WO2022140878A1 - 有机电致发光器件和显示装置 - Google Patents

有机电致发光器件和显示装置 Download PDF

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WO2022140878A1
WO2022140878A1 PCT/CN2020/139813 CN2020139813W WO2022140878A1 WO 2022140878 A1 WO2022140878 A1 WO 2022140878A1 CN 2020139813 W CN2020139813 W CN 2020139813W WO 2022140878 A1 WO2022140878 A1 WO 2022140878A1
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layer
homo
blocking layer
host
organic electroluminescent
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PCT/CN2020/139813
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English (en)
French (fr)
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孙玉倩
刘杨
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京东方科技集团股份有限公司
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Priority to US17/603,009 priority Critical patent/US20230107826A1/en
Priority to PCT/CN2020/139813 priority patent/WO2022140878A1/zh
Priority to CN202080003698.6A priority patent/CN115088089B/zh
Priority to CN202311161563.4A priority patent/CN117177600A/zh
Publication of WO2022140878A1 publication Critical patent/WO2022140878A1/zh

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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
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
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    • 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
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    • 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
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • 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
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
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    • 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
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes

Definitions

  • the embodiments of the present disclosure relate to, but are not limited to, the field of display technology, and in particular, relate to an organic electroluminescence device and a display device.
  • organic electroluminescence (OLED) devices are basically composed of an anode, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and a cathode, wherein the electron blocking layer and the hole blocking layer can block the Excess electrons, holes, and excitons that are not utilized by the light-emitting layer.
  • the electron blocking layer is unstable to electrons, it will crack during long-term use, resulting in device failure.
  • Embodiments of the present disclosure provide an organic electroluminescence device, including an anode, a cathode, a light-emitting layer disposed between the anode and the cathode, and an electron blocking layer disposed on a side of the light-emitting layer facing the anode layer;
  • the light-emitting layer includes a host material and a dopant material, and the host material includes an N-type material and a P-type material; the material of the electron blocking layer and the N-type material satisfy:
  • LUMO N-host is the lowest unoccupied molecular orbital energy level of the N-type material
  • HOMO EBL is the highest occupied molecular orbital energy level of the material of the electron blocking layer
  • HOMO N-host is the energy level of the N-type material. The highest occupied molecular orbital energy level
  • the difference between the peak wavelength of the emission spectrum curve of the exciplex formed by the material of the electron blocking layer and the N-type material and the absorption band edge wavelength of the absorption spectrum curve of the doping material is ⁇ , ⁇ >30nm.
  • the organic electroluminescence device further includes a hole transport layer disposed between the anode and the electron blocking layer, and the material of the hole transport layer and the material of the electron blocking layer satisfy the requirements. : 0eV ⁇ HOMO HTL -HOMO EBL ⁇ 0.2eV; wherein, HOMO HTL is the highest occupied molecular orbital energy level of the material of the hole transport layer.
  • the material of the electron blocking layer includes a compound of the following structural formula:
  • L1 is single bond, benzene ring or biphenyl
  • AR1 is any of the following: substituted or unsubstituted diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted spirofluorene xanthene.
  • the AR1 is selected from any of the following structures:
  • R represents H or hydrocarbon group on the spiro ring.
  • the material of the electron blocking layer includes any one or more of the following:
  • the N-type material includes a compound of the following structural formula:
  • L2, L3, L4 are independently single bond, benzene ring or biphenyl
  • AR2 is selected from the following structures:
  • AR3 and AR4 are independently selected from: substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted heteroaryl groups with 5-30 ring atoms.
  • the N-type material includes a compound having the following structural formula:
  • the P-type material includes a compound having the following structural formula:
  • the doping material includes any one or more of the following: coumarin dyes, copper quinacridine derivatives, polycyclic aromatic hydrocarbons, diamineanthracene derivatives, carbazole derivatives, metal complexes thing.
  • the material of the hole transport layer includes a compound having the following structural formula:
  • the organic electroluminescent device further includes a hole injection layer disposed between the hole transport layer and the anode, and the material of the hole injection layer includes 4, 4', 4" -Tris[2-naphthylphenylamino]triphenylamine.
  • the organic electroluminescent device further includes a hole blocking layer disposed on the side of the light-emitting layer facing the cathode, and the material of the hole blocking layer includes a compound having the following structural formula:
  • the organic electroluminescent device further includes an electron transport layer disposed between the hole blocking layer and the cathode, and the material of the electron transport layer includes any one or more of the following: 8 -Lithium quinolate or aluminum 8-quinolate.
  • Embodiments of the present disclosure also provide a display device, including the organic electroluminescence device.
  • FIG. 1 is a schematic plan view of a display area of a display substrate
  • FIG. 2 is a schematic cross-sectional structure diagram of the display substrate of FIG. 1;
  • FIG. 3 is a schematic structural diagram of an organic electroluminescent device according to an exemplary embodiment of the present disclosure
  • FIG. 4 is a schematic diagram of the material energy level relationship of some film layers in an organic electroluminescent device according to an exemplary embodiment of the present disclosure
  • FIG. 5 is a spectrogram of some film layer materials in an organic electroluminescent device according to an exemplary embodiment of the present disclosure.
  • FIG. 1 is a schematic plan view of a display area of a display substrate.
  • the display area may include a plurality of pixel units P arranged in a matrix, and at least one of the plurality of pixel units P includes a first sub-pixel P1 that emits light of a first color, and a sub-pixel P1 that emits light of a second color.
  • the second sub-pixel P2 and the third sub-pixel P3 emitting light of the third color, the first sub-pixel P1, the second sub-pixel P2 and the third sub-pixel P3 all include a light-emitting device and a pixel driving circuit for driving the light-emitting device to emit light.
  • the first subpixel P1, the second subpixel P2, and the third subpixel P3 may be configured to emit red, green, and blue light, respectively.
  • the pixel unit P may also include sub-pixels emitting other colors, such as sub-pixels emitting white light.
  • the shape of the sub-pixels in the pixel unit may be rectangular, rhombus, pentagon or hexagon, and the like.
  • the pixel unit includes three sub-pixels, the three sub-pixels can be arranged in rows, columns, or squares.
  • the pixel unit includes four sub-pixels, the four sub-pixels can be arranged in rows, columns, or squares, which are not limited in the present disclosure. .
  • FIG. 2 is a schematic cross-sectional structure diagram of a display area of a display substrate, illustrating the structure of three sub-pixels of an OLED display substrate.
  • the display substrate may include a driving circuit layer 102 disposed on a substrate 101 , a light emitting structure layer 103 disposed on a side of the driving circuit layer 102 away from the substrate 101 , and a The encapsulation structure layer 104 on the side of the light emitting structure layer 103 away from the substrate 101 .
  • the driver circuit layer 102 includes pixel driver circuits.
  • the light emitting structure layer 103 includes a plurality of OLED light emitting devices 310, and each OLED light emitting device 310 is connected to a corresponding pixel driving circuit.
  • the display substrate may include other film layers, such as spacer columns, etc., which are not limited in the present disclosure.
  • substrate 101 may be a flexible substrate, or may be a rigid substrate.
  • the flexible substrate may include a stacked first flexible material layer, a first inorganic material layer, a semiconductor layer, a second flexible material layer and a second inorganic material layer, and the materials of the first flexible material layer and the second flexible material layer may be made of polymer.
  • the materials of the first inorganic material layer and the second inorganic material layer can be silicon nitride (SiNx ) or silicon oxide (SiOx), etc., to improve the water and oxygen resistance of the substrate, and the material of the semiconductor layer can be amorphous silicon (a-si).
  • PI imide
  • PET polyethylene terephthalate
  • surface-treated soft polymer film the materials of the first inorganic material layer and the second inorganic material layer can be silicon nitride (SiNx ) or silicon oxide (SiOx), etc., to improve the water and oxygen resistance of the substrate, and the material of the semiconductor layer can be amorphous silicon (a-si).
  • each sub-pixel may include a plurality of transistors and storage capacitors constituting the pixel driving circuit.
  • each sub-pixel includes one driving transistor and one storage capacitor.
  • a storage capacitor is used as an example for illustration.
