WO2018192028A1 - 稠环化合物、电致发光器件及其制备方法 - Google Patents

稠环化合物、电致发光器件及其制备方法 Download PDF

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WO2018192028A1
WO2018192028A1 PCT/CN2017/084129 CN2017084129W WO2018192028A1 WO 2018192028 A1 WO2018192028 A1 WO 2018192028A1 CN 2017084129 W CN2017084129 W CN 2017084129W WO 2018192028 A1 WO2018192028 A1 WO 2018192028A1
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fused ring
compound
group
light
emitting layer
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谢华飞
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Shenzhen China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Shenzhen China Star Optoelectronics Semiconductor Display Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/546—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings polycyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition

Definitions

  • the invention relates to the field of organic electroluminescent devices, and in particular to a fused ring compound, an electroluminescent device and a preparation method thereof.
  • the organic electroluminescent device has the advantages of simple structure, high yield, low cost, active illumination, etc., and thus has become a research hotspot in the field of flat panel display in recent years.
  • fused ring compounds are classical fluorescent materials, and one of the earliest luminescent materials found in OLED devices with electroluminescence properties and the most widely used.
  • the inventors of the present invention have found during the long-term research that most of the fluorescent materials of the fused-ring compound have strong fluorescence in the dissolved state, and appear in the aggregated state or in the solid state due to the non-radiative relaxation of the excited state of the aggregate.
  • Aggregation-induced quenching (ACQ) phenomenon in most industrial processes, fluorescent materials need to be prepared into aggregated, solid or thin films, and the ACQ effect is unavoidable, which greatly limits the application of such materials.
  • the technical problem to be solved by the present invention is to provide a fused ring compound, an electroluminescent device and a preparation method thereof, which can reduce the aggregation-induced quenching phenomenon of a fused ring compound in an aggregate state or a solid state.
  • the present invention adopts a technical solution to provide a method for preparing an electroluminescent device, the method comprising: providing a substrate; and spin-coating or evaporating a hole transport layer on the substrate And evaporating a light-emitting layer on the hole transport layer, wherein the light-emitting layer is made of a fused ring compound, and the fused ring compound has the following formula:
  • -R1, -R2 and -CHO are bonded to any unsaturated carbon atom of the naphthalene ring;
  • -R1, -R2 are each hydrogen, an alkane group or a fused ring aromatic hydrocarbon group, the alkane group being -C n H 2n+1 , 1 ⁇ n ⁇ 12;
  • the fused ring aromatic hydrocarbon group is any one of a benzene, naphthalene, anthracene, anthracene, phenanthrene, anthracene group; and an electron transport layer is sequentially deposited on the light-emitting layer And a metal cathode layer.
  • one technical solution adopted by the present invention is to provide a fused ring compound having the following formula:
  • -R1, -R2 and -CHO are bonded to any unsaturated carbon atom of the naphthalene ring; -R1, -R2 are each a hydrogen, an alkane group or a fused ring aromatic hydrocarbon group.
  • an electroluminescence device comprising a light-emitting layer comprising the fused ring compound described in the above embodiment.
  • the fused ring compound provided by the present invention has the formula
  • the aldehyde group introduced on the fused ring compound changes the original conjugated planar configuration into a stereo configuration, and the conjugated center of the aldehyde group and the fused ring compound are linked by a rotatable single bond, when in a state of aggregation or solid state, Due to the presence of aldehyde groups, the intramolecular rotation is hindered, the non-radiative relaxation channels are inhibited, and the excited state molecules can only return to the ground state by radiation decay, thus reducing the aggregation-induced quenching of such fused ring compounds in the aggregated state or solid state. Phenomenon, thus broadening its application.
  • FIG. 1 is a schematic structural view of an embodiment of a fused ring compound of the present invention
  • FIG. 2 is a schematic structural view of an embodiment of an electroluminescent device of the present invention.
  • Figure 3 is a schematic representation of the nuclear magnetic characterization of Example 9 -furfural.
