WO2016058531A1 - 有机发光二极管及其制备方法、显示基板、显示装置 - Google Patents

有机发光二极管及其制备方法、显示基板、显示装置 Download PDF

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WO2016058531A1
WO2016058531A1 PCT/CN2015/091918 CN2015091918W WO2016058531A1 WO 2016058531 A1 WO2016058531 A1 WO 2016058531A1 CN 2015091918 W CN2015091918 W CN 2015091918W WO 2016058531 A1 WO2016058531 A1 WO 2016058531A1
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layer
cathode
energy level
organic light
transport layer
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PCT/CN2015/091918
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French (fr)
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吴长晏
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京东方科技集团股份有限公司
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17Carrier injection layers
    • H10K50/171Electron injection layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80Constructional details
    • H10K30/865Intermediate layers comprising a mixture of materials of the adjoining active layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/805Electrodes
    • H10K50/82Cathodes
    • H10K50/828Transparent cathodes, e.g. comprising thin metal layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00Properties of the organic materials covered by group H10K85/00
    • H10K2101/30Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00Properties of the organic materials covered by group H10K85/00
    • H10K2101/40Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301Details of OLEDs
    • H10K2102/302Details of OLEDs of OLED structures
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60Forming conductive regions or layers, e.g. electrodes

Definitions

  • the present invention relates to the field of display technologies, and in particular, to an organic light emitting diode (OLED) and a method of fabricating the same, and a display substrate and a display device including the foregoing organic light emitting diode.
  • OLED organic light emitting diode
  • organic electroluminescent displays have a series of advantages such as autonomous illumination, low voltage DC drive, full cure, wide viewing angle, and rich colors.
  • the organic electroluminescent display does not require a backlight, and has a large viewing angle, low power consumption, and a response speed of up to 1000 times that of the liquid crystal display, but its manufacturing cost is lower than that of the liquid crystal display of the same resolution. Therefore, organic electroluminescent displays have broader application prospects.
  • An organic electroluminescent diode is a light-emitting device that converts electrical energy into light energy in an organic material.
  • a conventional OLED structure includes an anode, a layer of luminescent material, and a cathode that are sequentially stacked. The principle of luminescence is that holes and electrons injected from the anode and the cathode are combined in the luminescent material layer to generate excitons to achieve luminescence. Depending on the direction of light emission, OLEDs are classified into bottom-emitting OLEDs and top-emitting OLEDs.
  • FIG. 1 is a schematic view showing the structure of a bottom-emitting OLED commonly used in the prior art, which includes a reflective cathode 11, an electron transport layer 12, a light-emitting layer 13, a hole transport layer 14, a transparent anode 15, and a substrate 16 which are sequentially arranged.
  • the device is grown on a transparent substrate, with indium tin oxide (ITO) as a transparent anode, and light is emitted from the ITO substrate 16 side, so it is called a Bottom-emitting OLED (BEOLED).
  • ITO indium tin oxide
  • BEOLED Bottom-emitting OLED
  • the light emitted from the top-emitting OLED (TEOLED) is from the side of the top electrode.
  • the device includes the cathode 21, the electron transport layer 22, the light-emitting layer 23, the hole transport layer 24, and the reflective anode. 25 and substrate 26, as shown in FIG. For the top emitting OLED, light is emitted from the cathode 21 side.
  • the current flexible OLED panel is generally driven by a thin film transistor TFT (Thin Film Transistor) array.
  • TFT Thin Film Transistor
  • the illumination of the flexible OLED panel can only be emitted from the opening provided on the TFT main board that drives the panel. Therefore, the light emitted from the outside of the panel is only It accounts for 30%-50% of the luminescence of the luminescent layer, and most of the luminescence is wasted.
  • the use of the top emission structure can solve the problem of low aperture ratio of the common bottom emission device, and directly obtain light from the top semi-transparent electrode surface of the device, which has little effect on the aperture ratio, and is advantageous for realizing large, high information content, high display brightness, High resolution organic flat panel display.
  • the top-emitting device structure can also achieve narrowing of the spectrum, selection of the emission wavelength, and improvement of the color purity of the device.
  • thin metal is generally used as the cathode material at the top.
  • the metal cathode is too thin, the conductivity of the device is not good, and the microcavity effect is formed, which makes the optical design of the device very complicated.
  • a thin conductive metal Transparent Conductive Oxide, TCO for short
  • TCO Transparent Conductive Oxide
  • TCO materials include indium tin oxide (ITO), indium zinc oxide (IZO) and other materials, but these TCO materials are generally suitable for the fabrication of anodes, so the use of TCO materials as cathodes to increase the penetration of top-emitting OLED devices At the time of overshoot, these materials do not match the energy level of the lowest unoccupied molecular orbital (LUMO) level of the electron transport layer (ETL), which will greatly reduce the lifetime of the OLED device.
  • the operating voltage is greatly increased. For example, if the cathode is made of IZO, since the work function of IZO is about 5 eV, it has a large difference from the LUMO level of the general electron transport layer. As shown in FIG. 3, electron injection is difficult, and the operating voltage of the OLED device rises. , life expectancy is reduced.
  • the present invention provides an organic light emitting diode, a method of fabricating the same, and a display substrate and display device including the foregoing organic light emitting diode.
  • an organic light emitting diode comprising an anode, a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer and a cathode, wherein:
  • the cathode is made of a transparent conductive oxide material
  • An energy level transition layer is formed between the electron transport layer and the cathode for transitioning between energy levels between the electron transport layer and the cathode to reduce the difficulty of electron injection.
  • the energy level transition layer comprises an n-type material layer and a low LUMO e-type material layer.
  • the n-type material layer is made of an electron injecting material doped with a metal material, doped with a base
  • An electron injecting material of a metal compound, a doping material obtained by doping LiQ and Ca, and an alkali metal compound are used.
  • the LUMO energy level of the low LUMO e type material is between 4 eV and 7 eV.
  • the material of the low LUMO e type material layer is one of HAT-CN, F4TCNQ, copper phthalocyanine, 2T-NaTa and TcTa.
