WO2018032604A1 - 一种有机电致发光二极管及其空穴传输层的制备方法 - Google Patents

一种有机电致发光二极管及其空穴传输层的制备方法 Download PDF

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WO2018032604A1
WO2018032604A1 PCT/CN2016/103053 CN2016103053W WO2018032604A1 WO 2018032604 A1 WO2018032604 A1 WO 2018032604A1 CN 2016103053 W CN2016103053 W CN 2016103053W WO 2018032604 A1 WO2018032604 A1 WO 2018032604A1
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film
organic electroluminescent
electroluminescent diode
layer
hole transport
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French (fr)
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张育楠
刘亚伟
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
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    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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Definitions

  • the invention relates to the field of manufacturing organic electroluminescent diodes, and in particular to a method for preparing an organic electroluminescent diode and a hole transporting layer thereof.
  • Organic electroluminescence refers to a phenomenon in which a thin film device made of an organic photoelectric functional material emits light under the excitation of an electric field, and the thin film device can be classified into organic electroluminescence according to the luminescent material used for preparing the functional film. Diodes and polymer electroluminescent diodes. In recent years, organic electroluminescent diodes have made great progress, and organic electroluminescent diodes have reached practical requirements in terms of luminance, luminous efficiency and lifetime of devices.
  • Electrochemical Polymerization refers to the electrolysis of a certain electrochemical method in an electrolytic cell with a suitable electrolyte to cause the monomer to be oxidized, reduced or decomposed into free radicals or ions on the electrode.
  • the polymerization, electrochemical polymerization may also be referred to as electrolytic polymerization, electropolymerization or electro-initiation polymerization.
  • the device is simple, the reaction conditions are easy to control, and the thickness of the polymer film can be controlled;
  • the polymer film has a uniform thickness and high reproducibility
  • Doping can be carried out while the monomer is polymerized.
  • inkjet printing microfabrication technology has been widely used in the manufacture of organic electroluminescent diodes.
  • a method of preparing a crosslinkable hole transport layer is generally adopted to solve the problem of mutual dissolution between layers in a solution processing device, but in the film. In the state, it is difficult to effectively adjust the degree of crosslinking and reactivity of the polymer or the small molecule hole transporting material.
  • the present invention proposes a method of preparing an organic electroluminescent diode and a hole transporting layer thereof.
  • the organic electroluminescent diode proposed by the present invention comprises a hole transporting layer which is a thin film produced by an electrochemical polymerization method.
  • the organic electroluminescent diode includes a substrate, and an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and a cathode which are sequentially stacked from the inside to the outside on the substrate.
  • the material of the hole transport layer is a "star" triphenylamine compound.
  • the anode is an indium tin oxide semiconductor transparent conductive film.
  • the hole injection layer is a poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) film.
  • the luminescent layer is a poly 9,9-dioctylfluorene film.
  • the electron injecting layer is a lithium fluoride film.
  • the cathode is an aluminum film.
  • a method for preparing a hole transport layer of an organic electroluminescent diode according to the present invention comprising:
  • the obtained electropolymerized film is washed and dried;
  • the electropolymerized film is used to form the hole transport layer;
  • the precursor in the electrolyte contains at least one electroactive substituent
  • Each precursor molecule contains at least two identical electroactive substituent groups.
  • the electroactive substituent group is one of a thiophene-substituted group, an aniline-substituted group or a carbazole-substituted group.
  • the organic electroluminescent diode proposed by the present invention comprises a hole transport layer by electrochemical polymerization
  • the film made by the method has good stability and corrosion resistance due to its highly crosslinked molecular structure characteristics, and can effectively resist the erosion of the solvent from the next layer of solution processing, and is prepared by the subsequent solution processing method.
  • Other functional layers in the multilayer structure provide convenience and serve as an interface modification and protection.
  • the properties of the electrochemically polymerized film can be set by specifying specific electrical polymerization parameters, including polymerization potential, scanning rate, solvent, electrolyte, eluent, and the like. Finely controlled, the present invention solves the problem that the prior art cannot effectively regulate the degree of crosslinking and reactivity of a polymer or a small molecule hole transporting material in a thin film state.
  • 1 is a schematic structural view of an organic electroluminescent diode in an embodiment, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light-emitting layer, and 6 is an electron injection layer, 7 It is a cathode.
  • N is a nitrogen group.
  • Figure 3 is a structural formula of the TDAB series "star" triphenylamine compound in the examples, and R is an R group.
  • Fig. 4 is a structural formula of the TDABP series "star" triphenylamine compound in the examples.
  • P is a chemical workstation
  • C is a counter electrode
  • F is a reference electrode
  • W is a working electrode
  • S is a switch.
  • Embodiment 1 This embodiment is described with reference to FIG. 1, FIG. 2, FIG. 3, FIG. 4 and FIG. 5.
  • the organic electroluminescent diode of the multilayer structure in this embodiment includes a substrate 1, and On the substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron injection layer 6, and a cathode 7 are sequentially stacked from the inside to the outside.