  • FIG. 1 is a schematic view showing the structure of an embodiment of a fused ring compound having the following formula:
  • -R1, -R2 and -CHO are bonded to any unsaturated carbon atom of the naphthalene ring;
  • -R1, -R2 are each hydrogen, an alkane group or a fused ring aromatic hydrocarbon group; when -R1, R2 are a hydrogen or an alkane group may be bonded to an unsaturated carbon atom at any position on the naphthalene ring; when -R1, -R2 are a fused ring aromatic hydrocarbon, it may be bonded to at least two unsaturated carbon atoms adjacent to the naphthalene ring.
  • This invention is not limited herein.
  • the alkane group is -C n H 2n+1 , 1 ⁇ n ⁇ 12, such as -CH 3 , -C 5 H 11 , -C 12 H 25 , etc.
  • the above alkane group may It is a linear alkane group, and may also have a branched alkane group; in another embodiment, the above fused ring aromatic hydrocarbon group is any one of a benzene, naphthalene, anthracene, anthracene, phenanthrene, anthracene group.
  • fused ring aromatic hydrocarbon group is benzene
  • the structure of the above fused ring compound may be:
  • fused ring aromatic hydrocarbon group is naphthalene
  • the structure of the above fused ring compound may be:
  • the structure of the above fused ring compound may be:
  • the structure of the above fused ring compound may be:
  • fused ring aromatic hydrocarbon group is phenanthrene
  • the structure of the above fused ring compound may be:
  • the structure of the above fused ring compound may be:
  • the structure of the fused ring compound of the present invention is not limited to the above examples, and may be selectively designed according to actual conditions.
  • the above -R3, -CHO are bonded to any unsaturated carbon atom
  • -R3 is a hydrogen or an alkane group
  • the alkane group is -C n H 2n+1 , 1 ⁇ n ⁇ 12, for example, -CH 3 , - C 5 H 11 , -C 12 H 25 and the like
  • the above alkane group may be a linear alkane group or a branched alkane group.
  • phosphorus oxychloride (POCl3) and dimethylformamide (DMF) are used as vilsmiere reagents, and the reaction is carried out by microwave or heating, and further, the naphthalene ring in the above reactants is used. Introduced -CHO.
  • the aldehyde group-introduced fused ring compound obtained by the above preparation has an aggregation-induced luminescence effect because Having a conjugated planar configuration in solid or agglomerated state, the ⁇ - ⁇ interaction between molecules or other non-radiative channels forms an excimer or exciplex, which in turn consumes the energy of the excited state, thereby Fluorescence weakens or even does not emit light; when an aldehyde group is introduced on a naphthalene ring, it forms When the molecular structure becomes a stereo configuration, the aldehyde group and the conjugate center are connected by a rotatable single bond.
  • the intramolecular rotation is limited due to space constraints, and the non-radiative decay channel is Inhibition, the excited state molecules can only return to the ground state by radiation decay, so that the fluorescence is significantly enhanced, that is, the fused ring compound has an aggregation-induced luminescence effect, thereby reducing aggregation-induced quenching of the fused ring compound in an aggregate state or a solid state.
  • the above fused ring compound since the above fused ring compound has an aggregation-induced luminescence effect, the above fused ring compound can be applied to a luminescent material, for example, as an optical organic film, an electroluminescent device, or the like.
  • FIG. 2 is a schematic structural diagram of an embodiment of an electroluminescent device according to the present invention.
  • the electroluminescent device includes a light-emitting layer 101.
  • the material of the light-emitting layer is a fused ring compound in any of the above embodiments.
  • the above electroluminescent device further includes:
  • the substrate 102 is located on the side of the light-emitting layer 101 and serves as an anode of the device.
