WO2022061938A1 - 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 PDFInfo
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- WO2022061938A1 WO2022061938A1 PCT/CN2020/118587 CN2020118587W WO2022061938A1 WO 2022061938 A1 WO2022061938 A1 WO 2022061938A1 CN 2020118587 W CN2020118587 W CN 2020118587W WO 2022061938 A1 WO2022061938 A1 WO 2022061938A1
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- layer
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- unsubstituted
- hole injection
- light
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
- C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—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
Definitions
- the present disclosure relates to, but is not limited to, the field of display technology, and in particular, to an organic electroluminescence device and a display device.
- OLED Organic Light Emitting Device
- OLED is an active light-emitting device, which has the advantages of light emission, ultra-thin, wide viewing angle, high brightness, high contrast, low power consumption, and extremely high response speed. Promising next-generation display technology.
- OLED includes an anode, a cathode, and a light-emitting layer arranged between the anode and the cathode.
- the light-emitting principle is to inject holes and electrons into the light-emitting layer from the anode and the cathode, respectively.
- the electrons and holes meet in the light-emitting layer, the electrons and The holes recombine to generate excitons, which emit light while transitioning from an excited state to a ground state.
- a hole injection layer and a hole transport layer are arranged between the anode and the light-emitting layer, and an electron injection layer is arranged between the cathode and the light-emitting layer. layer and electron transport layer.
- the design of the hole injection layer is more important.
- An organic electroluminescence device comprising an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode, a doping structure layer is disposed between the anode and the light-emitting layer, and the doping structure layer includes a host material and a guest material doped in the host material, the host material and guest material satisfying:
- LUMO(A) is the lowest unoccupied molecular orbital of the host material
- HOMO(B) is the highest occupied molecular orbital of the guest material
- the guest material also satisfies:
- the host material also satisfies:
- HOMO(A) is the highest occupied molecular orbital HOMO energy level of the host material.
- the doping ratio of the guest material in the doping structure layer is 0.1% to 40%.
- one of the host material and the guest material includes a ketone-based compound, and the other includes an aromatic amine-based compound.
- the guest material includes, but is not limited to, a compound having the structure of formula (I):
- Ar 1 to Ar 4 are each independently a substituted or unsubstituted aryl group having 5 to 50 ring atoms, and L is a substituted or unsubstituted arylene group having 5 to 50 ring atoms
- the connecting group formed, or the connecting group obtained by connecting a plurality of substituted or unsubstituted arylene groups with 5 to 50 ring atoms and M1, M1 is any one of the following: single bond, oxygen atom, Sulfur atom, nitrogen atom, saturated or unsaturated divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.
- At least one of Ar 1 to Ar 4 is selected from any one of the following structures:
- R1 to R25 are each independently any one of the following: a hydrogen atom, an aryl group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkyl group having Alkoxy of 1 to 50 carbon atoms, substituted or unsubstituted aralkyl of 6 to 50 ring atoms, substituted or unsubstituted aryloxy of 5 to 50 ring atoms, substituted or unsubstituted Arylthio group with 5 to 50 ring atoms, substituted or unsubstituted alkoxycarbonyl group with 1 to 50 carbon atoms, aryl group with 5 to 50 ring atoms substituted by M2, where M2 is amino, halogen atom , cyano, nitro, hydroxyl or carboxyl.
- the host material includes, but is not limited to, a compound having the structure of formula (II):
- Z is a substituted or unsubstituted benzene ring, pyridine ring, thiophene ring, quinoline, indole or thienothiophene ring;
- Ar 5 is Ar 6 is Ar
- Y1 to Y4 are each independently N or C - R35;
- R31 to R35 are each independently selected from any one of the following: hydrogen, deuterium, halogen group, nitrile group, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted haloalkoxy, substituted or unsubstituted aryl, substituted or unsubstituted haloaryl, substituted or unsubstituted silyl, substituted or unsubstituted heterocycles;
- X1 and X2 are each independently selected from any one of the following structures:
- R41 to R43 are each independently any one of hydrogen, a fluoroalkyl group, an alkyl group, an aryl group and a heterocyclic group, and R42 and R43 form a ring.
- the doped structure layer includes a hole injection layer.
- the doping ratio of the guest material to the hole injection layer is 0.5% to 30%.
- the hole injection layer has a thickness of 1 nm to 10 nm.
- At least one organic layer is further disposed between the hole injection layer and the light emitting layer, and the carrier mobility in the at least one organic layer is 10 ⁇ 3 cm 2 /Vs to 10 ⁇ 5 cm 2 /Vs, and/or, the electrical conductivity of the at least one organic layer is less than or equal to the electrical conductivity of the hole injection layer.
- the material of the at least one organic layer is the same as the guest material.
- the at least one organic layer is a hole transport layer, and the material of the hole transport layer satisfies:
- HOMO(D) is the highest occupied molecular orbital HOMO level of the hole transport layer.
- two organic layers are further disposed between the hole injection layer and the light emitting layer, and the carrier mobility in the two organic layers is both 10 -3 cm 2 /Vs to 10 -5 cm 2 /Vs, and/or, the electrical conductivity of the two organic layers is both less than or equal to the electrical conductivity of the hole injection layer.