  • the transparent conductive oxide material is one of indium zinc oxide, indium tin oxide, indium aluminum oxide, zinc aluminum oxide, and fluorine-doped tin oxide.
  • a sputtering protection layer is further disposed between the energy level transition layer and the cathode for protecting the energy level transition layer from damage when the cathode is formed by sputtering.
  • the sputter protection layer is made using CuPc.
  • a display substrate comprising the organic light emitting diode as described above.
  • a display device comprising the display substrate as described above.
  • a method of fabricating an organic light emitting diode comprising the steps of:
  • An anode, a hole injection layer, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially formed on the substrate;
  • a cathode is fabricated on the energy level transition layer, the cathode being made of a transparent conductive oxide material.
  • the step of fabricating the energy level transition layer further comprises the steps of: forming an n-type material layer on the electron transport layer, and fabricating a low LUMO e-type material layer on the n-type material layer.
  • the n-type material layer is formed using one of an electron injecting material doped with a metal material, an electron injecting material doped with an alkali metal compound, a doping material obtained by doping LiQ and Ca, and an alkali metal compound. .
  • the LUMO energy level of the low LUMO e type material is between 4 eV and 7 eV.
  • the low LUMO e type material layer is produced using one of HAT-CN, F4TCNQ, copper phthalocyanine, 2T-NaTa, and TcTa.
  • the transparent conductive oxide material is indium zinc oxide, indium tin oxide, indium aluminum oxide, One of zinc oxide aluminum and fluorine-doped tin oxide.
  • the step of forming a sputter protection layer on the energy level transition layer is further included.
  • the TCO material due to the energy level characteristics of the TCO material, it is generally suitable for the fabrication of an anode. Therefore, in a top-emitting OLED device which generally uses a transparent conductive oxide (TCO) as a cathode material, it is a LUMO with a general electron injecting layer. The energy levels do not match.
  • the present invention connects the electron transport layer and the cathode by using an energy level transition layer including an n-type material layer and a low LUMO e-type material layer, so that the energy level difference between the electron transport layer and the cathode is reduced. Small, making the TCO material a material suitable for making cathodes.
  • the energy level difference between the electron transport layer and the cathode is reduced, that is, the energy level transition between the electron transport layer and the cathode is smoother, electron injection is easier, and the operating voltage of the OLED device is greatly reduced. Therefore, the service life of the OLED device is greatly improved, and the problem that the lifetime of the OLED device is short and the operating voltage is too large due to the TCO process or energy level mismatch is improved.
  • FIG. 1 is a schematic structural view of a bottom-emitting OLED commonly used in the prior art
  • FIG. 2 is a schematic structural view of a top-emitting OLED commonly used in the prior art
  • FIG. 3 is a schematic diagram of energy level matching of an OLED device obtained by fabricating a cathode with IZO in the prior art
  • FIG. 4 is a schematic structural view of an organic light emitting diode of the present invention.
  • FIG. 5A is a schematic structural diagram of an organic light emitting diode according to an embodiment of the invention.
  • FIG. 5B is a schematic diagram of energy level matching of the organic light emitting diode shown in FIG. 5A; FIG.
  • 6A is a schematic structural view of an organic light emitting diode according to another embodiment of the present invention.
  • FIG. 6B is a schematic diagram of energy level matching of the organic light emitting diode shown in FIG. 6A.
  • TCO materials are generally suitable for making anodes, using TCO materials as cathodes to increase
  • the inventors noticed that the energy level characteristics of the TCO material did not match the LUMO energy level of the general electron transport layer. Therefore, the present invention solves this problem by providing an energy level transition layer between the electron transport layer and the cathode.
  • an organic light emitting diode As shown in FIG. 4, the organic light emitting diode comprises: an anode 1, a hole injection layer (HIL), and a hole transport layer (Hole). Transport Layer (HTL) 3, an organic light-emitting layer (EMM) 4, an electron transport layer (Electron Transport Layer, ETL) 5, an energy level transition layer 6 and a cathode 7, wherein:
  • the cathode 7 is made of a transparent conductive material.
  • the transparent conductive material is a transparent conductive oxide (TCO) material, such as an oxide containing a metal such as aluminum, indium, tin, zinc, gallium, such as: indium zinc oxide IZO, Indium tin oxide ITO, indium aluminum oxide AITO, zinc aluminum oxide AZO, fluorine doped tin oxide FTO, and the like.
  • TCO transparent conductive oxide
  • the energy level transition layer 6 formed between the electron transport layer 5 and the cathode 7 serves to transition the energy level between the electron transport layer 5 and the cathode 7 to reduce the difficulty of electron injection. The effect of the energy level difference between the electron transport layer and the cathode is reduced.
  • the LUMO energy level of the energy level transition layer 6 is between or close to the work function of the cathode 7 and the LUMO energy level of the electron transport layer 5, so that the electron transport layer 5 and the cathode 7 can be reduced.
  • the influence of the difference in energy level makes the energy level transition between the electron transport layer 5 and the cathode 7 smoother, and the electrons can be more easily injected into the electron transport layer 5, thereby reducing the accumulation of electrons in the interface or Reduce the operating voltage.
  • the energy level transition layer 6 includes an n-type material layer and a low LUMO e-type material layer.
  • the n-type material layer may be made of an electron injecting material doped with a metal material or an electron injecting material doped with an alkali metal compound, and the metal material may be lithium (Li), sodium (Na), or potassium ( K), ruthenium (Rb), ruthenium (Cs); or a doping material obtained by doping LiQ and Ca or an alkali metal compound such as Cs 2 CO 3 , CsF or NaF.
  • the low LUMO e type material layer is formed using a low LUMO e type material suitable for forming a hole injection layer.
  • a low LUMO e type material suitable for forming a hole injection layer for example, materials such as 1,4,5,8,9,11-hexaazatriphenylene-hexanitrile (HATCN), F4TCNQ, copper phthalocyanine (CuPc), 2T-NaTa, TcTa, etc., are preferably HAT-CN.