  • the material of the substrate 102 has a high work function, which may be ITO (indium tin oxide);
  • the hole transport layer 103 is located between the substrate 102 and the light emitting layer 101, and functions to enhance the hole in the device
  • the transport in the piece and preferably has a blocking effect on the electron
  • the material is PEDOT: PSS (poly(3,4-ethylenedioxythiophene): polystyrene sulfonate), NPB (N, N '-Di(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine);
  • the electron transport layer 104 is located on the other side of the light-emitting layer 101 facing away from the substrate 102, and functions to transport electrons, preferably to block holes, so that electrons can effectively enter the light-emitting layer, and the material thereof can be TPBi (1, 3, 5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene) and Alq3 (8-hydroxyquinoline aluminum);
  • the metal cathode layer 105 is located on the side of the electron transport layer 104 facing away from the light-emitting layer 101, and its work function is generally low.
  • the material may be LiF (lithium fluoride) / Al (aluminum), Mg (magnesium), Ag (silver), etc. .
  • the following method may be employed: cleaning the substrate 102; spin coating or vapor-depositing a hole transport layer 103 on the substrate 102; and steaming on the hole transport layer 103.
  • the light-emitting layer 101 is plated; the electron transport layer 104 and the metal cathode layer 105 are sequentially deposited on the light-emitting layer 101.
  • the structure of the electroluminescent device in the above embodiment is a multi-layer structure, and may be other structures in other embodiments, as long as it includes a light-emitting layer, and the light-emitting layer is made of the fused ring compound in the above embodiment;
  • the preparation method can also be changed according to actual conditions.
  • the illuminating process of the above electroluminescent device will be briefly described below.
  • the process includes the following steps: A.
  • Carrier injection electrons and holes are respectively from the cathode of the device (ie, the metal cathode layer 105) and the anode (ie, the substrate 102).
  • B carrier transport: electrons and holes migrate from the electron transport layer 104 and the hole transport layer 103 to the light-emitting layer 101, respectively;
  • C carriers recombine to form excitons: electrons and holes in the light-emitting layer 101 encounters and combines into excitons;
  • D diffusion of excitons: exciton diffusion transfers energy to the fused ring compound in the light-emitting layer 101, causing electrons in the fused ring compound to be excited from the ground state to the excited state;
  • E retreat Excitation light: The excited state is an unstable state.
  • the electroluminescent device has a luminance of 1000 cd/m 2 to 6000 cd/m 2 and an external quantum efficiency of 1% at a current density of 0.5 A/cm 2 to 5 A /cm 2 . ⁇ 3%.
  • Example 3 Preparation of an electroluminescent device using 9-furfural and characterizing its properties
  • a hole transport layer NPB (60 nm) was first deposited on the cleaned conductive ITO substrate, and then the light-emitting layer 9-furfural (50 nm) and the electron transport layer TPBI (20 nm) were sequentially evaporated.
  • the above electroluminescent device has been tested to have a yellow light emission peak at 520 nm, and at a current density of 3 A/cm 2 , the device has a luminance of 3500 cd/m 2 , a power of 27 m/W, and an external quantum efficiency of 2.2. %.
  • the fused ring compound provided by the present invention has a general formula different from the prior art.
  • the aldehyde group introduced on the fused ring compound changes the original conjugated planar configuration into a stereo configuration, and the conjugated center of the aldehyde group and the fused ring compound are linked by a rotatable single bond, when in a state of aggregation or solid state, Due to the presence of aldehyde groups, the intramolecular rotation is hindered, the non-radiative relaxation channels are inhibited, and the excited state molecules can only return to the ground state by radiation decay, thus reducing the aggregation-induced quenching of such fused ring compounds in the aggregated state or solid state. Phenomenon, thus broadening its application.