- a display device includes the aforementioned organic electroluminescence device.
- the display device includes a substrate and a plurality of sub-pixels formed on the substrate, the sub-pixels including the organic electroluminescent device; an orthographic projection of the hole injection layer on the substrate Both overlap with the orthographic projections of the light-emitting regions of at least two sub-pixels on the substrate.
- the area of the hole injection layer is larger than that of the light emitting layer.
- the sub-pixel further includes a pixel driving circuit, and the orthographic projection of the light emitting layer of at least part of the sub-pixel on the substrate overlaps the orthographic projection of the driving transistor of the pixel driving circuit on the substrate.
- FIG. 1 is a schematic structural diagram of an OLED display device
- FIG. 2 is a schematic plan view of a display area of a display substrate
- FIG. 3 is a schematic cross-sectional structure diagram of a display substrate
- FIG. 5 is a schematic diagram of an OLED structure according to an exemplary embodiment of the present disclosure.
- Fig. 6 is the SEM image of the hole injection layer evaporation film layer of the non-doped structure
- FIG. 7 is a SEM image of the vapor-deposited film layer of the hole injection layer according to an exemplary embodiment of the present disclosure.
- 10 anode
- 20 hole injection layer
- 30 hole transport layer
- 70 electron transport layer
- 80 electron injection layer
- 90 cathode
- 101 substrate
- 102 drive circuit layer
- 103 light emitting device
- 104 encapsulation layer
- 201 first insulating layer
- 202 second insulating layer
- 210 drive transistor
- 211 storage capacitor
- 301 anode
- 302 pixel definition layer
- 303 organic light-emitting layer
- 304 cathode
- 401 the first encapsulation layer
- 402 the second encapsulation layer
- 403 the third encapsulation layer.
- the terms “installed”, “connected” and “connected” should be construed broadly unless otherwise expressly specified and limited. For example, it may be a fixed connection, or a detachable connection, or an integral connection; it may be a mechanical connection, or an electrical connection; it may be a direct connection, or an indirect connection through an intermediate piece, or an internal communication between two elements.
- installed may be a fixed connection, or a detachable connection, or an integral connection; it may be a mechanical connection, or an electrical connection; it may be a direct connection, or an indirect connection through an intermediate piece, or an internal communication between two elements.
- a transistor refers to an element including at least three terminals of a gate electrode, a drain electrode, and a source electrode.
- the transistor has a channel region between the drain electrode (or drain electrode terminal, drain region or drain electrode) and the source electrode (or source electrode terminal, source region or source electrode), and current can flow through the drain electrode, channel region and source electrode.
- the channel region refers to a region through which current mainly flows.
- the first electrode may be the drain electrode and the second electrode may be the source electrode, or the first electrode may be the source electrode and the second electrode may be the drain electrode.
- the functions of the "source electrode” and the “drain electrode” may be interchanged. Therefore, herein, “source electrode” and “drain electrode” may be interchanged with each other.
- electrically connected includes the case where constituent elements are connected together by means of elements having some electrical function.
- the "element having a certain electrical effect” is not particularly limited as long as it can transmit and receive electrical signals between the connected constituent elements.
- the “element having a certain electrical effect” may be, for example, electrodes or wirings, or switching elements such as transistors, or other functional elements such as resistors, inductors, and capacitors.
- parallel refers to a state where the angle formed by two straight lines is -10° or more and 10° or less, and therefore, also includes a state where the angle is -5° or more and 5° or less.
- perpendicular refers to the state where the angle formed by two straight lines is 80° or more and 100° or less, and therefore includes the state where the angle is 85° or more and 95° or less.
- film and “layer” are interchangeable.
- conductive layer may be replaced by “conductive film” in some cases.
- insulating film may be replaced with “insulating layer” in some cases.
- FIG. 1 is a schematic structural diagram of an OLED display device.
- the OLED display device may include a scan signal driver, a data signal driver, a lighting signal driver, an OLED display substrate, a first power supply unit, a second power supply unit and an initial power supply unit.
- the OLED display substrate includes at least a plurality of scan signal lines (S1 to SN), a plurality of data signal lines (D1 to DM), and a plurality of light emission signal lines (EM1 to EMN), and the scan signal driver is configured
- the data signal driver is configured to supply the data signals to the plurality of data signal lines (D1 to DM)
- the light emission signal driver is configured to sequentially supply the plurality of light emission signals Lines (EM1 to EMN) provide lighting control signals.
- the plurality of scan signal lines and the plurality of light emitting signal lines extend in the horizontal direction
- the plurality of data signal lines extend in the vertical direction.
- the display device includes a plurality of sub-pixels, and one sub-pixel is connected to, for example, a scanning signal line, a light-emitting control line and a data signal line.
- the first power supply unit, the second power supply unit and the initial power supply unit are respectively configured to supply the first power supply voltage, the second power supply voltage and the initial power supply voltage to the pixel circuit through the first power supply line, the second power supply line and the initial signal line.
- FIG. 2 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 pixel driving circuit and a light-emitting device.