  • the driving circuit layer 102 of each sub-pixel may include: a first insulating layer 201 disposed on the substrate 101; an active layer disposed on the first insulating layer 201; a first insulating layer covering the active layer Two insulating layers 202; a gate electrode and a first capacitor electrode arranged on the second insulating layer 202; a third insulating layer 203 covering the gate electrode and the first capacitor electrode; a second capacitor electrode arranged on the third insulating layer 203
  • the fourth insulating layer 204 covering the second capacitor electrode, the second insulating layer 202, the third insulating layer 203 and the fourth insulating layer 204 are provided with via holes, and the via holes expose the active layer; set on the fourth insulating layer
  • the source and drain electrodes on 204 are respectively connected to the active layer through via holes; the flat layer 205 covering the aforementioned structure is provided with via holes, and the via holes expose the drain electrodes.
  • the active layer, the gate electrode, the source electrode and the drain electrode form the
  • the light emitting structure layer 103 may include an anode 301 , a pixel definition layer 300 , a cathode 303 , and an organic functional layer located between the anode 301 and the cathode 303 , and the organic functional layer at least includes Light-emitting layer 302 .
  • the anode 301 is arranged on the flat layer 205, and is connected to the drain electrode of the driving transistor 210 through a via hole opened on the flat layer 205; the pixel definition layer 300 is arranged on the anode 301 and the flat layer 205, and the pixel definition layer 300 is provided with a pixel opening, The pixel opening exposes the anode 301 .
  • light emitting layer 302 is disposed at least partially within the pixel opening and is connected to anode 301 ; cathode 303 is disposed on and connected to light emitting layer 302 .
  • the organic functional layer may further include a hole injection layer, a hole transport layer 305 and an electron blocking layer 306 which are located between the anode 301 and the light-emitting layer 302 and are stacked on the anode 301 in sequence, and are located in the light-emitting layer 301 .
  • a hole blocking layer, an electron transport layer 308 and an electron injection layer are sequentially stacked on the light emitting layer 302 between the layer 302 and the cathode 303 .
  • the anode 301 , the organic functional layer and the cathode 303 of each sub-pixel form an OLED light-emitting device 310, which is configured to emit light of a corresponding color under the driving of a corresponding pixel driving circuit.
  • the light-emitting layer 302 of each sub-pixel is located within the sub-pixel region where it is located, and the edges of the light-emitting layers of adjacent sub-pixels may overlap or be separated.
  • Any other film layer other than the light-emitting layer in the organic functional layers of all the sub-pixels may be an integral connected film layer covering all the sub-pixels, which may be referred to as a common layer.
  • the encapsulation structure layer 104 may include a stacked first encapsulation layer 401 , a second encapsulation layer 402 and a third encapsulation layer 403 , and the first encapsulation layer 401 and the third encapsulation layer 403 may use inorganic materials
  • the second encapsulation layer 402 can be made of organic materials, and the second encapsulation layer 402 is disposed between the first encapsulation layer 401 and the third encapsulation layer 403 to ensure that the outside water vapor cannot enter the light emitting device 310 .
  • exciplexes are used as the host material of the light-emitting layer, including N-type materials and P-type materials.
  • the material of the electron blocking layer is generally an aromatic amine material, which is a strong electron-donating material and is unstable to electrons and excitons.
  • the electron blocking layer may form an excimer complex with the N-type material in the host material at the interface in contact with the light-emitting layer. If the luminescence spectrum (PL spectrum) of the formed exciplex and the absorption spectrum of the dopant in the luminescent layer coincide well, then the electron blocking layer material and the N-type material in the host material of the luminescent layer are formed. The interfacial exciplex will participate in the luminescence process, thereby accelerating the cracking of the electron blocking layer, resulting in the degradation of device performance and device life.
  • PL spectrum luminescence spectrum
  • Embodiments of the present disclosure provide an organic electroluminescence device, including an anode, a cathode, a light-emitting layer disposed between the anode and the cathode, and an electron blocking layer disposed on a side of the light-emitting layer facing the anode layer;
  • the light-emitting layer includes a host material and a dopant material, and the host material includes an N-type material and a P-type material.
  • the N-type material in the host material of the light-emitting layer may be referred to as N-host material
  • the P-type material in the host material of the light-emitting layer may be referred to as P-host material
  • the electron blocking layer may be referred to as EBL.
  • the material of the electron blocking layer and the N-type material satisfy:
  • LUMO N-host is the lowest unoccupied molecular orbital energy level of the N-type material
  • HOMO EBL is the highest occupied molecular orbital energy level of the material of the electron blocking layer
  • HOMO N-host is the energy level of the N-type material. The highest occupied molecular orbital energy level
  • the difference between the peak wavelength of the emission spectrum curve of the exciplex formed by the material of the electron blocking layer and the N-type material and the absorption band edge wavelength of the absorption spectrum curve of the doping material is ⁇ , ⁇ >30nm.
  • the PL spectrum (luminescence emission) of the exciplex formed by the electron blocking layer material and the N-host material can be guaranteed. spectrum) away from the absorption spectrum of the doping material, so that the exciplex formed by the electron blocking layer material and the N-host material does not participate in luminescence, thereby reducing the cracking of the electron blocking layer material and improving the life of the device.
  • holes can be better injected into the light-emitting layer and the luminous efficiency of the device can be ensured.
  • the organic electroluminescent device further comprises a hole transport layer (HTL for short) disposed between the anode and the electron blocking layer, and the material of the hole transport layer is the same as the The material of the electron blocking layer satisfies: 0eV ⁇ HOMO HTL -HOMO EBL ⁇ 0.2eV ; wherein, HOMO HTL is the highest occupied molecular orbital energy level of the material of the hole transport layer.
  • HTL hole transport layer
  • the highest occupied molecular orbital energy level is referred to as the HOMO energy level
  • the lowest unoccupied molecular orbital energy level is referred to as the LUMO energy level.
  • the magnitude relationship between the HOMO or LUMO energy levels of different materials refers to the magnitude relationship between the absolute values of the numerical values of the HOMO or LUMO energy levels.
  • ⁇ E1 is the difference between the HOMO energy levels of the HTL material and the EBL material, 0 ⁇ E1 ⁇ 0.2.
  • ⁇ E2 is the difference between the LUMO energy level of the N-host material and the HOMO energy level of the EBL material, 2.75 ⁇ E2 ⁇ 3.05.
  • ⁇ E3 is the difference between the HOMO energy level of the EBL material and the HOMO energy level of the N-host material, and the HOMO energy level of the EBL material is smaller than that of the N-host material, where 0.3 ⁇ E3 ⁇ 1.
  • the material of the electron blocking layer may be as shown in formula (1):
  • L is single bond, benzene ring or biphenyl
  • AR1 is any of the following: substituted or unsubstituted diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted spirofluorene xanthene; any C atom in AR1 can be substituted by a heteroatom, so The heteroatom can be any one or more of O, S, N and Si.
  • AR1 can be selected from any of the following structures:
  • R represents H on the spiro ring or a hydrocarbyl group (H on the spiro ring may be substituted by an alkyl group or a hydrocarbyl group).
  • the material of the electron blocking layer may include any one or more of the following:
  • the structure of the N-type material in the host material of the light-emitting layer may be shown in formula (2):
  • L2, L3, L4 can be independently a single bond, a benzene ring or a biphenyl
  • AR2 can be selected from the following structures:
  • AR3 and AR4 are independently selected from: substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted heteroaryl groups with 5-30 ring atoms.
  • the N-type material in the host material of the light-emitting layer may be:
  • the P-type material in the host material of the light-emitting layer may be:
  • the electroluminescent device of embodiments of the present disclosure may be a green electroluminescent device.
  • the doping material of the light-emitting layer may be selected from any one or more of the following: coumarin dyes, copper quinacridine derivatives, polycyclic aromatic hydrocarbons, diamineanthracene derivatives compounds, carbazole derivatives, metal complexes, etc.
