WO2022213601A1 - 一种有机发光二极管结构和显示装置 - Google Patents

一种有机发光二极管结构和显示装置 Download PDF

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WO2022213601A1
WO2022213601A1 PCT/CN2021/129588 CN2021129588W WO2022213601A1 WO 2022213601 A1 WO2022213601 A1 WO 2022213601A1 CN 2021129588 W CN2021129588 W CN 2021129588W WO 2022213601 A1 WO2022213601 A1 WO 2022213601A1
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substituted
unsubstituted
host
blocking layer
light emitting
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French (fr)
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高荣荣
陈磊
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京东方科技集团股份有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • 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]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present disclosure relates to the field of display technology, and in particular, to an organic light emitting diode structure and a display device.
  • organic electroluminescence display Organic Light-Emitting Diode, OLED
  • OLED Organic Light-Emitting Diode
  • an embodiment of the present disclosure provides an organic light emitting diode structure, comprising a cathode, an electron transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, a hole transport layer and an anode that are stacked in sequence, the light emitting
  • the layer includes a host material and a guest material;
  • the host material has the structure:
  • Substituents R1, R2, R3, R4, R5, R6, R7, R8 are each independently selected from: hydrogen atom, deuterium atom, substituted or unsubstituted aryl group having 6 to 60 carbon atoms, having 6 to 60 carbon atoms Substituted or unsubstituted heteroaryl groups of carbon atoms, substituted or unsubstituted alkyl groups of 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl groups of 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl groups of 1 to 50 carbon atoms Substituted or unsubstituted alkoxy groups of carbon atoms, substituted or unsubstituted aralkyl groups of 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups of 5 to 50 ring atoms, substituted or unsubstituted aryloxy groups of 5 to 50 carbon atoms
  • Substituent Ar1 is substituted or unsubstituted aryl
  • Substituent Ar2 is selected from any of the following:
  • L is a single bond, substituted or unsubstituted aryl
  • R is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and multiple Rs are the same or different;
  • a is an integer from 0 to 5
  • b is an integer from 0 to 5;
  • the light-emitting layer, the hole blocking layer and the electron blocking layer satisfy the following conditions:
  • the materials of the electron blocking layer and the hole transport layer include aromatic amine materials or carbazole materials, the hole mobility of the hole transport layer ranges from 10 -4 to 10 -6 cm 2 V -1 s -1 , and the electron blocking layer The hole mobility ranges from 10 -4 to 10 -7 cm 2 V -1 s -1 ;
  • the T1(HBL) is the lowest triplet energy of the hole blocking layer material
  • the T1(Host) is the lowest triplet energy of the host material
  • the T1(EBL) is the lowest triplet energy of the electron blocking layer material Triplet energy
  • T1(Dopant) is the lowest triplet energy of the guest material
  • S1(Host) is the lowest singlet energy of the host material
  • S1(Dopant) is the lowest singlet energy of the guest material singlet energy.
  • the hole blocking layer and the electron transport layer meet the following conditions:
  • the LUMO(HBL) is the lowest unoccupied molecular orbital of the material of the hole blocking layer
  • the LUMO(ETL) is the lowest unoccupied molecular orbital of the material of the electron transport layer.
  • the hole transport layer and the electron blocking layer meet the following conditions:
  • the HOMO(HTL) is the highest occupied molecular orbital of the hole transport layer
  • the HOMO(EBL) is the highest occupied molecular orbital of the electron blocking layer.
  • the electron mobility of the hole blocking layer is in the range of 10 -7 to 10 -9 cm 2 V -1 s -1
  • the electron mobility of the electron transport layer is in the range of 10 -5 to 10 -7 cm 2 V - 1 s -1 ;
  • the electron mobility of the host material of the light-emitting layer is in the range of 10 -5 to 10 -8 cm 2 V -1 s -1
  • the hole mobility is in the range of 10 -8 to 10 -12 cm 2 V -1 s -1 .
  • the main body material is selected from:
  • the material of the electron transport layer has the structure:
  • X1, X2 and X3 are C or N, and at least one of X1, X2 and X3 is N;
  • L1 is a single bond, substituted or unsubstituted C6 to 60 arylene
  • Ar3 and Ar4 are substituted or unsubstituted C6 to 60 aryl; or
  • Ar3 and Ar4 are substituted or unsubstituted C2-60 heteroaryl groups containing at least one of O, N, Si and S;
  • Ar3 and Ar4 are the same or different;
  • Substituent A is selected from any of the following:
  • Substituents Ar5, Ar6, Ar7 are independently selected from: hydrogen, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 carbon atoms, Aromatic or heteroaromatic ring systems having substituted or unsubstituted silyl groups having 1 to 20 carbon atoms, having 5 to 30 aromatic ring atoms;
  • Y is C, O, S, N or a single bond.
  • At least two of p, m and n are greater than 0, at least two of the substituents (Ar5)p, (Ar6)q, (Ar7)m are the same, or the substituents ( Any two of Ar5)p, (Ar6)q, and (Ar7)m are different.
  • the material of the electron transport layer is selected from:
  • an embodiment of the present disclosure provides a display device including the organic light emitting diode structure according to any one of the first aspects.
  • the light emitting layer, the hole blocking layer and the electron blocking layer in the organic light emitting diode structure satisfy the following conditions: T1(HBL)>T1(Host); T1(EBL)>T1(Host) ); T1(Dopant)>T1(Host); S1(Host)>S1(Dopant); wherein, the T1(HBL) is the lowest triplet energy of the hole blocking layer material, and the T1(Host) is the the lowest triplet energy of the host material, the T1(EBL) is the lowest triplet energy of the electron blocking layer material, T1(Dopant) is the lowest triplet energy of the guest material, and the S1(Host) is the The lowest singlet energy of the host material, and the S1 (Dopant) is the lowest singlet energy of the guest material.