- the pixel driving circuits in the first sub-pixel P1, the second sub-pixel P2 and the third sub-pixel P3 are respectively connected to the scanning signal line, the data signal line and the light-emitting signal line, and the pixel driving circuit is configured to connect the scanning signal line and the light-emitting signal line. Under the control of the line, the data voltage transmitted by the data signal line is received, and the corresponding current is output to the light-emitting device.
- the light-emitting devices in the first sub-pixel P1, the second sub-pixel P2, and the third sub-pixel P3 are respectively connected to the pixel driving circuit of the sub-pixel, and the light-emitting device is configured to respond to the current output by the pixel driving circuit of the sub-pixel. Brightness of light.
- the pixel unit P may include red (R) sub-pixels, green (G) sub-pixels, and blue (B) sub-pixels, or may include red sub-pixels, green sub-pixels, and blue sub-pixels and white (W) sub-pixels, which are not limited in this disclosure.
- the shape of the sub-pixels in the pixel unit may be rectangular, diamond, pentagon or hexagonal.
- the pixel unit includes three sub-pixels, the three sub-pixels can be arranged horizontally, vertically, or in a zigzag manner.
- the pixel unit includes four sub-pixels, the four sub-pixels can be arranged in a horizontal, vertical, or square manner. The arrangement is not limited in this disclosure.
- FIG. 3 is a schematic cross-sectional structure diagram of a display substrate, illustrating the structure of three sub-pixels of the OLED display substrate.
- the display substrate may include a driving circuit layer 102 disposed on a substrate 101 , a light emitting device 103 disposed on a side of the driving circuit layer 102 away from the substrate 101 , and a light emitting device 103 disposed on the substrate 101 .
- 103 is the encapsulation layer 104 on the side away from the substrate 101 .
- the display substrate may include other film layers, such as spacer columns, etc., which are not limited in the present disclosure.
- the substrate may be a flexible substrate, or it 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).
- the driving circuit layer 102 of each sub-pixel may include a plurality of transistors and storage capacitors constituting the pixel driving circuit.
- FIG. 3 is illustrated by taking each sub-pixel including one driving transistor and one storage capacitor as an example.
- the driving circuit layer 102 of each sub-pixel may include: a first insulating layer 201 disposed on the substrate; an active layer disposed on the first insulating layer; a second insulating layer covering the active layer layer 202; the gate electrode and the first capacitor electrode disposed on the second insulating layer 202; the third insulating layer 203 covering the gate electrode and the first capacitor electrode; the second capacitor electrode disposed on the third insulating layer 203; covering
- the fourth insulating layer 204 of 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; they are arranged on the fourth insulating layer 204
- the source electrode and the drain electrode are
- the light emitting device 103 may include an anode 301 , a pixel definition layer 302 , an organic light emitting layer 303 and a cathode 304 .
- 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 302 is arranged on the anode 301 and the flat layer 205, and a pixel opening is arranged on the pixel definition layer 302 , the pixel opening exposes the anode 301;
- the organic light-emitting layer 303 is at least partially disposed in the pixel opening, and the organic light-emitting layer 303 is connected to the anode 301;
- the cathode 304 is disposed on the organic light-emitting layer 303, and the cathode 304 is connected to the organic light-emitting layer 303;
- the layer 303 is driven by the anode 301 and
- the encapsulation layer 104 may include a stacked first encapsulation layer 401, a second encapsulation layer 402 and a third encapsulation layer 403.
- the first encapsulation layer 401 and the third encapsulation layer 403 may be made of 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 103 .
- the organic light emitting layer 303 may include at least the hole injection layer 20 , the hole transport layer 30 , the light emitting layer 50 and the hole blocking layer 60 stacked on the anode 301 .
- the hole injection layers 20 of all subpixels are a common layer connected together
- the hole transport layers 30 of all subpixels are a common layer connected together
- the light emitting layers 50 of adjacent subpixels may be There is a small amount of overlap, or may be isolated
- the hole blocking layer 60 is a common layer connected together.
- the pixel driving circuit may be a 3T1C, 4T1C, 5T1C, 5T2C, 6T1C or 7T1C structure.
- FIG. 4 is an equivalent circuit diagram of a pixel driving circuit.
- the pixel driving circuit may include 7 switching transistors (the first transistor T1 to the seventh transistor T7 ), 1 storage capacitor C and 8 signal lines (the data signal line DATA, the first scan signal line S1, The second scan signal line S2, the first initial signal line INIT1, the second initial signal line INIT2, the first power supply line VSS, the second power supply line VDD, and the light emitting signal line EM).
- the control electrode of the first transistor T1 is connected to the second scan signal line S2, the first electrode of the first transistor T1 is connected to the first initial signal line INIT1, and the second electrode of the first transistor is connected to the second scan signal line S2.
- Node N2 is connected.
- the control electrode of the second transistor T2 is connected to the first scan signal line S1, the first electrode of the second transistor T2 is connected to the second node N2, and the second electrode of the second transistor T2 is connected to the third node N3.
- the control electrode of the third transistor T3 is connected to the second node N2, the first electrode of the third transistor T3 is connected to the first node N1, and the second electrode of the third transistor T3 is connected to the third node N3.