  • coumarin 6 C-6
  • coumarin 545T C-525T
  • copper quinacridone Q
  • N,N'-dimethylquinacridone DMQA
  • DPT 5, 12-Diphenylnaphthylnaphthalene
  • BA-NPB N10,N10'-diphenyl-N10,N10'-diphthaloyl-9,9'-dianthracene-10,10'-diamine
  • BA-NPB N10,N10'-diphenyl-N10,N10'-diphthaloyl-9,9'-dianthracene-10,10'-diamine
  • BA-NPB N10,N10'-diphenyl-N10,N10'-diphthaloyl-9,9'-dianthracene-10,10'-diamine
  • BA-NPB N10,N10'-diphenyl-N10,N10'-diphthaloyl-9,9'-dianthracene
  • the doping ratio of the doping material may be 1 wt %-10 wt %.
  • the doping ratio refers to the proportion of the doping material in the light-emitting layer in the film layer, which can be a mass percentage.
  • the host material and doping material of the light-emitting layer can be co-evaporated through a multi-source evaporation process, so that the host material and the doping material are uniformly dispersed in the light-emitting layer, and the doping can be controlled during the evaporation process.
  • the doping ratio can be regulated by the evaporation rate of the material, or the doping ratio can be regulated by controlling the evaporation rate ratio of the host material and the doping material.
  • FIG. 5 shows the luminescence spectrum (PL spectrum) curve f of the exciplex formed by the electron blocking layer material (EBL-1) and the N-host material in some devices of the present disclosure, and the PL spectrum of the N-host material Curve c, PL spectrum curve b of P-host material, PL spectrum curve d of N-host:P-host blend material, electron blocking layer material (EBL-1') and N-host material in the device of the comparative example
  • Dopant dopant material
  • the abscissa ⁇ represents the wavelength
  • the ordinate represents the luminescence intensity of the PL spectrum and the absorbance (Abs) of the absorption spectrum.
  • the absorbance of the doping material of the light-emitting layer is measured by ultraviolet-visible spectrophotometry (UV-vis), and the absorption spectrum curve a of the doping material of the light-emitting layer is obtained.
  • UV-vis ultraviolet-visible spectrophotometry
  • the electron blocking layer material EBL-1 in the device of the example of the present disclosure is The N-host material is P-host material is The electron blocking layer material EBL-1' in the device of the comparative example is The doping material of the light-emitting layer is Ir(ppy) 3 .
  • the electron blocking layer material (EBL-1) in the device of the example of the present disclosure is formed with the N-host material in the light emitting layer
  • the emission spectrum curve f of the exciplex is far from the absorption spectrum curve a of the dopant material in the light-emitting layer, and the peak wavelength of the emission spectrum curve f of the formed excimer complex is the absorption band of the absorption spectrum curve a of the dopant material
  • the difference between the edge wavelengths is ⁇ , and ⁇ >30nm.
  • the electron blocking layer material adopts the compound of the above-mentioned formula (1)
  • the N-host material adopts the compound of the above-mentioned formula (2)
  • the electron blocking layer material and the N-host material meet the above-mentioned requirements.
  • the emission spectrum of the exciplex formed by the electron blocking layer material and the N-host material is far away from the absorption spectrum of the doping material of the light-emitting layer, and does not participate in the light-emitting process, so that the cracking of the electron blocking layer material is delayed. Effectively improve the life of the device.
  • the material of the hole transport layer may be selected from aromatic amine or carbazole materials with hole transport properties.
  • aromatic amine or carbazole materials with hole transport properties.
  • NPB 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl
  • TPD N,N'-bis(3-methylphenyl)-N,N'- Diphenyl-[1,1'-biphenyl]-4,4'-diamine
  • TPD N,N'-bis(3-methylphenyl)-N,N'- Diphenyl-[1,1'-biphenyl]-4,4'-diamine
  • BAFLP 4-phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine
  • BAFLP 4,4'-bis[N-(9,9-dimethylfluoren-2-yl)-N-phenylamino]biphenyl
  • DFLDPBi 4,
  • the material of the hole transport layer may include:
  • the electroluminescent device includes an anode 301 , a hole injection layer 304 , a hole transport layer 305 , an electron blocking layer 306 , a light emitting layer 302 , an empty A hole blocking layer 307 , an electron transport layer 308 , an electron injection layer 309 and a cathode 303 .
  • the hole injection layer 304 can reduce the hole injection barrier and improve the hole injection efficiency.
  • the hole transport layer 305 can improve the hole transport rate, lower the hole injection barrier, and improve the hole injection efficiency.
  • the electron blocking layer 306 can block electrons and excitons in the light-emitting layer from migrating to the side where the anode is located, so as to improve the light-emitting efficiency.
  • the hole blocking layer 307 can block holes and excitons in the light-emitting layer from migrating to the side where the cathode is located, thereby improving the light-emitting efficiency.
  • the electron transport layer 308 can increase the electron transport rate.
  • the electron injection layer 309 can reduce the electron injection barrier and improve the electron injection efficiency.
  • anode 301 may employ a material with a high work function.
  • the anode 301 can be made of a transparent oxide material, such as indium tin oxide (ITO) or indium zinc oxide (IZO), and the thickness of the anode can be about 80 nm to 200 nm.
  • the anode 301 can adopt a composite structure of metal and transparent oxide, such as Ag/ITO, Ag/IZO or ITO/Ag/ITO, etc.
  • the thickness of the metal layer in the anode can be about 80nm to 100nm, and the anode 301
  • the thickness of the medium transparent oxide may be about 5 nm to 20 nm.
  • the cathode 303 may be made of a metal material and formed by an evaporation process, and the metal material may be magnesium (Mg), silver (Ag) or aluminum (Al), or an alloy material such as Mg:Ag alloy.
  • the thickness of the cathode may be about 150 nm.
  • the material of the hole injection layer may be 4,4',4"-tris[2-naphthylphenylamino]triphenylamine (2-TNATA), and the structural formula of 2-TNATA is :
  • the material of the hole injection layer can be a mixed material of hole transport material (host material) and p-type dopant material, for example, MoO 3 (molybdenum trioxide) doped in TAPC (4,4'-cyclohexyldicarbonate) [N,N-bis(4-methylphenyl)aniline]), namely TAPC:MoO 3 .
  • the thickness of the hole injection layer may be about 60 nm.
  • the material of the electron transport layer may include any one or more of the following: lithium 8-quinolate (Liq), aluminum 8-quinolate (Alq 3 ).
  • Liq lithium 8-quinolate
  • Alq 3 aluminum 8-quinolate
  • the structural formulas of 8-hydroxyquinoline lithium (Liq) and 8-hydroxyquinoline aluminum (Alq 3 ) are respectively as follows:
  • the material of the electron injection layer may be lithium fluoride (LiF), ytterbium (Yb), magnesium (Mg), or calcium (Ca).
  • the thickness of the hole injection layer may be about 60 nm
  • the thickness of the hole transport layer may be about 60 nm
  • the thickness of the electron blocking layer may be about 30 nm
  • the thickness of the light emitting layer may be about 30 nm
  • the thickness of the empty layer may be about 30 nm.
  • the thickness of the hole blocking layer may be about 10 nm
  • the thickness of the electron transport layer may be about 40 nm
  • the thickness of the electron injection layer may be about 0.2 nm.
  • a display substrate including an OLED device may be fabricated using the following fabrication methods.
  • a driving circuit layer is formed on a substrate through a patterning process, and the driving circuit layer of each sub-pixel may include a driving transistor and a storage capacitor constituting a pixel driving circuit.
  • a flat layer is formed on the substrate on which the aforementioned structure is formed, and a via hole exposing the drain electrode of the driving transistor is formed on the flat layer of each sub-pixel.
  • an anode is formed through a patterning process, and the anode of each sub-pixel is connected to the drain electrode of the driving transistor through a via hole on the flat layer.
  • a pixel definition layer is formed through a patterning process, and a pixel opening exposing the anode is formed on the pixel definition layer of each sub-pixel, and each pixel opening serves as a light-emitting area of each sub-pixel.
  • the hole injection layer and the hole transport layer are sequentially evaporated using an open mask.
  • the hole injection layer and the hole transport layer are a common layer, that is, the holes of all sub-pixels
  • the injection layer is integrally connected, and the hole transport layers of all sub-pixels are integrally connected.