  • the technical solution of this embodiment helps to improve the luminous efficiency and lifespan of the display device.
  • FIG. 1 is a schematic structural diagram of an organic light emitting diode structure provided by a first embodiment of the present disclosure.
  • Embodiments of the present disclosure provide an organic light emitting diode structure.
  • the organic light emitting diode structure includes a cathode 101, an electron injection layer (EIL) 102, an electron transport layer (ETL) 103, a hole blocking layer (HBL) 104,
  • the light emitting layer 105, the electron blocking layer (EBL) 106, the hole transport layer (HTL) 107, the hole injection layer (HIL) 108 and the anode 109, the light emitting layer 105 includes a host material and a guest material.
  • OLEDs organic light-emitting diodes
  • fluorescent OLED light-emitting devices During operation, when a voltage is applied, holes are injected from the anode, and electrons are injected from the anode. injected from the cathode. Holes and electrons recombine in the light-emitting layer to form excitons.
  • the electron spin statistics theory singlet excitons and triplet excitons are generated in a ratio of 25%:75%.
  • the limit value of the internal quantum efficiency is considered to be 25%, as shown in Figure 1, which corresponds to an external quantum efficiency of about 5%, resulting in lower practical luminous efficiency.
  • the light-emitting layer, the hole-blocking layer, and the electron-blocking layer satisfy the following conditions:
  • T1(HBL) is the lowest triplet energy of the hole blocking layer material
  • T1(Host) is the lowest triplet energy of the host material
  • T1(EBL) is the lowest triplet energy of the electron blocking layer material
  • T1(Dopant) is the lowest triplet energy of the guest material
  • S1(Host) is the lowest singlet energy of the host material
  • S1(Dopant) is the lowest singlet energy of the guest material.
  • the accumulation of carriers at the interface between the electron blocking layer and the light-emitting layer can be reduced, which is helpful for reducing excitons and confining them to light-emitting more effectively.
  • the energy of the light-emitting layer is prevented from diffusing to other structures and film layers, thereby helping to improve the service life.
  • TTA triplet-triplet annihilation
  • the hole blocking layer and the electron transport layer satisfy the following conditions:
  • LUMO represents the lowest unoccupied molecular orbital
  • LUMO(HBL) is the lowest unoccupied molecular orbital of the hole blocking layer material
  • LUMO(ETL) is the lowest unoccupied molecular orbital of the material of the electron transport layer.
  • the hole transport layer and the electron blocking layer satisfy the following conditions:
  • HOMO represents the highest occupied molecular orbital
  • HOMO(HTL) is the highest occupied molecular orbital of the hole transport layer
  • HOMO(EBL) is the electron blocking layer the highest occupied molecular orbital.
  • the host material has the structure:
  • the substituents R1, R2, R3, R4, R5, R6, R7, R8 are each independently selected from: hydrogen atom H, deuterium atom D, substituted or unsubstituted with 6 to 60 carbon atoms aryl, substituted or unsubstituted heteroaryl with 6 to 60 carbon atoms, substituted or unsubstituted alkyl with 1 to 50 carbon atoms, substituted or unsubstituted with 1 to 50 carbon atoms Cycloalkyl, substituted or unsubstituted alkoxy having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl having 6 to 50 carbon atoms, substituted or unsubstituted having 5 to 50 ring atoms aryloxy group, substituted or unsubstituted arylthio group having 5 to 50 ring atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms.
  • any two of the substituents R1 to R8 may be the same or different.
  • the substituent Ar1 is a substituted or unsubstituted aryl group
  • Substituent Ar2 is selected from any one of the following substituents Ar-1 to Ar-7:
  • L is a single bond, a substituted or unsubstituted aryl group;
  • R is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group;
  • a is an integer of 0-5, and
  • b is an integer of 0-5.
  • the general formula of the host material represents an anthracene compound, and the electron cloud of the highest occupied molecular orbital/lowest unoccupied molecular orbital is concentrated on the anthracene nucleus, which can make electrons and holes relatively stable.
  • oxygen-containing O and sulfur S groups on the anthracene nucleus such as groups such as dibenzofuran
  • the voltage of the device can be reduced to a certain extent.
  • oxygen-containing O and sulfur S groups which can make the molecule exhibit a certain polarity, which helps to improve the interaction between the host material and the electron blocking layer, and helps to optimize the energy level of the interface adjacent to the light-emitting layer and the electron blocking layer.
  • the host material is selected from any of the following Host-1 to Host-6:
  • the material of the electron transport layer has the structure:
  • X1, X2 and X3 are C or N, and at least one of X1, X2 and X3 is nitrogen N.
  • L1 is a single bond, substituted or unsubstituted C6 to 60 arylene;
  • Ar3 and Ar4 are substituted or unsubstituted C6 to 60 aryl; or
  • Ar3 and Ar4 are substituted or unsubstituted C2-60 heteroaryl groups containing at least one of oxygen O, nitrogen N, silicon Si and sulfur S;
  • Ar3 and Ar4 are the same or different.
  • the structure of the substituent A is selected from any one of the following A-1 to A-3:
  • the substituents Ar5, Ar6 and Ar7 are each independently selected from: hydrogen H, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, substituted with 3 to 20 carbon atoms or Unsubstituted cycloalkyl, substituted or unsubstituted silyl groups having 1 to 20 carbon atoms, aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms.
  • p is an integer from 0 to 4
  • q is an integer from 0 to 4
  • m is an integer from 0 to 4
  • n is an integer from 0 to 4
  • Y is carbon C, oxygen O, sulfur S, nitrogen N or a single bond .
  • At least two of p, m, and n are greater than 0, at least two of the substituents (Ar5)p, (Ar6)q, (Ar7)m are the same, or Any two of the substituents (Ar5)p, (Ar6)q, and (Ar7)m are different.