- the control electrode of the fourth transistor T4 is connected to the first scan signal line S1, the first electrode of the fourth transistor T4 is connected to the data signal line DATA, and the second electrode of the fourth transistor T4 is connected to the first node N1.
- the control electrode of the fifth transistor T5 is connected to the light-emitting signal line EM, the first electrode of the fifth transistor T5 is connected to the second power supply line VDD, and the second electrode of the fifth transistor T5 is connected to the first node N1.
- the control electrode of the sixth transistor T6 is connected to the light emitting signal line EM, the first electrode of the sixth transistor T6 is connected to the third node N3, and the second electrode of the sixth transistor T6 is connected to the first electrode of the light emitting device.
- the control electrode of the seventh transistor T7 is connected to the first scan signal line S1, the first electrode of the seventh transistor T7 is connected to the second initial signal line INIT2, and the second electrode of the seventh transistor T7 is connected to the first electrode of the light emitting device.
- the first end of the storage capacitor C is connected to the second power line VDD, and the second end of the storage capacitor C is connected to the second node N2.
- the first to seventh transistors T1 to T7 may be P-type transistors, or may be N-type transistors. Using the same type of transistors in the pixel driving circuit can simplify the process flow, reduce the process difficulty of the display panel, and improve the product yield. In some possible implementations, the first to seventh transistors T1 to T7 may include P-type transistors and N-type transistors.
- the second pole of the light emitting device is connected to the first power supply line VSS, the signal of the first power supply line VSS is a low-level signal, and the signal of the second power supply line VDD is a continuous high-level signal.
- the first scan signal line S1 is the scan signal line in the pixel driving circuit of the display row
- the second scan signal line S2 is the scan signal line in the pixel driving circuit of the previous display row, that is, for the nth display row, the first scan signal
- the line S1 is S(n)
- the second scanning signal line S2 is S(n-1)
- the second scanning signal line S2 of this display line is the same as the first scanning signal line S1 in the pixel driving circuit of the previous display line
- the signal lines can reduce the signal lines of the display panel and realize the narrow frame of the display panel.
- the organic light-emitting layer of the OLED light-emitting element may include an emission layer (Emitting Layer, referred to as EML), and a hole injection layer (Hole Injection Layer, referred to as HIL), a hole transport layer (Hole Transport Layer, HTL for short), Hole Block Layer (HBL), Electron Block Layer (EBL), Electron Injection Layer (EIL), Electron Transport Layer (EIL) one or more film layers in ETL).
- EML emission layer
- HIL hole injection layer
- HTL hole transport layer
- HBL Hole Block Layer
- EBL Electron Block Layer
- EIL Electron Injection Layer
- EIL Electron Transport Layer
- the light-emitting layers of OLED light-emitting elements of different colors are different.
- a red light-emitting element includes a red light-emitting layer
- a green light-emitting element includes a green light-emitting layer
- a blue light-emitting element includes a blue light-emitting layer.
- the hole injection layer and the hole transport layer on one side of the light emitting layer can use a common layer
- the electron injection layer and the electron transport layer on the other side of the light emitting layer can use a common layer.
- any one or more of the hole injection layer, hole transport layer, electron injection layer, and electron transport layer may be fabricated by one process (one evaporation process or one inkjet printing process), However, isolation is achieved by the surface step difference of the formed film layer or by means of surface treatment.
- any one or more of the hole injection layer, hole transport layer, electron injection layer and electron transport layer corresponding to adjacent sub-pixels may be isolated.
- the organic light-emitting layer may be formed by using a fine metal mask (FMM, Fine Metal Mask) or an open mask (Open Mask) evaporation deposition, or by using an inkjet process.
- FMM fine metal mask
- Open Mask Open Mask
- the material used in the hole injection layer HIL is similar to the material used in the hole transport layer HTL, and the highest occupied molecular orbital (Highest Occupied Molecular Orbit, HOMO) energy level of the hole injection layer material is between the anode work function. Between the HOMO energy level of the hole transport layer material, the effect of hole injection is achieved by reducing the potential barrier between the anode and the hole transport layer. Studies have shown that there are still potential barriers between the layers of the structure, and the implantation effect is poor.
- HOMO Highest Occupied Molecular Orbit
- the hole injection layer adopts a doped structure
- the hole injection layer includes a host material and a doping material
- the doping material is a P-doping material, such as 2, 3, 5, 6-tetrafluoro-7,7',8,8'-tetracyanodimethyl (F4-TCNQ), etc.
- the host material and the doping material are doped according to a certain proportion to form a doped structure.
- the P-type doping material is a material with strong electron-absorbing ability, it lacks electrons and has the ability to strongly pull electrons. Therefore, the P-type doping has the characteristics of strong electron-absorbing ability, so that the electrons can move to the anode under the action of the electric field.
- the hole injection layer adopts a material with strong electron-withdrawing properties, which can not only improve the hole injection performance, but also improve the display defects caused by P-type doping. Studies have shown that materials with this characteristic usually have strong molecular polarity, are easy to crystallize, have poor stability, and are difficult to process.