  • the hole injection layer and the hole transport layer have approximately the same area and different thicknesses.
  • the electron blocking layer and the red light-emitting layer, the electron blocking layer and the green light-emitting layer, and the electron blocking layer and the blue light-emitting layer were respectively evaporated on different sub-pixels using a fine metal mask.
  • the light emitting layers may overlap slightly or may be isolated.
  • the hole blocking layer, the electron transport layer, the electron injection layer and the cathode are sequentially evaporated using an open mask.
  • the hole blocking layer, the electron transport layer, the electron injection layer and the cathode are all common layers, that is, the The hole blocking layers are integrally connected, the electron transport layers of all sub-pixels are integrally connected, the electron injection layers of all sub-pixels are integrally connected, and the cathodes of all sub-pixels are integrally connected.
  • the multi-source co-evaporation method can be used to evaporate the light-emitting layer to form a light-emitting layer including a host material and a dopant material, which can be regulated by controlling the evaporation rate of the dopant material during the evaporation process
  • the doping ratio of the doping material, or the doping ratio of the doping material is regulated by controlling the evaporation rate ratio of the host material and the doping material.
  • the device of the embodiment of the present disclosure and the devices of the two comparative examples include an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and a cathode stacked in sequence.
  • the material of the film layer in the device structure in the device of the embodiment of the present disclosure, the material of the other film layers is the same except that the material of the electron blocking layer is different from that of the two comparative examples.
  • the materials of the electron blocking layers of the device of Example 1, the device of Example 2, the device of Example 3, and the device of Example 4 of the present disclosure are EBL-1, EBL-2, EBL-3, and EBL-4, respectively.
  • the materials of the electron blocking layers of the device of Example 1 and the device of Comparative Example 2 are EBL-1' and EBL-2', respectively.
  • Doping material of light-emitting layer tris(2-phenylpyridine) iridium (Ir(ppy) 3 );
  • HIL 2-TNATA
  • the energy level relationship between the electron blocking layer material (EBL-1) and the N-host material is calculated by taking the device of Example 1 of the present disclosure as an example.
  • the difference between the HOMO energy level of the EBL-1 material and the HOMO energy level of the N-host material is:
  • the efficiency and voltage of the devices of Example 1 to Example 4 of the present disclosure are comparable to those of Comparative Example 1 and Comparative Example 2, but the device life is significantly improved compared with Comparative Example 1 and Comparative Example 2, which shows that: due to the implementation of the present disclosure
  • the emission spectrum of the exciplex formed by the electron blocking layer material in the device of the example and the N-type material in the host material of the light-emitting layer is far away from the absorption spectrum of the doping material of the light-emitting layer, and does not participate in the light-emitting process, so that it does not affect the device.
  • the life of the device is effectively improved.
  • the device lifetime is measured by T95, which refers to the luminous time required for the brightness of the light emitted by the device to decay to 95% of the initial brightness.
  • Embodiments of the present disclosure also provide a display device including the aforementioned organic electroluminescence device.
