsulation include its monomers, prepolymers, polymers, initiators and other additives.

本申请实施例中，有机发光二极管可以通过逐层制备各功能层实现。In the embodiment of the present application, the organic light emitting diode can be realized by preparing each functional layer layer by layer.

示例性的，一种有机发光二极管器件的制备，包括：Exemplarily, the preparation of an organic light emitting diode device includes:

（1）在ITO玻璃表面制备隔离柱。(1) Prepare spacers on the surface of ITO glass.

在一些实施例中，在制备隔离柱之前，对ITO玻璃进行清洗，彻底清除基片表面的污染物。清洗可采用化学清洗法，超声波清洗法或紫外线清洗法等。在一些实施例中，在对ITO玻璃进行清洗后，对ITO玻璃表面薄膜进行预处理，提高ITO玻璃的表面功能函数。预处理可采用酸碱处理法或等离子体处理方法等。In some embodiments, before preparing the isolation column, the ITO glass is cleaned to completely remove the pollutants on the surface of the substrate. Cleaning can be done by chemical cleaning, ultrasonic cleaning or ultraviolet cleaning. In some embodiments, after the ITO glass is cleaned, the surface film of the ITO glass is pretreated to improve the surface function of the ITO glass. Pretreatment can use acid-base treatment or plasma treatment.

在一些实施例中，隔离柱的材质可采用有机绝缘材料（PI、聚四氟乙烯等）和光刻胶（KPR、KTFR、KOP、KMER）等。In some embodiments, the material of the isolation column can be organic insulating material (PI, polytetrafluoroethylene, etc.) and photoresist (KPR, KTFR, KOP, KMER) and the like.

在一些实施例中，在ITO玻璃表面制备隔离柱可采用旋涂方法。示例性的，在ITO玻璃表面旋涂第一层光敏型有机绝缘材料，前烘后曝光形成曝光图案，进行后烘；在有机绝缘材料上旋涂第二层光敏型有机绝缘材料，前烘后进行曝光。在一些实施例中，隔离柱采用倒立梯形结构，倒立梯形结构的隔离柱，可以避免相邻像素之间的短路问题，且具有可较好的遮蔽效果，有利于批量生产。当然，隔离柱并不限于倒立梯形结构，也可以为其他结构，如长方体，正梯形等。In some embodiments, a spin-coating method may be used to prepare the isolation columns on the surface of the ITO glass. Exemplarily, the first layer of photosensitive organic insulating material is spin-coated on the surface of ITO glass, exposed after pre-baking to form an exposure pattern, and post-baked; the second layer of photosensitive organic insulating material is spin-coated on the organic insulating material, pre-baked and post-baked. Make an exposure. In some embodiments, the isolation column adopts an inverted trapezoidal structure, and the isolation column of the inverted trapezoidal structure can avoid the problem of short circuit between adjacent pixels, and has a better shielding effect, which is beneficial to mass production. Of course, the isolation column is not limited to the inverted trapezoidal structure, and can also be other structures, such as cuboid, regular trapezoidal and so on.

（2）在隔离柱之间的ITO玻璃上制备纳米石墨层。(2) The nano-graphite layer was prepared on the ITO glass between the spacer columns.

在一些实施例中，在隔离柱间利用喷涂打印的方法将纳米石墨打印液喷涂在ITO玻璃上，纳米石墨离子自组装，形成纳米石墨层。一方面，纳米石墨表面的等离子基元可以在几纳米的尺度内上产生局部强烈电场，可加强电子的通过速率，进而加强激子的产生速率；另一方面，纳米石墨的独特的结构表面，不会对激子产生解离。上述两方面可以有效提高激子对有机物刺激强度，从而增加发光效率。In some embodiments, the nano-graphite printing solution is sprayed on the ITO glass between the isolation columns by spraying and printing, and the nano-graphite ions self-assemble to form a nano-graphite layer. On the one hand, the plasmonic elements on the surface of nano-graphite can generate a local strong electric field within a few nanometers, which can enhance the passage rate of electrons, thereby enhancing the generation rate of excitons; on the other hand, the unique structural surface of nano-graphite, Does not dissociate excitons. The above two aspects can effectively increase the intensity of excitons to stimulate organic matter, thereby increasing the luminous efficiency.

（3）在纳米石墨层表面制作OLED的其他功能层。(3) Fabricate other functional layers of the OLED on the surface of the nano-graphite layer.

OLED的其他功能层至少包括有机发光层和阴极。在一些实施例中，OLED的其他功能层包括电子注入层、电子传输层、空穴传输层和空穴注入层中的至少一层。Other functional layers of an OLED include at least an organic light-emitting layer and a cathode. In some embodiments, the other functional layers of the OLED include at least one of an electron injection layer, an electron transport layer, a hole transport layer, and a hole injection layer.

