WO2020042626A1 - 有机电致发光器件及其制备方法和显示装置 - Google Patents

有机电致发光器件及其制备方法和显示装置 Download PDF

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WO2020042626A1
WO2020042626A1 PCT/CN2019/082695 CN2019082695W WO2020042626A1 WO 2020042626 A1 WO2020042626 A1 WO 2020042626A1 CN 2019082695 W CN2019082695 W CN 2019082695W WO 2020042626 A1 WO2020042626 A1 WO 2020042626A1
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thermally activated
activated delayed
delayed fluorescent
energy level
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段炼
蔡明瀚
宋晓增
魏金贝
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Tsinghua University
Kunshan Govisionox Optoelectronics Co Ltd
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Tsinghua University
Kunshan Govisionox Optoelectronics Co Ltd
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Definitions

  • the present application relates to the technical field of organic electroluminescence, and in particular, to an organic electroluminescence device, a preparation method thereof, and a display device.
  • Organic Light Emitting Diode (Organic Light Emitting Diode, abbreviation: OLED) is a device that achieves the purpose of light emission by current driving. Its main characteristics come from the organic light emitting layer. When an appropriate voltage is applied, electrons and holes Excitons are combined in the organic light emitting layer to emit light with different wavelengths according to the characteristics of the organic light emitting layer. At this stage, the light-emitting layer is composed of a host material and a doped dye, and the dye is mostly selected from traditional fluorescent materials and traditional phosphorescent materials. Specifically, traditional fluorescent materials have the defect that triplet excitons cannot be used.
  • phosphorescent materials can achieve singlet exciton transition to triplet by introducing heavy metal atoms, such as iridium or platinum, to achieve 100% energy use efficiency,
  • heavy metals such as iridium and platinum are very scarce, expensive and easily cause environmental pollution, so phosphorescent materials cannot be the first choice for dyes.
  • TADF Thermally Activated Delayed Fluorescence
  • the application provides an organic electroluminescence device, a preparation method thereof, and a display device.
  • the organic light-emitting layer of the organic electroluminescence device uses a wide band gap material as a main material, and uses TADF as a sensitizer material to assist the sensitized resonance type TADF.
  • the dye emits light, thereby overcoming the defects of short device life and wide spectrum caused by the current use of traditional TADF materials to emit light.
  • the present application provides an organic electroluminescent device, including an organic light emitting layer, the organic light emitting layer including a host material, a sensitizer material, and a resonance-type thermally activated delayed fluorescent material;
  • the host material is a wide band gap material
  • the sensitizer material is a thermally activated delayed fluorescent material
  • the singlet energy level of the wide band gap material is greater than the singlet energy level of the sensitizer material, and the triplet energy level of the wide band gap material is greater than the triplet energy level of the sensitizer material;
  • the singlet energy level of the sensitizer material is greater than the singlet energy level of the resonance type thermally activated delayed fluorescent material, and the triplet energy level of the sensitizer material is greater than the triplet level of the resonant thermally activated delayed fluorescent material State energy level.
  • the resonance-type thermally activated delayed fluorescent material has a structure represented by formula [1]:
  • R 1 is selected from hydrogen, substituted or unsubstituted C 1 -C 36 alkyl, substituted or unsubstituted Substituted C 6 -C 30 aryl, substituted or unsubstituted C 3 -C 30 heteroaryl;
  • A is selected from a substituted or unsubstituted C 6 -C 30 aryl group, a substituted or unsubstituted C 3 -C 30 heteroaryl group, a substituted or unsubstituted C 6 -C 30 arylamino group;
  • M 1 and M 2 are each independently selected from H, substituted or unsubstituted C 1 -C 36 alkyl, substituted or unsubstituted C 6 -C 30 aryl, substituted or unsubstituted C 6 -C 30 Heteroaryl
  • At least three of adjacent X, A, M 1 , and M 2 are connected to form a ring, and the ring includes X;
  • a is an integer from 1 to 12;
  • the substituents are each independently selected from halogen, cyano, C 1 -C 10 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy Or one or more of a thioalkoxy group, a C 6 -C 30 aryl group, and a C 3 -C 30 heteroaryl group.
  • three of adjacent X, A, M 1 , and M 2 are connected to form a six-membered ring containing two heteroatoms;
  • the hetero atom is selected from two kinds of B, P, Si, O, S, N, and Se.
  • the molecular weight of the resonant thermally activated delayed fluorescent material is 200-2000.
  • a is an integer from 1-6.
  • the resonance-type thermally activated delayed fluorescent material is a compound having one of the general formulae (F-1) to (F-29) in the present application, and the general formulae (F-1) to (F-29) ),
  • R is independently selected from hydrogen, halogen, cyano, C 1 -C 10 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or thioalkoxy, One or more of C 6 -C 30 aryl and C 3 -C 30 heteroaryl;
  • Y is independently selected from O, S, Se.
  • the resonant thermally activated delayed fluorescent material is a compound having one of (M-1)-(M-72) of the present application.
  • the thermally activated delayed fluorescent material is a compound including an electron donating group and an electron accepting group.
  • the electron-donating group includes at least one of a carbazolyl group, a phenothiazinyl group, a phenoxazinyl group, an indolocarbazolyl group, a diphenylamino group, a triphenylamino group, an acridine group, and a phenazine group.
  • a carbazolyl group a phenothiazinyl group, a phenoxazinyl group, an indolocarbazolyl group, a diphenylamino group, a triphenylamino group, an acridine group, and a phenazine group.
  • the electron-donating group is selected from at least one group D1-D17 in the present application.
  • the electron accepting group includes a triazinyl group, a pyrimidinyl group, a sulfone group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a triazolyl group, a boron group, a pyrazinyl group, At least one of a carbonyl group, a cyano group, and a pyridyl group.
  • the electron accepting group is selected from at least one group of A1-A23 in the present application.
  • the energy level difference between the singlet state and triplet state of the thermally activated delayed fluorescent material is ⁇ 0.3 eV.
  • the thermally activated delayed fluorescent material is a compound having one of (T-1)-(T-88) of the present application.
  • the difference between the HOMO energy level and the LUMO energy level of the wide band gap material is ⁇ 2eV.
  • the wide band gap material is a compound including at least one group of a carbazolyl group, a carbolinyl group, a spirofluorenyl group, a fluorenyl group, a silicon group, and a phosphino group.
  • the wide band gap material is a compound having one of (W-1)-(W-46) of the present application.
  • the mass ratio (doping concentration) of the sensitizer material in the organic light emitting layer is 1-60 wt%;
  • the mass ratio (doping concentration) of the wide band gap material in the organic light emitting layer is 20-98.9 wt%;
  • the mass ratio (doping concentration) of the resonance-type thermally activated delayed fluorescent material in the organic light emitting layer is 0.1-20 wt%.
  • the present application also provides a method for preparing an organic electroluminescent device, including the following steps: forming an organic light-emitting layer by co-evaporation of a wide band gap material material source, a thermally activated delayed fluorescent material source, and a resonance-type thermally activated delayed fluorescent material source.
  • the present application further provides a display device including any one of the organic electroluminescence devices described above.
  • the organic electroluminescent device of the present application uses a wide band gap material as a host material, and uses a TADF material as an auxiliary host material to sensitize the resonant TADF material to emit light.
  • a TADF material as an auxiliary host material to sensitize the resonant TADF material to emit light.
  • the singlet excitons and triplet excitons of the sensitizer TADF material can be used and transferred to the singlet and triplet energy levels of the resonant TADF material, respectively.
  • resonant TADF materials can emit light using both singlet and triplet excitons at the same time.
  • the sensitizer material can convert a part of its triplet energy into a singlet state, it suppresses the Dexter energy transfer process and promotes Energy transfer process, therefore, while effectively improving the luminous efficiency of the organic electroluminescent device of the present application, it also reduces the efficiency roll-off caused by the long triplet life at high brightness; meanwhile, the wide-gap body can effectively dilute the sensitizer material
  • the exciton concentration of the resonant TADF reduces triplet-triplet annihilation (TTA) and triplet-polaron annihilation (TPA), and enhances the stability of the device.