  • the display device can be any product or component with a display function, such as a mobile phone, a tablet computer, a TV, a monitor, a notebook computer, a digital photo frame, a navigator, a car monitor, a smart watch, a smart bracelet, etc.

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Abstract

一种有机电致发光器件（310），包括阳极（301）、阴极（303），设于阳极（301）和阴极（303）之间的发光层（302），以及设于发光层（302）的朝向阳极（301）一侧的电子阻挡层（306）；发光层（302）包括主体材料和掺杂材料，主体材料包括N型材料和P型材料；电子阻挡层（306）的材料与N型材料满足： 2.75eV≤│LUMON-host-HOMOEBL│＜3.05eV； 0.3＜│HOMON-host-HOMOEBL│≤1eV，且│HOMOEBL│＜│HOMON-host│；电子阻挡层（306）的材料与N型材料形成的激基复合物的发光光谱曲线的峰值波长与掺杂材料的吸收光谱曲线的吸收带边波长的差值为△λ，△λ＞30nm。

Description

有机电致发光器件和显示装置 技术领域
本公开实施例涉及但不限于显示技术领域，尤其涉及一种有机电致发光器件和显示装置。
背景技术
目前，有机电致发光(OLED)器件基本由阳极、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层和阴极构成，其中，电子阻挡层和空穴阻挡层可以阻挡未被发光层利用的多余的电子、空穴，及激子。但是由于电子阻挡层对电子不稳定，在长期使用时会裂解，导致器件失效。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本公开实施例提供一种有机电致发光器件，包括阳极、阴极，设于所述阳极和所述阴极之间的发光层，以及设于所述发光层的朝向所述阳极一侧的电子阻挡层；所述发光层包括主体材料和掺杂材料，所述主体材料包括N型材料和P型材料；所述电子阻挡层的材料与所述N型材料满足：
2.75eV≤│LUMO N-host-HOMO EBL│＜3.05eV；
0.3＜│HOMO N-host-HOMO EBL│≤1eV，且│HOMO EBL│＜│HOMO N-host│；
其中，LUMO N-host为所述N型材料的最低未占分子轨道能级，HOMO EBL为所述电子阻挡层的材料的最高占据分子轨道能级，HOMO N-host为所述N型材料的最高占据分子轨道能级；
所述电子阻挡层的材料与所述N型材料形成的激基复合物的发光光谱曲线的峰值波长与所述掺杂材料的吸收光谱曲线的吸收带边波长的差值为△λ，△λ＞30nm。
可选地，所述的有机电致发光器件还包括设于所述阳极和所述电子阻挡层之间的空穴传输层，所述空穴传输层的材料与所述电子阻挡层的材料满足： 0eV≤│HOMO HTL-HOMO EBL│≤0.2eV；其中，HOMO HTL为所述空穴传输层的材料的最高占据分子轨道能级。
可选地，所述电子阻挡层的材料包括如下结构式的化合物：
Figure PCTCN2020139813-appb-000001
其中，L1为单键、苯环或联苯；
R1、R2、R3、R4独立地选自：氢、CHO、C(＝O)R5、P(＝O)R5、S(＝O)R5、氰基、硝基硅烷基、硼烷基、羟基、羧基、C1-C4的直链烷基、C3-C40的环烷基或支链烷基、C2-C40的烯基或炔基、环原子数为5-60的芳基或杂芳基；其中，C(＝O)R5、P(＝O)R5和S(＝O)R5中的R5独立地选自：C1-C4的直链烷基、C3-C40的环烷基或支链烷基、C2-C40的烯基或炔基、环原子数为5-60的芳基或杂芳基；
AR1为以下任一种：取代或未取代的二苯基芴、取代或未取代的螺二芴、取代或未取代的螺芴杂蒽。
可选地，所述AR1选自以下任一种结构：
Figure PCTCN2020139813-appb-000002
Figure PCTCN2020139813-appb-000003
其中，
Figure PCTCN2020139813-appb-000004
表示与L1连接位置，R表示螺环上的H或者烃基。
可选地，所述电子阻挡层的材料包括以下任一种或多种：
Figure PCTCN2020139813-appb-000005
可选地，所述N型材料包括如下结构式的化合物：
Figure PCTCN2020139813-appb-000006
其中，L2、L3、L4独立地为单键、苯环或联苯；
AR2选自以下结构：
Figure PCTCN2020139813-appb-000007
Figure PCTCN2020139813-appb-000008
其中，
Figure PCTCN2020139813-appb-000009
表示与L3连接位置；
AR3、AR4独立地选自：取代或未取代的C6-C30的芳基、取代或未取代的环原子数为5-30的杂芳基。
可选地，所述N型材料包括具有如下结构式的化合物：
Figure PCTCN2020139813-appb-000010
可选地，所述P型材料包括具有如下结构式的化合物：
Figure PCTCN2020139813-appb-000011
可选地，所述掺杂材料包括以下任一种或多种：香豆素染料、喹吖啶铜类衍生物、多环芳香烃、二胺蒽类衍生物、咔唑衍生物、金属配合物。
可选地，所述空穴传输层的材料包括具有如下结构式的化合物：
Figure PCTCN2020139813-appb-000012
可选地，所述的有机电致发光器件还包括设于所述空穴传输层和所述阳极之间的空穴注入层，所述空穴注入层的材料包括4,4',4”-三[2-萘基苯基氨基]三苯基胺。
可选地，所述的有机电致发光器件还包括设于所述发光层的朝向所述阴极一侧的空穴阻挡层，所述空穴阻挡层的材料包括具有如下结构式的化合物：
Figure PCTCN2020139813-appb-000013
可选地，所述的有机电致发光器件还包括设于所述空穴阻挡层和所述阴极之间的电子传输层，所述电子传输层的材料包括以下任一种或多种：8-羟基喹啉锂或者8-羟基喹啉铝。
本公开实施例还提供一种显示装置，包括所述的有机电致发光器件。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本公开技术方案的进一步理解，并且构成说明书的一部分，与本公开实施例一起用于解释本公开的技术方案，并不构成对本公开技术方案的限制。附图中各部件的形状和大小不反映真实比例，目的只是示意说明本公开内容。
图1为一种显示基板的显示区域的平面结构示意图；
图2为图1的显示基板的剖面结构示意图；
图3为本公开示例性实施例的一种有机电致发光器件的结构示意图；
图4为本公开示例性实施例的一种有机电致发光器件中一些膜层的材料能级关系示意图；
图5为本公开示例性实施例的一种有机电致发光器件中一些膜层材料的光谱图。
附图标记为：
101、基底，102、驱动电路层，103、发光结构层，104、封装结构层；
201、第一绝缘层，202、第二绝缘层，203、第三绝缘层，204、第四绝 缘层，205、平坦层，210、驱动晶体管，211、存储电容；
300、像素定义层；
301、阳极，302、发光层，303、阴极，304、空穴注入层，305、空穴传输层，306、电子阻挡层，307、空穴阻挡层，308、电子传输层，309、电子注入层；
310、发光器件；
401、第一封装层，402、第二封装层，403、第三封装层。
具体实施方式
本文中的实施方式可以以多个不同形式来实施。所属技术领域的普通技术人员可以很容易地理解一个事实，就是实现方式和内容可以在不脱离本公开的宗旨及其范围的条件下被变换为各种各样的形式。因此，本公开不应该被解释为仅限定在下面的实施方式所记载的内容中。在不冲突的情况下，本公开中的实施例及实施例中的特征可以相互任意组合。
在附图中，有时为了明确起见，可能夸大表示了构成要素的大小、层的厚度或区域。因此，本公开的任意一个实现方式并不一定限定于图中所示尺寸，附图中部件的形状和大小不反映真实比例。此外，附图示意性地示出了理想的例子，本公开的任意一个实现方式不局限于附图所示的形状或数值等。
图1为一种显示基板的显示区域的平面结构示意图。如图1所示，显示区域可以包括以矩阵方式排布的多个像素单元P，多个像素单元P中的至少一个包括出射第一颜色光线的第一子像素P1、出射第二颜色光线的第二子像素P2和出射第三颜色光线的第三子像素P3，第一子像素P1、第二子像素P2和第三子像素P3均包括发光器件和驱动发光器件发光的像素驱动电路。第一子像素P1、第二子像素P2和第三子像素P3可以配置为分别发红光、绿光和蓝光。像素单元P还可以包括出射其他颜色的子像素，比如出射白光的子像素。像素单元中子像素的形状可以是矩形状、菱形、五边形或六边形等。像素单元包括三个子像素时，三个子像素可以呈行、列或品字方式排列，像素单元包括四个子像素时，四个子像素可以呈行、列或正方形方式排列，本公开在此不做限定。