在一些实施例中，利用喷墨打印制作成空穴注入层；利用旋涂法在空穴注入层表面制备空穴传输层，以形成均匀膜，减小了针孔等缺陷的影响。In some embodiments, the hole injection layer is made by inkjet printing; the hole transport layer is prepared on the surface of the hole injection layer by spin coating to form a uniform film and reduce the influence of defects such as pinholes.

在一些实施例中，利用喷墨打印制成有机发光层。In some embodiments, the organic emissive layer is made using inkjet printing.

在一些实施例中，采用蒸镀法制成电子传输层、电子注入层和阴极。In some embodiments, the electron transport layer, the electron injection layer and the cathode are formed by vapor deposition.

（4）对制得的有机发光器件进行封装。(4) Encapsulating the prepared organic light-emitting device.

下面结合具体实施例进行说明。The following will be described in conjunction with specific embodiments.

实施例1Example 1

一种纳米石墨打印液，包括如下重量百分含量的下列组分：纳米石墨粒子0.4%，失水山梨醇油酸酯0.5%，粘度调节剂氧化聚乙烯蜡4%，基材润湿剂烷基酚醚表面活性剂余量，其中，纳米石墨粒子的平均粒径为10~30nm。A kind of nano-graphite printing liquid, comprises the following component of following percentage by weight: nano-graphite particle 0.4%, sorbitan oleate 0.5%, viscosity regulator oxidized polyethylene wax 4%, substrate wetting agent alkane Base phenol ether surfactant balance, wherein, the average particle diameter of nano-graphite particles is 10 ~ 30nm.

纳米石墨打印液的制备方法为：The preparation method of nano-graphite printing liquid is:

取纳米石墨粒子、失水山梨醇油酸酯、粘度调节剂和基材润湿剂，将纳米石墨粒子和基材润湿剂搅拌混合，得到纳米石墨溶液。The nano-graphite particles, sorbitan oleate, viscosity modifier and base material wetting agent are taken, and the nano-graphite particles and the base material wetting agent are stirred and mixed to obtain a nano-graphite solution.

在纳米石墨溶液中加入高分子分散剂和粘度调节剂后，对得到的混合物料进行机械搅拌，搅拌30min，得到第一混合体系。After adding the polymer dispersant and the viscosity regulator into the nano-graphite solution, mechanically stir the obtained mixed material for 30 minutes to obtain the first mixed system.

在微米级波长、超声频率大于或等于20KHz的条件下，将第一混合体系进行超声震荡处理，得到纳米石墨打印液。Under the conditions of micron-scale wavelength and ultrasonic frequency greater than or equal to 20KHz, the first mixed system is subjected to ultrasonic vibration treatment to obtain nano-graphite printing liquid.

实施例2Example 2

一种纳米石墨打印液，与实施例1的不同之处在于：纳米石墨粒子0.5%。A nano-graphite printing solution, the difference from Example 1 is: 0.5% of nano-graphite particles.

实施例3Example 3

一种纳米石墨打印液，与实施例1的不同之处在于：纳米石墨粒子0.3%。A nano-graphite printing solution, the difference from Example 1 is: 0.3% of nano-graphite particles.

实施例4Example 4

一种纳米石墨打印液，与实施例1的不同之处在于：高分子分散剂为硬脂酸单甘油酯。A nano-graphite printing liquid, the difference from Example 1 is: the polymer dispersant is monoglyceride stearate.

实施例5Example 5

一种纳米石墨打印液，与实施例1的不同之处在于：基材润湿剂为聚氧乙烯脂肪醇醚。A nano-graphite printing solution, the difference from Example 1 is that the substrate wetting agent is polyoxyethylene fatty alcohol ether.

将实施例1-6得到的纳米石墨打印液和对比例1提供的纳米铜打印液，分别用作OLED器件阳极表面的纳米功能层。OLED器件的制备方法包括如下步骤：The nano-graphite printing solution obtained in Examples 1-6 and the nano-copper printing solution provided in Comparative Example 1 were respectively used as the nano-functional layer on the surface of the anode of the OLED device. The preparation method of OLED device comprises the steps:

提供六组ITO玻璃，分别命名为D1-D6，对ITO玻璃进行清洗后进行等离子体处理，采用旋涂方法，在基片上旋涂第一层光敏型有机绝缘材料，前烘后曝光形成曝光图案后，进行后烘；在有机绝缘材料上旋涂第二层光敏型有机绝缘材料，前烘后进行曝光；Provide six sets of ITO glass, respectively named D1-D6, after cleaning the ITO glass, perform plasma treatment, use the spin coating method, spin coat the first layer of photosensitive organic insulating material on the substrate, and expose the exposure pattern after pre-baking Afterwards, post-baking is carried out; the second layer of photosensitive organic insulating material is spin-coated on the organic insulating material, and exposure is performed after pre-baking;