  • the hole transport layer 4 is a film formed by an electrochemical polymerization method, and the film is made of a "star" triphenylamine compound having a thickness of 0.1 nm to 100 nm.
  • the triphenylamine compound has an energy level of up to 10 -3 cm 2 ⁇ V -1 ⁇ s -1 , which has a high intrinsic hole mobility, good electron donating property, and low ionization potential. Solubility, strong fluorescence and photostability, amorphous film forming properties, etc., triphenylamine compounds have always been a research hotspot in the field of organic semiconductor materials.
  • Star triphenylamines are mainly classified into TDATA series (centered on triphenylamine), TDAB series (centered on benzene ring) and TDABP series (centered on 1,3,5 triphenylbenzene), and their structures
  • the general formula is as shown in FIG. 2, FIG. 3 and FIG. 4, respectively, and the R group in FIG. 3 may be an alkoxy group, an alkyl group, an alkene group, an aromatic ring or a fused ring, etc., and these different series of "star” three
  • the aniline compounds all have a high glass transition temperature, good film forming properties, and good light transmission to visible light.
  • the star geometry makes it difficult to form agglomerates, and the solubility in a solvent is more linear. Aniline is much better, and most importantly, the star structure increases the conjugated area of the triphenylamine compound, and its HOMO (Highest Occupied Molecular) energy level is significantly improved, which is more favorable for the injection of holes.
  • the organic electroluminescent diode When a certain amount of bias is applied to the organic electroluminescent diode, electrons and holes are injected through the cathode and the anode, respectively, and the two charges are transferred to the corresponding transport layer, and then the carrier reaches the light-emitting layer under the driving of the external electric field. Excitons (electron-hole pairs) are formed at the interface, and the excited excitons have higher energy and are in an unstable state, releasing energy in the form of light or heat and returning to the steady state. Selecting different luminescent materials, the organic electroluminescent diode will emit light of different colors.
  • a hole transporting material needs to satisfy the following conditions: (1) high hole mobility, (2) formation of a uniform stable film, and (3) suitable orbital level It can match other functional layers, (4) good thermal stability, difficult to form crystals; triphenylamine compounds can form cationic radicals under electric field, which has good hole mobility and high The glass transition temperature, good thermal stability, and chemical stability, therefore, the "star" triphenylamine compound was selected as the material of the hole transport layer in this example.
  • the "star" triphenylamine compound film is produced by electrochemical polymerization, and the steps of the method are as follows:
  • Step 1 preparing an electrolyte containing an aniline substituent group
  • Step 2 as shown in FIG. 5, a three-electrode system device is constructed, and the counter electrode C, the reference electrode F and the working electrode W are all located in the electrolyte;
  • Step 3 closing the switch S, and controlling the thickness of the obtained electropolymerized film by controlling the number of polymerization turns It is in the range of 0.1 nm to 100 nm.
  • an electropolymerized film of different materials By preparing an electrolyte containing different precursors, an electropolymerized film of different materials can be obtained, and the precursor molecules in the electrolyte contain at least an electroactive substitution such as a thiophene-substituted group, an aniline-substituted group or a carbazole-substituted group.
  • an electroactive substitution such as a thiophene-substituted group, an aniline-substituted group or a carbazole-substituted group.
  • the electrochemical polymerization method in this embodiment is preferably a cyclic voltammetry method, which is a commonly used electrochemical research method.
  • the method controls the electrode potential to scan at a different rate with a triangular waveform one or more times over time.
  • the potential range allows different reduction and oxidation reactions to occur alternately on the electrode, and the current-potential curve is recorded. According to the shape of the curve, the degree of reversibility of the electrode reaction, the possibility of intermediate, phase boundary adsorption or formation of a new phase, and the nature of the coupling chemical reaction can be judged. It is often used to measure electrode reaction parameters, determine its control steps and reaction mechanism, and observe which reactions occur within the entire potential sweep range, and how they are.
  • the preferred research method is often cyclic voltammetry, which can be called "electrochemical spectrum.”
  • the method can also use platinum, gold, glassy carbon, carbon fiber microelectrodes, and chemically modified electrodes.
  • the basic principle of cyclic voltammetry is as follows: If the pulse voltage of the isosceles triangle is applied to the working electrode, the current-voltage curve obtained includes two branches. If the potential of the first half is scanned toward the cathode, the electroactive substance is reduced on the electrode. When a reduction wave is generated, when the potential of the second half is scanned toward the anode, the reduction product is again oxidized on the electrode to generate an oxidation wave. Therefore, a triangular wave scan completes a cycle of reduction and oxidation processes, so the process is called cyclic voltammetry, and its current-voltage curve is called cyclic voltammogram.
  • the voltage sweep speed in cyclic voltammetry can range from a few millivolts per second to 1 volt.
  • the structure and degree of polymerization of the film prepared by electrochemical polymerization are relatively clear. Compared with the conventional crosslinking method, electrochemical polymerization facilitates the control of the polymerization process, and the structural characterization and control of the subsequent polymer film, and the electropolymerized film.
  • the preparation method is simple and the equipment investment is small.
  • the hole transport layer in this embodiment serves as an interface modification layer for the anode, which is advantageous for the preparation of a multilayer solution processing device.