  • the nitrogen-containing azine is a strong electron withdrawing group, and the material of the electron transport layer with such a substituent has a relatively deep HOMO/LUMO energy level, which is conducive to the increase of charge. transmission.
  • the spiro ring structure is a fragment with a higher T1 energy level, which can effectively confine the excitons to the higher T1 of the light-emitting layer. More specifically, it is mainly determined by the T1 of the fragment; in addition, the spiro ring has a better spatial structure.
  • the large and large sterically hindered groups can inhibit the crystallization of materials to a certain extent.
  • the material of the electron transport layer is selected from any of the following ETL-1 to ETL-11:
  • the mobility of the hole blocking layer is smaller than that of the electron transport layer, so as to slow down the electron transport speed.
  • the electron mobility of the hole blocking layer is controlled to be in the range of 10 -7 to 10 -9 cm 2 V -1 s -1
  • the electron mobility of the electron transport layer is controlled to be in the range of 10 -5 to 10 ⁇ 7 cm 2 V -1 s -1 , in this way, the transmission efficiency of electrons can be suppressed to a certain extent.
  • the hole mobility of the hole transport layer is in the range of 10 -4 to 10 -6 cm 2 V -1 s -1
  • the hole mobility of the electron blocking layer is in the range of 10 -4 to 10 -7 cm 2 V -1 s -1 , thereby improving the hole transport efficiency.
  • the electron mobility of the host material of the light-emitting layer is controlled at 10 -5 to 10 -8 cm 2 V -1 s -1
  • the hole mobility is controlled at 10 -8 to 10 -12 cm 2 V -1 s -1 , so that Helps to increase hole-electron transport speed and suppress electron transport speed.
  • Embodiments of the present disclosure provide a display device including any one of the organic light emitting diode structures above.
  • the display device of this embodiment includes all the technical solutions of the above organic light emitting diode structure embodiments, at least all the above technical effects can be achieved, which will not be repeated here.
  • the organic light emitting diode has a structure including a cathode 101 , an electron injection layer (EIL) 102 , an electron transport layer (ETL) 103 , and a hole blocking layer (HBL) that are stacked in sequence.
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the light emitting layer 105 includes host material and guest material.
  • the material of the electron injection layer can be selected from metal or alkali metal, such as lithium fluoride LiF, ytterbium Yb, LIQ (C 9 H 6 NOLi, 8-hydroxyquinoline-lithium) and other materials.
  • metal or alkali metal such as lithium fluoride LiF, ytterbium Yb, LIQ (C 9 H 6 NOLi, 8-hydroxyquinoline-lithium) and other materials.
  • the material of the electron transport layer in the related art is usually an aromatic heterocyclic compound, TPBi, Bphen and other materials, and the material of the above general formula (2) is specifically used in this embodiment.
  • the material of the hole blocking layer is usually an aromatic heterocyclic compound, such as BCP, Bphen and other materials.
  • the host material of the light-emitting layer can be selected from the above-mentioned general formula (1), and the guest material can be selected from Dpvbi, DPAVB, DSA-Ph and other materials.
  • the material of the electron blocking layer can be selected from aromatic amines or carbazole materials with hole transport properties, such as mCBP, Tris-PCz and other materials.
  • the material of the hole transport layer can be selected from aromatic amines or carbazole materials with hole transport properties, such as NPB, m-MTDATA, TPD and other materials.
  • the material of the hole injection layer can be inorganic oxide, such as molybdenum trioxide MoO 3 , F4-TCNQ, HAT-CN and other materials.
  • the selection of the P-type dopant material of the hole injection layer is as follows:
  • the material selection of the hole injection layer is as follows:
  • the material selection of the electron blocking layer is not limited
  • the electron transport layer material in the comparative example can be selected to compare the ETL:
  • the material selection of the hole blocking layer is not limited
  • the main material of the comparative example can choose to compare the Host:
  • the present disclosure exemplarily provides a number of comparative examples and examples.
  • the electron transport layer material is selected to compare with ETL, and the host material is selected to be compared with Host.
  • Comparative Example 3 the above-mentioned ETL-3 was selected as the material of the electron transport layer, and the host material was selected as the comparison Host.
  • the electron transport layer material is selected to compare with ETL, and the host material is selected from the above-mentioned Host-1.
  • the electron transport layer material is selected to compare with ETL, and the host material is the above-mentioned Host-4.
  • Example 1 the above-mentioned ETL-2 was selected as the electron transport layer material, and the above-mentioned Host-1 was selected as the host material.
  • Example 2 the above-mentioned ETL-2 was selected as the electron transport layer material, and the above-mentioned Host-4 was selected as the host material.
  • Example 3 the above-mentioned ETL-3 was selected as the electron transport layer material, and the above-mentioned Host-1 was selected as the host material.
  • Example 4 the above-mentioned ETL-3 was selected as the electron transport layer material, and the above-mentioned Host-4 was selected as the host material.
  • the material properties of the electron transport layer used in this example are shown in Table 1, and the physical properties of the host material of the light-emitting layer used are shown in Table 2. Voltage, luminous efficiency and lifetime tests were performed on the organic light emitting diode structures of Comparative Examples 1 to 5 and Examples 1 to 4, wherein the lifetime tests were performed according to LT95@1000nit, and the test results are shown in Table 3.
  • Host HOMO LUMO T1 Host-1 -6.00 -3.01 1.77 Host-4 -6.01 -2.98 1.71
  • the light-emitting efficiency of the light-emitting device is improved and the service life is increased.