  • TTA triplet-triplet annihilation
  • TPA triplet-polaron annihilation
  • the resonant TADF material used in this application does not have obvious intramolecular electron transfer, so it is beneficial to narrow the spectrum and improve the color purity of the device.
  • FIG. 1 is a schematic structural diagram of an organic electroluminescent device of the present application.
  • FIG. 1 is a schematic structural diagram of an organic electroluminescent device of the present application.
  • the organic electroluminescent device of the present application includes an anode 2, a hole transporting region 3, and an organic light emitting layer 4 which are sequentially deposited on a substrate 1. , Electron transport region 5 and cathode 6.
  • the substrate 1 may be made of glass or a polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency.
  • the substrate 1 may be provided with a thin film transistor (TFT).
  • TFT thin film transistor
  • the anode 2 can be formed by sputtering or depositing an anode material on a substrate.
  • the anode material can be indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO 2 ), or zinc oxide (ZnO).
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • SnO 2 tin dioxide
  • ZnO zinc oxide
  • the cathode 6 can use magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium- Metals or alloys such as indium (Mg-In), magnesium-silver (Mg-Ag), and any combination thereof.
  • the hole-transporting region 3, the organic light-emitting layer 4, and the organic material layer of the electron-transporting region 5 can be sequentially prepared on the anode 2 by methods such as vacuum thermal evaporation, spin coating, and printing.
  • the compounds used as the organic material layer may be organic small molecules, organic macromolecules and polymers, and combinations thereof.
  • TADF materials have certain defects as dye luminescence. For example, due to the intramolecular charge transfer of TADF materials, the electroluminescence spectrum is often too wide and the light color is not pure. At the same time, due to the higher triplet energy level and triplet state of TADF materials The exciton has a long life, which results in large device roll-off and short life. In addition, most host materials have the characteristics of unipolar transmission, resulting in uneven transfer of electrons and holes in the light-emitting layer, and also caused serious efficiency roll-off at high brightness, and poor spectral stability.
  • the organic light-emitting layer of the present application includes a host material, a sensitizer material, and a resonance-type thermally activated delayed fluorescent material;
  • the host material is a wide-band gap material;
  • the sensitizer material is a thermally-activated delayed fluorescent material;
  • the energy level of the heavy state is greater than the singlet energy level of the sensitizer material, and the triplet energy level of the wide band gap material is greater than the triplet energy level of the sensitizer material;
  • the singlet energy level of the sensitizer material is greater than the resonant thermal activation
  • the singlet energy level of the delayed fluorescent material and the triplet energy level of the sensitizer material are greater than the triplet energy level of the resonant thermally activated delayed fluorescent material.
  • the main material of the present application is a wide band gap material, which can dilute the concentration of the sensitizer material and the resonant TADF material, effectively reduce the exciton density, and thus effectively suppress triplet-triplet annihilation (TTA) and excitons.
  • TTA triplet-triplet annihilation
  • -Polaron Quenching (TPA) which further enhances the stability of organic electroluminescent devices, improves device life, and reduces efficiency roll-off.
  • the difference between the HOMO energy level and the LUMO energy level of the wide band gap material of the present application is greater than or equal to 2eV, thereby ensuring that the singlet state and triplet state of the wide band gap material are at higher energy levels, which is beneficial to the wide band gap material to the sensitizer material. occur Energy transfer process and Dexter energy transfer process.
  • the sensitizer material of the present application is a TADF material, which is a material used to assist the wide-gap host material to sensitize the resonance type TADF.
  • the sensitizer material can absorb the environmental heat and undergo an up-conversion process to convert the triplet excitons into Singlet excitons emit fluorescence.
  • the resonance-type TADF material of the present application emits light as a dye. Since the resonance-type TADF molecules mostly have a planar aromatic rigid structure, the structure is stable. In resonant TADF molecules, the different resonance effects of different atoms lead to the spatial separation of HOMO and LUMO on different atoms, and the overlap area is small, which leads to the singlet and triplet energy of resonant TADF. The phase difference is small, so the resonant TADF material can undergo reverse intersystem crossover.
  • the energy level difference between the singlet state and the triplet state of the resonant TADF of the present application is 0.3 eV or less, and the intersystem crossover can be performed by absorbing ambient heat. At the same time, there is no obvious donor group and acceptor group in the resonant TADF molecule, so the resonant TADF molecule has weak charge transfer and high stability.
  • the singlet energy level of the wide band gap material of the host material is greater than the singlet energy level of the sensitizer material TADF, and the singlet energy level of the sensitizer TADF is greater than the singlet energy level of the resonant TADF.
  • the triplet energy level of the host material wide band gap material is greater than the triplet energy level of the sensitizer material TADF, and the triplet energy level of the sensitizer material TADF is greater than the triplet energy level of the resonant TADF.
  • the singlet and triplet exciton energy of the wide band gap material can be transferred to the singlet and triplet states of the sensitizer material, or holes and electrons are directly recombined on the sensitizer.
  • the sensitizer material is a thermally activated delayed fluorescent material.
  • the triplet exciton of the sensitizer material will transition to the singlet state of the sensitizer material TADF, and then the energy will be transferred from the singlet state of the sensitizer material to the resonant TADF.
  • the triplet excitons of the resonant TADF also crossover to their own singlet state. In the end, the singlet state and triplet energy in the organic electroluminescent device are fully utilized.
  • the present application can effectively reduce the concentration of triplet excitons, thereby solving the problem of serious roll-off decline under high brightness, and effectively enhancing the stable performance of the organic electroluminescent device.
  • the present application uses a resonance type TADF as a dye, and there is no obvious intramolecular charge transfer excited state inside the resonance type TADF molecule, so a narrow emission spectrum can be obtained.
  • This application innovates the composition of the organic light-emitting layer, so that the TADF sensitizer assists the wide-band gap material to sensitize the resonance type TADF, which can not only improve the life of the organic electroluminescent device, reduce roll-off, narrow the spectrum, but also for industrial applications It is of great significance.
  • the mass ratio of the sensitizer in the organic light emitting layer is 1 wt% to 60 wt%; the mass ratio of the wide band gap material in the organic light emitting layer is 20 wt% to 98.9 wt%; the resonance type The mass ratio of the thermally activated delayed fluorescent material in the organic light emitting layer is 0.1 wt% to 20 wt%.
  • the above-mentioned resonance-type thermally activated delayed fluorescent material has a structure represented by formula [1]:
  • R 1 is selected from hydrogen, substituted or unsubstituted C 1 -C 36 alkyl, substituted or unsubstituted C 6 -C 30 aryl, substituted or unsubstituted C 3 -C 30 heteroaryl;
  • A is selected from substituted or unsubstituted C 6 -C 30 aryl, substituted or unsubstituted C 3- C 30 heteroaryl, substituted or unsubstituted C 6 -C 30 arylamino;
  • M 1 and M 2 are each independently selected from H, substituted or unsubstituted C 1 -C 36 alkyl, substituted or Unsubstituted C 6 -C 30 aryl, substituted or unsubstituted C 3 -C 30 heteroaryl, substituted or unsubstituted C 6 -C 30 heteroarylamino; adjacent X, A, At least three
  • a X, M 1 , and M 2 can be selected independently from each other, that is, each unit including X, M 1 , and M 2 may be the same or different, and each unit M 1 and M 2 may be the same or different.
  • at least one ring is connected by at least three of adjacent X, A, M 1 , and M 2 , and X is included in the ring.
  • TADF resonant TADF shown in formula [1] of the present application
  • three of adjacent X, A, M 1 , and M 2 are connected to form a six-membered ring containing two heteroatoms; the heteroatoms are selected from Two of B, P, Si, O, S, N, Se.