  • the LUMO energy level of the low LUMO e-type material is between 4 eV and 7 eV, such that electron transfer is connected by using an energy level transition layer 6 including an n-type material layer and a low LUMO e-type material layer.
  • the transmission layer and the cathode, that is, the TCO material is connected to the LUMO of the hole-type material through the energy level transition layer 6, to reduce the difficulty of electron injection and reduce the influence of the energy level difference between the electron transport layer and the cathode, This makes the TCO material a material suitable for making cathodes.
  • the OLED device of the present invention Compared with a top-emitting OLED device in which a cathode is fabricated using a TCO material alone, the OLED device of the present invention has a smoother transition of energy between the electron transport layer and the cathode, so that electron injection is easier, and the operating voltage of the OLED device It is greatly reduced, which greatly improves the service life of the OLED device, and improves the short life and excessive operating voltage of the OLED device due to the TCO process or energy level mismatch.
  • the anode 1 is made of a material having a high work function and a light transmissive property, such as a transparent conductive oxide (TCO) material, preferably an IZO transparent conductive film.
  • TCO transparent conductive oxide
  • the OLED device further includes a substrate on which the anode 1 is formed.
  • the substrate is a substrate substrate or a substrate on which other functional film layers are formed.
  • the substrate substrate is made of a material such as glass, silicon wafer, quartz, plastic, and silicon wafer, preferably glass.
  • a sputtering protection layer 8 is further disposed between the energy level transition layer 6 and the cathode 7 for protecting the energy level transition layer 6 from damage when the cathode 7 is formed by sputtering. .
  • the sputter protection layer 8 is made of a p-type organic material, such as CuPc.
  • CuPc is a hole transporting material, and directly forming it between the cathode and the electron transporting layer causes the operating voltage of the OLED device to be large and the lifetime to be lowered.
  • CuPc may react with the carrier of the low LUMO e-type material layer in the energy level transition layer 6, so that holes are more smoothly injected into the cathode, and the operating voltage of the OLED device is prevented from becoming large. The problem of reduced life.
  • FIG. 5A is a schematic structural view of an OLED device according to an embodiment of the invention.
  • the OLED device includes an anode 1, a hole injection layer (HIL) 2, a hole transport layer (HTL) 3, an organic light emitting layer (EML) 4, an electron transport layer (ETL) 5, and an energy level.
  • HIL hole injection layer
  • HTL hole transport layer
  • EML organic light emitting layer
  • ETL electron transport layer
  • a transition layer 6 a sputter protection layer 8 and a cathode 7, wherein:
  • the cathode 7 is made of a transparent conductive material.
  • the transparent conductive material is a transparent conductive oxide (TCO) material, such as an oxide containing a metal such as aluminum, indium, tin, zinc or gallium.
  • TCO transparent conductive oxide
  • IZO indium zinc oxide
  • ITO indium tin oxide
  • AITO indium aluminum oxide AITO
  • zinc aluminum oxide AZO zinc aluminum oxide AZO
  • fluorine doped tin oxide FTO etc.
  • an IZO material is preferred as the cathode.
  • the energy level transition layer 6 formed between the electron transport layer 5 and the cathode 7 serves to transition the energy level between the electron transport layer 5 and the cathode 7 to reduce the difficulty of electron injection. The effect of the energy level difference between the electron transport layer 5 and the cathode 7 is reduced.
  • the LUMO energy level of the energy level transition layer 6 is between or close to the work function of the cathode 7 and the LUMO energy level of the electron transport layer 5, so that the electron transport layer 5 and the cathode 7 can be reduced.
  • the influence of the difference in energy level makes the energy level transition between the electron transport layer 5 and the cathode 7 smoother, and the electrons can be more easily injected into the electron transport layer 5, thereby reducing the accumulation of electrons in the interface or Reduce the operating voltage.
  • the energy level transition layer 6 includes an n-type material layer and a HAT-CN material layer.
  • the n-type material layer is made of an electron injecting material doped with lithium (Li).
  • the LUMO energy level of the HAT-CN material is between 4 eV and 7 eV, such that the electron transport layer and the cathode are connected by using the energy level transition layer 6 including the n-type material layer and the HAT-CN material layer, that is, by the The energy level transition layer 6 connects the TCO material to the LUMO energy level of the HAT-CN material, which allows the energy level transition between the electron transport layer and the cathode to be smoother, as shown in FIG. 5B.
  • the cathode is fabricated using the TCO material alone, since the energy level transition between the electron transport layer and the cathode is smoother, the electron injection of the OLED device in this embodiment is easier, and the operating voltage of the OLED device is easier. It is greatly reduced, which greatly improves the service life of the OLED device, and improves the short life and excessive operating voltage of the OLED device due to the TCO process or energy level mismatch.
  • the anode 1 is made of a material having a high work function and a light transmissive property, such as a transparent conductive oxide (TCO) material, preferably an IZO transparent conductive film.
  • TCO transparent conductive oxide
  • the sputter protection layer 8 is made of CuPc for protecting the level transition layer 6 from damage when the cathode is formed by sputtering.
  • CuPc is a hole transporting material, and directly forming it between the cathode and the electron transporting layer causes the operating voltage of the OLED device to be large and the lifetime to be lowered.
  • CuPc may react with the carrier of the low LUMO e-type material layer in the energy level transition layer 6, so that holes are more smoothly injected into the cathode, as shown in FIG. 5B. The problem that the operating voltage of the OLED device becomes large and the lifetime is lowered is avoided.
  • the OLED device further includes a substrate on which the anode 1 is formed.
  • the substrate is a substrate substrate or a substrate on which a film layer is formed.
  • the substrate substrate is made of a material such as glass, silicon wafer, quartz, plastic, and silicon wafer, preferably glass.
  • the OLED device includes an anode 1, a hole injection layer (HIL) 2, a hole transport layer (HTL) 3, and an organic An illuminating layer (EML) 4, an electron transporting layer (ETL) 5, an energy level transition layer 6 and a cathode 7.