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Abstract

提供一种有机发光二极管结构和显示装置。有机发光二极管结构中的发光层、空穴阻挡层和电子阻挡层满足以下条件：T1(HBL)>T1(Host)；T1(EBL)＞T1(Host)；T1(Dopant)＞T1(Host)；S1(Host)＞S1(Dopant)；其中，T1(HBL)为空穴阻挡层材料的最低三重态能量，T1(Host)为主体材料的最低三重态能量，T1(EBL)为电子阻挡层材料的最低三重态能量，T1(Dopant)为客体材料的最低三重态能量，S1(Host)为主体材料的最低单重态能量，S1(Dopant)为客体材料的最低单重态能量。实施例的技术方案有助于提高显示器件的发光效率和寿命。

Description

一种有机发光二极管结构和显示装置
相关申请的交叉引用
本申请主张在2021年4月6日在中国提交的中国专利申请号202110367717.X的优先权，其全部内容通过引用包含于此。
技术领域
本公开涉及显示技术领域，尤其涉及一种有机发光二极管结构和显示装置。
背景技术
有机电致发光显示器(OrganicLight-Emitting Diode，OLED)作为一种新型的显示技术逐渐受到更多的关注。由于其具有主动发光、发光亮度高、分辨率高、宽视角、响应速度快、低能耗以及可柔性化等特点，成为目前市场上炙手可热的主流显示产品。
发明内容
第一方面，本公开实施例提供了一种有机发光二极管结构，包括依次层叠设置的阴极、电子传输层、空穴阻挡层、发光层、电子阻挡层、空穴传输层和阳极，所述发光层包括主体材料和客体材料；
所述主体材料具有结构：
Figure PCTCN2021129588-appb-000001
取代基R1、R2、R3、R4、R5、R6、R7、R8各自独立的选自：氢原子、氘原子、具有6至60个碳原子的取代或未取代的芳基、具有6至60个碳原子的取代或未取代的杂芳基、具有1至50个碳原子的取代或未取代的烷基、具有1至50个碳原子的取代或未取代的环烷基、具有1至50个碳原子的取代 或未取代的烷氧基、具有6至50个碳原子的取代或未取代的芳烷基、具有5至50个环原子的取代或未取代的芳氧基、具有5至50个环原子的取代或未取代的芳硫基、具有1至50个碳原子的取代或未取代的烷氧基羰基；
取代基Ar1为取代或未取代的芳基；
取代基Ar2选自以下任一项：
Figure PCTCN2021129588-appb-000002
Figure PCTCN2021129588-appb-000003
其中，L为单键、取代或未取代的芳基；
R为取代或未取代的芳基、取代或未取代的杂芳基，多个R相同或不同；
a为0～5的整数，b为0～5的整数；
所述发光层、所述空穴阻挡层和所述电子阻挡层满足以下条件：
T1(HBL)>T1(Host)；
T1(EBL)＞T1(Host)；
T1(Dopant)＞T1(Host)；
S1(Host)＞S1(Dopant)；
电子阻挡层和空穴传输层的材料包括芳胺类材料或咔唑材料，空穴传输层的空穴迁移率范围位于10 -4～10 -6cm 2V -1s -1，电子阻挡层的空穴迁移率范围位于10 -4～10 -7cm 2V -1s -1；
其中，所述T1(HBL)为空穴阻挡层材料的最低三重态能量，所述T1(Host)为所述主体材料的最低三重态能量，所述T1(EBL)为电子阻挡层材料的最低三重态能量，T1(Dopant)为所述客体材料的最低三重态能量，所述S1(Host)为所述主体材料的最低单重态能量，所述S1(Dopant)为所述客体材料的最低单重态能量。
可选的，所述空穴阻挡层和所述电子传输层满足以下条件：
0.4eV≤LUMO(HBL)-LUMO(ETL)≤1eV；
其中，所述LUMO(HBL)为所述空穴阻挡层的材料的最低未占分子轨道，所述LUMO(ETL)为所述电子传输层的材料的最低未占分子轨道。
可选的，所述空穴传输层和所述电子阻挡层满足以下条件：
0.3eV≤HOMO(HTL)-HOMO(EBL)≤1eV；
其中，所述HOMO(HTL)为所述空穴传输层的最高占据分子轨道，所述HOMO(EBL)为所述电子阻挡层的最高占据分子轨道。
可选的，空穴阻挡层的电子迁移率范围位于10 -7～10 -9cm 2V -1s -1，电子传输层的电子迁移率范围位于10 -5～10 -7cm 2V -1s -1；
发光层的主体材料的电子迁移率位于10 -5～10 -8cm 2V -1s -1，空穴迁移率 位于10 -8～10 -12cm 2V -1s -1。
可选的，取代基R1、R2、R3、R4、R5、R6、R7、R8中，存在相邻的两个取代基键合成环。
可选的，存在相邻的两个R键合成环。
可选的，所述主体材料选自：
Figure PCTCN2021129588-appb-000004
Figure PCTCN2021129588-appb-000005
可选的，所述电子传输层的材料具有结构：
Figure PCTCN2021129588-appb-000006
其中，X1、X2和X3为C或N，且X1、X2和X3中的至少一个为N；
L1为单键、经取代或未经取代的C6至60亚芳基；
Ar3和Ar4为经取代或未经取代的C6至60芳基；或者
Ar3和Ar4为经取代或未经取代的含有O、N、Si和S中的至少一者的C2-60杂芳基；
Ar3和Ar4相同或不同；
取代基A的结构选自以下任一项：
Figure PCTCN2021129588-appb-000007
Figure PCTCN2021129588-appb-000008
取代基Ar5、Ar6、Ar7各自独立的选自：氢、具有碳原子数为1至20的取代或未取代的烷基、具有碳原子书为3至20的取代或未取代的环烷基、具有碳原子数为1至20的取代或未取代的硅烷基、具有5至30个芳族环原子的芳族或杂芳族环体系；
p为0至4的整数；q为0至4的整数；m为0至4的整数；n为0至4的整数；
Y为C、O、S，N或单键。