  • Embodiment 2 The organic electroluminescent diode of the multilayer structure in the present embodiment is described with reference to FIG. 1.
  • the substrate 1 includes a substrate 1 and an anode 2 stacked on the substrate 1 from the inside to the outside.
  • Layer 3 hole transport layer 4, light-emitting layer 5, electron injection layer 6, and cathode.
  • the anode 2 is an indium tin oxide semiconductor transparent conductive film formed by a magnetron sputtering method and has a thickness of 20 nm to 200 nm.
  • Indium tin oxide is a mixture of indium oxide and tin oxide, usually in a mass ratio of 90% indium oxide and 10% tin oxide. Indium tin oxide is transparent and colorless in the form of a film, and yellowish gray in the block state; the main characteristic of indium tin oxide is its combination of electrical conduction and optical transparency. However, compromises are required in thin film deposition because high concentrations of charge carriers will increase the conductivity of the material, but will reduce its transparency. Indium tin oxide films are usually deposited by electron beam evaporation, physical vapor deposition or sputtering. Technology is deposited onto the surface.
  • the indium tin oxide semiconductor transparent conductive film in this embodiment is made by a magnetron sputtering method, and has the characteristics of suitable shielding performance in the range of 150 kHz to 1 GHz, and the light transmittance is much better than that of the common grid material shielding glass.
  • the resistivity is between 10 -3 and 10 -4 ⁇ cm, and the light transmittance can reach more than 85%.
  • Magnetron sputtering is a kind of physical vapor deposition (PVD).
  • the general sputtering method can be used to prepare materials such as metals, semiconductors and insulators, and has simple equipment, easy control, large coating area and adhesion.
  • the advantages are strong, and the magnetron sputtering method achieves high speed, low temperature and low damage, because high-speed sputtering is performed at a low pressure, and the ionization rate of the gas must be effectively increased.
  • Magnetron sputtering increases the plasma density by introducing a magnetic field on the surface of the target cathode and utilizing the constraints of the magnetic field on the charged particles to increase the sputtering rate.
  • Embodiment 3 The organic electroluminescent diode of the multilayer structure in the present embodiment is described with reference to FIG. 1.
  • the substrate 1 includes a substrate 1 and an anode 2 which is sequentially stacked on the substrate 1 from the inside to the outside.
  • the hole injection layer 3 is a poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) film formed by an inkjet printing method, and has a thickness of from 1 nm to 100 nm.
  • PEDT/PSS Poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate), abbreviated as PEDT/PSS, is a high molecular polymer polymerized by using EDOT monomer as a raw material, which has high conductivity and Bright characteristics, good light stability and good thermal stability, good electrochemical performance, can play a role in the thin layer of less than 1im on the surface of the object, have good hydrolysis resistance, and are widely used in antistatic In coatings, highly conductive coatings and organic light-emitting diodes.
  • Inkjet printing is to spray a hole transporting material and a solution of red, green and blue luminescent materials onto a sub-pixel pit on a previously patterned ITO substrate through a micron-sized print head to form a red-green color.
  • the thickness of the film layer is determined by the amount of solute printed in the pixel, and a film having a uniform thickness can be obtained by adjusting the volatility of the solvent.
  • This non-contact printing method avoids contact contamination of the functional solution. Because this method can greatly save expensive luminescent materials, and by using The nozzles of multiple ejection ports are printed to greatly shorten the film forming time.
  • inkjet printing technology has been recognized as a mainstream technology for industrialization in the field of OLED manufacturing, and equipment, raw materials and device manufacturing processes have been obtained in recent years. Great progress has been made. Compared with the prior art, inkjet printing technology has significant advantages in saving raw materials and reducing costs. Inkjet printing technology requires an accurate positioning system to improve pixel resolution and high accuracy requirements. In addition, how to formulate a printable high-efficiency luminescent material solution to achieve a uniform thickness of the polymer film layer is the key to this technology.
  • Inkjet printed OLEDs are simple in structure, do not require the complex backlights and color filters required to prepare LCDs, and use inkjet printing technology to save significant material. Therefore, the cost of OLEDs prepared by inkjet printing technology will have Larger downside.
  • the equalization of the droplet capacity ejected from each ejection port and the deviation of the ejection trajectory of the ejection orifice from the vertical direction are the key factors for measuring the quality of the printing needle.
  • the former determines the thickness and uniformity of the film in the pixel, while the latter relates to the positioning accuracy of the droplet.
  • the use of inkjet printing technology to prepare high-performance OLED displays must have three conditions, namely high-precision inkjet printing equipment, high-performance soluble polymer luminescent materials and printing inks.
  • Embodiment 4 The present embodiment is described with reference to FIG. 1.
  • the organic electroluminescent diode of the multilayer structure in the present embodiment includes a substrate 1, and an anode 2, which is sequentially stacked on the substrate 1 from the inside to the outside.
  • the light-emitting layer 5 is a poly 9,9-dioctylfluorene film produced by an inkjet printing method, and the film has a thickness of from 1 nm to 100 nm.