  • the n-type material layer is formed of a doping material obtained by doping LiQ and Ca, although not provided
  • the sputter protection layer 8, as shown in Fig. 6B, can still be connected to the transparent IZO cathode through HATCN. Because of the matching of the HATCN and IZO levels, the electron injection characteristics can still be improved by this level transition layer.
  • the present invention is not limited to the material, the size, and the corresponding thickness of each film layer of the OLED device in the above technical solution, as long as all possible and reasonable fabrications of the object of the present invention can be achieved. Means are all included in the scope of protection of the present invention.
  • a display substrate comprising the organic light emitting diode of any of the above embodiments.
  • a display device comprising the display substrate of any of the above embodiments.
  • a method of fabricating an organic light emitting diode comprising the steps of:
  • An anode, a hole injection layer, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially formed on the substrate;
  • a cathode is fabricated on the level transition layer, the cathode being made of a transparent conductive oxide material.
  • the substrate is a substrate substrate or a substrate on which a film layer is formed.
  • the substrate substrate is made of a material such as glass, silicon wafer, quartz, plastic, and silicon wafer, preferably glass.
  • the anode is made of a material having a high work function and a light transmissive property, such as a transparent conductive oxide (TCO) material, preferably an IZO transparent conductive film.
  • TCO transparent conductive oxide
  • an energy level transition layer is formed on the electron transport layer for transitioning between energy levels between the electron transport layer and the cathode, so that the energy level transition between the electron transport layer and the cathode is smoother, and electron injection is easier.
  • the LUMO energy level of the energy level transition layer is between the work function of the cathode and the LUMO energy level of the electron transport layer, or is close to one of them, so that the energy level transition between the electron transport layer and the cathode can be made more. For smoothing, electrons can be more easily injected into the electron transport layer, thereby reducing the accumulation of electrons in the interface or lowering the operating voltage.
  • the above step of fabricating the level transition layer further includes the steps of forming an n-type material layer on the electron transport layer and forming a low LUMO e-type material layer on the n-type material layer.
  • the n-type material layer can be formed using an electron injecting material doped with a metal material or an electron injecting material doped with an alkali metal compound.
  • the metal material is preferably lithium (Li); or a doping material obtained by doping LiQ and Ca or an alkali metal compound such as Cs 2 CO 3 , CsF or NaF may be used.
  • the low LUMO e type material layer is formed using a low LUMO e type material suitable for forming a hole injection layer.
  • a low LUMO e type material suitable for forming a hole injection layer for example, 1,4,5,8,9,11-hexaazatriphenylene-hexanitrile (HATCN), F4TCNQ, copper phthalocyanine (CuPc), 2T-NaTa, TcTa, etc., preferably HAT-CN.
  • the LUMO energy level of the low LUMO e-type material is between 4 eV and 7 eV, thus connecting the electron transport layer and the cathode by using an energy level transition layer including an n-type material layer and a low LUMO e-type material layer, that is, through energy level transition
  • the layer connects the TCO material to the LUMO of the hole-type material to reduce the difficulty of electron injection and reduce the influence of the energy level difference between the electron transport layer and the cathode, thereby making the TCO material a material suitable for the cathode.
  • the OLED device produced by the preparation method provided by the present invention is easier to inject electrons due to a smoother transition of the energy level between the electron transport layer and the cathode.
  • the operating voltage of the OLED device is greatly reduced, thereby greatly improving the service life of the OLED device, and improving the short life and excessive operating voltage of the OLED device due to the TCO process or energy level mismatch.
  • the cathode is made of a transparent conductive material.
  • the transparent conductive material is a transparent conductive oxide (TCO) material, such as a metal including aluminum, indium, tin, zinc, gallium, and the like.
  • TCO transparent conductive oxide
  • the oxides are, for example, indium zinc oxide IZO, indium tin oxide ITO, indium aluminum oxide AITO, zinc aluminum oxide AZO, fluorine doped tin oxide FTO, and the like.
  • the method further includes the step of forming a sputtering protection layer on the energy level transition layer, wherein the sputtering protection layer is used for forming the cathode by sputtering To protect the energy level transition layer from damage.
  • the sputter protection layer is made of a p-type organic material, such as CuPc.
  • CuPc is a hole transporting material, and directly forming it between the cathode and the electron transporting layer causes the operating voltage of the OLED device to be large and the lifetime to be lowered.
  • CuPc may react with the carrier of the low LUMO e-type material layer in the energy level transition layer 6, so that holes are more smoothly injected into the cathode, and the operating voltage of the OLED device is prevented from becoming large. The problem of reduced life.
  • the present invention is not limited to the material, the size, and the corresponding thickness of each film layer of the OLED device in the above technical solution, as long as all possible and reasonable manufacturing means capable of achieving the object of the present invention are included. Within the scope of protection of the present invention.