可选的，在p、m和n中的至少两个大于0的情况下，取代基(Ar5)p、(Ar6)q、(Ar7)m中存在至少两个取代基相同，或者取代基(Ar5)p、(Ar6)q、(Ar7)m中的任意两个均不相同。
可选的，取代基(Ar5)p、(Ar6)q、(Ar7)m中，存在相邻的两个键合成环。
可选的，所述电子传输层的材料选自：
Figure PCTCN2021129588-appb-000009
Figure PCTCN2021129588-appb-000010
Figure PCTCN2021129588-appb-000011
第二方面，本公开实施例提供了一种显示装置，包括第一方面中任一项所述的有机发光二极管结构。
这样，本公开实施例的提供的一种有机发光二极管结构中的发光层、空穴阻挡层和电子阻挡层满足以下条件：T1(HBL)>T1(Host)；T1(EBL)＞ T1(Host)；T1(Dopant)＞T1(Host)；S1(Host)＞S1(Dopant)；其中，所述T1(HBL)为空穴阻挡层材料的最低三重态能量，所述T1(Host)为所述主体材料的最低三重态能量，所述T1(EBL)为电子阻挡层材料的最低三重态能量，T1(Dopant)为所述客体材料的最低三重态能量，所述S1(Host)为所述主体材料的最低单重态能量，所述S1(Dopant)为所述客体材料的最低单重态能量。通过控制发光层、空穴阻挡层和电子阻挡层之间的能级关系，能够减少电子阻挡层界面的载流子积累，此外，还有助于将激子限制在发光层中，防止发光层能量向其他结构扩散，通过对主体材料和客体材料的能级限定，能够使得主体材料中的激子产生三重态-三重态湮灭，并将能量有效的传递至客体材料。这样，本实施例的技术方案有助于提高显示器件的发光效率和寿命。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对本公开实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本公开的一些实施例，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取其他的附图。
图1是本公开第一实施例提供的有机发光二极管结构的结构示意图。
具体实施方式
下面将结合本公开实施例中的附图，对本公开实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本公开一部分实施例，而不是全部的实施例。基于本公开中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获取的所有其他实施例，都属于本公开保护的范围。
本公开实施例提供了一种有机发光二极管结构。
如图1所示，在一个实施例中，该有机发光二极管结构包括依次层叠设置的阴极101、电子注入层(EIL)102、电子传输层(ETL)103、空穴阻挡层(HBL)104、发光层105、电子阻挡层(EBL)106、空穴传输层(HTL)107、空穴注入层(HIL)108和阳极109，发光层105包括主体材料和客体材料。
本公开的发明人在研究过程中发现，有机发光二极管(OLED)可以分为 荧光OLED发光器件和磷光OLED发光器件两种，在工作过程中，当施加电压时，空穴从阳极中注入，电子从阴极中注入。空穴和电子在发光层中复合从而形成激子。根据电子自旋统计理论，单重态激子和三重态激子以25％∶75％的比例被产生。由单重态激子发光的荧光器件中，内量子效率的极限值被认为是25％,如图1，这相当于约5％的外量子效率，导致实际发光效率较低。
发明人经过进一步研究发现，工作过程中，电子的传输速率和空穴的传输速率是不同的，一般来说，电子的传输速率大于空穴的传输速率，这样，激子在发光层中的复合区域更偏向电子阻挡层的，尤其是电子阻挡层和发光层相交的界面。这种现象进而可能导致电子阻挡层的材料上电子的堆积，而电荷可能导致材料劣化，对发光器件的性能造成影响。
被公开实施例中，发光层、空穴阻挡层和电子阻挡层满足以下条件：
T1(HBL)>T1(Host)；
T1(EBL)＞T1(Host)；
T1(Dopant)＞T1(Host)；
S1(Host)＞S1(Dopant)；
其中，T1(HBL)为空穴阻挡层材料的最低三重态能量，T1(Host)为主体材料的最低三重态能量，T1(EBL)为电子阻挡层材料的最低三重态能量，T1(Dopant)为客体材料的最低三重态能量，S1(Host)为主体材料的最低单重态能量，S1(Dopant)为客体材料的最低单重态能量。
本公开实施例中，通过控制空穴阻挡层和电子阻挡层的能级，能够减小电子阻挡层和发光层的界面处的载流子积累，有助于降激子更有效的限制在发光层中，防止发光层的能量向其他结构和膜层扩散，从而有助于提高使用寿命。
通过对主体材料和客体材料的能级限定，能够使得主体材料中的激子产生三重态-三重态湮灭(Triple-Triple Annihilation，缩写为TTA)，TTA指的是通过两个三重态激子的碰撞和融合来产生单重态激子的现象，能够产生更多的单重态激子，将能量有效的传递至客体材料，有助于提高发光效率。
在其中一些实施例中，空穴阻挡层和电子传输层满足以下条件：
0.4eV≤LUMO(HBL)-LUMO(ETL)≤1eV；本实施例中，LUMO代表最低未占分子轨道，LUMO(HBL)为空穴阻挡层的材料的最低未占分子轨道，LUMO(ETL)为电子传输层的材料的最低未占分子轨道，这样，本实施例通过增加空穴阻挡层与电子传输层之间的能级势垒，能够减缓电子的传输速率，降低由于电子传输速率大于空穴传输速率导致激子复合区域偏向电子阻挡层一侧的可能性。
在其中一些实施例中，空穴传输层和电子阻挡层满足以下条件：
0.3eV≤HOMO(HTL)-HOMO(EBL)≤1eV；本实施例中，HOMO代表最高占据分子轨道，HOMO(HTL)为空穴传输层的最高占据分子轨道，HOMO(EBL)为电子阻挡层的最高占据分子轨道。这样，本实施例能够降 低由于能级势垒造成的空穴传输慢的现象，有助于提高空穴传输速度，从而降低由于空穴传输速率小于电子传输速率导致激子复合区域偏向电子阻挡层一侧的可能性。