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Abstract

一种稠环化合物、电致发光器件及其制备方法，该稠环化合物具有如图１通式，其中，-R 1、-R 2和-CHO连接在萘环任意不饱和碳原子上；-R 1、-R 2各自为氢、烷烃基团或稠环芳香烃基团中任一种。通过上述方式，所提供的实施方式能够减少稠环化合物在聚集态或固态时的聚集诱导淬灭现象。

Description

稠环化合物、电致发光器件及其制备方法 【技术领域】
本发明涉及有机电致发光器件领域，特别是涉及一种稠环化合物、电致发光器件及其制备方法。
【背景技术】
有机电致发光器件(OLED)具有结构简单、成品率高、成本低、主动发光等优点，因此成为近年来平板显示领域的一个研究热点。
在OLED的制备和优化过程中，发光材料的选择至关重要，其性质是决定器件性能的重要因素之一。目前，稠环类化合物是经典的荧光材料，也是OLED器件中最早被发现具有电致发光性能和目前最广泛应用的主体发光材料之一。
本发明的发明人在长期研究过程中发现，稠环类化合物荧光材料大多数在溶解状态下具有很强的荧光，而在聚集态或固态时由于聚集体的激发态出现非辐射弛豫而出现聚集诱导淬灭(ACQ)现象；而在大多数工业工艺情况下，荧光材料需要制备成聚集态、固态或薄膜，ACQ效应不可避免，从而在很大程度上限制了此类材料的应用。
【发明内容】
本发明主要解决的技术问题是提供一种稠环化合物、电致发光器件及其制备方法，能够减少稠环化合物在聚集态或固态时的聚集诱导淬灭现象。
为解决上述技术问题，本发明采用的一个技术方案是：提供一种电致发光器件的制备方法，所述方法包括：提供基底；在所述基底上旋涂或蒸镀一层空穴传输层；在所述空穴传输层上蒸镀发光层，其中所述发光层的材质为稠环化合物，所述稠环化合物具有以下通式：
Figure PCTCN2017084129-appb-000001
-R1、-R2和-CHO连接在萘环任意不饱和碳原子上；-R1、-R2各自为氢、烷烃基团或稠环芳香烃基团中任一种，所述烷烃基团为-CnH2n+1，1≤n≤12；所述稠环芳香烃基团为苯、萘、蒽、芘、菲、苝基团中任一种；在所述发光层上依次蒸镀电子传输层和金属阴极层。
为解决上述技术问题，本发明采用的一个技术方案是：提供一种稠环化合物，所述化合物具有以下通式：
Figure PCTCN2017084129-appb-000002
其中，-R1、-R2和-CHO连接在萘环任意不饱和碳原子上；-R1、-R2各自为氢、烷烃基团或稠环芳香烃基团中任一种。
为解决上述技术问题，本发明采用的另一个技术方案是：提供一种电致发光器件，所述电致发光器件包括发光层，所述发光层包括上述实施例中的所述的稠环化合物。
本发明的有益效果是：区别于现有技术的情况，本发明所提供的稠环化合物的通式为
Figure PCTCN2017084129-appb-000003
该稠环化合物上引入的醛基使原本的共轭平面构型变成立体构型，醛基与该稠环化合物的共轭中心通过可旋转的单键连接，当处于聚集态或者固态时，由于醛基的存在，使得分子内旋转受阻，非辐射弛豫渠道被抑制，激发态分子只能通过辐射衰变回到基态，因此可以降低该类稠环化合物在聚集态或者固态的聚集诱导淬灭现象，从而拓宽其应用。
【附图说明】
图1是本发明稠环化合物一实施方式的结构示意图；
图2是本发明电致发光器件一实施方式的结构示意图；
图3是实施例9-蒽醛的核磁表征示意图。
【具体实施方式】
请参阅图1，图1为本发明稠环化合物一实施方式的结构示意图，该稠环化合物具有以下通式：
Figure PCTCN2017084129-appb-000004
其中，-R1、-R2和-CHO连接在萘环任意不饱和碳原子上；-R1、-R2各自为氢、烷烃基团或稠环芳香烃基团中任一种；当-R1、R2为氢或烷烃基团时，可以与萘环上任一位置的不饱和碳原子相连；当-R1、-R2为稠环芳香烃时，可以与萘环任意相邻的至少两个不饱和碳原子相连，本发明此不作限定。在一个实施例中，上述烷烃基团为-CnH2n+1，1≤n≤12，例如-CH3、-C5H11、-C12H25等，另外，上述烷烃基团可以是直链烷烃基团，也可以带有支链的烷烃基团；在另一个实施例中，上述稠环芳香烃基团为苯、萘、蒽、芘、菲、苝基团中任一种。