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Abstract

一种有机发光二极管及其制备方法以及包括该有机发光二极管的显示基板和显示装置。该有机发光二极管包括阳极(1)、空穴注入层(2)、空穴传输层(3)、有机发光层(4)、电子传输层(5)和阴极(7),其中,阴极(7)由透明导电氧化物材料制成;电子传输层(5)与阴极(7)之间形成有能级过渡层(6),用于对于电子传输层(5)与阴极(7)之间的能级进行过渡,以降低电子注入的难度。相较于现有技术中的OLED器件,该OLED器件的电子注入更为容易,OLED器件的操作电压大大降低,从而大大提高了OLED器件的使用寿命,进而改善了因TCO制程或能级不匹配造成的OLED器件的寿命较短和操作电压过大的问题。

Description

有机发光二极管及其制备方法、显示基板、显示装置 技术领域
本发明涉及显示技术领域,尤其涉及有机发光二极管(OLED)及其制备方法,以及包括前述有机发光二极管的显示基板和显示装置。
背景技术
随着多媒体技术的发展以及信息化程度的不断提高,人们对于平板显示装置性能的要求越来越高。与液晶显示器相比,有机电致发光显示器具有自主发光、低电压直流驱动、全固化、视角宽、颜色丰富等一系列优点。同时,有机电致发光显示器不需要背光源,并且视角大,功耗低,其响应速度可达液晶显示器的1000倍,但其制造成本却低于同等分辨率的液晶显示器。因此,有机电致发光显示器有着更为广阔的应用前景。
有机电致发光二极管(OLED)是在有机材料中将电能转化为光能的发光器件。常规的OLED结构包括顺序叠置的阳极、发光材料层和阴极。其发光原理是从阳极和阴极注入的空穴和电子在发光材料层中复合产生激子从而实现发光。根据光的出射方向,OLED分为底发射OLED和顶发射OLED。图1为现有技术常用的底发射OLED的结构示意图,其包括依次排列的反射阴极11、电子传输层12、发光层13、空穴传输层14、透明阳极15和基底16。这种器件生长在透明基底上,以氧化铟锡(ITO)为透明阳极,光从ITO基底16侧射出,故称为底发射器件(Bottom-emitting OLED,简称BEOLED)。而顶发射OLED(Top-emitting OLED,简称TEOLED)射出的光则是来自顶电极一侧,该器件包括依次排列的阴极21、电子传输层22、发光层23、空穴传输层24、反射阳极25和基底26,如图2所示。对于顶发射OLED,光从阴极21侧射出。
目前的柔性OLED面板一般采用薄膜晶体管TFT(Thin Film Transistor)阵列驱动,若采用常规的底发射结构器件,柔性OLED面板的发光只能从驱动该面板的TFT主板上设置的开口部射出。因此,透出面板外的发光仅 占发光层发光的30%-50%,大部分发光都被浪费。而采用顶发射结构可以解决普通的底发射器件开口率低的不足,从器件的顶部半透明电极表面直接获取发光,对开口率几乎没有影响,有利于实现大型、高信息含量、高显示亮度、高分辨率的有机平板显示器。另外,顶发射器件结构还可以实现光谱的窄化,对发射波长的选择并提高器件发光的色纯度。
对于顶发射OLED器件,一般使用薄金属作为位于顶端的阴极制作材料,但金属阴极太薄会使得器件的导电率不好,且会形成微腔效应,使得器件的光学设计变得非常复杂,故常以透明导电氧化物(Transparent Conductive Oxide,简称TCO)代替薄金属作为顶发射OLED器件的阴极。目前常用的TCO材料包括氧化铟锡(ITO)、铟锌氧化物(IZO)等材料,但这些TCO材料通常适合用于制作阳极,因此在使用TCO材料作为阴极以增大顶发射OLED器件的透过率时,这些材料由于功函数与电子传输层(Election Transport Layer,简称ETL)的最低未占据分子轨道(Lowest Unoccupied Molecular Orbital,简称LUMO)能级不匹配,会使得OLED器件的寿命大幅降低,操作电压大大上升。比如,若以IZO制作阴极,由于IZO的功函数大约为5eV,其与一般电子传输层的LUMO能级相差较大,如图3所示,就会使得电子注入困难,OLED器件的操作电压上升,寿命降低。
发明内容
为了解决上述现有技术中存在的问题,本发明提出一种有机发光二极管及其制备方法以及包括前述有机发光二极管的显示基板和显示装置。
根据本发明的一方面,提出一种有机发光二极管,该有机发光二极管包括阳极、空穴注入层、空穴传输层、有机发光层、电子传输层和阴极,其中:
所述阴极由透明导电氧化物材料制成;
所述电子传输层与阴极之间形成有能级过渡层,用于对于电子传输层与阴极之间的能级进行过渡,以降低电子注入的难度。
其中,所述能级过渡层包括n型材料层和低LUMO e型材料层。
其中,所述n型材料层由掺杂有金属材料的电子注入材料、掺杂有碱 金属化合物的电子注入材料、LiQ与Ca掺杂得到的掺杂材料和碱金属化合物中的一种来制作。
其中,所述低LUMO e型材料的LUMO能级在4eV~7eV之间。
其中,所述低LUMO e型材料层的材料为HAT-CN、F4TCNQ、酞菁铜、2T-NaTa和TcTa中的一种。
其中,所述透明导电氧化物材料为铟锌氧化物、氧化铟锡、氧化铟铝、氧化锌铝和氟掺杂锡氧化物中的一种。
其中,所述能级过渡层与阴极之间还设有溅镀保护层,用于在以溅镀方式制作阴极时,保护能级过渡层免受损害。
其中,所述溅镀保护层使用CuPc来制作。
根据本发明的另一方面,还提出一种显示基板,所述显示基板包括如上所述的有机发光二极管。
根据本发明的另一方面,还提出一种显示装置,所述显示装置包括如上所述的显示基板。
根据本发明的再一方面,还提出一种有机发光二极管的制备方法,该制备方法包括以下步骤:
在基板上依次制作得到阳极、空穴注入层、空穴传输层、有机发光层和电子传输层;