在其中一些实施例中，主体材料具有结构：
Figure PCTCN2021129588-appb-000012
在其中一些实施例中，取代基R1、R2、R3、R4、R5、R6、R7、R8各自独立的选自：氢原子H、氘原子D、具有6至60个碳原子的取代或未取代的芳基、具有6至60个碳原子的取代或未取代的杂芳基、具有1至50个碳原子的取代或未取代的烷基、具有1至50个碳原子的取代或未取代的环烷基、具有1至50个碳原子的取代或未取代的烷氧基、具有6至50个碳原子的取代或未取代的芳烷基、具有5至50个环原子的取代或未取代的芳氧基、具有5至50个环原子的取代或未取代的芳硫基、具有1至50个碳原子的取代或未取代的烷氧基羰基。
本实施例中，取代基R1至R8中的任意两个可以相同，也可以不相同。
在其中一些实施例中，取代基R1、R2、R3、R4、R5、R6、R7、R8中，存在相邻的两个取代基键合成环。
在其中一些实施例中，取代基Ar1为取代或未取代的芳基；
取代基Ar2选自以下取代基Ar-1至Ar-7中的任一项：
Ar-1：
Figure PCTCN2021129588-appb-000013
Ar-2：
Figure PCTCN2021129588-appb-000014
Ar-3：
Figure PCTCN2021129588-appb-000015
Ar-4：
Figure PCTCN2021129588-appb-000016
Ar-5：
Figure PCTCN2021129588-appb-000017
Ar-6：
Figure PCTCN2021129588-appb-000018
Ar-7：
Figure PCTCN2021129588-appb-000019
其中，L为单键、取代或未取代的芳基；R为取代或未取代的芳基、取代或未取代的杂芳基；a为0～5的整数，b为0～5的整数。
本实施例中，主体材料的通式代表蒽类化合物，其最高占据分子轨道/最低未占分子轨道的电子云集中在蒽核上，能够使得电子和空穴相对稳定。进一步的，通过在蒽核上引入含氧O、硫S的基团，例如二苯并呋喃等集团，能够一定程度上减低器件的电压，通式，通过引入含氧O、硫S的基团，能够使得分子呈现一定的极性，有助于提高主体材料和电子阻挡层之间的相互 作用，有助于优化发光层和电子阻挡层相邻的界面的能级。
在其中一些实施例中，主体材料选自以下Host-1至Host-6中的任一项：
Host-1：
Figure PCTCN2021129588-appb-000020
Host-2：
Figure PCTCN2021129588-appb-000021
Host-3：
Figure PCTCN2021129588-appb-000022
Host-4：
Figure PCTCN2021129588-appb-000023
Host-5：
Figure PCTCN2021129588-appb-000024
Host-6：
Figure PCTCN2021129588-appb-000025
在其中一些实施例中，电子传输层的材料具有结构：
Figure PCTCN2021129588-appb-000026
其中，X1、X2和X3为C或N，且X1、X2和X3中的至少一个为氮N。
在其中一些实施例中，L1为单键、经取代或未经取代的C6至60亚芳基；
Ar3和Ar4为经取代或未经取代的C6至60芳基；或者
Ar3和Ar4为经取代或未经取代的含有氧O、氮N、硅Si和硫S中的至少一者的C2-60杂芳基；
Ar3和Ar4相同或不同。
在其中一些实施例中，取代基A的结构选自以下A-1至A-3中的任一项：
A-1：
Figure PCTCN2021129588-appb-000027
A-2：
Figure PCTCN2021129588-appb-000028
A-3：
Figure PCTCN2021129588-appb-000029
在本实施例中，取代基Ar5、Ar6、Ar7各自独立的选自：氢H、具有碳原子数为1至20的取代或未取代的烷基、具有碳原子书为3至20的取代或未取代的环烷基、具有碳原子数为1至20的取代或未取代的硅烷基、具有5至30个芳族环原子的芳族或杂芳族环体系。其中，p为0至4的整数；q为0至4的整数；m为0至4的整数；n为0至4的整数；Y为碳C、氧O、硫S，氮N或单键。
在其中一些实施例中，在p、m和n中的至少两个大于0的情况下，取代基(Ar5)p、(Ar6)q、(Ar7)m中存在至少两个取代基相同，或者取代基(Ar5)p、(Ar6)q、(Ar7)m中的任意两个均不相同。
在其中一些实施例中，取代基(Ar5)p、(Ar6)q、(Ar7)m中，存在相邻的两个键合成环。
本实施例的电子传输层的材料中，含氮的吖嗪为很强的吸电子基团，具有这样取代基的电子传输层的材料具有较深的HOMO/LUMO能级，有助于电荷的传输。
螺环结构为具有较高T1能级的片段，可将激子有效的限制在发光层较高的T1，更为具体的，主要由片段的T1决定；此外、螺环为较好的空间构型、较大的空间位阻基团，在一定程度上可以抑制材料的结晶。
在其中一些实施例中，电子传输层的材料选自以下ETL-1至ETL-11中的任一项：
ETL-1：
Figure PCTCN2021129588-appb-000030
ETL-2：
Figure PCTCN2021129588-appb-000031
ETL-3：
Figure PCTCN2021129588-appb-000032
ETL-4：
Figure PCTCN2021129588-appb-000033
ETL-5：
Figure PCTCN2021129588-appb-000034
ETL-6：
Figure PCTCN2021129588-appb-000035
ETL-7：
Figure PCTCN2021129588-appb-000036
ETL-8：
Figure PCTCN2021129588-appb-000037
ETL-9：
Figure PCTCN2021129588-appb-000038