  • the luminescent material of the organic electroluminescent diode can be classified into three categories: an organic small molecule luminescent material, a polymer luminescent material, and an organic metal complex luminescent material.
  • polymer luminescent materials as a kind of important luminescent materials for organic electroluminescent diodes must have the following characteristics:
  • Fluorescence characteristics of high quantum efficiency the fluorescence spectrum of which is mainly distributed in the visible light region of 400 nm to 700 nm.
  • polymer luminescent materials are mainly conjugated polymer materials and have excellent carrier transport properties.
  • polyphenylene ethylene and its derivatives, polythiophene and its derivatives, polyparaphenylene and its derivatives, polyfluorene and its derivatives the material of the light-emitting layer in this embodiment belongs to polyfluorene and its Derivatives.
  • Embodiment 5 The present embodiment is described with reference to FIG. 1.
  • the organic electroluminescent diode of the multilayer structure in this embodiment includes a substrate 1, and an anode 2, which is sequentially stacked on the substrate 1 from the inside to the outside.
  • the electron injecting layer is a lithium fluoride thin film formed by a vacuum evaporation method and has a thickness of 0.5 nm to 10 nm.
  • LiF Lithium fluoride
  • the application of LiF at the cathode can reduce the barrier between the work function of the electrode material and the LUMO level of the organic material.
  • the electron injection is enhanced by increasing electron puncturing or forming a dipole at the interface, and thus LiF, particularly a LiF/Al composite electrode used in combination with aluminum (Al), has been widely used in OLEDs and N-type OTFTs.
  • LiF electrode modification layer can ensure electrode stability and device lifetime, and enhance electron injection to improve device performance.
  • LiF is an insulating material, and its thickness will be used as an electrode modification layer. Will significantly affect the performance of the device.
  • the second change brought by LiF is to add an additional barrier at the interface. Due to the insulating material in LiF, the barrier can be understood as an increased resistance barrier at the interface, which will cause certain transmission of electrons. Obstruction. However, when the thickness of LiF is moderate, the total barrier will still be smaller than the barrier without LiF.
  • Embodiment 6 The present embodiment is described with reference to FIG. 1.
  • the organic electroluminescent diode of the multilayer structure in the present embodiment includes a substrate 1, and an anode 2, which is sequentially stacked on the substrate 1 from the inside to the outside.
  • the cathode 7 is an aluminum film produced by a vacuum evaporation method and has a thickness of 50 nm to 1000 nm. In order to improve the injection efficiency of electrons, it is required to select a material with a work function as low as possible as a cathode.
  • the luminance and service life of the organic electroluminescent diode are closely related to the work function of the cathode. The lower the work function, the higher the luminance. The longer the service life.
  • the cathode of an organic electroluminescent diode mainly has a single metal cathode (one of Mg, Mg, Al, Li or Ca), an alloy cathode (Mg-Ag or One of Li-Al), a layered cathode, a doped composite electrode, etc.
  • the cathode in this embodiment is an aluminum film, on which is a LiF film, which is substantially an alloy electrode.
  • vacuum evaporation In a vacuum environment, heating and plating a material onto a substrate is called vacuum evaporation, which is a process in which a substance to be film is placed in a vacuum to be evaporated or sublimated to precipitate on a surface of a workpiece or a substrate.
  • the metal plating in vacuum evaporation is usually an aluminum film, but other metals can also be deposited by evaporation.
  • the principle of vacuum evaporation is that the metal is heated to the evaporation temperature. The steam is then transferred from the vacuum chamber and condensed on the low temperature parts. The process is carried out in a vacuum and the metal vapor does not oxidize when it reaches the surface.