当稠环芳香烃基团为苯时，上述稠环化合物的结构可以是：
Figure PCTCN2017084129-appb-000005
等；
当稠环芳香烃基团为萘时，上述稠环化合物的结构可以是：
Figure PCTCN2017084129-appb-000006
Figure PCTCN2017084129-appb-000007
等；
当稠环芳香烃基团为蒽时，上述稠环化合物的结构可以是：
Figure PCTCN2017084129-appb-000008
等；
当稠环芳香烃基团为芘时，上述稠环化合物的结构可以是：
Figure PCTCN2017084129-appb-000009
等；
当稠环芳香烃基团为菲时，上述稠环化合物的结构可以是：
Figure PCTCN2017084129-appb-000010
等；
当稠环芳香烃基团为苝时，上述稠环化合物的结构可以是：
Figure PCTCN2017084129-appb-000011
等；
当然，本发明稠环化合物的结构不限于上述实例，可以根据实际情况进行选择设计。另外，上述-R3、-CHO连接在任一不饱和碳原子上，-R3为氢或烷烃基团，烷烃基团为-CnH2n+1，1≤n≤12，例如-CH3、-C5H11、-C12H25等，上述烷烃基团可以是直链烷烃基团，也可以带有支链的烷烃基团。
为制备上述稠环化合物，在一个实施方式中，可利用维尔斯迈尔-哈克反应制备获得，其化学反应方程式如下所示：
Figure PCTCN2017084129-appb-000012
具体为，利用三氯氧磷(POCl3)和二甲基甲酰胺(DMF)为vilsmiere(维尔斯迈尔)试剂，利用微波或者加热的方式促进上述反应的进行，进而在上述反应物的萘环上引入-CHO。
上述制备所得的引入醛基的稠环化合物具有聚集诱导发光效应，这是因为，
Figure PCTCN2017084129-appb-000013
在固态或者聚集态下时具有共轭平面构型，分子间的π-π作用或其他非辐射渠道形成了激基缔合物或激基复合物，进而消耗了激发态的能量，从而使得其荧光减弱甚至不发光；而当在萘环上引入醛基时，即形成
Figure PCTCN2017084129-appb-000014
时，该分子结构变为立体构型，醛基与共轭中心通过可旋转的单键连接，当其在固态或聚集态下时，由于空间的限制，分子内旋转受限，非辐射衰变渠道被抑制，激发态分子只能通过辐射衰变回到基态，从而使荧光显著增强，即该稠环化合物具有聚集诱导发光效应，因此可以降低该类稠环化合物在聚集态或者固态的聚集诱导淬灭现象，从而拓宽其应用。
在一个应用场景中，由于上述稠环化合物具有聚集诱导发光效应，因此可将上述稠环化合物应用到发光材料上，例如，可用作光学有机薄膜、电致发光器件等。
下面以电致发光器件为例，对上述稠环化合物在发光材料的应用上作进一步描述。
请参阅图2，图2为本发明电致发光器件一实施方式的结构示意图，该电致发光器件包括发光层101，发光层的材质为上述任一实施例中的稠环化合物，在此不再赘述；在其他实施例中，上述电致发光器件还包括：
基底102，位于发光层101一侧，用作器件的阳极；在一个应用场景中，该基底102材料的功函数较高，可以是ITO(氧化铟锡)；
空穴传输层103，位于基底102与发光层101之间，其作用为增强空穴在器 件中的输运，并最好能对电子有阻挡的作用，其材质为PEDOT：PSS(聚(3，4-乙撑二氧噻吩)：聚苯乙烯磺酸盐)、NPB(N，N′-二(1-萘基)-N，N′-二苯基-1，1′-联苯-4-4′-二胺)等；
电子传输层104，位于发光层101背向基底102的另一侧，其作用为传输电子，最好能阻挡空穴，使电子能有效地进入发光层，其材质可以为TPBi(1，3，5-三(1-苯基-1H-苯并咪唑-2-基)苯)和Alq3(8-羟基喹啉铝)；