在所述电子传输层上制作能级过渡层,用于对于电子传输层与阴极之间的能级进行过渡,以降低电子注入的难度;以及
在所述能级过渡层上制作阴极,所述阴极由透明导电氧化物材料制成。
其中,所述制作能级过渡层的步骤进一步包括在所述电子传输层上制作n型材料层,以及在所述n型材料层上制作低LUMO e型材料层的步骤。
其中,所述n型材料层使用掺杂有金属材料的电子注入材料、掺杂有碱金属化合物的电子注入材料、LiQ与Ca掺杂得到的掺杂材料和碱金属化合物中的一种来制作。
其中,所述低LUMO e型材料的LUMO能级在4eV~7eV之间。
其中,所述低LUMO e型材料层使用HAT-CN、F4TCNQ、酞菁铜、2T-NaTa和TcTa中的一种来制作。
其中,所述透明导电氧化物材料为铟锌氧化物、氧化铟锡、氧化铟铝、 氧化锌铝和氟掺杂锡氧化物中的一种。
其中,在制作得到能级过渡层之后还包括在所述能级过渡层上制作溅镀保护层的步骤。
由前文可知,由于TCO材料的能级特性,其通常适合用于制作阳极,因此在通常使用透明导电氧化物(TCO)作为阴极制作材料的顶发射OLED器件中,其与一般电子注入层的LUMO能级并不相匹配。而本发明通过利用包括n型材料层和低LUMO e型材料(deeper LUMO e-type material)层的能级过渡层来连接电子传输层与阴极,使得电子传输层与阴极之间的能级差减小,从而使得TCO材料成为适合制作阴极的材料。本发明中的OLED器件由于电子传输层与阴极之间的能级差减小,即电子传输层与阴极之间的能级过渡更为平滑,因此电子注入更为容易,OLED器件的操作电压大大降低,从而大大提高了OLED器件的使用寿命,改善了因TCO制程或能级不匹配造成的OLED器件的寿命较短和操作电压过大的问题。
附图说明
图1是现有技术中常用的底发射OLED的结构示意图;
图2是现有技术中常用的顶发射OLED的结构示意图;
图3是现有技术中以IZO制作阴极得到的OLED器件的能级匹配示意图;
图4是本发明有机发光二极管的结构示意图;
图5A是根据本发明一实施例的有机发光二极管的结构示意图;
图5B是图5A所示的有机发光二极管的能级匹配示意图;
图6A是根据本发明另一实施例的有机发光二极管的结构示意图;以及
图6B是图6A所示的有机发光二极管的能级匹配示意图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图,对本发明进一步详细说明。
TCO材料通常适合用于制作阳极,在使用TCO材料作为阴极以增大 顶发射OLED器件的透过率时,发明人注意到TCO材料的能级特性与一般电子传输层的LUMO能级并不相匹配。因此,本发明通过在电子传输层与阴极之间设置能级过渡层来解决这一问题。
根据本发明的一方面,提出一种有机发光二极管,如图4所示,所述有机发光二极管包括:阳极1、空穴注入层(Hole Injection Layer,简称HIL)2、空穴传输层(Hole Transport Layer,简称HTL)3、有机发光层(Emitting Material Layer,简称EML)4、电子传输层(Electron Transport Layer,简称ETL)5、能级过渡层6和阴极7,其中:
所述阴极7由透明导电材料制成。可选地,所述透明导电材料为透明导电氧化物(Transparent Conductive Oxide,简称TCO)材料,比如包含有铝、铟、锡、锌、镓等金属的氧化物,如:铟锌氧化物IZO、氧化铟锡ITO、氧化铟铝AITO、氧化锌铝AZO、氟掺杂锡氧化物FTO等。
在前述的有机发光二极管中,形成在电子传输层5与阴极7之间的能级过渡层6用于对于电子传输层5与阴极7之间的能级进行过渡,以降低电子注入的难度,减小电子传输层与阴极之间的能级差带来的影响。
能级过渡层6的LUMO能级介于阴极7的逸出功与电子传输层5的LUMO能级之间,或是与其中之一接近,这样就可以减小电子传输层5与阴极7之间的能级差带来的影响,使得电子传输层5与阴极7之间的能级过渡更为平滑,电子就可以更容易地注入到电子传输层5中,从而减少电子在介面的堆积或是降低操作电压。
能级过渡层6包括n型材料层和低LUMO e型材料(deeper LUMO e-type material)层。其中,n型材料层既可使用掺杂有金属材料的电子注入材料、掺杂有碱金属化合物的电子注入材料来制作,所述金属材料可以为锂(Li)、钠(Na)、钾(K)、铷(Rb)、铯(Cs);也可使用LiQ与Ca掺杂得到的掺杂材料或者Cs2CO3、CsF、NaF等碱金属化合物来制作。
其中,所述低LUMO e型材料层使用适于制作空穴注入层的低LUMO e型材料来制作。比如,1,4,5,8,9,11-hexaazatriphenylene-hexanitrile(HATCN)、F4TCNQ、酞菁铜(CuPc)、2T-NaTa、TcTa等材料,优选为HAT-CN。
所述低LUMO e型材料的LUMO能级在4eV~7eV之间,这样,通过利用包括n型材料层和低LUMO e型材料层的能级过渡层6来连接电子传 输层与阴极,即通过所述能级过渡层6使得TCO材料与空穴型材料的LUMO连接,以降低电子注入的难度,减小电子传输层与阴极之间的能级差带来的影响,从而使得TCO材料成为适合制作阴极的材料。相较于单独使用TCO材料制作阴极的顶发射OLED器件,本发明中的OLED器件由于电子传输层与阴极之间的能级过渡更为平滑,因此电子的注入更为容易,OLED器件的操作电压大大降低,从而大大提高了OLED器件的使用寿命,改善了因TCO制程或能级不匹配造成的OLED器件的寿命较短和操作电压过大的问题。
其中,阳极1由具有高功函数与可透光性的材料制成,比如透明导电氧化物(TCO)材料,优选为IZO透明导电膜。
在本发明一实施例中,所述OLED器件还包括基板,阳极1形成在所述基板上。
其中,所述基板为衬底基板或形成有其他功能膜层的基板。