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Abstract

一种多层结构的有机电致发光二极管及其空穴传输层（4）的制备方法。该有机电致发光二极管所包含的空穴传输层为通过电化学聚合法制成的薄膜，其空穴传输层的制备方法包括制备电解液、电解液进行电聚合、控制电聚合薄膜厚度和对所得电聚合薄膜进行清洗与干燥，通过设置具体的电聚合参数，对电聚合薄膜的交联度和反应活性进行精细调控，因此解决了无法对薄膜状态下的聚合物或是小分子空穴传输材料的交联度和反应活性进行有效调控的问题。

Description

一种有机电致发光二极管及其空穴传输层的制备方法
相关申请的交叉引用
本申请要求享有于2016年8月19日提交的名称为“一种有机电致发光二极管及其空穴传输层的制备方法”的中国专利申请CN201610697355.X的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本发明涉及有机电致发光二极管制造领域，尤其涉及一种有机电致发光二极管及其空穴传输层的制备方法。
背景技术
有机电致发光是指由有机光电功能材料制成的薄膜器件在电场的激发作用下发光的现象，根据制备功能薄膜所采用的发光材料的不同，可将所述薄膜器件分为有机电致发光二极管和聚合物电致发光二极管。近年来，有机电致发光二极管取得了长足的发展，就器件的发光亮度、发光效率和寿命而言，有机电致发光二极管已经达到了实用的要求。
电化学聚合(Electrochemical Polymerization，ECP)是指在有适当电解液的电解池里，通过一定的电化学方式进行电解，使单体在电极上因氧化、还原或分解为自由基或离子等而发生的聚合反应，电化学聚合亦可被称为电解聚合、电聚合或电引发聚合。
电化学聚合具有以下特点：
(1)装置简单，反应条件易于控制，能控制高聚物膜的厚度；
(2)聚合物膜厚度均匀且再现性高；
(3)能够得到结构、性质不同的功能膜；
(4)能够合成各种导电性聚合物；
(5)可在单体聚合的同时进行掺杂。
近年来，喷墨打印微制造技术被广泛地应用于有机电致发光二极管制造领 域，在现有喷墨打印法制备有机电致发光二极管的过程中，通常采用制备可交联的空穴传输层的方式，来解决溶液加工器件中层与层之间的互溶问题，但是在薄膜状态下，很难有效地调控聚合物或是小分子空穴传输材料的交联度和反应活性。
发明内容
为了解决上述现有技术存在的问题，本发明提出了一种有机电致发光二极管及其空穴传输层的制备方法。
本发明提出的有机电致发光二极管，包括空穴传输层，该空穴传输层为通过电化学聚合法制成的薄膜。
作为可选的，所述有机电致发光二极管包括基板，以及在该基板上从内至外依次堆叠的阳极、空穴注入层、空穴传输层、发光层、电子注入层和阴极。
作为可选的，所述空穴传输层的材质为“星型”三苯胺类化合物。
作为可选的，所述阳极为铟锡氧化物半导体透明导电膜。
作为可选的，所述空穴注入层为聚(3，4-乙烯基二氧噻吩)聚(苯乙烯磺酸盐)薄膜。
作为可选的，所述发光层为聚9,9-二辛基芴薄膜。
作为可选的，所述电子注入层为氟化锂薄膜。
作为可选的，所述阴极为铝膜。
本发明提出的有机电致发光二极管的空穴传输层的制备方法，该方法包括：
制备电解液；
采用基于三电极体系的循环伏安法对所述电解液进行电聚合；
控制电聚合薄膜厚度；
对所得电聚合薄膜进行清洗与干燥；
所述电聚合薄膜用于构成所述空穴传输层；
所述电解液中的前驱体至少包含一种电活性取代基团；
每个前驱体分子至少包含两个同类电活性取代基团。
作为可选的，所述电活性取代基团为噻吩类取代基团、苯胺类取代基团或咔唑类取代基团中的一种。
本发明提出的有机电致发光二极管，其包含的空穴传输层为通过电化学聚合 法制成的薄膜，该薄膜因其自身高度交联的分子结构特性而具有良好的稳定性和耐腐蚀性，能够有效地抵御来自下一层溶液加工时溶剂的侵蚀，为后续采用溶液加工方法制备多层结构中的其他功能层提供便利，起到了界面修饰和保护的作用。
更为重要的是，电化学聚合薄膜的交联度、反应活性、厚度和表面形貌等性质能够通过设置具体的电聚合参数，包括聚合电位、扫描速率、溶剂、电解质、洗脱剂等，进行精细地调控，因此本发明很好地解决了现有技术无法对薄膜状态下的聚合物或是小分子空穴传输材料的交联度和反应活性进行有效调控的问题。
附图说明
在下文中将基于实施例并参考附图来对本发明提出的多层结构的有机电致发光二极管及其空穴传输层的制备方法进行更详细的描述，其中：
图1是实施例中的有机电致发光二极管的结构示意图，1为基板，2为阳极，3为空穴注入层，4为空穴传输层，5为发光层，6为电子注入层，7为阴极。
图2是实施例中的TDATA系列“星型”三苯胺类化合物的结构通式，N为氮基团。