ETL-10：
Figure PCTCN2021129588-appb-000039
ETL-11：
Figure PCTCN2021129588-appb-000040
本实施例中，空穴阻挡层的迁移率小于电子传输层的迁移率，以减缓电子传输速度。
在其中一些实施例中，控制空穴阻挡层的电子迁移率范围在10 -7～10 -9cm 2V -1s -1，控制电子传输层的电子迁移率范围在10 -5～10 -7cm 2V -1s -1，这样，能够一定程度上抑制电子的传输效率。空穴传输层的空穴迁移率范围在 10 -4～10 -6cm 2V -1s -1，电子阻挡层的空穴迁移率范围在10 -4～10 -7cm 2V -1s -1，从而提高空穴传输效率。发光层的主体材料的电子迁移率控制在10 -5～10 -8cm 2V -1s -1，空穴迁移率控制在10 -8～10 -12cm 2V -1s -1，从而有助于提高空穴电子传输速度并抑制电子传输速度。
本公开实施例提供了一种显示装置，包括以上任一项的有机发光二极管结构。
由于本实施例的显示装置包括了上述有机发光二极管结构实施例的全部技术方案，因此至少能够实现上述全部技术效果，此处不再赘述。
下面，参考具体实施例对本公开作进一步的示例性说明。
如图1所示，在一个实施例中，有机发光二级管有结构包括依次层叠设置的阴极101、电子注入层(EIL)102、电子传输层(ETL)103、空穴阻挡层(HBL)104、发光层105、电子阻挡层(EBL)106、空穴传输层(HTL)107、空穴注入层(HIL)108和阳极109，发光层105包括主体材料和客体材料。
本公开实施例中，电子注入层的材料可以选择金属或碱金属，例如氟化锂LiF、镱Yb、LIQ(C 9H 6NOLi，8-羟基喹啉-锂)等材料。
相关技术中的电子传输层的材料通常为芳族杂环化合物，TPBi，Bphen等材料，本实施例中具体以上述通式(2)的材料。
空穴阻挡层的材料通常为芳族杂环化合物，如BCP、Bphen等材料。
本实施例中发光层的主体材料选择上述通式(1)的材料，客体材料可以选择Dpvbi、DPAVB、DSA-Ph等材料。
电子阻挡层的材料可以选择空穴传输特性的芳胺类或者咔唑材料，如mCBP、Tris-PCz等材料。
空穴传输层的材料可以选择具有空穴传输特性的芳胺类或者咔唑材料，如NPB、m-MTDATA、TPD等材料。
空穴注入层的材料可以为无机氧化物，如三氧化钼MoO 3，F4-TCNQ、HAT-CN等材料。
本公开实施例和对比例中，空穴注入层的P形掺杂材料选择：
Figure PCTCN2021129588-appb-000041
本公开实施例和对比例中，空穴注入层材料选择：
Figure PCTCN2021129588-appb-000042
本公开实施例和对比例中，电子阻挡层的材料选择：
Figure PCTCN2021129588-appb-000043
对比例中的电子传输层材料可以选择对比ETL：
Figure PCTCN2021129588-appb-000044
本公开实施例和对比例中，空穴阻挡层的材料选择：
Figure PCTCN2021129588-appb-000045
对比例的主体材料可以选择对比Host：
Figure PCTCN2021129588-appb-000046
本公开实施例和对比例中，客体材料选择：
Figure PCTCN2021129588-appb-000047
本公开示例性的提供多个对比例和实施例。
在对比例1中，电子传输层材料选择对比ETL，主体材料选择对比Host。
在对比例2中，电子传输层材料选择上述ETL-2，主体材料选择对比Host。
在对比例3中，电子传输层材料选择上述ETL-3，主体材料选择对比Host。
在对比例4中，电子传输层材料选择对比ETL，主体材料选择上述Host-1。
在对比例5中，电子传输层材料选择对比ETL，主体材料选择上述Host-4。
在实施例1中，电子传输层材料选择上述ETL-2，主体材料选择上述Host-1。
在实施例2中，电子传输层材料选择上述ETL-2，主体材料选择上述Host-4。
在实施例3中，电子传输层材料选择上述ETL-3，主体材料选择上述Host-1。
在实施例4中，电子传输层材料选择上述ETL-3，主体材料选择上述Host-4。
本实施例中所使用的电子传输层的材料物性如表1所示，所使用的发光层的主体材料的物性如表2所示。对对比例1至5以及实施例1至4的有机发光二极管结构进行电压、发光效率和寿命测试，其中，寿命测试按照LT95@1000nit进行，测试结果见表3。
表1：电子传输层材料物性
ETL HOMO(eV) LUMO(eV) T1(eV)
ETL-2 -6.50 -3.4 2.52
ETL-3 -6.4 -2.51 2.58
表2：主体材料物性
Host HOMO LUMO T1
Host-1 -6.00 -3.01 1.77
Host-4 -6.01 -2.98 1.71
表3：对比例和实施例的OLED结构测试结果
Figure PCTCN2021129588-appb-000048
Figure PCTCN2021129588-appb-000049
由上表可知，通过对电子传输层的材料和发光层的主体材料进行改进，使得发光器件的发光效率提高，使用寿命增加。
以上，仅为本公开的具体实施方式，但本公开的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本公开揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本公开的保护范围之内。因此，本公开的保护范围应以权利要求的保护范围为准。

Claims (12)

  1. 一种有机发光二极管结构，包括依次层叠设置的阴极、电子传输层、空穴阻挡层、发光层、电子阻挡层、空穴传输层和阳极，所述发光层包括主体材料和客体材料；
    所述主体材料具有结构：
    Figure PCTCN2021129588-appb-100001