金属阴极层105，位于电子传输层104背向发光层101一侧，其功函数一般较低，材质可以是LiF(氟化锂)/Al(铝)、Mg(镁)、Ag(银)等。
在一个实施例中，为制备上述结构的电致发光器件，可采用如下方法：清洗基底102；在基底102上旋涂或蒸镀一层空穴传输层103；在空穴传输层103上蒸镀发光层101；在发光层101上依次蒸镀上电子传输层104和金属阴极层105。
上述实施例中电致发光器件的结构为多层结构，在其他实施例中也可为其他结构，只需其包括发光层，且发光层材质为上述实施例中的稠环化合物即可；其制备方法也可根据实际情况进行变动。
下面将简单介绍下上述电致发光器件的发光过程，该过程包括以下步骤：A、载流子注入：电子和空穴分别从器件的阴极(即金属阴极层105)和阳极(即基底102)注入器件内；B、载流子传输：电子和空穴分别从电子传输层104和空穴传输层103向发光层101迁移；C、载流子复合形成激子：电子和空穴在发光层101中相遇并复合成激子；D、激子的扩散：激子扩散将能量传递给发光层101中的稠环化合物，使稠环化合物中的电子从基态被激发到激发态；E、退激发光：激发态是一个不稳定的状态，稠环化合物中处于激发态的电子回到基态，将能量以光子的形式释放出来，进而使上述电致发光器件开始发光。在一个应用场景中，上述电致发光器件在0.5A/cm2-5A/cm2的电流密度下，电致发光器件的亮度为1000cd/m2-6000cd/m2，外量子效率为1％～3％。
下面将给出具体实施例来对本发明作进一步解释。
实施例1：制备稠环化合物9-蒽醛
Figure PCTCN2017084129-appb-000015
将55g POCl3和30g蒽混合并加热到90℃-95℃，缓慢滴加19g DMF，反应15h得产物9-蒽醛；其核磁表征图谱如图3所示。
实施例2：表征9-蒽醛的荧光量子产率
如下表1所示，当溶剂为DMSO(二甲基亚砜)时，9-蒽醛在DMSO中溶解度大，9-蒽醛中的醛基绕单键自由旋转，消耗激发态的能量，成为非辐射衰变，因此9-蒽醛几乎没有荧光，量子产率几乎为0；当9-蒽醛分散在DMSO∶H2O＝1∶99的混合液中时，由于9-蒽醛在水中的溶解度较低，因此9-蒽醛在该混合液中处于聚集态，且发射出黄色荧光，其量子产率为14.2％，从而印证了本发明的稠环化合物具有聚集诱导发光的特性。
表1 9-蒽醛的荧光量子产率数据
Figure PCTCN2017084129-appb-000016
实施例3：利用9-蒽醛制备电致发光器件，并表征其性能
在高真空条件下，在经过清洗的导电ITO基板上先蒸镀一层空穴传输层NPB(60nm)，然后依次蒸镀发光层9-蒽醛(50nm)、电子传输层TPBI(20nm)/Alq3(30nm)和金属阴极层LiF(1nm)/Al(100nm)；
经测试，上述电致发光器件在520nm处具有黄光发射峰，且在3A/cm2的电流密度下，该器件的亮度可达3500cd/m2，功率为27m/W，外量子效率达到2.2％。
总而言之，区别于现有技术的情况，本发明所提供的稠环化合物的通式为
Figure PCTCN2017084129-appb-000017
该稠环化合物上引入的醛基使原本的共轭平面构型变成立体构型，醛基与该稠环化合物的共轭中心通过可旋转的单键连接，当处于聚集态或者固态时，由于醛基的存在，使得分子内旋转受阻，非辐射弛豫渠道被抑制，激发态分子只能通过辐射衰变回到基态，因此可以降低该类稠环化合物在聚集态或者固态的聚集诱导淬灭现象，从而拓宽其应用。
以上仅为本发明的实施方式，并非因此限制本发明的专利范围，凡是利用 本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (14)

  1. 一种电致发光器件的制备方法，其中，所述方法包括：
    提供基底；
    在所述基底上旋涂或蒸镀一层空穴传输层；