图3是实施例中的TDAB系列“星型”三苯胺类化合物的结构通式，R为R基团。
图4是实施例中的TDAPB系列“星型”三苯胺类化合物的结构通式。
图5是实施例中的三电极体系装置的结构示意图，P为化学工作站，C为对电极，F为参比电极，W为工作电极，S为开关。
在附图中，相同的部件使用相同的附图标记，附图并未按照实际的比例。
具体实施方式
下面将结合附图对本发明提出的有机电致发光二极管及其空穴传输层的制备方法作进一步说明。
实施例1：结合图1、图2、图3、图4和图5说明本实施例，如图1所示，本实施例中的多层结构的有机电致发光二极管，包括基板1，以及在该基板1上从内至外依次堆叠的阳极2、空穴注入层3、空穴传输层4、发光层5、电子注入层6和阴极7。
所述空穴传输层4为通过电化学聚合法制成的薄膜，该薄膜的材质为“星型”三苯胺类化合物，该薄膜的厚度为0.1nm至100nm。
三苯胺类化合物的能量级高达10-3cm2·V-1·s-1，其具有较高的本征空穴迁移率，良好的给电子性，较低的离子化电位，较好的溶解性，较强的荧光性与光稳定性，无定型成膜性等优点，因此三苯胺类化合物一直都是有机半导体材料领域的研究热点。
“星型”三苯胺类化合物主要分为TDATA系列(以三苯胺为中心)、TDAB系列(以苯环为中心)和TDAPB系列(以1，3，5三苯基苯为中心)，其结构通式分别如图2、图3和图4所示，图3中的R基团可以是烷氧基、烷基、烯烃基、芳环或稠环等，这些不同系列的“星型”三苯胺类化合物均具有较高的玻璃化转变温度，良好的成膜性，对可见光有良好的透光性，此外，星型的几何结构使其不易成团，在溶剂中的溶解性较线性三苯胺好得多，最为重要的是，星型结构使三苯胺类化合物的共轭面积增大，其HOMO(Highest Occupied Molecular)能级显著提高，更有利于空穴的注入。
当向有机电致发光二极管施加一定大小的偏压时，电子和空穴分别经由阴极和阳极注入，两种电荷转移至相应的传输层中，然后在外电场的驱动下，载流子到达发光层的界面处并形成激发态的激子(电子-空穴对)，此时激发态的激子能量较高，处于不稳定的状态，将以光或热的形式释放能量而回到稳态，选择不同的发光材料，有机电致发光二极管将发出不同颜色的光。
空穴传输材料作为有机电致发光二极管器件中的功能层材料，需要满足以下条件：(1)高的空穴迁移率，(2)能够形成均一稳定的薄膜，(3)合适的轨道能级，能与其他功能层相匹配，(4)好的热稳定性，不易形成晶体；三苯胺类化合物在电场下能形成阳离子自由基，使其具有良好的空穴迁移率，而且具有较高的玻璃化转变温度、良好的热稳定性和化学稳定性，因此本实施例选择“星型”三苯胺类化合物作为空穴传输层的材料。
“星型”三苯胺类化合物薄膜为通过电化学聚合法制成的，该方法的步骤为：
步骤一、制备含有苯胺类取代基团的电解液；
步骤二、如图5所示搭建三电极体系装置，对电极C、参比电极F和工作电极W均位于电解液内；
步骤三、闭合开关S，并通过控制聚合圈数，将所得电聚合薄膜的厚度控制 在0.1nm至100nm的范围内。
通过制备含有不同前驱体的电解液，可以得到不同材质的电聚合薄膜，电解液中的前驱体分子至少包含噻吩类取代基团、苯胺类取代基团或咔唑类取代基团等电活性取代基团中的一种。
本实施例中的电化学聚合法优选为循环伏安法，该方法是一种常用的电化学研究方法。该方法控制电极电势以不同的速率，随时间以三角波形一次或多次反复扫描，电势范围使电极上能交替发生不同的还原和氧化反应，并记录电流-电势曲线。根据曲线形状可以判断电极反应的可逆程度，中间体、相界吸附或新相形成的可能性，以及偶联化学反应的性质等。常用来测量电极反应参数，判断其控制步骤和反应机理，并观察整个电势扫描范围内发生哪些反应，及其性质如何。对于一个新的电化学体系，首选的研究方法往往就是循环伏安法，可称之为“电化学的谱图”。该方法除了使用汞电极外，还可以用铂、金、玻璃碳、碳纤维微电极以及化学修饰电极等。
循环伏安法的基本原理为：如以等腰三角形的脉冲电压加在工作电极上，得到的电流电压曲线包括两个分支，如果前半部分电位向阴极方向扫描，电活性物质在电极上还原，产生还原波，那么后半部分电位向阳极方向扫描时，还原产物又会重新在电极上氧化，产生氧化波。因此一次三角波扫描，完成一个还原和氧化过程的循环，故该法称为循环伏安法，其电流—电压曲线称为循环伏安图。如果电活性物质可逆性差，则氧化波与还原波的高度就不同，对称性也较差。循环伏安法中电压扫描速度可从每秒钟数毫伏到1伏。
通过电化学聚合法制成的薄膜的结构和聚合度较为明确，相比于传统交联的方法，电化学聚合有利于聚合过程的控制，以及后续聚合物薄膜的结构表征和控制，电聚合薄膜的制备方法工艺较为简单，设备投资少。
本实施例中的空穴传输层作为阳极的界面修饰层，有利于多层溶液加工器件的制备。