- Exemplary embodiments of the present disclosure provide an organic electroluminescence device including an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode, the doped structure layer including a host material and doped in the host
- the guest material in the material, the host material and the guest material satisfy:
- LUMO(A) is the lowest unoccupied molecular orbital LUMO energy level of the host material
- HOMO(B) is the highest occupied molecular orbital HOMO energy level of the guest material.
- the doping ratio of the guest material in the doping structure layer is 0.1% to 40%.
- one of the host material and the guest material includes a ketone-based compound, and the other includes an aromatic amine-based compound.
- the host material includes a ketone compound, and the guest material includes an aromatic amine compound.
- the doped structure layer includes a hole injection layer.
- the hole injection layer has a thickness of 1 nm to 10 nm.
- FIG. 5 is a schematic diagram of an OLED structure according to an exemplary embodiment of the present disclosure.
- the OLED includes an anode 10 , a cathode 90 and an organic light-emitting layer disposed between the anode 10 and the cathode 90 .
- the organic light emitting layer includes a stacked hole injection layer 20 , a hole transport layer 30 , an electron blocking layer 40 , a light emitting layer 50 , a hole blocking layer 60 , an electron transport layer 70 and an electron injection layer 80 .
- the hole injection layer 20 is configured to lower a barrier for injecting holes from the anode, so that holes can be efficiently injected from the anode into the light-emitting layer 50 .
- the hole transport layer 30 is configured to achieve controlled migration of the directional order of the injected holes.
- the electron blocking layer 40 is configured to form a migration barrier for electrons, preventing electrons from migrating out of the light emitting layer 50 .
- the light-emitting layer 50 is configured to recombine electrons and holes to emit light.
- the hole blocking layer 60 is configured to form a migration barrier for holes, preventing the holes from migrating out of the light emitting layer 50 .
- Electron transport layer 70 is configured to achieve controlled migration of the directional order of injected electrons.
- the electron injection layer 80 is configured to lower a barrier for injecting electrons from the cathode, so that electrons can be efficiently injected from the cathode to the light-emitting layer 50 .
- the doped structure layer is a hole injection layer 20
- the hole injection layer 20 of the doped structure includes a host material A and a guest material B doped in the host material A, the host material A and the guest material
- the highest occupied molecular orbital HOMO energy level and the lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbit, referred to as LUMO) energy level of B satisfy:
- LUMO(A) is the lowest unoccupied molecular orbital LUMO energy level of the host material A
- HOMO(B) is the highest occupied molecular orbital HOMO energy level of the guest material B.
- the HOMO energy level and the LUMO energy level of the host material A satisfy:
- HOMO(A) is the highest occupied molecular orbital HOMO energy level of the host material A.
- the HOMO energy level of the guest material B satisfies:
- may be greater than or equal to
- the host material A and the guest material B may be co-evaporated through a multi-source evaporation process to form the hole injection layer of the doped structure.
- the doping ratio of the guest material B in the hole injection layer is about 0.1% to 40%.
- the doping ratio refers to the ratio of the mass of the guest material to the mass of the hole injection layer, that is, the mass percentage.
- the host material and the guest material are co-evaporated, so that the host material and the guest material are uniformly dispersed in the hole injection layer, and the doping ratio can be regulated by controlling the evaporation rate of the guest material during the evaporation process, Alternatively, the doping ratio can be regulated by controlling the evaporation rate ratio of the host material and the guest material.
- the doping ratio of the guest material B in the hole injection layer may be about 0.5% to 30%.
- the doping ratio of the guest material B in the hole injection layer may be about 5% to 20%.
- the doping ratio of the guest material B in the hole injection layer may be about 0.5% to 10%.
- the doping ratio of the guest material B in the hole injection layer may be about 5% to 10%.
- the thickness of the hole injection layer 20 is about 1 nm to 10 nm. Since the guest material is doped in the host material, it will affect the characteristics of the host material to a certain extent. Too thick film will lead to a decrease in lifespan, while too thin film will affect the film formation and uniformity, resulting in discontinuity of the film, affecting the Inject performance.
- the guest material B may use an aromatic amine compound.
- Aromatic amine compounds are hole transport materials with high mobility, high stability and not easy to crystallize.
- the guest material B includes, but is not limited to, the structure shown in formula (I):
- L may be a linking group formed via a substituted or unsubstituted arylene group having 5 to 50 ring atoms, or a plurality of substituted or unsubstituted arylene groups having 5 to 50 ring atoms.
- Ar 1 to Ar 4 may not be exactly the same, each independently a substituted or unsubstituted aryl group having 5 to 50 ring atoms, and at least one of Ar 1 to Ar 4 is selected from the following structures: any of:
- R1 to R25 are each independently any one of the following:
- the host material A is a ketone compound
- the ketone compound is a hole injection material with strong electron withdrawing ability. level and LUMO energy level.
- the host material A includes, but is not limited to, the structure shown in formula (II):
- Z may be a substituted or unsubstituted benzene ring, pyridine ring, thiophene ring, quinoline, indole or thienothiophene ring and the like.
- Y 1 to Y 4 may each independently be N or C-R35. Y 1 to Y 4 may be the same as each other, or may be different from each other.