  • adjacent X, A, and M 1 may be connected to form a six-membered ring containing two heteroatoms
  • adjacent X, A, and M 2 may be connected to form a six-membered ring containing two heteroatoms.
  • X, M 1 , and M 2 may be connected to form a six-membered ring containing two heteroatoms.
  • one heteroatom in the six-membered ring is derived from X, that is, it may specifically be B, P, Si, and the other heteroatom is selected from one of O, S, N, and Se.
  • the heteroatom is In the case of N, since the N atom is trivalent, in addition to being connected to a hydrogen atom, the N atom may also be connected to an alkyl substituent.
  • the specific substituents are halogen, cyano, C 1 -C 10 alkyl or naphthenic Alkyl, C 2 -C 6 alkenyl or cycloalkenyl, C 1 -C 6 alkoxy or thioalkoxy, C 6 -C 30 aryl, C 3 -C 30 heteroaryl One or more.
  • a resonance type TADF material with a molecular weight of 200-2000 is selected as a dye in this application, because if the molecule of the resonance type TADF material is too large, it is not beneficial to evaporation during actual operation.
  • the molecular weight of resonant TADF can be controlled by limiting a to an integer of 1-6, that is, the resonant TADF of the present application may include 1-6 units having X, M 1 , and M 2 . .
  • the resonant TADF material of the present application may have a structure represented by one of the following general formulae (F-1) to (F-29):
  • R is independently selected from hydrogen, halogen, cyano, C 1 -C 10 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or thioalkoxy, C 6- One or more of C 30 aryl, C 3 -C 30 heteroaryl;
  • Y is independently selected from O, S, and Se.
  • the resonant thermally activated delayed fluorescent material of the present application has a compound having one of the following structures:
  • the sensitizer material TADF of the present application is a compound including an electron-donating group and an electron-accepting group, wherein the electron-donating group and the electron-accepting group may be directly bonded or may be connected through a linking group shown by La-Lm connection.
  • the electron-donating group includes at least one of a carbazolyl group, a phenothiazinyl group, a phenoxazinyl group, an indolocarbazolyl group, a diphenylamino group, a triphenylamino group, an acridinyl group, and a phenazine group; and
  • the electron accepting group includes triazinyl, pyrimidyl, sulfone, thiazolyl, oxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, boron, pyrazinyl, carbonyl, cyano And at least one of a pyridyl group and a pyridyl group.
  • the electron-donating group is selected from at least one of the following groups:
  • the electron-accepting group is selected from at least one of the following groups:
  • a TADF material having a singlet and triplet energy difference ⁇ 0.3 eV may be preferred as the sensitizer.
  • the TADF material of the present application may be a compound having one of the following structures:
  • the wide band gap material of the present application is a compound including at least one kind of a carbazolyl group, a carbolinyl group, a spirofluorenyl group, a fluorenyl group, a silicon group, and a phosphino group.
  • the wide band gap material is selected from compounds having one of the following structures:
  • the hole transporting region 3 is located between the anode 2 and the organic light emitting layer 4.
  • the hole-transporting region 3 may be a single-layer hole-transporting layer (HTL), including a single-layer hole-transporting layer containing only one compound and a single-layer hole-transporting layer containing multiple compounds.
  • the hole transport region 3 may also have a multilayer structure including at least two layers of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • the material of the hole transporting region 3 may be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers, or polymers containing conductive dopants such as polyphenylene vinylene, polyaniline / Dodecylbenzenesulfonic acid (Pani / DBSA), poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly (4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives.
  • phthalocyanine derivatives such as CuPc
  • conductive polymers or polymers containing conductive dopants such as polyphenylene vinylene, polyaniline / Dodecylbenzenesulfonic acid (Pani / DBSA), poly (3,4-ethylenedioxythiophene)
  • the aromatic amine derivative is a compound represented by the following HT-1 to HT-34. If the material of the hole transporting region 3 is an aromatic amine derivative, it may be one or more of the compounds represented by HT-1 to HT-34.
  • the hole injection layer is located between the anode 2 and the hole transport layer.
  • the hole injection layer may be a single compound material or a combination of a plurality of compounds.
  • the hole injection layer may use one or more compounds of the above-mentioned HT-1 to HT-34, or one or more compounds of the following HI1-HI3; or may use HT-1 to HT-34
  • One or more of the compounds are doped with one or more of the following HI1-HI3.
  • the electron transport region 5 may be a single-layered electron transport layer (ETL), including a single-layer electron-transport layer containing only one compound and a single-layer electron-transport layer containing multiple compounds.
  • the electron transporting region 5 may also have a multilayer structure including at least two of an electron injection layer (EIL), an electron transporting layer (ETL), and a hole blocking layer (HBL).
  • EIL electron injection layer
  • ETL electron transporting layer
  • HBL hole blocking layer
  • the material of the electron transport layer may be selected from, but not limited to, a combination of one or more of ET-1 to ET-57 listed below.
  • the structure of the light emitting device may further include an electron injection layer located between the electron transport layer and the cathode 6, and the material of the electron injection layer includes but is not limited to one or more combinations listed below.
  • the thickness of each of the above-mentioned layers can adopt the conventional thickness of these layers in the art.
  • This application also provides a method for preparing the organic electroluminescence device.
  • FIG. 1 includes sequentially depositing an anode 2, a hole transport region 3, an organic light emitting layer 4, an electron transport region 5, and a cathode 6 on a substrate 1. Then encapsulate it.
  • the organic light emitting layer 4 is prepared, the organic light emitting layer 4 is formed by a co-evaporation method of a wide band gap material source, a sensitizer material source, and a resonant TADF material source.
  • the method for preparing the organic electroluminescent device of the present application includes the following steps:
  • the glass plate coated with anode material is sonicated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone: ethanol, and baked in a clean environment to completely remove water. Light and ozone cleaning and bombarding the surface with a low-energy cation beam;
  • the above glass plate with anode was placed in a vacuum chamber, and evacuated to 1 ⁇ 10 -5 to 9 ⁇ 10 -3 Pa, and a hole injection layer was vacuum-evaporated on the anode layer film.
  • the evaporation rate was 0.1-0.5nm / s;
  • the hole transport layer is vacuum-evaporated on the hole injection layer, and the evaporation rate is 0.1-0.5nm / s.
  • the organic light-emitting layer of the device is vacuum-evaporated on the hole-transport layer.
  • the organic light-emitting layer includes a host material, a sensitizer material, and a TADF dye.
  • a multi-source co-evaporation method is used to adjust the evaporation rate and sensitivity of the host material.
  • the evaporation rate of the chemical agent material and the evaporation rate of the dye enable the dye to reach a preset doping ratio;
  • Vacuum-evaporate the electron transport layer material of the device on the organic light-emitting layer, and its evaporation rate is 0.1-0.5nm / s;
  • 0.1-0.5 nm / s vacuum-evaporated LiF is used as the electron injection layer, and 0.5-1 nm / s vacuum-evaporated Al layer is used as the cathode of the device.
  • An embodiment of the present application further provides a display device, which includes the organic electroluminescence device provided as described above.
  • the display device may specifically be a display device such as an OLED display, and any product or component having a display function, such as a television, a digital camera, a mobile phone, and a tablet computer, including the display device.
  • This display device has the same advantages as the above-mentioned organic electroluminescence device over the prior art, and is not repeated here.
  • the organic electroluminescence device of the present application is further described below through specific examples.
  • the anode is ITO; the material of the hole injection layer is HI-2, and the total thickness is 5-30nm, which is 10nm in this embodiment; the material of the hole transport layer is HT-27, and the total thickness is generally 5-50nm.