可选地,所述衬底基板的制作材料包括玻璃、硅片、石英、塑料以及硅片等材料,优选为玻璃。
在本发明一实施例中,所述能级过渡层6与阴极7之间还设有溅镀保护层8,用于在以溅镀方式制作阴极7时,保护能级过渡层6免受损害。
其中,所述溅镀保护层8使用p型有机材料制作,比如CuPc。
CuPc是一种空穴传输材料,将它直接制作于阴极与电子传输层之间会使得OLED器件的操作电压较大,寿命降低。而利用本发明的上述结构,CuPc可能与能级过渡层6中的低LUMO e型材料层发生载子产生的作用,从而使空穴更顺利地注入阴极,避免出现OLED器件的操作电压变大,寿命降低的问题。
接下来以具体的实施例对于本发明进行详细的说明。
图5A是根据本发明一实施例的OLED器件的结构示意图。如图5A所示,所述OLED器件包括阳极1、空穴注入层(HIL)2、空穴传输层(HTL)3、有机发光层(EML)4、电子传输层(ETL)5、能级过渡层6、溅镀保护层8和阴极7,其中:
所述阴极7由透明导电材料制成。可选地,所述透明导电材料为透明导电氧化物(TCO)材料,比如包含有铝、铟、锡、锌、镓等金属的氧化 物,如:铟锌氧化物IZO、氧化铟锡ITO、氧化铟铝AITO、氧化锌铝AZO、氟掺杂锡氧化物FTO等,本实施例优选IZO材料作为阴极。
在前述的有机发光二极管中,形成在电子传输层5与阴极7之间的能级过渡层6用于对于电子传输层5与阴极7之间的能级进行过渡,以降低电子注入的难度,减小电子传输层5与阴极7之间的能级差带来的影响。
能级过渡层6的LUMO能级介于阴极7的逸出功与电子传输层5的LUMO能级之间,或是与其中之一接近,这样就可以减小电子传输层5与阴极7之间的能级差带来的影响,使得电子传输层5与阴极7之间的能级过渡更为平滑,电子就可以更容易地注入到电子传输层5中,从而减少电子在介面的堆积或是降低操作电压。
能级过渡层6包括n型材料层和HAT-CN材料层。其中,n型材料层由掺杂有锂(Li)的电子注入材料来制作。
所述HAT-CN材料的LUMO能级在4eV~7eV之间,这样,通过利用包括n型材料层和HAT-CN材料层的能级过渡层6来连接电子传输层与阴极,即通过所述能级过渡层6使得TCO材料与HAT-CN材料的LUMO能级连接,可以使得电子传输层与阴极之间的能级过渡更为平滑,如图5B所示。相较于单独使用TCO材料制作阴极的顶发射OLED器件,由于电子传输层与阴极之间的能级过渡更为平滑,本实施例中的OLED器件的电子注入更为容易,OLED器件的操作电压大大降低,从而大大提高了OLED器件的使用寿命,改善了因TCO制程或能级不匹配造成的OLED器件的寿命较短和操作电压过大的问题。
其中,阳极1由具有高功函数与可透光性的材料制成,比如透明导电氧化物(TCO)材料,优选为IZO透明导电膜。
溅镀保护层8使用CuPc来制作,用于在以溅镀方式制作阴极时,保护能级过渡层6免受损害。
上文提及,CuPc是一种空穴传输材料,将它直接制作于阴极与电子传输层之间会使得OLED器件的操作电压较大,寿命降低。而利用本发明实施例的上述结构,CuPc可能与能级过渡层6中的低LUMO e型材料层发生载子产生的作用,从而使空穴更顺利地注入阴极,如图5B所示,可避免出现OLED器件的操作电压变大,寿命降低的问题。
另外,所述OLED器件还包括基板,阳极1形成在所述基板上。
其中,所述基板为衬底基板或形成有膜层的基板。
可选地,所述衬底基板的制作材料包括玻璃、硅片、石英、塑料以及硅片等材料,优选为玻璃。
图6A是根据本发明另一实施例的OLED器件的结构示意图,如图6A所示,所述OLED器件包括阳极1、空穴注入层(HIL)2、空穴传输层(HTL)3、有机发光层(EML)4、电子传输层(ETL)5、能级过渡层6和阴极7,本实施例中,n型材料层由LiQ与Ca掺杂得到的掺杂材料形成,虽然并未设置溅镀保护层8,如图6B所示,其仍可通过HATCN连接透明IZO阴极,因为HATCN与IZO能级的匹配,通过此能级过渡层仍可以改进其电子注入特性。
其余膜层的结构与制作材料均与上一实施例相同,在此不作赘述。
需要说明的是,除了上述限定,本发明对于上述技术方案中OLED器件各膜层的制作材料、尺寸及相应的厚度均不作额外限定,只要能够实现本发明的发明目的的所有可能、合理的制作手段均包含在本发明的保护范围内。
根据本发明的另一方面,还提出一种显示基板,所述显示基板包括如上任一实施例所述的有机发光二极管。
根据本发明的另一方面,还提出一种显示装置,所述显示装置包括如上任一实施例所述的显示基板。
根据本发明的再一方面,还提出一种有机发光二极管的制备方法,所述制备方法包括以下步骤:
在基板上依次制作得到阳极、空穴注入层、空穴传输层、有机发光层和电子传输层;
在电子传输层上制作能级过渡层,用于对于电子传输层与阴极之间的能级进行过渡,以降低电子注入的难度;以及
在能级过渡层上制作阴极,所述阴极由透明导电氧化物材料制成。
其中,所述基板为衬底基板或形成有膜层的基板。
可选地,所述衬底基板的制作材料包括玻璃、硅片、石英、塑料以及硅片等材料,优选为玻璃。
其中,所述阳极由具有高功函数与可透光性的材料制成,比如透明导电氧化物(TCO)材料,优选为IZO透明导电膜。
其中,在电子传输层上制作能级过渡层,用于对于电子传输层与阴极之间的能级进行过渡,使得电子传输层与阴极之间能级过渡更为平滑,电子的注入更为容易。
能级过渡层的LUMO能级介于阴极的逸出功与电子传输层的LUMO能级之间,或是与其中之一接近,这样就可以使电子传输层与阴极之间的能级过渡更为平滑,电子就可以更容易地注入到电子传输层中,从而减少电子在介面的堆积或是降低操作电压。
上述制作能级过渡层的步骤进一步包括在电子传输层上制作n型材料层,以及在n型材料层上制作低LUMO e型材料层的步骤。
其中,n型材料层可使用掺杂有金属材料的电子注入材料、掺杂有碱金属化合物的电子注入材料来制作。金属材料优选为锂(Li);也可使用LiQ与Ca掺杂得到的掺杂材料或者Cs2CO3、CsF、NaF等碱金属化合物来制作。