- R31 to R34 may be the same as each other, or may be different from each other, and each independently any one of the following: hydrogen, deuterium, halogen group, nitrile group, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted haloalkoxy, substituted or unsubstituted aryl, substituted or unsubstituted halo substituted aryl, substituted or unsubstituted silyl, substituted or unsubstituted heterocycle.
- R35 can be any of the following: hydrogen, deuterium, halogen group, nitrile group, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted Substituted alkoxy, substituted or unsubstituted haloalkoxy, substituted or unsubstituted aryl, substituted or unsubstituted haloaryl, substituted or unsubstituted silyl , substituted or unsubstituted heterocycles.
- Ar 5 in formula (II) may be:
- Ar in formula (II) may be:
- X1 and X2 in Ar 5 and Ar 6 may be the same, or may be different.
- X1 and X2 may each be independently selected from any one of the following structures:
- R41 to R43 are each hydrogen, fluoroalkyl, alkyl, aryl or heterocyclyl, and R42 and R43 may form a ring.
- the anode may employ a material with a high work function.
- the anode 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 can use 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 transparent oxide in the anode can be used.
- the thickness of the material can be about 5 nm to 20 nm, so that the average reflectivity of the anode in the visible light region is about 85% to 95%.
- the cathode may be made of a metal material, which may be 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 magnesium
- Al aluminum
- the ratio of Mg:Ag is about 3:7 to 1:9
- the thickness of the cathode can be about 10nm to 20nm, so that the average transmittance of the cathode at a wavelength of 530nm is about 50% to 60%.
- the cathode can be magnesium (Mg), silver (Ag), aluminum (Al) or Mg:Ag alloy, and the thickness of the cathode can be greater than about 80 nm, so that the cathode 90 has good reflectivity.
- the hole transport layer may be formed of materials with high hole mobility, such as carbazole, methylfluorene, spirofluorene, dibenzothiophene, or furan, etc., through an evaporation process.
- the thickness of the hole transport layer may be about 90 nm to 140 nm
- the carrier mobility of the hole transport layer material may be about 10 -3 cm 2 /Vs to 10 -5 cm 2 /Vs
- the conductivity of the hole transport layer Less than or equal to the conductivity of the hole injection layer.
- the material of the hole transport layer may be the same as the guest material B in the hole injection layer.
- the HOMO energy level of the material of the hole transport layer satisfies:
- HOMO(D) is the highest occupied molecular orbital HOMO level of the hole transport layer.
- two organic layers are further disposed between the hole injection layer and the light emitting layer, and the two organic layers may be a hole transport layer and an electron blocking layer.
- the electron blocking layer may have a thickness of about 1 nm to 10 nm, is configured to transfer holes, block electrons, and block excitons generated in the light emitting layer, and the electron blocking layer has a conductivity less than or equal to the hole injection layer the conductivity.
- the light-emitting layer may include a light-emitting host material and a light-emitting guest material.
- the light-emitting host material may adopt a bipolar single host, or may adopt a double host formed by blending a hole-type host and an electron-type host.
- the light-emitting guest material can be a phosphorescent material, a fluorescent material, a delayed fluorescent material, etc., and the doping ratio of the light-emitting guest material is about 5% to 15%.
- the hole blocking layer has a thickness of about 2 nm to 10 nm, and is configured to block holes and block excitons generated within the light emitting layer.
- the electron transport layer can be prepared by using thiophene, imidazole or azine derivatives, etc., by blending with lithium quinolate, and the doping ratio of lithium quinolate in the electron transport layer is about 30%. % to 70%, the thickness of the electron transport layer may be about 20 nm to 70 nm.
- the electron injection layer may be formed by an evaporation process using materials such as lithium fluoride (LiF), lithium 8-hydroxyquinolate (LiQ), ytterbium (Yb) or calcium (Ca).
- materials such as lithium fluoride (LiF), lithium 8-hydroxyquinolate (LiQ), ytterbium (Yb) or calcium (Ca).
- LiF lithium fluoride
- LiQ lithium 8-hydroxyquinolate
- Yb ytterbium
- Ca calcium
- the OLED may include an encapsulation layer, and the encapsulation layer may be encapsulated with a sealant, or may be encapsulated with a thin film.
- the thickness of the organic light-emitting layer between the anode and the cathode can be designed to meet the optical path requirement of the optical micro-resonator to obtain optimal light intensity and color.
- the display substrate including the OLED structure may be formed in the following manner.
- a driving circuit layer is formed on the 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 by 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, the hole transport layer and the electron blocking layer are sequentially evaporated using an open mask, and the hole injection layer, the hole transport layer and the electron blocking layer are formed on the display substrate. That is, the hole injection layers of all sub-pixels are connected, the hole transport layers of all sub-pixels are connected, and the electron blocking layers of all sub-pixels are connected.
- the respective areas of the first hole injection layer, the second hole injection layer, the hole transport layer, and the electron blocking layer are approximately the same, and the thicknesses are different.
- the red light-emitting layer, the green light-emitting layer and the blue light-emitting layer are respectively evaporated on different sub-pixels by using a fine metal mask, and the light-emitting layers of adjacent sub-pixels may have a small amount of overlap (for example, the overlapping portion accounts for the respective light-emitting layers)
- the area of the layer pattern is less than 10%), or may be isolated.