  • This embodiment is 40 nm; the host material of the organic light-emitting layer is a wide band gap material W-7, the sensitizer material is T-37 and the doping concentration is 20 wt%, the dye is a resonant TADF material M-3 and the doping concentration is 3wt%, the thickness of the organic light-emitting layer is generally 1-60nm, this embodiment is 30nm; the material of the electron transport layer is ET-53, the thickness is generally 5-30nm, this embodiment is 30nm; the choice of the electron injection layer and the cathode material LiF (0.5 nm) and metallic aluminum (150 nm).
  • the device structure of this comparative example is:
  • the device structure of this comparative example is:
  • the device structure of this comparative example is:
  • the device structure of this comparative example is:
  • the device structure of this comparative example is:
  • the device structure of this comparative example is:
  • the device structure of this comparative example is:
  • the device structure of this comparative example is:
  • the device structure of this comparative example is:
  • Example 4 3.6eV 0.26eV 0.16eV Example 5 3.6eV 0.26eV 0.19eV Example 6 3.6eV 0.26eV 0.21eV Example 7 4.0eV 0.15eV 0.21eV Example 8 4.0eV 0.15eV 0.20eV Example 9 4.0eV 0.15eV 0.20eV Example 10 3.8eV 0.18eV 0.22eV Example 11 4.0eV 0.11eV 0.11eV Example 12 3.7eV 0.20eV 0.19eV Example 13 3.9eV 0.17eV 0.21eV Example 14 4.2eV 0.10eV 0.20eV Example 15 4.1eV 0.20eV 0.14eV Example 16 3.5eV 0.15eV 0.12eV Comparative Example 1 4.0eV 0.15eV 0.12eV Comparative Example 2 4.0eV 0.15eV 0.12eV Comparative Example 3 4.0eV 0.15eV 0.12eV
  • the life test of LT90 is as follows: By setting different test brightness, the brightness and life decay curve of the organic electroluminescent device is obtained, so as to obtain the life value of the device under the required decay brightness. That is, set the test brightness to 5000cd / m 2 and maintain a constant current, and measure the time for the brightness of the organic electroluminescent device to decrease to 4500cd / m 2 , the unit is hour;
  • the technical solution provided in this application namely, when the organic light emitting layer is a wide band gap material as a host material, traditional TADF as a sensitizer, and resonant TADF as a dye, organic electroluminescence
  • the device has a low efficiency roll-off under high brightness, a narrow half-value width and good color purity. At the same time, the device has a longer life and its overall characteristics are significantly better than those of the comparative examples 1-9;
  • Example 1-16 According to the comparison between Example 1-16 and Comparative Example 1-3, it can be known that the proportion of the sensitizer material in the organic light-emitting layer of the present application is 1 wt% to 60 wt%, and the proportion of the wide band gap material in the organic light-emitting layer.
  • the ratio is 20 wt% to 98.9 wt%, and the ratio of the resonance type thermally activated delayed fluorescent material in the organic light emitting layer is 0.1 wt% to 20 wt%, the device performs better in roll-off, lifetime, and peak width.

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Abstract

一种有机电致发光器件及其制备方法和显示装置，有机电致发光器件包括有机发光层（4），有机发光层（4）包括主体材料、敏化剂材料以及共振型热活化延迟荧光材料；主体材料为宽带隙材料；敏化剂材料为热活化延迟荧光材料；热活化延迟荧光材料的单重态能级处于宽带隙材料的单重态能级与共振型热活化延迟荧光材料的单重态能级之间，热活化延迟荧光材料的三重态能级处于宽带隙材料的三重态能级与共振型热活化延迟荧光材料的三重态能级之间。能够克服现阶段使用传统TADF材料发光导致的器件寿命短、光谱宽的缺陷。

Description

有机电致发光器件及其制备方法和显示装置
本申请要求于2018年8月31日提交中国专利局、申请号为201811012898.9、发明名称为“一种有机电致发光器件和显示装置”的中国专利申请的优先权。上述申请的全部内容通过引用结合在本申请中。
技术领域
本申请涉及有机电致发光技术领域，尤其涉及有机电致发光器件及其制备方法和显示装置。
背景技术
有机电致发光二极管(Organic Light Emitting Diode，简称：OLED)，是一种通过电流驱动而达到发光目的的器件，其主要特性来自于其中的有机发光层，当施加适当电压后，电子和空穴会在有机发光层中结合产生激子并根据有机发光层的特性发出不同波长的光。现阶段中，发光层由主体材料和掺杂染料构成，而染料多选自传统荧光材料、传统磷光材料。具体地，传统荧光材料具有无法利用三重态激子的缺陷，传统磷光材料虽然可以通过引入重金属原子，例如铱或铂，实现单重态激子跃迁至三重态而达到100％的能量使用效率，但是铱、铂等重金属非常稀缺，成本昂贵且极易造成环境污染，因此磷光材料也无法成为染料的首选。
热活化延迟荧光(Thermally Activated Delayed Fluorescence,简称：TADF)材料与传统磷光材料和传统荧光材料相比，能够通过吸收环境热量实现三重态激子向单重态的反向系间窜越，进而从单重态发出荧光，从而实现激子的100％利用，并且无需借助任何重金属。因此，目前主要通过主体材料掺杂TADF材料来实现100％的能量使用效率。但是，大多数TADF材料自身也存在一定的缺陷，例如发光光谱过宽、器件滚降大、寿命短。
发明内容