图2为一种显示基板的显示区域的剖面结构示意图，示意了OLED显示基板三个子像素的结构。如图2所示，在垂直于显示基板的平面上，显示基板了可以包括设置在基底101上的驱动电路层102、设置在驱动电路层102远离基底101一侧的发光结构层103，以及设置在发光结构层103的远离基底101一侧的封装结构层104。驱动电路层102包括像素驱动电路。发光结构层103包括多个OLED发光器件310，每个OLED发光器件310与对应的像素驱动电路连接。在一些可能的实现方式中，显示基板可以包括其它膜层，如隔垫柱等，本公开在此不做限定。
在一些示例性实施方式中，基底101可以是柔性基底，或者可以是刚性基底。柔性基底可以包括叠设的第一柔性材料层、第一无机材料层、半导体层、第二柔性材料层和第二无机材料层，第一柔性材料层和第二柔性材料层的材料可以采用聚酰亚胺(PI)、聚对苯二甲酸乙二酯(PET)或经表面处理的聚合物软膜等材料，第一无机材料层和第二无机材料层的材料可以采用氮化硅(SiNx)或氧化硅(SiOx)等，用于提高基底的抗水氧能力，半导体层的材料可以采用非晶硅(a-si)。
在一些示例性实施方式中，如图2所示，每个子像素的驱动电路层102可以包括构成像素驱动电路的多个晶体管和存储电容，图2中以每个子像素中包括一个驱动晶体管和一个存储电容为例进行示意。在一些可能的实现方式中，每个子像素的驱动电路层102可以包括：设置在基底101上的第一绝缘层201；设置在第一绝缘层201上的有源层；覆盖有源层的第二绝缘层202；设置在第二绝缘层202上的栅电极和第一电容电极；覆盖栅电极和第一电容电极的第三绝缘层203；设置在第三绝缘层203上的第二电容电极；覆盖第二电容电极的第四绝缘层204，第二绝缘层202、第三绝缘层203和第四绝缘层204上开设有过孔，过孔暴露出有源层；设置在第四绝缘层204上的源电极和漏电极，源电极和漏电极分别通过过孔与有源层连接；覆盖前述结构的平坦层205，平坦层205上开设有过孔，过孔暴露出漏电极。有源层、栅电极、源电极和漏电极组成驱动晶体管210，第一电容电极和第二电容电极组成存储电容211。
在一些示例性实施方式中，如图2所示，发光结构层103可以包括阳极 301、像素定义层300、阴极303，以及位于阳极301和阴极303之间的有机功能层，有机功能层至少包括发光层302。阳极301设置在平坦层205上，通过平坦层205上开设的过孔与驱动晶体管210的漏电极连接；像素定义层300设置在阳极301和平坦层205上，像素定义层300设置有像素开口，像素开口暴露出阳极301。在一些示例中，发光层302至少部分设置在像素开口内并与阳极301连接；阴极303设置在发光层302上并与发光层302连接。在另一些示例中，有机功能层还可以包括位于阳极301和发光层302之间，并在阳极301上依次叠设的空穴注入层、空穴传输层305和电子阻挡层306，以及位于发光层302和阴极303之间，并在发光层302上依次叠设的空穴阻挡层、电子传输层308和电子注入层。每个子像素的阳极301、有机功能层和阴极303形成OLED发光器件310，配置为在相应的像素驱动电路的驱动下出射相应颜色的光线。在一些示例中，每个子像素的发光层302位于其所在的子像素区域内，相邻子像素的发光层的边缘可以交叠或者隔离。所有子像素的有机功能层中除发光层以外的其他任一膜层可以是覆盖所有子像素的一体连通膜层，可以称之为共通层。
在一些示例性实施方式中，封装结构层104可以包括叠设的第一封装层401、第二封装层402和第三封装层403，第一封装层401和第三封装层403可采用无机材料，第二封装层402可采用有机材料，第二封装层402设置在第一封装层401和第三封装层403之间，可以保证外界水汽无法进入发光器件310。
本申请的发明人发现，一些OLED器件中，比如绿光OLED器件，发光层的主体材料采用激基复合物，包括N型材料和P型材料。电子阻挡层的材料一般为芳胺类材料，是强给电子材料，对电子和激子不稳定，电子阻挡层在与发光层接触的界面有可能与主体材料中的N型材料形成激基复合物，如果形成的激基复合物的发光光谱(PL光谱)与发光层中的掺杂材料(dopant)的吸收光谱重合很好，则电子阻挡层材料与发光层主体材料中的N型材料形成的界面激基复合物则会参与发光过程，从而加速电子阻挡层的裂解，导致器件性能下降，降低器件寿命。
本公开实施例提供一种有机电致发光器件，包括阳极、阴极，设于所述 阳极和所述阴极之间的发光层，以及设于所述发光层的朝向所述阳极一侧的电子阻挡层；所述发光层包括主体材料和掺杂材料，所述主体材料包括N型材料和P型材料。
本公开实施例中，发光层的主体材料中的N型材料可简称N-host材料，发光层的主体材料中的P型材料可简称P-host材料，电子阻挡层可简称EBL。
在一些示例性实施例中，所述电子阻挡层的材料与所述N型材料满足：
2.75eV≤│LUMO N-host-HOMO EBL│＜3.05eV；
0.3＜│HOMO N-host-HOMO EBL│≤1eV，且│HOMO EBL│＜│HOMO N-host│；
其中，LUMO N-host为所述N型材料的最低未占分子轨道能级，HOMO EBL为所述电子阻挡层的材料的最高占据分子轨道能级，HOMO N-host为所述N型材料的最高占据分子轨道能级；
所述电子阻挡层的材料与所述N型材料形成的激基复合物的发光光谱曲线的峰值波长与所述掺杂材料的吸收光谱曲线的吸收带边波长的差值为△λ，△λ＞30nm。
本公开实施例中，通过限定LUMO N-host与HOMO EBL的上述能级关系，以及限定△λ＞30nm，可以保证电子阻挡层材料与N-host材料形成的激基复合物的PL光谱(发光光谱)远离所述掺杂材料的吸收光谱，使电子阻挡层材料与N-host材料形成的激基复合物不参与发光，由此，减少电子阻挡层材料的裂解，提高器件的寿命。此外，通过搭配HOMO N-host与HOMO EBL的能级关系可以保证空穴更好地注入发光层，保证器件发光效率。
在一些示例性实施例中，所述的有机电致发光器件还包括设于所述阳极和所述电子阻挡层之间的空穴传输层(简称HTL)，所述空穴传输层的材料与所述电子阻挡层的材料满足：0eV≤│HOMO HTL-HOMO EBL│≤0.2eV；其中，HOMO HTL为所述空穴传输层的材料的最高占据分子轨道能级。
本示例中，通过搭配空穴传输层材料与电子阻挡层材料的HOMO能级关系，有利于空穴到电子阻挡层的传输，从而有利于提高器件发光效率。
本文中，最高占据分子轨道能级简称HOMO能级，最低未占分子轨道能级简称LUMO能级。不同材料的HOMO或LUMO能级的大小关系均是指 HOMO或LUMO能级的数值的绝对值的大小关系。
如图4所示，△E1为HTL材料与EBL材料的HOMO能级之差，0≤△E1≤0.2。△E2为N-host材料的LUMO能级与EBL材料的HOMO能级之差，2.75≤△E2＜3.05。△E3为EBL材料的HOMO能级与N-host材料的HOMO能级之差，且EBL材料的HOMO能级比N-host材料的HOMO能级小，其中0.3＜△E3≤1。
在一些示例性实施例中，所述电子阻挡层的材料，可以如式(1)所示：
Figure PCTCN2020139813-appb-000014
其中，式(1)中，L1为单键、苯环或联苯；
R1、R2、R3、R4独立地选自：氢、CHO、C(＝O)R5、P(＝O)R5、S(＝O)R5、氰基、硝基硅烷基、硼烷基、羟基、羧基、C1-C4的直链烷基、C3-C40的环烷基或支链烷基、C2-C40的烯基或炔基、环原子数为5-60的芳基或杂芳基，且可彼此成环；其中，C(＝O)R5、P(＝O)R5和S(＝O)R5中的R5独立地选自：C1-C4的直链烷基、C3-C40的环烷基或支链烷基、C2-C40的烯基或炔基、环原子数为5-60的芳基或杂芳基；
AR1为以下任一种：取代或未取代的二苯基芴、取代或未取代的螺二芴、取代或未取代的螺芴杂蒽；AR1中的任意的C原子可以被杂原子取代，所述杂原子可以为O、S、N、Si中的任一种或多种。
在一些示例中，AR1可以选自以下任一种结构：
Figure PCTCN2020139813-appb-000015
其中，
Figure PCTCN2020139813-appb-000016
表示与L1连接位置，R表示螺环上的H或者烃基(螺环上的H可被烷基、烃基取代)。
本实施例的一些示例中，电子阻挡层的材料可以包括以下任一种或多种：
Figure PCTCN2020139813-appb-000017
在一些示例性实施例中，所述发光层的主体材料中的N型材料，其结构可以如式(2)所示：
Figure PCTCN2020139813-appb-000018
其中，L2、L3、L4可独立地为单键、苯环或联苯；
AR2可以选自以下结构：
Figure PCTCN2020139813-appb-000019
其中，
Figure PCTCN2020139813-appb-000020
表示与L3连接位置。
AR3、AR4独立地选自：取代或未取代的C6-C30的芳基、取代或未取代的环原子数为5-30的杂芳基。
本实施例的一个示例中，所述发光层的主体材料中的N型材料可以为：
Figure PCTCN2020139813-appb-000021
在一些示例性实施例中，所述发光层的主体材料中的P型材料可以为：
Figure PCTCN2020139813-appb-000022
在一些示例性实施例中，本公开实施例的电致发光器件可以为绿光电致发光器件。