    在所述空穴传输层上蒸镀发光层，其中所述发光层的材质为稠环化合物，所述稠环化合物具有以下通式：
    Figure PCTCN2017084129-appb-100001
    -R1、-R2和-CHO连接在萘环任意不饱和碳原子上；-R1、-R2各自为氢、烷烃基团或稠环芳香烃基团中任一种，所述烷烃基团为-CnH2n+1，1≤n≤12；所述稠环芳香烃基团为苯、萘、蒽、芘、菲、苝基团中任一种；
    在所述发光层上依次蒸镀电子传输层和金属阴极层。
  2. 根据权利要求1所述的方法，
    所述稠环化合物为下列中任一种：
    Figure PCTCN2017084129-appb-100002
    其中，-R3、-CHO连接在任一不饱和碳原子上，-R3为氢或烷烃基团，所述烷烃基团为-CnH2n+1，1≤n≤12。
  3. 根据权利要求1所述的方法，其中，
    所述化合物由对应的反应物
    Figure PCTCN2017084129-appb-100003
    经维尔斯迈尔-哈克反应制备获得。
  4. 一种稠环化合物，其中，所述化合物具有以下通式：
    Figure PCTCN2017084129-appb-100004
    其中，-R1、-R2和-CHO连接在萘环任意不饱和碳原子上；-R1、-R2各自为氢、烷烃基团或稠环芳香烃基团中任一种。
  5. 根据权利要求4所述的化合物，其中，
    所述烷烃基团为-CnH2n+1，1≤n≤12；所述稠环芳香烃基团为苯、萘、蒽、芘、菲、苝基团中任一种。
  6. 根据权利要求5所述的化合物，其中，所述稠环化合物为下列中任一种：
    Figure PCTCN2017084129-appb-100005
    其中，-R3、-CHO连接在任一不饱和碳原子上，-R3为氢或烷烃基团，所述烷烃基团为-CnH2n+1，1≤n≤12。
  7. 根据权利要求4所述的化合物，其中，
    所述化合物由对应的反应物
    Figure PCTCN2017084129-appb-100006
    经维尔斯迈尔-哈克反应制备获得。
  8. 根据权利要求4所述的化合物，其中，所述化合物具有聚集诱导发光性能。
  9. 一种电致发光器件，包括发光层，其中，所述发光层包括稠环化合物，所述稠环化合物具有以下通式：
    Figure PCTCN2017084129-appb-100007
    其中，-R1、-R2和-CHO连接在萘环任意不饱和碳原子上；-R1、-R2各自为氢、烷烃基团或稠环芳香烃基团中任一种。
  10. 根据权利要求9所述的器件，其中，
    所述烷烃基团为-CnH2n+1，1≤n≤12；所述稠环芳香烃基团为苯、萘、蒽、芘、菲、苝基团中任一种。
  11. 根据权利要求10所述的器件，其中，所述稠环化合物为下列中任一种：
    Figure PCTCN2017084129-appb-100008
    其中，-R3、-CHO连接在任一不饱和碳原子上，-R3为氢或烷烃基团，所述烷烃基团为-CnH2n+1，1≤n≤12。
  12. 根据权利要求9所述的器件，其中，
    所述化合物由对应的反应物
    Figure PCTCN2017084129-appb-100009
    经维尔斯迈尔-哈克反应制备获得。
  13. 根据权利要求9所述的器件，其中，所述器件进一步包括：
    基底，位于所述发光层一侧，用作所述器件的阳极；
    空穴传输层，位于所述基底与所述发光层之间；
    电子传输层，位于所述发光层背向所述基底的另一侧；
    金属阴极层，位于所述电子传输层背向所述发光层一侧。
  14. 根据权利要求9所述的器件，其中，在0.5A/cm2-5A/cm2的电流密度下，所述电致发光器件的亮度为1000cd/m2-6000cd/m2，外量子效率为1％～3％。
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