本申请提供一种有机电致发光器件及其制备方法和显示装置，该有机电致发光器件的有机发光层以宽带隙材料为主体材料，并且利用TADF作为敏化剂材料辅助敏化共振型TADF染料发光，从而克服现阶段使用传统TADF材料发光导致的器件寿命短、光谱宽的缺陷。
本申请提供一种有机电致发光器件，包括有机发光层，所述有机发光层包括主体材料、敏化剂材料以及共振型热活化延迟荧光材料；
所述主体材料为宽带隙材料；
所述敏化剂材料为热活化延迟荧光材料；
所述宽带隙材料的单重态能级大于所述敏化剂材料的单重态能级，所述宽带隙材料的三重态能级大于所述敏化剂材料的三重态能级；所述敏化剂材料的单重态能级大 于所述共振型热活化延迟荧光材料的单重态能级，所述敏化剂材料的三重态能级大于所述共振型热活化延迟荧光材料的三重态能级。
可选地，所述共振型热活化延迟荧光材料具有式[1]所示的结构：
Figure PCTCN2019082695-appb-000001
其中，X独立的选自B、P、P＝O、P＝S、SiR 1中的一种；R 1选自为氢、取代或未取代的C 1-C 36的烷基、取代或未取代的C 6-C 30的芳基、取代或未取代的C 3-C 30的杂芳基；
A选自取代或未取代的C 6-C 30的芳基、取代或未取代的C 3-C 30的杂芳基、取代或未取代的C 6-C 30的芳基氨基；
M 1和M 2各自独立的选自H、取代或未取代的C 1-C 36的烷基、取代或未取代的C 6-C 30的芳基、取代或未取代的C 6-C 30的杂芳基；
相邻的X、A、M 1、M 2中至少三个连接成环且所述环中包括X；
a为1-12的整数；
当上述基团存在取代基时，所述取代基分别独立地选自卤素、氰基、C 1-C 10的烷基、C 2-C 6的烯基、C 1-C 6的烷氧基或硫代烷氧基、C 6-C 30的芳基、C 3-C 30的杂芳基中的一种或多种。
可选地，相邻的X、A、M 1、M 2中的三个连接成含有两个杂原子的六元环；
所述杂原子选自B、P、Si、O、S、N、Se中的两种。
可选地，所述共振型热活化延迟荧光材料的分子量为200-2000。
可选地，a为1-6的整数。
可选地，所述共振型热活化延迟荧光材料为具有本申请中通式(F-1)-(F-29)之一所示的化合物，通式(F-1)-(F-29)中，R分别独立地选自氢、卤素、氰基、C 1-C 10的烷基、C 2-C 6的烯基、C 1-C 6的烷氧基或硫代烷氧基、C 6-C 30的芳基、C 3-C 30的杂芳基中的一种或多种；Y独立的选自O、S、Se。
可选地，所述共振型热活化延迟荧光材料为具有本申请(M-1)-(M-72)之一的化合物。
可选地，所述热活化延迟荧光材料为包括给电子基团和受电子基团的化合物。
可选地，所述给电子基团包括咔唑基、吩噻嗪基、吩噁嗪基、吲哚并咔唑基、二苯胺基、三苯胺基、吖啶基、吩嗪基中的至少一种。
可选地，所述给电子基团选自本申请中D1-D17至少一种基团。
可选地，所述受电子基团包括三嗪基、嘧啶基、砜基、噻唑基、噁唑基、噁二唑基、噻二唑基、三氮唑基、硼基、吡嗪基、羰基、氰基、吡啶基中的至少一种。
可选地，所述受电子基团选自本申请中A1-A23至少一种基团。
可选地，所述热活化延迟荧光材料的单重态与三重态的能级差≤0.3eV。
可选地，所述热活化延迟荧光材料为具有本申请(T-1)-(T-88)之一的化合物。
可选地，所述宽带隙材料的HOMO能级与LUMO能级之差≥2eV。
可选地，所述宽带隙材料为包括咔唑基、咔啉基、螺芴基、芴基、硅基、膦氧基 中的至少一种基团的化合物。
可选地，所述宽带隙材料为具有本申请(W-1)-(W-46)之一的化合物。
可选地，所述敏化剂材料在所述有机发光层中的质量比例(掺杂浓度)为1-60wt％；
所述宽带隙材料在所述有机发光层中的质量比例(掺杂浓度)为20-98.9wt％；
所述共振型热活化延迟荧光材料在所述有机发光层中的质量比例(掺杂浓度)为0.1-20wt％。
本申请还提供一种有机电致发光器件的制备方法，包括以下步骤：通过宽带隙材料材料源、热活化延迟荧光材料源和共振型热活化延迟荧光材料源共同蒸镀形成有机发光层。
本申请还提供一种显示装置，包括上述任一所述的有机电致发光器件。
本申请的有机电致发光器件采用宽带隙材料作为主体材料的同时，利用TADF材料作为辅助主体材料来敏化共振型TADF材料发光。当吸收外部热量后，敏化剂TADF材料的单重态激子和三重态激子都能加以利用，分别传递给共振型TADF材料的单重态和三重态能级。同时，共振型TADF材料能够同时利用单重态和三重态激子进行发光。另外，由于敏化剂材料能够将自身的一部分三重态能量转化为单重态，抑制了Dexter能量传递过程，促进了
Figure PCTCN2019082695-appb-000002
能量传递过程，因此在有效提高了本申请有机电致发光器件的发光效率的同时也降低高亮度下由于三重态寿命过长导致的效率滚降；同时，宽带隙主体能够有效稀释敏化剂材料和共振型TADF的激子浓度，降低了三重态-三重态湮灭(TTA)以及三重态-极化子湮灭(TPA)，增强了器件的稳定性。而且本申请采用的共振型TADF材料不存在明显的分子内电子转移，因此有利于光谱的窄化，提高器件的色纯度。
附图说明
图1为本申请的有机电致发光器件的结构示意图。
具体实施方式
图1为本申请的有机电致发光器件的结构示意图，如图1所示，本申请的有机电致发光器件包括在基板1上依次沉积的阳极2、空穴传输区3、有机发光层4、电子传输区5以及阴极6。
具体地，基板1可以采用具有机械强度、热稳定性、防水性、透明度优异的玻璃或聚合物材料。此外，基板1上也可以带有薄膜晶体管(TFT)。
阳极2可以通过在基板上溅射或者沉积阳极材料的方式来形成，其中，阳极材料可以采用氧化铟锡(ITO)、氧化铟锌(IZO)、二氧化锡(SnO 2)、氧化锌(ZnO)等氧化物透明导电材料和它们之间的任意组合；阴极6可以采用镁(Mg)、银(Ag)、铝(Al)、铝-锂(Al-Li)、钙(Ca)、镁-铟(Mg-In)、镁-银(Mg-Ag)等金属或合金以及它们之间的任意组合。
空穴传输区3、有机发光层4以及电子传输区5的有机材料层可以通过真空热蒸镀、旋转涂敷、打印等方法依次制备于阳极2之上。其中，用作有机材料层的化合物可以为有机小分子、有机大分子和聚合物，以及它们的组合。
以下，对有机发光层4进行详细的介绍。
大多数TADF材料作为染料发光存在一定的缺陷，例如由于TADF材料存在分子内电荷转移，因此往往导致电致发光光谱过宽，光色不纯；同时由于TADF材料三重态能级较高且三重态激子寿命长，导致器件滚降大、寿命短等。此外，大多数主体材料具有单极传输的特点，导致电子和空穴在发光层传递不均衡，也引起了高亮度下严重的效率滚降(roll-off)，光谱稳定性较差。
有鉴于此，本申请的有机发光层包括主体材料、敏化剂材料以及共振型热活化延迟荧光材料；主体材料为宽带隙材料；敏化剂材料为热活化延迟荧光材料；宽带隙材料的单重态能级大于敏化剂材料的单重态能级，宽带隙材料的三重态能级大于敏化剂材料的三重态能级；敏化剂材料的单重态能级大于共振型热活化延迟荧光材料的单重态能级，敏化剂材料的三重态能级大于共振型热活化延迟荧光材料的三重态能级。
本申请的主体材料为宽带隙材料，该宽带隙材料能够稀释敏化剂材料以及共振型TADF材料的浓度，有效降低了激子密度，从而有效抑制三线态-三线态湮灭(TTA)以及激子-极化子淬灭(TPA)，进一步增强了有机电致发光器件的稳定性，提升器件的寿命、降低效率滚降。优选地，本申请的宽带隙材料的HOMO能级与LUMO能级之差≥2eV，从而能够保证宽带隙材料的单重态及三重态处于较高能级，有利于宽带隙材料向敏化剂材料发生
Figure PCTCN2019082695-appb-000003
能量传递过程和Dexter能量传递过程。
本申请的敏化剂材料为TADF材料，是用于辅助宽带隙主体材料敏化共振型TADF的材料，该敏化剂材料可以通过吸收环境热量，经历上转换过程，使三重态激子转化为单重态激子发射荧光。
本申请的共振型TADF材料作为染料发光，由于共振型TADF分子多为平面芳香刚性结构，因此结构稳定。在共振型TADF分子中，不同原子的共振效果不同导致了分子的HOMO与LUMO在不同原子上存在着空间上的分离，重叠面积较小，进而导致共振型TADF的单重态和三重态的能级相差很小，因此共振型TADF材料能够发生反向系间窜越。优选地，本申请的共振型TADF的单重态和三重态的能级之差小于等于0.3eV，能够通过吸收环境热量进行反系间窜越。同时，共振型TADF分子中不存在明显的给体基团和受体基团，因此该共振型TADF分子内电荷转移较弱，稳定性高。
在本申请中，主体材料宽带隙材料的单重态能级大于敏化剂材料TADF的单重态能级，敏化剂TADF的单重态能级大于共振型TADF的单重态能级，主体材料宽带隙材料的三重态能级大于敏化剂材料TADF的三重态能级，敏化剂材料TADF的三重态能级大于共振型TADF的三重态能级，因此，在有机电致发光器件在受到电激发后，宽带隙材料的单重态以及三重态激子能量都能够分别传递给敏化剂材料的单重态和三重态，或者空穴和电子直接复合在敏化剂上，由于敏化剂材料为热活化延迟荧光材料，敏化剂材料的三重态激子会跃迁至敏化剂材料TADF的单重态，随后能量再从敏化剂材料的单重态传递给共振型TADF的单重态，而共振型TADF的三重态激子也会发生反系间窜越至自身的单重态，最终有机电致发光器件中的单重态以及三重态能量都得到了充分利用，提升了有机电致发光器件的发光效率；同时，由于敏化剂能够将自身的三重态激子转化为单重态，有效抑制了敏化剂与共振型染料之间的Dexter能量 传递，增加了
Figure PCTCN2019082695-appb-000004
能量传递过程，因此本申请能够有效降低三重态激子的浓度，进而解决了高亮度下roll-off下降严重的问题，有效地增强了有机电致发光器件的稳定性能。