在一些示例性实施例中，所述发光层的掺杂材料可以选自以下任一种或多种：香豆素染料、喹吖啶铜类衍生物、多环芳香烃、二胺蒽类衍生物、咔唑衍生物、金属配合物等。比如可以为：香豆素6(C-6)、香豆素545T(C-525T)、喹吖啶铜(QA)、N,N'-二甲基喹吖啶酮(DMQA)、5,12-二苯基萘并萘(DPT)、N10,N10'-二苯基-N10,N10'-二苯二甲酰-9,9'-二蒽-10,10'-二胺(简称:BA-NPB)、三(8-羟基喹啉)合铝(III)(简称:Alq 3)、三(2-苯基吡啶)合铱(Ir(ppy) 3)、乙酰丙酮酸二(2-苯基吡啶)铱(Ir(ppy) 2(acac))。
其中，三(2-苯基吡啶)合铱(Ir(ppy) 3)的结构式为：
Figure PCTCN2020139813-appb-000023
在一些示例性实施例中，所述发光层中，所述掺杂材料的掺杂比例可以为1wt％-10wt％。掺杂比例是指发光层中掺杂材料在该膜层中的占比，可以为质量百分比。在发光层制备中，可以通过多源蒸镀工艺共同蒸镀发光层的主体材料和掺杂材料，使主体材料和掺杂材料均匀分散在发光层中，可以在蒸镀过程中通过控制掺杂材料的蒸镀速率来调控掺杂比例，或者通过控制主体材料和掺杂材料的蒸镀速率比来调控掺杂比例。
图5示出了一些本公开示例的器件中的电子阻挡层材料(EBL-1)与N-host材料形成的激基复合物的发光光谱(PL光谱)曲线f、N-host材料的PL光谱曲线c、P-host材料的PL光谱曲线b、N-host:P-host共混材料的PL光谱曲线d，对比例的器件中的电子阻挡层材料(EBL-1’)与N-host材料的共混材料的PL光谱曲线e，以及本公开示例的器件中的发光层的掺杂材料(Dopant)的吸收光谱曲线a。图5中，横坐标λ代表波长，纵坐标代表PL光谱的发光强度和吸收光谱的吸光度(Abs)。采用紫外-可见分光光度法(UV-vis)测量发光层的掺杂材料的吸光度，得到发光层的掺杂材料的吸收光谱曲线a。其中，图5所示光谱图中，本公开示例的器件中的电子阻挡层材料EBL-1为
Figure PCTCN2020139813-appb-000024
N-host材料为
Figure PCTCN2020139813-appb-000025
P-host材料为
Figure PCTCN2020139813-appb-000026
对比例的器件中的电子阻挡层材料EBL-1’为
Figure PCTCN2020139813-appb-000027
发光层的掺杂材料为Ir(ppy) 3。
从图5可以看出：相较于曲线b、曲线c、曲线d和曲线e来讲，本公开示例的器件中的电子阻挡层材料(EBL-1)与发光层中的N-host材料形成的激基复合物的发光光谱曲线f远离发光层中掺杂材料的吸收光谱曲线a，且形成的激基复合物的发光光谱曲线f的峰值波长与掺杂材料的吸收光谱曲线a的吸收带边波长的差值为△λ，△λ＞30nm。如此，在一些示例性实施例中，电子阻挡层材料采用上述式(1)结构的化合物，N-host材料采用上述式(2)结构的化合物，且电子阻挡层材料与N-host材料满足上述能级关系时，电子阻挡层材料与N-host材料形成的激基复合物的发光光谱远离发光层的掺杂材料的吸收光谱，不参与发光过程，使电子阻挡层材料裂解得到延缓，从而可有效提高器件的寿命。
在一些示例性实施例中，所述空穴传输层(简称HTL)的材料可以选自具有空穴传输特性的芳胺类或者咔唑材料。例如：4,4’-双[N-(1-萘基)-N-苯基氨基]联苯(NPB)、N,N’-双(3-甲基苯基)-N,N’-二苯基-[1,1’-联苯]-4,4’ -二胺(TPD)、4-苯基-4’-(9-苯基芴-9-基)三苯基胺(BAFLP)、4,4’-双[N-(9,9-二甲基芴-2-基)-N-苯基氨基]联苯(DFLDPBi)、4,4’-二(9-咔唑基)联苯(CBP)、9-苯基-3-[4-(10-苯基-9-蒽基)苯基]-9H-咔唑(PCzPA)等。
在一些示例中，所述空穴传输层(简称HTL)的材料可以包括：
Figure PCTCN2020139813-appb-000028
在一些示例性实施例中，如图3所示，所述电致发光器件包括依次叠设的阳极301、空穴注入层304、空穴传输层305、电子阻挡层306、发光层302、空穴阻挡层307、电子传输层308、电子注入层309和阴极303。其中，空穴注入层304可以降低空穴注入势垒，提高空穴注入效率。空穴传输层305可以提高空穴传输速率，还可以降低空穴注入势垒，提高空穴注入效率。电子阻挡层306可以阻挡发光层中的电子、激子向阳极所在侧迁移，提高发光效率。空穴阻挡层307可以阻挡发光层中的空穴、激子向阴极所在侧迁移，提高发光效率。电子传输层308可以提高电子传输速率。电子注入层309可以降低电子注入势垒，提高电子注入效率。
在一些示例性实施例中，阳极301可以采用具有高功函数的材料。对于底发射型OLED，阳极301可以采用透明氧化物材料，如氧化铟锡(ITO)或氧化铟锌(IZO)等，阳极的厚度可以约为80nm至200nm。对于顶发射型OLED，阳极301可以采用金属和透明氧化物的复合结构，如Ag/ITO、Ag/IZO或者ITO/Ag/ITO等，阳极中金属层的厚度可以约为80nm至100nm，阳极301中透明氧化物的厚度可以约为5nm至20nm。
在一些示例性实施方式中，阴极303可以采用金属材料，通过蒸镀工艺形成，金属材料可以采用镁(Mg)、银(Ag)或铝(Al)，或者采用合金材料，如Mg:Ag的合金。阴极的厚度可以约为150nm。
在一些示例性实施方式中，空穴注入层的材料可以采用4,4',4”-三[2-萘基苯基氨基]三苯基胺(2-TNATA)，2-TNATA的结构式为：
Figure PCTCN2020139813-appb-000029
或者，空穴注入层的材料可以采用空穴传输材料(主体材料)和p型掺杂材料的混合材料，比如，MoO 3(三氧化钼)掺杂在TAPC(4,4'-环己基二[N,N-二(4-甲基苯基)苯胺])里形成的材料，即TAPC:MoO 3。空穴注入层的厚度可以约为60nm。
在一些示例性实施方式中，电子传输层的材料可以包括以下任一种或多种：8-羟基喹啉锂(Liq)、8-羟基喹啉铝(Alq 3)。其中，8-羟基喹啉锂(Liq)、8-羟基喹啉铝(Alq 3)的结构式分别如下：
Figure PCTCN2020139813-appb-000030
在一些示例性实施方式中，电子注入层的材料可以采用氟化锂(LiF)、镱(Yb)、镁(Mg)或钙(Ca)等材料。
在一些示例性实施方式中，空穴注入层的厚度可以约为60nm，空穴传输层的厚度可以约为60nm，电子阻挡层的厚度可以约为30nm，发光层的厚度可以约为30nm，空穴阻挡层的厚度可以约为10nm，电子传输层的厚度可以约为40nm，电子注入层的厚度可以约为0.2nm。
在一些示例性实施方式中，可以采用如下制备方法制备包括OLED器件的显示基板。首先，通过图案化工艺在基底上形成驱动电路层，每个子像素的驱动电路层可以包括构成像素驱动电路的驱动晶体管和存储电容。随后，在形成前述结构的基底上形成平坦层，每个子像素的平坦层上形成有暴露出驱动晶体管的漏电极的过孔。随后，在形成前述结构的基底上，通过图案化工艺形成阳极，每个子像素的阳极通过平坦层上的过孔与驱动晶体管的漏电极连接。随后，在形成前述结构的基底上，通过图案化工艺形成像素定义层，每个子像素的像素定义层上形成有暴露出阳极的像素开口，每个像素开口作为每个子像素的发光区域。随后，在形成前述结构的基底上，先采用开放式掩膜版依次蒸镀空穴注入层和空穴传输层，空穴注入层和空穴传输层为共通层，即所有子像素的空穴注入层是一体连通的，所有子像素的空穴传输层是一体连通的。空穴注入层和空穴传输层的面积大致是相同的，厚度不同。随后，采用精细金属掩模版在不同的子像素分别蒸镀电子阻挡层和红色发光层、电子阻挡层和绿色发光层、以及电子阻挡层和蓝色发光层，相邻子像素的电子阻挡层和发光层是可以有少量的交叠或者可以是隔离的。随后，采用开放式掩膜版依次蒸镀空穴阻挡层、电子传输层、电子注入层和阴极，空穴阻挡层、电子传输层、电子注入层和阴极均为共通层，即所有子像素的空穴阻挡层是一体连通的，所有子像素的电子传输层是一体连通的，所有子像素电子注入层的是一体连通的，所有子像素的阴极是一体连通的。
在一些示例性实施方式中，蒸镀发光层可以采用多源共蒸镀方式，形成包含主体材料和掺杂材料的发光层，可以在蒸镀过程中通过控制掺杂材料的蒸镀速率来调控掺杂材料的掺杂比例，或者通过控制主体材料和掺杂材料的蒸镀速率比来调控掺杂材料的掺杂比例。
下面将本公开实施例的器件与两个对比例的器件的性能进行比较。其中，本公开实施例的器件和两个对比例的器件均包括依次叠设的阳极、空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层和阴极。关于器件结构中膜层的材料，本公开实施例的器件中除电子阻挡层的材料与两个对比例不同外，其余膜层的材料均相同。本公开实施例1的器件、实施例2的器件、实施例3的器件、实施例4的器件的电子阻挡层的材料分别为 EBL-1、EBL-2、EBL-3、EBL-4，对比例1的器件、对比例2的器件的电子阻挡层的材料分别为EBL-1’、EBL-2’。
本公开实施例的器件与两个对比例的器件的相关膜层的材料如下：
EBL-1’：
Figure PCTCN2020139813-appb-000031