其中,低LUMO e型材料层使用适于制作空穴注入层的低LUMO e型材料来制作。比如1,4,5,8,9,11-hexaazatriphenylene-hexanitrile(HATCN)、F4TCNQ、酞菁铜(CuPc)、2T-NaTa、TcTa等材料,优选为HAT-CN。
低LUMO e型材料的LUMO能级在4eV~7eV之间,这样,通过利用包括n型材料层和低LUMO e型材料层的能级过渡层来连接电子传输层与阴极,即通过能级过渡层使得TCO材料与空穴型材料的LUMO连接,以降低电子注入的难度,减小电子传输层与阴极之间的能级差带来的影响,从而使得TCO材料成为适合制作阴极的材料。相较于单独使用TCO材料制作阴极的顶发射OLED器件,根据本发明提供的制备方法制得的OLED器件由于电子传输层与阴极之间的能级过渡更为平滑,因此电子的注入更为容易,OLED器件的操作电压大大降低,从而大大提高了OLED器件的使用寿命,改善了因TCO制程或能级不匹配造成的OLED器件的寿命较短和操作电压过大的问题。
其中,所述阴极由透明导电材料制成。可选地,所述透明导电材料为透明导电氧化物(TCO)材料,比如包含有铝、铟、锡、锌、镓…等金属 的氧化物,如:铟锌氧化物IZO、氧化铟锡ITO、氧化铟铝AITO、氧化锌铝AZO、氟掺杂锡氧化物FTO等。
在本发明一实施例中,在制作得到能级过渡层之后还包括在所述能级过渡层上制作溅镀保护层的步骤,所述溅镀保护层用于在以溅镀方式制作阴极时,以保护能级过渡层免受损害。
其中,所述溅镀保护层使用p型有机材料制作,比如CuPc。
上文提及,CuPc是一种空穴传输材料,将它直接制作于阴极与电子传输层之间会使得OLED器件的操作电压较大,寿命降低。而利用本发明的上述结构,CuPc可能与能级过渡层6中的低LUMO e型材料层发生载子产生的作用,从而使空穴更顺利地注入阴极,避免出现OLED器件的操作电压变大,寿命降低的问题。
需要说明的是,上述各膜层的制作方法均可采用现有技术中常用的OLED材料层的制作工艺,在此不作赘述。
另外,除了上述限定,本发明对于上述技术方案中OLED器件各膜层的制作材料、尺寸及相应的厚度均不作额外限定,只要能够实现本发明的发明目的的所有可能、合理的制作手段均包含在本发明的保护范围内。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (17)

  1. 一种有机发光二极管,其特征在于,该有机发光二极管包括阳极、空穴注入层、空穴传输层、有机发光层、电子传输层和阴极,
    所述阴极由透明导电氧化物材料制成;
    所述电子传输层与所述阴极之间形成有能级过渡层,用于对所述电子传输层与所述阴极之间的能级进行过渡,以降低电子注入的难度。
  2. 根据权利要求1所述的有机发光二极管,其特征在于,所述能级过渡层包括n型材料层和低LUMO e型材料层。
  3. 根据权利要求2所述的有机发光二极管,其特征在于,所述n型材料层由掺杂有金属材料的电子注入材料、掺杂有碱金属化合物的电子注入材料、LiQ与Ca掺杂得到的掺杂材料和碱金属化合物中的一种来制作。
  4. 根据权利要求2所述的有机发光二极管,其特征在于,所述低LUMO e型材料的LUMO能级在4eV~7eV之间。
  5. 根据权利要求2所述的有机发光二极管,其特征在于,所述低LUMO e型材料层的材料为HAT-CN、F4TCNQ、酞菁铜、2T-NaTa和TcTa中的一种。
  6. 根据权利要求1所述的有机发光二极管,其特征在于,所述透明导电氧化物材料为铟锌氧化物、氧化铟锡、氧化铟铝、氧化锌铝和氟掺杂锡氧化物中的一种。
  7. 根据权利要求1-6任一所述的有机发光二极管,其特征在于,所述能级过渡层与所述阴极之间还设有溅镀保护层,用于在以溅镀方式制作阴极时,保护能级过渡层免受损害。
  8. 根据权利要求7所述的有机发光二极管,其特征在于,所述溅镀保护层的材料为CuPc。
  9. 一种显示基板,其特征在于,所述显示基板包括如权利要求1-8中任一项所述的有机发光二极管。
  10. 一种显示装置,其特征在于,所述显示装置包括如权利要求9所述的显示基板。
  11. 一种有机发光二极管的制备方法,其特征在于,该制备方法包括 以下步骤:
    在基板上依次制作得到阳极、空穴注入层、空穴传输层、有机发光层和电子传输层;
    在所述电子传输层上制作能级过渡层,用于对于电子传输层与阴极之间的能级进行过渡,以降低电子注入的难度;以及
    在所述能级过渡层上制作阴极,所述阴极由透明导电氧化物材料制成。
  12. 根据权利要求11所述的制备方法,其特征在于,所述制作能级过渡层的步骤进一步包括在所述电子传输层上制作n型材料层,以及在所述n型材料层上制作低LUMO e型材料层的步骤。
  13. 根据权利要求12所述的制备方法,其特征在于,所述n型材料层使用掺杂有金属材料的电子注入材料、掺杂有碱金属化合物的电子注入材料、LiQ与Ca掺杂得到的掺杂材料和碱金属化合物中的一种来制作。
  14. 根据权利要求12所述的制备方法,其特征在于,所述低LUMO e型材料的LUMO能级在4eV~7eV之间。
  15. 根据权利要求12所述的制备方法,其特征在于,所述低LUMO e型材料层使用HAT-CN、F4TCNQ、酞菁铜、2T-NaTa和TcTa中的一种来制作。
  16. 根据权利要求11所述的制备方法,其特征在于,所述透明导电氧化物材料为铟锌氧化物、氧化铟锡、氧化铟铝、氧化锌铝和氟掺杂锡氧化物中的一种。
  17. 根据权利要求8-16任一所述的制备方法,其特征在于,在制作得到能级过渡层之后还包括在所述能级过渡层上制作溅镀保护层的步骤。
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