另外，本申请采用共振型TADF作为染料，该共振型TADF分子内部不存在明显的分子内电荷转移激发态，因此能够获得较窄的发光光谱。
本申请对有机发光层的组成进行了创新，使TADF敏化剂辅助宽带隙材料敏化共振型TADF，不仅能够提高有机电致发光器件的寿命、降低滚降、窄化光谱，更对工业应用具有十分重要的意义。
为了进一步降低器件的滚降效率，敏化剂在有机发光层中的质量占比为1wt％-60wt％；宽带隙材料在有机发光层中的质量占比为20wt％-98.9wt％；共振型热活化延迟荧光材料在有机发光层中的质量占比为0.1wt％-20wt％。
进一步地，上述的共振型热活化延迟荧光材料具有式[1]所示的结构：
Figure PCTCN2019082695-appb-000005
其中，X独立的选自B、P、P＝O、P＝S、SiR 1中的一种；R 1选自氢、取代或未取代的C 1-C 36的烷基、取代或未取代的C 6-C 30的芳基、取代或未取代的C 3-C 30的杂芳基；A选自取代或未取代的C 6-C 30的芳基、取代或未取代的C 3-C 30的杂芳基、取代或未取代的C 6-C 30的芳基氨基；M 1和M 2各自独立的选自H、取代或未取代的C 1-C 36的烷基、取代或未取代的C 6-C 30的芳基、取代或未取代的C 3-C 30的杂芳基、取代或未取代的C 6-C 30的杂芳基氨基；相邻的X、A、M 1、M 2中至少三个连接成环且所述环中包括X；a为1-12的整数；当上述基团存在取代基时，取代基分别独立地选自卤素、氰基、C 1-C 10的烷基、C 2-C 6的烯基、C 1-C 6的烷氧基或硫代烷氧基、C 6-C 30的芳基、C 3-C 30的杂芳基中的一种或多种。
可以理解的是，当X独立的选自P＝O、P＝S时，P分别与M 1和M 2连接；当X选自SiR 1时，Si分别与M 1和M 2连接。
需要强调的是，在式[1]的结构中，a个X、M 1、M 2可以相互独立的选择，即包含X、M 1、M 2的每个单元可以相同或不同，每个单元中的M 1、M 2也可以相同或不同。并且，在本申请的共振型TADF中，至少有一个通过相邻的X、A、M 1、M 2中的至少三个连接成的环且所述环中包括X。
进一步地，在本申请式[1]所示的共振型TADF中，相邻的X、A、M 1、M 2中的三个连接成含有两个杂原子的六元环；杂原子选自B、P、Si、O、S、N、Se中的两种。
具体地，相邻的X、A、M 1可连接成含有两个杂原子的六元环，相邻的X、A、M 2可连接成含有两个杂原子的六元环，相邻的X、M 1、M 2可连接成含有两个杂原子的六元环。
可以理解的是，该六元环中的一个杂原子来自于X，即具体可以为B、P、Si，另 一个杂原子选自O、S、N、Se中的一种，当杂原子为N时，由于N原子为三价，因此N原子除了与氢原子连接外，还可以与烷基取代基连接，具体的取代基为卤素、氰基、C 1-C 10的烷基或环烷基、C 2-C 6的烯基或环烯基、C 1-C 6的烷氧基或硫代烷氧基、C 6-C 30的芳基、C 3-C 30的杂芳基中的一种或多种。
作为优选的方案，本申请选择分子量为200-2000的共振型TADF材料作为染料，原因在于若共振型TADF材料的分子过大，在实际操作过程中不利于蒸镀。
作为一种实现方式，可以通过将a限定为1-6的整数，即本申请的共振型TADF可以包括1-6个具有X、M 1、M 2的单元，实现对共振型TADF分子量的控制。
优选地，本申请的共振型TADF材料可以具有下述通式(F-1)-(F-29)之一所示的结构：
Figure PCTCN2019082695-appb-000006
Figure PCTCN2019082695-appb-000007
R分别独立地选自氢、卤素、氰基、C 1-C 10的烷基、C 2-C 6的烯基、C 1-C 6的烷氧基或硫代烷氧基、C 6-C 30的芳基、C 3-C 30的杂芳基中的一种或多种；
Y独立的选自O、S、Se。
优选地，本申请共振型热活化延迟荧光材料具有以下结构之一的化合物：
Figure PCTCN2019082695-appb-000008
Figure PCTCN2019082695-appb-000009
Figure PCTCN2019082695-appb-000010
Figure PCTCN2019082695-appb-000011
本申请的敏化剂材料TADF为包括给电子基团和受电子基团的化合物，其中，给电子基团和受电子基团可以直接键结，也可以通过La-Lm所示的连接基团连接。
Figure PCTCN2019082695-appb-000012
*代表给电子基团连接位点；**代表受电子基团连接位点。
其中，给电子基团包括咔唑基、吩噻嗪基、吩噁嗪基、吲哚并咔唑基、二苯胺基、三苯胺基、吖啶基、吩嗪基中的至少一种；和/或，受电子基团包括三嗪基、嘧啶基、砜基、噻唑基、噁唑基、噁二唑基、噻二唑基、三氮唑基、硼基、吡嗪基、羰基、氰基、吡啶基中的至少一种。
进一步地，给电子基团选自以下至少一种基团：
Figure PCTCN2019082695-appb-000013
和/或，受电子基团选自以下至少一种基团：
Figure PCTCN2019082695-appb-000014
Figure PCTCN2019082695-appb-000015
具体地，为了更易实现敏化剂的反系间窜越，可以优选单重态与三重态能差≤0.3eV的TADF材料作为敏化剂。优选地，本申请的TADF材料可以为具有以下结构之一的化合物：
Figure PCTCN2019082695-appb-000016
Figure PCTCN2019082695-appb-000017
Figure PCTCN2019082695-appb-000018
Figure PCTCN2019082695-appb-000019
Figure PCTCN2019082695-appb-000020
另外，本申请的宽带隙材料为包括咔唑基、咔啉基、螺芴基、芴基、硅基、膦氧基中的至少一种基团的化合物。
本申请不限制宽带隙材料的具体结构，优选地，宽带隙材料选自具有以下结构之一的化合物：
Figure PCTCN2019082695-appb-000021
Figure PCTCN2019082695-appb-000022
Figure PCTCN2019082695-appb-000023
依然参考图1，对本申请的空穴传输区3、电子传输区5以及阴极6进行介绍。空穴传输区3位于阳极2和有机发光层4之间。空穴传输区3可以为单层结构的空穴传输层(HTL)，包括只含有一种化合物的单层空穴传输层和含有多种化合物的单层空穴传输层。空穴传输区3也可以为包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)中的至少两层的多层结构。
空穴传输区3的材料(包括HIL、HTL以及EBL)可以选自、但不限于酞菁衍生物如CuPc、导电聚合物或含导电掺杂剂的聚合物如聚苯撑乙烯、聚苯胺/十二烷基苯磺酸(Pani/DBSA)、聚(3,4-乙撑二氧噻吩)/聚(4-苯乙烯磺酸盐)(PEDOT/PSS)、聚苯胺/樟脑磺酸(Pani/CSA)、聚苯胺/聚(4-苯乙烯磺酸盐)(Pani/PSS)、芳香胺衍生物。
其中，芳香胺衍生物如下面HT-1至HT-34所示的化合物。若空穴传输区3的材料为芳香胺衍生物，可以为HT-1至HT-34所示的化合物的一种或多种。
Figure PCTCN2019082695-appb-000024
Figure PCTCN2019082695-appb-000025
空穴注入层位于阳极2和空穴传输层之间。空穴注入层可以是单一化合物材料，也可以是多种化合物的组合。例如，空穴注入层可以采用上述HT-1至HT-34的一种或多种化合物，或者采用下述HI1-HI3中的一种或多种化合物；也可以采用HT-1至HT-34的一种或多种化合物掺杂下述HI1-HI3中的一种或多种化合物。
Figure PCTCN2019082695-appb-000026
电子传输区5可以为单层结构的电子传输层(ETL)，包括只含有一种化合物的单层电子传输层和含有多种化合物的单层电子传输层。电子传输区5也可以为包括电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)中的至少两层的多层结构。
本申请的一方面，电子传输层材料可以选自、但不限于以下所罗列的ET-1至ET-57的一种或多种的组合。
Figure PCTCN2019082695-appb-000027
Figure PCTCN2019082695-appb-000028
Figure PCTCN2019082695-appb-000029
发光器件的结构中还可以包括位于电子传输层与阴极6之间的电子注入层，电子注入层材料包括但不限于以下罗列的一种或多种的组合。
LiQ,LiF,NaCl,CsF,Li 2O,Cs 2CO 3,BaO,Na,Li,Ca。
上述各层的厚度可以采用本领域中的这些层的常规厚度。
本申请还提供该有机电致发光器件的制备方法，以图1为例说明，包括在基板1上依次沉积阳极2、空穴传输区3、有机发光层4、电子传输区5、阴极6，然后封装。其中，在制备有机发光层4时，通过宽带隙材料源、敏化剂材料源和共振型TADF材料源共同蒸镀的方法形成有机发光层4。
具体地，本申请的有机电致发光器件的制备方法包括以下步骤：
1、将涂布了阳极材料的玻璃板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮：乙醇混合溶剂中超声除油，在洁净环境下烘烤至完全除去水份，用紫外光和臭氧清洗，并用低能阳离子束轰击表面；
2、把上述带有阳极的玻璃板置于真空腔内，抽真空至1×10 -5～9×10 -3Pa，在上述阳极层膜上真空蒸镀空穴注入层，蒸镀速率为0.1-0.5nm/s；