实施例2：结合图1说明本实施例，本实施例中的多层结构的有机电致发光二极管，包括基板1，以及在该基板1上从内至外依次堆叠的阳极2、空穴注入层3、空穴传输层4、发光层5、电子注入层6和阴极。
所述阳极2为通过磁控溅射法制成的铟锡氧化物半导体透明导电膜，其厚度为20nm至200nm。
铟锡氧化物是一种铟氧化物和锡氧化物的混合物，通常质量比为90％铟氧化物，10％锡氧化物。铟锡氧化物在薄膜状时，为透明无色，在块状态时，它呈黄偏灰色；铟锡氧化物主要的特性是其电学传导和光学透明的组合。然而，薄膜沉积中需要作出妥协，因为高浓度电荷载流子将会增加材料的电导率，但会降低它的透明度，铟锡氧化物薄膜通常是用电子束蒸发、物理气相沉积或者溅射沉积技术沉积到表面。
本实施例中的铟锡氧化物半导体透明导电膜为通过磁控溅射法制成的，其特点是在150KHz～1GHz范围内有适宜的屏蔽效能，透光性较普通网栅材料屏蔽玻璃好很多，电阻率介于10-3～10-4Ω·cm之间，透光率可达到85％以上。
磁控溅射是物理气相沉积(Physical Vapor Deposition，PVD)的一种，一般的溅射法可被用于制备金属、半导体和绝缘体等材料，且具有设备简单、易于控制、镀膜面积大和附着力强等优点，而磁控溅射法更是实现了高速、低温和低损伤，因为是在低气压下进行高速溅射，必须有效地提高气体的离化率。磁控溅射通过在靶阴极表面引入磁场，利用磁场对带电粒子的约束来提高等离子体密度以增加溅射率。
实施例3：结合图1说明本实施例，本实施例中的多层结构的有机电致发光二极管，包括基板1，以及在该基板1上从内至外依次堆叠的阳极2、空穴注入层3、空穴传输层4、发光层5、电子注入层6和阴极7。
所述空穴注入层3为通过喷墨打印法制成的聚(3，4-乙烯基二氧噻吩)聚(苯乙烯磺酸盐)薄膜，其厚度为1nm至100nm。
聚(3，4-乙烯基二氧噻吩)聚(苯乙烯磺酸盐)，简称PEDT/PSS，是以EDOT单体为原料，聚合而成的一些列高分子聚合物，具有高导电性和通明的特性，具有良好的光稳定性及良好的热稳定性，电化学性能好，在物体表面小于1im的薄层内能产生作用，具有很好的抗水解性，被广泛的使用于抗静电涂层、高导电涂层和有机发光二极管中。
喷墨打印是通过微米级的打印喷头将空穴传输材料，以及红、绿、蓝三色发光材料的溶液分别喷涂在预先已经图案化了的ITO衬底上的子像素坑中，形成红绿蓝三基色发光像素单元。膜层的厚度由打印在像素内的溶质数量决定，通过调整溶剂的挥发性可得到厚度均匀的膜层。这种非接触式打印方式避免了对功能溶液的接触性污染。由于这种方法能极大地节省昂贵的发光材料，而且通过使用有 多个喷射口的喷头打印以大幅缩短制膜时间，因此，喷墨打印技术在OLED制造领域已被确认为向产业化发展的主流技术，设备、原材料和器件制造工艺等在近几年都取得了很大的进展。与现有技术相比，喷墨打印技术在节约原料、降低成本方面优势显著。喷墨打印技术需要准确的定位系统才能提高像素分辨率，对设备的精度要求较高。另外，如何配制可打印的高效率发光材料溶液，实现厚度均匀的聚合物膜层是这种技术的关键。
喷墨打印制备的OLED结构简单，不需要如制备LCD所需的复杂的背光源和滤色片，加上使用喷墨打印技术能够显著节省材料，因此用喷墨打印技术制备的OLED成本将有较大的下降空间。
一般来说，各喷射口喷出的液滴容量均衡性及喷射口喷出液滴运动轨迹与垂直方向的偏差度是衡量打印针头质量的关键因素。前者决定像素内薄膜的厚度及均匀性，后者则关系到液滴的定位准确性。使用喷墨打印技术制备高性能OLED示屏必须具备3个条件，即高精度喷墨打印设备、高性能可溶性聚合物发光材料和打印墨水的配制。
实施例4：结合图1说明本实施例，本实施例中的多层结构的有机电致发光二极管，包括基板1，以及在该基板1上从内至外依次堆叠的阳极2、空穴注入层3、空穴传输层4、发光层5、电子注入层6和阴极7。
所述发光层5为通过喷墨打印法制成的聚9,9-二辛基芴薄膜，该膜的厚度为1nm至100nm。
有机电致发光二极管的发光材料可以分成有机小分子发光材料、聚合物发光材料和有机金属配合物发光材料三大类。
其中，聚合物发光材料作为一类重要的有机电致发光二极管的发光材料，必须具备以下特性：
(1)高量子效率的荧光特性，其荧光光谱主要分布在400nm至700nm可见光区域。
(2)具有良好的化学和热稳定性，不与电极和载流子传输材料发生反应。
(3)良好的成膜性，在几十个纳米的薄层中不产生针孔。
(4)良好的半导体特性，即具有高导电率，或能传输电子，或能传输空穴，或二者皆具。
目前，聚合物发光材料主要为共轭高分子材料，具有优良的载流子传输性能， 包括聚苯撑乙烯及其衍生物类、聚噻吩及其衍生物类、聚对苯及其衍生物类、聚芴及其衍生物类，本实施例中的发光层的材质属于聚芴及其衍生物类。