- a red light-emitting layer, a green light-emitting layer and a blue light-emitting layer are respectively evaporated on different sub-pixels using a fine metal mask, and the light-emitting layers of adjacent sub-pixels are isolated.
- the hole blocking layer, the electron transport layer, the electron injection layer and the cathode are sequentially evaporated using an open mask to form a common layer of the hole blocking layer, the electron transport layer, the electron injection layer and the cathode on the display substrate, that is, all the The hole blocking layers of the sub-pixels are connected, the electron transport layers of all the sub-pixels are connected, the electron injection layers of all the sub-pixels are connected, and the cathodes of all the sub-pixels are connected.
- first hole injection layer, the second hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer, the electron injection layer, and the cathode The orthographic projection of the layer on the substrate is continuous.
- first hole injection layer, the second hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer, the electron injection layer, and the cathode of the at least one row or column of subpixels At least one of the layers is connected.
- At least one of a first hole injection layer, a second hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode of the plurality of subpixels Layers are connected.
- the organic light emitting layer may include a microcavity adjustment layer between the hole transport layer and the light emitting layer.
- a fine metal mask can be used to vapor-deposit the red microcavity adjusting layer and the red light-emitting layer, the green microcavity adjusting layer and the green light-emitting layer, and the blue microcavity adjusting layer on different sub-pixels respectively. layer and blue light-emitting layer.
- the area of the hole injection layer may be approximately equal, and the orthographic projection of the hole injection layer on the substrate includes at least two sub-pixel light-emitting regions on the substrate.
- the orthographic projection that is, the orthographic projection of the hole injection layer on the substrate overlaps the orthographic projection of the light-emitting regions of at least two sub-pixels on the substrate.
- the orthographic projection of the hole injection layer on the substrate includes the orthographic projection of the light-emitting layer on the substrate, and the holes The area of the injection layer is larger than that of the light emitting layer.
- the orthographic projection of the light-emitting layer of at least part of the sub-pixels on the substrate overlaps with the orthographic projection of the pixel driving circuit driving on the substrate.
- Table 1 shows the performance comparison results of different hole injection layer structures in OLEDs.
- the three comparative structures adopt the structure shown in Fig. 5, the anode adopts ITO, and the cathode adopts Mg:Ag alloy.
- the hole injection layer of structure 1 is a doped structure with 3% P-type doping
- the hole injection layer of structure 2 is a non-doped structure
- the hole injection layer of structure 2 includes a single host material A
- the hole injection layer of structure 3 is a non-doped structure.
- the hole injection layer is a doping structure of an exemplary embodiment of the present disclosure
- the hole injection layer of structure 3 includes a host material A and a guest material B.
- LT95 represents the time when the OLED decreases from the initial brightness (100%) to 95% brightness. Since the lifetime curve follows a multi-exponential decay model, the lifetime of the OLED can be estimated based on LT95. As shown in Table 1, compared with structures 1 and 2, structure 3 has a significant improvement in prolonging the lifetime, indicating that the hole injection layer of the doped structure proposed by the exemplary embodiment of the present disclosure can optimize the crystallinity of the material and stability, increasing device life.
- Table 2 shows the performance comparison results of different doping ratios of the hole injection layer in the OLED.
- the three comparative structures all adopt the structure shown in FIG. 5 , the anode adopts ITO, the cathode adopts Mg:Ag alloy, the hole injection layer is the doped structure of the exemplary embodiment of the present disclosure, and the hole injection layer includes a host material A and a guest Material B.
- the doping ratio of guest material B in structure 4 is 5%
- the doping ratio of guest material B in structure 5 is 10%
- the doping ratio of guest material B in structure 6 is 30%.
- Table 2 compared with the hole injection layer of a single material (structure 2 in Table 1), different doping ratios can effectively prolong the lifetime.
- the doping ratio of the guest material B is 5% and 10%, the voltage and efficiency of the hole injection layer do not change much, and the lifetime is significantly improved, indicating that the doping ratio of more than 5% will not cause crosstalk between sub-pixels, effectively The problem of low doping ratio of the P-type doped structure is avoided.
- the doping ratio of the guest material B is equal to 30%, although the lifetime increases more, the voltage increases and the efficiency decreases.
- Table 3 is yet another comparative result of the disclosed exemplary embodiment OLEDs.
- the three comparative structures all adopt the structure shown in FIG. 5 , the anode adopts ITO, the cathode adopts Mg:Ag alloy, the hole injection layer is the doped structure of the exemplary embodiment of the present disclosure, and the hole injection layer includes a host material A and a guest Material B.
- the thickness of the hole injection layer in structure 7 is 1 nm
- the thickness of the hole injection layer in structure 8 is 5 nm
- the thickness of the hole injection layer in structure 9 is 10 nm.
- Table 3 when the thickness of the hole injection layer is 5 nm, the voltage decreases slightly and the efficiency increases slightly.
- an appropriate hole injection layer thickness can be selected according to the compatibility of each structural layer of the device.