    取代基R1、R2、R3、R4、R5、R6、R7、R8各自独立的选自：氢原子、氘原子、具有6至60个碳原子的取代或未取代的芳基、具有6至60个碳原子的取代或未取代的杂芳基、具有1至50个碳原子的取代或未取代的烷基、具有1至50个碳原子的取代或未取代的环烷基、具有1至50个碳原子的取代或未取代的烷氧基、具有6至50个碳原子的取代或未取代的芳烷基、具有5至50个环原子的取代或未取代的芳氧基、具有5至50个环原子的取代或未取代的芳硫基、具有1至50个碳原子的取代或未取代的烷氧基羰基；
    取代基Ar1为取代或未取代的芳基；
    取代基Ar2选自以下任一项：
    Figure PCTCN2021129588-appb-100002
    Figure PCTCN2021129588-appb-100003
    其中，L为单键、取代或未取代的芳基；
    R为取代或未取代的芳基、取代或未取代的杂芳基，多个R相同或不同；
    a为0～5的整数，b为0～5的整数；
    所述发光层、所述空穴阻挡层和所述电子阻挡层满足以下条件：
    T1(HBL)>T1(Host)；
    T1(EBL)＞T1(Host)；
    T1(Dopant)＞T1(Host)；
    S1(Host)＞S1(Dopant)；
    电子阻挡层和空穴传输层的材料包括芳胺类材料或咔唑材料，空穴传输层的空穴迁移率范围位于10 -4～10 -6cm 2V -1s -1，电子阻挡层的空穴迁移率范围位于10 -4～10 -7cm 2V -1s -1；
    其中，所述T1(HBL)为空穴阻挡层材料的最低三重态能量，所述T1(Host)为所述主体材料的最低三重态能量，所述T1(EBL)为电子阻挡层材料的最低三重态能量，T1(Dopant)为所述客体材料的最低三重态能量，所述S1(Host)为所述主体材料的最低单重态能量，所述S1(Dopant)为所述客体材料的最低单重态能量。
  2. 根据权利要求1所述的有机发光二极管结构，其中，所述空穴阻挡层和所述电子传输层满足以下条件：
    0.4eV≤LUMO(HBL)-LUMO(ETL)≤1eV；
    其中，所述LUMO(HBL)为所述空穴阻挡层的材料的最低未占分子轨道，所述LUMO(ETL)为所述电子传输层的材料的最低未占分子轨道。
  3. 根据权利要求1所述的有机发光二极管结构，其中，所述空穴传输层和所述电子阻挡层满足以下条件：
    0.3eV≤HOMO(HTL)-HOMO(EBL)≤1eV；
    其中，所述HOMO(HTL)为所述空穴传输层的最高占据分子轨道，所述HOMO(EBL)为所述电子阻挡层的最高占据分子轨道。
  4. 根据权利要求1所述的有机发光二极管结构，其中，空穴阻挡层的电子迁移率范围位于10 -7～10 -9cm 2V -1s -1，电子传输层的电子迁移率范围位于10 -5～10 -7cm 2V -1s -1；
    发光层的主体材料的电子迁移率位于10 -5～10 -8cm 2V -1s -1，空穴迁移率位于10 -8～10 -12cm 2V -1s -1。
  5. 根据权利要求1所述的有机发光二极管结构，其中，取代基R1、R2、R3、R4、R5、R6、R7、R8中，存在相邻的两个取代基键合成环。
  6. 根据权利要求1所述的有机发光二极管结构，其中，存在相邻的两个R键合成环。
  7. 根据权利要求1所述的有机发光二极管结构，其中，所述主体材料选自：
    Figure PCTCN2021129588-appb-100004
    Figure PCTCN2021129588-appb-100005
  8. 根据权利要求1所述的有机发光二极管结构，其中，所述电子传输层的材料具有结构：
    Figure PCTCN2021129588-appb-100006
    其中，X1、X2和X3为C或N，且X1、X2和X3中的至少一个为N；
    L1为单键、经取代或未经取代的C6至60亚芳基；
    Ar3和Ar4为经取代或未经取代的C6至60芳基；或者
    Ar3和Ar4为经取代或未经取代的含有O、N、Si和S中的至少一者的C2-60杂芳基；
    Ar3和Ar4相同或不同；
    取代基A的结构选自以下任一项：
    Figure PCTCN2021129588-appb-100007
    Figure PCTCN2021129588-appb-100008
    取代基Ar5、Ar6、Ar7各自独立的选自：氢、具有碳原子数为1至20的取代或未取代的烷基、具有碳原子书为3至20的取代或未取代的环烷基、具有碳原子数为1至20的取代或未取代的硅烷基、具有5至30个芳族环原子的芳族或杂芳族环体系；
    p为0至4的整数；q为0至4的整数；m为0至4的整数；n为0至4的整数；
    Y为C、O、S，N或单键。
  9. 根据权利要求8所述的有机发光二极管结构，其中，在p、m和n中的至少两个大于0的情况下，取代基(Ar5)p、(Ar6)q、(Ar7)m中存在至少两个取代基相同，或者取代基(Ar5)p、(Ar6)q、(Ar7)m中的任意两个均不相同。
  10. 根据权利要求9所述的有机发光二极管结构，其中，取代基(Ar5)p、(Ar6)q、(Ar7)m中，存在相邻的两个键合成环。
  11. 根据权利要求1至10中任一项所述的有机发光二极管结构，其中，所述电子传输层的材料选自：
    Figure PCTCN2021129588-appb-100009
    Figure PCTCN2021129588-appb-100010
    Figure PCTCN2021129588-appb-100011
    Figure PCTCN2021129588-appb-100012
  12. 一种显示装置，包括权利要求1至11中任一项所述的有机发光二极管结构。
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