EBL-2’：
Figure PCTCN2020139813-appb-000032
EBL-1：
Figure PCTCN2020139813-appb-000033
EBL-2：
Figure PCTCN2020139813-appb-000034
EBL-3：
Figure PCTCN2020139813-appb-000035
EBL-4：
Figure PCTCN2020139813-appb-000036
P-host：
Figure PCTCN2020139813-appb-000037
N-host：
Figure PCTCN2020139813-appb-000038
发光层的掺杂材料：三(2-苯基吡啶)合铱(Ir(ppy) 3)；
HIL:2-TNATA；
HTL：
Figure PCTCN2020139813-appb-000039
HBL：
Figure PCTCN2020139813-appb-000040
ETL：8-羟基喹啉铝(Alq 3)；
EIL：LiF。
本公开实施例的器件与两个对比例的器件的电子阻挡层、P-host、N-host的材料能级如下表1所示：
表1 材料能级参数
  HOMO/eV LUMO/eV
EBL-1’ -5.44 -2.31
EBL-2’ -5.57 -2.45
EBL-1 -5.38 -2.41
EBL-2 -5.30 -2.32
EBL-3 -5.19 -2.09
EBL-4 -5.25 -2.19
P-host -5.47 -2.19
N-host -5.83 -2.39
表1中，以本公开实施例1的器件为例计算其电子阻挡层材料(EBL-1)与N-host材料的能级大小关系。N-host材料的LUMO能级与EBL-1材料的HOMO能级之差为：△E2＝│-2.39-(-5.38)│＝2.99，满足：2.75≤△E2＜3.05。EBL-1材料的HOMO能级与N-host材料的HOMO能级之差为：
△E3＝│-5.38-(-5.83)│＝0.45，满足：0.3＜△E3≤1，且EBL-1材料的HOMO能级比N-host材料的HOMO能级浅。同样地，本公开实施例2、实施例3和实施例4的器件的电子阻挡层材料与N-host材料满足上述能级关系。
本公开实施例的器件与两个对比例的器件的性能对比结果如表2所示：
表2 器件性能对比结果
  电压 效率 寿命(T95)
对比例1 100％ 100％ 100％
对比例2 113％ 102％ 105％
实施例1 103％ 98.5％ 153％
实施例2 101％ 99.3％ 138％
实施例3 103％ 97.8％ 169％
实施例4 105％ 96.5％ 192％
表2中，对比例2、实施例1-实施例4的器件性能数据均是以对比例1的器件性能数据作为参考进行对比说明。从表2可以看出，对比例2的器件的效率与寿命相较于对比例1增加不明显，但是电压较大。而本公开实施例1-实施例4的器件的效率和电压与对比例1和对比例2相当，但是器件寿命明显比对比例1和对比例2有较大提高，这说明：由于本公开实施例的器件中的电子阻挡层材料与发光层的主体材料中的N型材料形成的激基复合物的发光光谱远离发光层的掺杂材料的吸收光谱，不参与发光过程，从而在不影响器件电压和效率的基础上，有效提高了器件的寿命。表2中，器件寿命用T95来衡量，T95是指器件发出的光的亮度衰减至初始亮度的95％所需的发光时长。
本公开实施例还提供一种显示装置，包括前述的有机电致发光器件。显示装置可以为手机、平板电脑、电视机、显示器、笔记本电脑、数码相框、导航仪、车载显示器、智能手表、智能手环等任何具有显示功能的产品或部件。
虽然本公开所揭露的实施方式如上，但所述的内容仅为便于理解本公开 而采用的实施方式，并非用以限定本公开。任何所属领域内的技术人员，在不脱离本公开所揭露的精神和范围的前提下，可以在实施的形式及细节上进行任何的修改与变化，但本申请的专利保护范围，仍须以所附的权利要求书所界定的范围为准。

Claims (14)

  1. 一种有机电致发光器件，包括阳极、阴极，设于所述阳极和所述阴极之间的发光层，以及设于所述发光层的朝向所述阳极一侧的电子阻挡层；所述发光层包括主体材料和掺杂材料，所述主体材料包括N型材料和P型材料；
    所述电子阻挡层的材料与所述N型材料满足：
    2.75eV≤│LUMO N-host-HOMO EBL│＜3.05eV；
    0.3＜│HOMO N-host-HOMO EBL│≤1eV，且│HOMO EBL│＜│HOMO N-host│；
    其中，LUMO N-host为所述N型材料的最低未占分子轨道能级，HOMO EBL为所述电子阻挡层的材料的最高占据分子轨道能级，HOMO N-host为所述N型材料的最高占据分子轨道能级；
    所述电子阻挡层的材料与所述N型材料形成的激基复合物的发光光谱曲线的峰值波长与所述掺杂材料的吸收光谱曲线的吸收带边波长的差值为△λ，△λ＞30nm。
  2. 如权利要求1所述的有机电致发光器件，还包括设于所述阳极和所述电子阻挡层之间的空穴传输层，所述空穴传输层的材料与所述电子阻挡层的材料满足：0eV≤│HOMO HTL-HOMO EBL│≤0.2eV；其中，HOMO HTL为所述空穴传输层的材料的最高占据分子轨道能级。
  3. 如权利要求1所述的有机电致发光器件，其中，所述电子阻挡层的材料包括如下结构式的化合物：
    Figure PCTCN2020139813-appb-100001
    其中，L1为单键、苯环或联苯；
    R1、R2、R3、R4独立地选自：氢、CHO、C(＝O)R5、P(＝O)R5、S(＝O)R5、氰基、硝基硅烷基、硼烷基、羟基、羧基、C1-C4的直链烷基、C3-C40的环 烷基或支链烷基、C2-C40的烯基或炔基、环原子数为5-60的芳基或杂芳基；其中，C(＝O)R5、P(＝O)R5和S(＝O)R5中的R5独立地选自：C1-C4的直链烷基、C3-C40的环烷基或支链烷基、C2-C40的烯基或炔基、环原子数为5-60的芳基或杂芳基；
    AR1为以下任一种：取代或未取代的二苯基芴、取代或未取代的螺二芴、取代或未取代的螺芴杂蒽。
  4. 如权利要求3所述的有机电致发光器件，其中，所述AR1选自以下任一种结构：
    Figure PCTCN2020139813-appb-100002
    其中，
    Figure PCTCN2020139813-appb-100003
    表示与L1连接位置，R表示螺环上的氢或者烃基。
  5. 如权利要求3所述的有机电致发光器件，其中，所述电子阻挡层的材料包括以下任一种或多种：
    Figure PCTCN2020139813-appb-100004
    Figure PCTCN2020139813-appb-100005
  6. 如权利要求1所述的有机电致发光器件，其中，所述N型材料包括如下结构式的化合物：
    Figure PCTCN2020139813-appb-100006
    其中，L2、L3、L4独立地为单键、苯环或联苯；
    AR2选自以下结构：
    Figure PCTCN2020139813-appb-100007
    Figure PCTCN2020139813-appb-100008
    其中，
    Figure PCTCN2020139813-appb-100009
    表示与L3连接位置；
    AR3、AR4独立地选自：取代或未取代的C6-C30的芳基、取代或未取代的环原子数为5-30的杂芳基。
  7. 如权利要求6所述的有机电致发光器件，其中，所述N型材料包括具有如下结构式的化合物：
    Figure PCTCN2020139813-appb-100010
  8. 如权利要求1所述的有机电致发光器件，其中，所述P型材料包括具有如下结构式的化合物：
    Figure PCTCN2020139813-appb-100011
  9. 如权利要求1所述的有机电致发光器件，其中，所述掺杂材料包括以下任一种或多种：香豆素染料、喹吖啶铜类衍生物、多环芳香烃、二胺蒽类衍生物、咔唑衍生物、金属配合物。
  10. 如权利要求2所述的有机电致发光器件，其中，所述空穴传输层的材料包括具有如下结构式的化合物：
    Figure PCTCN2020139813-appb-100012
  11. 如权利要求2所述的有机电致发光器件，还包括设于所述空穴传输层和所述阳极之间的空穴注入层，所述空穴注入层的材料包括4,4',4”-三[2-萘基苯基氨基]三苯基胺。
  12. 如权利要求1所述的有机电致发光器件，还包括设于所述发光层的朝向所述阴极一侧的空穴阻挡层，所述空穴阻挡层的材料包括具有如下结构式的化合物：
    Figure PCTCN2020139813-appb-100013
  13. 如权利要求12所述的有机电致发光器件，还包括设于所述空穴阻挡层和所述阴极之间的电子传输层，所述电子传输层的材料包括以下任一种或多种：8-羟基喹啉锂或者8-羟基喹啉铝。
  14. 一种显示装置，包括权利要求1-13任一项所述的有机电致发光器件。
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