- FIG. 6 is a SEM image of a hole injection layer vapor-deposited film of a non-doped structure
- FIG. 7 is a SEM image of a hole injection layer vapor-deposited film according to an exemplary embodiment of the disclosure.
- SEM scanning electron microscope
- Exemplary embodiments of the present disclosure provide an OLED.
- the hole injection layer adopts a doping structure different from P-type doping, which can effectively improve the crystallinity and thermal stability of the hole injection material, reduce defects in the evaporation process, and achieve Stable injection performance can effectively reduce device voltage and improve device efficiency and service life. Since the doping material is different from the P-type doping material, the problem of low doping ratio of the P-type doping structure is avoided, and a large doping ratio (greater than 5%) will not cause crosstalk between sub-pixels, effectively improving the display. quality.
- the hole injection layer provided by the exemplary embodiment of the present disclosure has good preparation process compatibility, does not increase the evaporation chamber, and has good mass production.
- the present disclosure also provides a display device including the aforementioned organic electroluminescent device.
- the display device can be any product or component that has 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 watch, a wristband, etc.
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Abstract
Description
Claims (18)
- 一种有机电致发光器件,包括阳极、阴极以及设置在所述阳极和阴极之间的发光层,所述阳极和发光层之间设置有掺杂结构层,所述掺杂结构层包括主体材料和掺杂在所述主体材料中的客体材料,所述主体材料和客体材料满足:-1.5eV<│LUMO(A)│-│HOMO(B)│<1.5eV;其中,LUMO(A)为所述主体材料的最低未占分子轨道LUMO能级,HOMO(B)为所述客体材料的最高占据分子轨道HOMO能级。
- 根据权利要求1所述的有机电致发光器件,其中,所述客体材料还满足:5eV≤│HOMO(B)│≤6.5eV。
- 根据权利要求1所述的有机电致发光器件,其中,所述主体材料还满足:│HOMO(A)│≥6eV,│LUMO(A)│≥4eV;其中,HOMO(A)为所述主体材料的最高占据分子轨道HOMO能级。
- 根据权利要求1所述的有机电致发光器件,其中,所述客体材料占所述掺杂结构层的掺杂比例为0.1%至40%。
- 根据权利要求1所述的有机电致发光器件,其中,所述主体材料和所述客体材料中的一个包括酮类化合物,另一个包括芳胺类化合物。
- 根据权利要求1至5任一项所述的有机电致发光器件,其中,所述主体材料包括但不限于具有式(Ⅱ)结构的化合物:式(Ⅱ)中,Z为经取代或未经取代的苯环、吡啶环、噻吩环、喹啉、吲哚或噻吩并噻吩环;Y 1至Y 4各自独立地为N或C-R35;R31至R35各自独立地选自如下任意一种:氢、氘、卤素基团、腈基、经取代或未经取代的烷基、经取代或未经取代的卤代烷基、经取代或未经取代的烷氧基、经取代或未经取代的卤代烷氧基、经取代或未经取代的芳基、经取代或未经取代的卤代芳基、经取代或未经取代的甲硅烷基、经取代或未经取代的杂环;X1和X2各自独立地选自如下结构中的任意一种:R41至R43各自独立地为如下任意一种:氢、氟代烷基、烷基、芳基和杂环基,R42和R43形成环。
- 根据权利要求1至5任一项所述的有机电致发光器件,其中,所述掺杂结构层包括空穴注入层。
- 根据权利要求9所述的有机电致发光器件,其中,所述空穴注入层的厚度为1nm至10nm。
- 根据权利要求9所述的有机电致发光器件,其中,所述空穴注入层与发光层之间还设置有至少一层有机层,所述至少一层有机层中的载流子迁移率为10 -3cm 2/Vs至10 -5cm 2/Vs,和/或,所述至少一层有机层的导电率小于或等于所述空穴注入层的导电率。
- 根据权利要求11所述的有机电致发光器件,其中,所述至少一层有机层的材料与所述客体材料相同。
- 根据权利要求11所述的有机电致发光器件,其中,所述至少一层有机层为空穴传输层,所述空穴传输层的材料满足:5eV≤│HOMO(D)│≤6.5eV;HOMO(D)为所述空穴传输层的最高占据分子轨道HOMO能级。
- 根据权利要求11所述的有机电致发光器件,其中,所述空穴注入层和发光层之间还设置有两层有机层,所述两层有机层中的载流子迁移率均为10 -3cm 2/Vs至10 -5cm 2/Vs,和/或,所述两层有机层的导电率均小于或等于所述空穴注入层的导电率。
- 一种显示装置,包括权利要求1至14任一项所述的有机电致发光器件。
- 根据权利要求15所述显示装置,所述显示装置包括基板和形成于所述基板上的多个子像素,所述子像素包括所述有机电致发光器件;所述空穴注入层在基板上的正投影均与至少两个子像素的发光区域在基板上的正投影有交叠。
- 根据权利要求16所述显示装置,所述空穴注入层的面积大于所述发光层的面积。
- 根据权利要求16所述显示装置,所述子像素还包括像素驱动电路,至少部分子像素的发光层在基板上的正投影与所述像素驱动电路的驱动晶体管在基板上的正投影有交叠。
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