3、在空穴注入层之上真空蒸镀空穴传输层，蒸镀速率为0.1-0.5nm/s，
4、在空穴传输层之上真空蒸镀器件的有机发光层，有机发光层包括主体材料、敏化剂材料和TADF染料，利用多源共蒸的方法，调节主体材料的蒸镀速率、敏化剂材料的蒸镀速率和染料的蒸镀速率使染料达到预设掺杂比例；
5、在有机发光层之上真空蒸镀器件的电子传输层材料，其蒸镀速率为0.1-0.5nm/s；
6、在电子传输层上以0.1-0.5nm/s真空蒸镀LiF作为电子注入层，以0.5-1nm/s真空蒸镀Al层作为器件的阴极。
本申请实施例还提供一种显示装置，所述显示装置包括如上述提供的有机电致发光器件。该显示装置具体可以为OLED显示器等显示器件，以及包括该显示器件的电视、数码相机、手机、平板电脑等任何具有显示功能的产品或者部件。该显示装置与上述有机电致发光器件相对于现有技术所具有的优势相同，在此不再赘述。
以下通过具体实施例对本申请的有机电致发光器件进行进一步的介绍。
实施例1
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-7:20wt％T-37:3wt％M-3(30nm)/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
其中，阳极为ITO；空穴注入层的材料为HI-2，一般总厚度为5-30nm，本实施例为10nm；空穴传输层的材料为HT-27，总厚度一般为5-50nm，本实施例为40nm；有机发光层的主体材料为宽带隙材料W-7，敏化剂材料为T-37且掺杂浓度为20wt％，染料为共振型TADF材料M-3且掺杂浓度为3wt％，有机发光层的厚度一般为1-60nm，本实施例为30nm；电子传输层的材料为ET-53，厚度一般为5-30nm，本实施例为30nm；电子注入层及阴极材料选择LiF(0.5nm)和金属铝(150nm)。
另外，主体材料的HOMO能级与LUMO能级之差E g、敏化剂的单重态与三重态能级差ΔE ST以及共振型TADF染料的单重态与三重态能级差ΔE ST如表1所示。
实施例2
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-7:15wt％T-37:5wt％M-8(30nm)/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例3
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-7:8wt％T-37:1wt％M-10/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例4
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-10:40wt％T-16:3wt％M-24/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例5
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-10:25wt％T-16:0.5wt％M-28/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例6
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-10:50wt％T-16:5wt％M-44/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例7
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-45:15wt％T-9:15wt％M-54/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例8
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-45:20wt％T-9:3wt％M-56/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例9
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-45:22wt％T-9:5wt％M-58/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例10
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-12:8wt％T-17:7wt％M-16/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例11
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-13:10wt％T-25:13wt％M-20/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例12
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-15:15wt％T-26:15wt％M-28/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例13
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-17:20wt％T-28:8wt％M-54/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例14
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-34:25wt％T-32:9wt％M-56/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例15
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-39:30wt％T-69:10wt％M-66/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
实施例16
本实施例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-43:35wt％T-81:6wt％M-71/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
对比例1
本对比例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-45:0.5wt％T-9:5wt％M-71/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
对比例2
本对比例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-45:70wt％T-9:5wt％M-71/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
对比例3
本对比例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-45:15wt％T-9:30wt％M-71/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
对比例4
本对比例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-7:15wt％T-37/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
对比例5
本对比例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-7:15wt％M-8/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
对比例6
本对比例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-10:15wt％T-16/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
对比例7
本对比例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-10:15wt％M-28/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
对比例8
本对比例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-45:15wt％T-9/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
对比例9
本对比例的器件结构为：
ITO/HI-2(10nm)/HT-27(40nm)/W-45:15wt％M-58/ET-53(30nm)/LiF(0.5nm)/Al(150nm)
表1
  主体材料的E g 敏化剂的ΔE ST 共振型TADF的ΔE ST
实施例1 4.1eV 0.01eV 0.09eV
实施例2 4.1eV 0.01eV 0.11eV