在隔离柱间利用喷涂打印的方法将实施例1-6得到的纳米石墨打印液和对比例1提供的纳米铜打印液分别喷涂在D1-D6号ITO玻璃上，待纳米石墨打印液和纳米铜打印液自组装成膜后，在其表面喷墨打印制作成空穴注入层，在空穴注入层表面旋涂制作空穴传输层；利用喷墨打印在空穴传输层表面制成发光层；采用蒸镀法在发光层表面依次制作电子传输层、电子注入层和阴极；The nano-graphite printing solution obtained in Examples 1-6 and the nano-copper printing solution provided by Comparative Example 1 were sprayed on the No. D1-D6 ITO glass by spraying and printing between the isolation columns, and the nano-graphite printing solution and nano-copper After the printing liquid is self-assembled into a film, the hole injection layer is made by inkjet printing on its surface, and the hole transport layer is made by spin coating on the surface of the hole injection layer; the luminescent layer is made on the surface of the hole transport layer by inkjet printing; The electron transport layer, the electron injection layer and the cathode are sequentially fabricated on the surface of the light-emitting layer by evaporation;

进行封装，得到六组OLED器件。Packaging was carried out to obtain six groups of OLED devices.

以上仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本申请的保护范围之内。The above are only preferred embodiments of the application, and are not intended to limit the application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the application should be included in the protection scope of the application. Inside.

Claims (14)

1. 一种纳米石墨打印液，其特征在于，以所述纳米石墨打印液的总质量为100%计，所述纳米石墨打印液包括如下质量百分含量的下列组分： A nano-graphite printing liquid, characterized in that, based on the total mass of the nano-graphite printing liquid as 100%, the nano-graphite printing liquid includes the following components in the following mass percentages:

   纳米石墨粒子      0.1~0.7%，Nano Graphite Particles 0.1~0.7%,

   高分子分散剂      0.2~0.8%，polymer dispersant 0.2~0.8%,

   粘度调节剂        2.5~4%，Viscosity modifiers 2.5~4%,

   基材润湿剂余量。Substrate wetting agent balance.
2. 如权利要求1所述的纳米石墨打印液，其特征在于，所述纳米石墨粒子的粒径小于或等于50nm。 The nano-graphite printing fluid according to claim 1, wherein the particle size of the nano-graphite particles is less than or equal to 50nm.
3. 如权利要求2所述的纳米石墨打印液，其特征在于，所述纳米石墨粒子的粒径为10~30nm。 The nano-graphite printing solution according to claim 2, wherein the particle diameter of the nano-graphite particles is 10-30nm.
4. 如权利要求1至3任一项所述的纳米石墨打印液，其特征在于，所述高分子分散剂吸附在所述纳米石墨粒子表面，形成高分子吸附层。 The nano-graphite printing fluid according to any one of claims 1 to 3, wherein the polymer dispersant is adsorbed on the surface of the nano-graphite particles to form a polymer adsorption layer.
5. 如权利要求1至4任一项所述的纳米石墨打印液，其特征在于，所述高分子分散剂选自失水山梨醇油酸酯、硬脂酸单甘油酯、乙撑基双硬脂酰胺中的至少一种。 The nano-graphite printing liquid as claimed in any one of claims 1 to 4, wherein the polymer dispersant is selected from the group consisting of sorbitan oleate, monoglyceride stearate, ethylene distearate At least one of amides.
6. 如权利要求1至3任一项所述的纳米石墨打印液，其特征在于，所述基材润湿剂选自非离子型表面活性剂。 The nano-graphite printing solution according to any one of claims 1 to 3, wherein the substrate wetting agent is selected from nonionic surfactants.
7. 如权利要求5所述的纳米石墨打印液，其特征在于，所述基材润湿剂选自烷基酚醚表面活性剂、聚氧乙烯脂肪醇醚表面活性剂、聚氧乙烯聚氧丙烯嵌段共聚物表面活性剂、硅醇类表面活性剂中的至少一种。 The nano-graphite printing solution according to claim 5, wherein the substrate wetting agent is selected from the group consisting of alkylphenol ether surfactants, polyoxyethylene fatty alcohol ether surfactants, polyoxyethylene polyoxypropylene embedded At least one of segment copolymer surfactants and silanol surfactants.
8. 如权利要求1至3、7任一项所述的纳米石墨打印液，其特征在于，还包括其他助剂。 The nano-graphite printing liquid according to any one of claims 1 to 3, 7, further comprising other additives.
9. 一种纳米石墨打印液的制备方法，其特征在于，包括以下步骤： A kind of preparation method of nano-graphite printing liquid, it is characterized in that, comprises the following steps:

   取纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂，将纳米石墨粒子和基材润湿剂混合处理，得到纳米石墨溶液；Taking nano-graphite particles, polymer dispersant, viscosity regulator and substrate wetting agent, mixing the nano-graphite particles and substrate wetting agent to obtain nano-graphite solution;

   在所述纳米石墨溶液中加入所述高分子分散剂和所述粘度调节剂后，对得到的混合物料进行机械搅拌，得到第一混合体系；After adding the polymer dispersant and the viscosity modifier into the nano-graphite solution, mechanically stir the obtained mixed material to obtain the first mixed system;

   将所述第一混合体系进行超声震荡处理，得到纳米石墨打印液；Ultrasonic vibration treatment is performed on the first mixed system to obtain nano-graphite printing liquid;

   其中，所述纳米石墨粒子、高分子分散剂、粘度调节剂和基材润湿剂在所述纳米石墨打印液中的质量百分含量如下：Wherein, the mass percentages of the nano-graphite particles, polymer dispersant, viscosity regulator and substrate wetting agent in the nano-graphite printing liquid are as follows:

   纳米石墨粒子      0.1~0.7%，Nano Graphite Particles 0.1~0.7%,

   高分子分散剂      0.2~0.8%，polymer dispersant 0.2~0.8%,

   粘度调节剂        2.5~4%，Viscosity modifiers 2.5~4%,

   基材润湿剂余量。Substrate wetting agent balance.
10. 如权利要求9所述的纳米石墨打印液的制备方法，其特征在于，所述机械搅拌时间为30~60min；和/或 The preparation method of nanographite printing liquid as claimed in claim 9, is characterized in that, described mechanical stirring time is 30～60min; And/or

    在所述机械搅拌处理中，促进所述高分子分散剂在所述纳米石墨粒子表面的吸附。During the mechanical stirring treatment, the adsorption of the polymer dispersant on the surface of the graphite nano particles is promoted.
11. 如权利要求9-10任一项所述的纳米石墨打印液的制备方法，其特征在于，所述超声震荡处理的波长为微米级波长，超声频率大于或等于20KHz，超声震荡处理的时间30~120min。 The method for preparing nano-graphite printing liquid according to any one of claims 9-10, wherein the wavelength of the ultrasonic oscillation treatment is a micron-scale wavelength, the ultrasonic frequency is greater than or equal to 20KHz, and the ultrasonic oscillation treatment takes 30~ 120min.
12. 如权利要求9-11任一项所述的纳米石墨打印液的制备方法，其特征在于，所述机械搅拌时间为30~60min；所述超声震荡处理的波长为微米级波长，超声频率大于或等于20KHz，超声震荡处理的时间30~120min。 The preparation method of nano-graphite printing liquid as claimed in any one of claims 9-11, characterized in that, the mechanical stirring time is 30 to 60 minutes; the wavelength of the ultrasonic oscillation treatment is a micron-scale wavelength, and the ultrasonic frequency is greater than or Equal to 20KHz, the time of ultrasonic shock treatment is 30~120min.
13. 一种有机发光二极管，其特征在于，包括相对设置的阳极和阴极，在所述阳极和所述阴极之间层叠设置的有机发光层，在有机发光层和所述阳极之间层叠设置的纳米石墨层，所述纳米石墨层由权利要求1至8任一项所述的纳米石墨打印液打印形成。 An organic light-emitting diode, characterized in that it includes an anode and a cathode arranged oppositely, an organic light-emitting layer is stacked between the anode and the cathode, and a nano-graphite is stacked between the organic light-emitting layer and the anode layer, and the nano-graphite layer is formed by printing the nano-graphite printing liquid according to any one of claims 1 to 8.
14. 如权利要求13所述的有机发光二极管，其特征在于，所述有机发光二极管还包括层叠设置在所述纳米石墨层和所述有机发光层之间的空穴注入层和空穴传输层之间的至少一层；和/或 The organic light emitting diode according to claim 13, wherein the organic light emitting diode further comprises a hole injection layer and a hole transport layer stacked between the nanographite layer and the organic light emitting layer at least one layer of ; and/or

    所述有机发光二极管还包括层叠设置在所述阴极和所述有机发光层之间的电子注入层和电子传输层之间的至少一层。The organic light emitting diode further includes at least one layer between an electron injection layer and an electron transport layer stacked between the cathode and the organic light emitting layer.