实施例5：结合图1说明本实施例，本实施例中的多层结构的有机电致发光二极管，包括基板1，以及在该基板1上从内至外依次堆叠的阳极2、空穴注入层3、空穴传输层4、发光层5、电子注入层6和阴极7。
所述电子注入层为通过真空蒸镀法制成的氟化锂薄膜，其厚度为0.5nm至10nm。
大量研究结果表明，薄膜的结晶性越高越有利于载流子的传输，一般认为载流子在有机半导体薄膜中的传输需要跨越连续的晶胞，晶界之间存在着大量的陷阱态，这将对载流子的传输造成阻碍，提高有源层薄膜的结晶性，则晶粒粒径更大，形成陷阱态的晶界就越少，进而就能提高器件的载流子迁移率。
氟化锂(LiF)是使用范围最广，研究最为成熟的电极修饰层材料，在一般的解释中，LiF在阴极处的运用可以降低电极材料功函数与有机材料LUMO能级之间的势垒，通过增加电子遂穿或者在界面处形成偶极子而增强电子注入，因此LiF，特别是配合铝(Al)使用的LiF/Al复合电极已经在OLED中和N型OTFT中广泛运用。
高功函数金属配合LiF电极修饰层的使用可以保证电极稳定和器件寿命，同时增强电子注入以提高器件性能，除此之外，LiF是一种绝缘材料，作为电极修饰层时，它的厚度将会显著影响器件的性能。
LiF带来的第二种改变是在界面处增加了一个额外的势垒，由于LiF时绝缘材料，该势垒可以理解成界面处增加的电阻势垒，这将会对电子的传输造成一定的阻碍。然而，当LiF的厚度适度时，总的势垒依然会小于没有LiF时的势垒。
实施例6：结合图1说明本实施例，本实施例中的多层结构的有机电致发光二极管，包括基板1，以及在该基板1上从内至外依次堆叠的阳极2、空穴注入层3、空穴传输层4、发光层5、电子注入层6和阴极7。
所述阴极7为通过真空蒸镀法发制成的铝膜，其厚度为50nm至1000nm。为了提高电子的注入效率，要求选用功函数尽可能低的材料做阴极，有机电致发光二极管的发光亮度、使用寿命与阴极的功函数有密切的联系，功函数越低，发光亮度越高，使用寿命越长。目前，有机电致发光二极管的阴极主要有单金属阴极(Mg、Mg、Al、Li或Ca中的一种)、合金阴极(Mg-Ag或 Li-Al中的一种)、层状阴极和掺杂复合型电极等，本实施例中的阴极为铝膜，其上为LiF膜，其实质上为合金电极。
在真空环境中，将材料加热并镀到基片上称为真空蒸镀，是将待成膜的物质置于真空中进行蒸发或升华，使之在工件或基片表面析出的过程。
真空蒸镀中的金属镀层通常为铝膜，但其它金属也可通过蒸发沉积。
真空蒸镀的原理为：金属加热至蒸发温度。然后蒸汽从真空室转移，在低温零件上凝结。该工艺在真空中进行，金属蒸汽到达表面不会氧化。
虽然在本文中参照了特定的实施方式来描述本发明，但是应该理解的是，这些实施例仅仅是本发明的原理和应用的示例。因此应该理解的是，可以对示例性的实施例进行许多修改，并且可以设计出其他的布置，只要不偏离所附权利要求所限定的本发明的精神和范围。应该理解的是，可以通过不同于原始权利要求所描述的方式来结合不同的从属权利要求和本文中所述的特征。还可以理解的是，结合单独实施例所描述的特征可以使用在其他所述实施例中。

Claims (10)

  1. 一种有机电致发光二极管，其中，包括空穴传输层，所述空穴传输层为通过电化学聚合法制成的薄膜。
  2. 如权利要求1所述的有机电致发光二极管，其中，所述有机电致发光二极管包括基板，以及在所述基板上从内至外依次堆叠的阳极、空穴注入层、所述空穴传输层、发光层、电子注入层和阴极。
  3. 如权利要求2所述的有机电致发光二极管，其中，所述空穴传输层的材质为“星型”三苯胺类化合物。
  4. 如权利要求2所述的有机电致发光二极管，其中，所述阳极为铟锡氧化物半导体透明导电膜。
  5. 如权利要求2所述的有机电致发光二极管，其中，所述空穴注入层为聚(3，4-乙烯基二氧噻吩)聚(苯乙烯磺酸盐)薄膜。
  6. 如权利要求2所述的有机电致发光二极管，其中，所述发光层为聚9,9-二辛基芴薄膜。
  7. 如权利要求2所述的有机电致发光二极管，其中，所述电子注入层为氟化锂薄膜。
  8. 如权利要求2所述的有机电致发光二极管，其中，所述阴极为铝膜。
  9. 制备权利要求1所述有机电致发光二极管的空穴传输层的方法，其中，该方法包括：
    制备电解液；
    采用基于三电极体系的循环伏安法对所述电解液进行电聚合；
    控制电聚合薄膜厚度；
    对所得电聚合薄膜进行清洗与干燥；
    所述电聚合薄膜用于构成所述空穴传输层；
    所述电解液中的前驱体至少包含一种电活性取代基团；
    每个前驱体分子至少包含两个同类电活性取代基团。
  10. 根据权利要求9所述的方法，其中，所述电活性取代基团为噻吩类取代基团、苯胺类取代基团或咔唑类取代基团。
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