实施例3 4.1eV 0.01eV 0.18eV
实施例4 3.6eV 0.26eV 0.16eV
实施例5 3.6eV 0.26eV 0.19eV
实施例6 3.6eV 0.26eV 0.21eV
实施例7 4.0eV 0.15eV 0.21eV
实施例8 4.0eV 0.15eV 0.20eV
实施例9 4.0eV 0.15eV 0.20eV
实施例10 3.8eV 0.18eV 0.22eV
实施例11 4.0eV 0.11eV 0.11eV
实施例12 3.7eV 0.20eV 0.19eV
实施例13 3.9eV 0.17eV 0.21eV
实施例14 4.2eV 0.10eV 0.20eV
实施例15 4.1eV 0.20eV 0.14eV
实施例16 3.5eV 0.15eV 0.12eV
对比例1 4.0eV 0.15eV 0.12eV
对比例2 4.0eV 0.15eV 0.12eV
对比例3 4.0eV 0.15eV 0.12eV
试验例
1、对由上述过程制备的有机电致发光器件(实施例1-16、对比例1-9)进行如下性能测定：制备得到器件的电流、电压、亮度、发光光谱、电流效率、外量子效率等特性采用PR 655光谱扫描亮度计和Keithley K 2400数字源表系统同步测试，寿命通过MC-6000测试完成。
2、LT90的寿命测试如下：通过设定不同的测试亮度，得出有机电致发光器件的亮度与寿命衰减曲线，从而取得器件在要求衰减亮度下的寿命数值。即设定测试亮度为5000cd/m 2，保持恒定的电流，测量有机电致发光器件的亮度降为4500cd/m 2的时间，单位为小时；
上述具体测试结果见表2。 表2
Figure PCTCN2019082695-appb-000030
Figure PCTCN2019082695-appb-000031
根据表2可知：
1、与对比例1-9相比，本申请所提供的技术方案，即，有机发光层为宽带隙材料作为主体材料、传统TADF作为敏化剂、共振型TADF作为染料时，有机电致发光器件在高亮度下效率滚降小，半峰宽较窄进而表现出较好的色纯度，同时器件的寿命较长，其整体特性明显优于对比例1-9；
2、对比例4/6/8中以宽带隙主体敏化普通的TADF染料进行发光，高亮度下效率滚降严重，半峰宽较宽，色纯度差，且寿命较短；对比例5/7/9中以宽带隙主体敏化共振型TADF染料进行发光，高亮度下效率滚降严重且寿命较短，但是半峰宽较窄，因此采用共振型TADF染料进行发光时，能够有效窄化光谱；
3、根据实施例1-16与对比例1-3对比可知，本申请的敏化剂材料在有机发光层中的占比为1wt％-60wt％，宽带隙材料在有机发光层中的占比为20wt％-98.9wt％，共振型热活化延迟荧光材料在有机发光层中的占比为0.1wt％-20wt％时，器件在滚降、寿命以及峰宽中表现更为优越。
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。

Claims (20)

  1. 一种有机电致发光器件，包括有机发光层，其中，所述有机发光层包括主体材料、敏化剂材料以及共振型热活化延迟荧光材料；
    所述主体材料为宽带隙材料；
    所述敏化剂材料为热活化延迟荧光材料；
    所述宽带隙材料的单重态能级大于所述敏化剂材料的单重态能级，所述宽带隙材料的三重态能级大于所述敏化剂材料的三重态能级；所述敏化剂材料的单重态能级大于所述共振型热活化延迟荧光材料的单重态能级，所述敏化剂材料的三重态能级大于所述共振型热活化延迟荧光材料的三重态能级。
  2. 根据权利要求1所述的有机电致发光器件，其中，所述共振型热活化延迟荧光材料具有式[1]所示的结构：
    Figure PCTCN2019082695-appb-100001
    其中，X独立的选自B、P、P＝O、P＝S、SiR 1中的一种；R 1选自氢、取代或未取代的C 1-C 36的烷基、取代或未取代的C 6-C 30的芳基、取代或未取代的C 3-C 30的杂芳基；
    A选自取代或未取代的C 6-C 30的芳基、取代或未取代的C 3-C 30的杂芳基、取代或未取代的C 6-C 30的芳基氨基；
    M 1和M 2各自独立的选自H、取代或未取代的C 1-C 36的烷基、取代或未取代的C 6-C 30的芳基、取代或未取代的C 3-C 30的杂芳基；
    相邻的X、A、M 1、M 2中至少三个连接成环且所述环中包括X；
    a为1-12的整数；
    当上述基团存在取代基时，所述取代基分别独立地选自卤素、氰基、C 1-C 10的烷基、C 2-C 6的烯基、C 1-C 6的烷氧基或硫代烷氧基、C 6-C 30的芳基、C 3-C 30的杂芳基中的一种或多种。
  3. 根据权利要求2所述的有机电致发光器件，其中，相邻的X、A、M 1、M 2中的三个连接成含有两个杂原子的六元环；
    所述杂原子选自B、P、Si、O、S、N、Se中的两种。
  4. 根据权利要求3所述的有机电致发光器件，其中，所述共振型热活化延迟荧光材料的分子量为200-2000。
  5. 根据权利要求4所述的有机电致发光器件，其中，a为1-6的整数。
  6. 根据权利要求3所述的有机电致发光器件，其中，所述共振型热活化延迟荧光材料为具有如下通式之一的化合物：
    Figure PCTCN2019082695-appb-100002
    Figure PCTCN2019082695-appb-100003
    R分别独立地选自氢、卤素、氰基、C 1-C 10的烷基、C 2-C 6的烯基、C 1-C 6的烷氧基或硫代烷氧基、C 6-C 30的芳基、C 3-C 30的杂芳基中的一种或多种；
    Y独立的选自O、S、Se。
  7. 根据权利要求6所述的有机电致发光器件，其中，所述共振型热活化延迟荧光材料为具有如下结构之一的化合物：
    Figure PCTCN2019082695-appb-100004
    Figure PCTCN2019082695-appb-100005
    Figure PCTCN2019082695-appb-100006
    Figure PCTCN2019082695-appb-100007
  8. 根据权利要求1所述的有机电致发光器件，其中，所述热活化延迟荧光材料为包括给电子基团和受电子基团的化合物。
  9. 根据权利要求8所述的有机电致发光器件，其中，所述给电子基团包括咔唑基、吩噻嗪基、吩噁嗪基、吲哚并咔唑基、二苯胺基、三苯胺基、吖啶基、吩嗪基中的至少一种。
  10. 根据权利要求9所述的有机电致发光器件，其中，所述给电子基团选自以下至少一种基团：
    Figure PCTCN2019082695-appb-100008
    Figure PCTCN2019082695-appb-100009
    R分别独立地选自氢、卤素、氰基、C 1-C 10的烷基、C 2-C 6的烯基、C 1-C 6的烷氧基或硫代烷氧基、C 6-C 30的芳基、C 3-C 30的杂芳基中的一种或多种。
  11. 根据权利要求8所述的有机电致发光器件，其中，所述受电子基团包括三嗪基、嘧啶基、砜基、噻唑基、噁唑基、噁二唑基、噻二唑基、三氮唑基、硼基、吡嗪基、羰基、氰基、吡啶基中的至少一种。
  12. 根据权利要求11所述的有机电致发光器件，其中，所述受电子基团选自以下至少一种基团：
    Figure PCTCN2019082695-appb-100010
    R分别独立地选自氢、卤素、氰基、C 1-C 10的烷基、C 2-C 6的烯基、C 1-C 6的烷氧基或硫代烷氧基、C 6-C 30的芳基、C 3-C 30的杂芳基中的一种或多种。
  13. 根据权利要求8所述的有机电致发光器件，其中，所述热活化延迟荧光材料的单重态与三重态的能级差≤0.3eV。
  14. 根据权利要求8所述的有机电致发光器件，其中，所述热活化延迟荧光材料为具有如下结构之一的化合物：
    Figure PCTCN2019082695-appb-100011
    Figure PCTCN2019082695-appb-100012
    Figure PCTCN2019082695-appb-100013
    Figure PCTCN2019082695-appb-100014
  15. 根据权利要求1所述的有机电致发光器件，其中，所述宽带隙材料的HOMO能级与LUMO能级之差≥2eV。
  16. 根据权利要求1所述的有机电致发光器件，其中，所述宽带隙材料为包括咔唑基、咔啉基、螺芴基、芴基、硅基、膦氧基中的至少一种基团的化合物。
  17. 根据权利要求16所述的有机电致发光器件，其中，所述宽带隙材料为具有如下结构之一的化合物：
    Figure PCTCN2019082695-appb-100015
    Figure PCTCN2019082695-appb-100016
    Figure PCTCN2019082695-appb-100017
  18. 根据权利要求1所述的有机电致发光器件，其中，所述敏化剂材料在所述有机发光层中的质量占比为1wt％-60wt％；
    所述宽带隙材料在所述有机发光层中的质量占比为20wt％-98.9wt％；
    所述共振型热活化延迟荧光材料在所述有机发光层中的质量占比为0.1wt％-20wt％。
  19. 一种有机电致发光器件的制备方法，其中，包括以下步骤：通过宽带隙材料材料源、热活化延迟荧光材料源和共振型热活化延迟荧光材料源共同蒸镀形成有机发光层。
  20. 一种显示装置，其中，包括权利要求1-18任一所述的有机电致发光器件。
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