WO2013078590A1 - 一种聚合物电致发光器件及其制备方法 - Google Patents

一种聚合物电致发光器件及其制备方法 Download PDF

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WO2013078590A1
WO2013078590A1 PCT/CN2011/083044 CN2011083044W WO2013078590A1 WO 2013078590 A1 WO2013078590 A1 WO 2013078590A1 CN 2011083044 W CN2011083044 W CN 2011083044W WO 2013078590 A1 WO2013078590 A1 WO 2013078590A1
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layer
electroluminescent device
electron
polymer electroluminescent
lithium
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English (en)
French (fr)
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周明杰
王平
黄辉
梁禄生
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Priority to CN201180074548.5A priority Critical patent/CN104025333A/zh
Priority to EP11876402.6A priority patent/EP2787552A4/en
Priority to PCT/CN2011/083044 priority patent/WO2013078590A1/zh
Priority to JP2014542672A priority patent/JP2015504605A/ja
Priority to US14/360,923 priority patent/US20140332788A1/en
Publication of WO2013078590A1 publication Critical patent/WO2013078590A1/zh
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/167—Electron transporting layers between the light-emitting layer and the anode
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H10K50/181—Electron blocking layers

Definitions

  • the present invention relates to a polymer electroluminescent device and a method of preparing the same.
  • the principle of OLED illumination is based on the lowest unoccupied molecular orbital of electrons injected from the cathode into the organic matter under the action of an applied electric field (LUMO). ), and the highest occupied orbit of holes injected from the anode to the organic matter (HOMO ). Electrons and holes meet and recombine in the luminescent layer to form excitons. The excitons migrate under the action of an electric field, transfer energy to the luminescent material, and excite the electrons from the ground state to the excited state. The excited state energy is deactivated by radiation to generate photons. , release light energy.
  • LUMO applied electric field
  • HOMO organic matter
  • an organic material having a high LUMO level is generally used as an electron blocking layer, and a hole transport path is an anode.
  • the hole transport layer - the light-emitting layer, and the electron transport path is a cathode - electron transport layer - a light-emitting layer, and when holes and electrons reach the light-emitting layer, they are combined to form exciton light.
  • the lower energy level barrier causes electrons to pass through the light-emitting layer to the hole transport layer, causing electrons and holes to not be effectively combined, and the luminous efficiency is low.
  • the traditional method for blocking electrons is to deposit a layer of high between the light-emitting layer and the hole transport layer.
  • An organic material of LUMO level (about 3.2 eV) is used to block electrons and confine electrons to the light-emitting layer.
  • the LUMO barrier between the general electron blocking layer and the light-emitting layer is about 0.5 ev.
  • the left and right can effectively block, but the LUMO level of the traditionally used materials is mostly different from the luminescent layer (the LUMO level of the luminescent layer is about 3.5 eV), and the blocking effect is not obvious.
  • a polymer electroluminescent device comprising an anode conductive substrate, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, which are sequentially stacked, the electron blocking layer
  • the material is selected from one of lithium fluoride, lithium carbonate, lithium oxide, and lithium chloride.
  • the anode conductive substrate is selected from the group consisting of indium tin oxide glass, fluorine-doped tin oxide glass, aluminum-doped zinc oxide glass, and indium-doped zinc oxide glass.
  • the material of the hole injection layer is selected from the group consisting of molybdenum oxide, tungsten trioxide, and vanadium pentoxide.
  • the material of the hole transport layer is selected from the group consisting of 1,1-di[4-[N, N'-di(p-tolyl) Amino] phenyl] cyclohexane, N, N'-bis(3-methylphenyl)-N, N'-diphenyl-4,4'-biphenyldiamine, 4,4',4 ''- ⁇ ( carbazole -9-yl) Triphenylamine and one of N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-biphenyldiamine.
  • the material of the electron transport layer is selected from the group consisting of 2-(4-biphenyl)-5-(4-tert-butyl)phenyl -1,3,4-oxadiazole, 8-hydroxyquinoline aluminum, 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivatives and N-arylbenzene One of the imidazoles.
  • the material of the light-emitting layer is an organic light-emitting material; or the organic light-emitting material is doped as a guest material in a host material, and the mixed material is composed, and the doping mass ratio of the guest material is 1 %-20%
  • the host material is one or two of a hole transporting material and an electron transporting material;
  • the organic light-emitting material is selected from the group consisting of 4-(dinitylmethyl)-2-butyl-6-(1,7,7-tetramethyljuroxidine-9-vinyl)-4H-pyran , 8-hydroxyquinoline aluminum, bis(4,6-difluorophenylpyridine-N,C 2 )pyridine hydrazide, bis(2-methyl-diphenyl[f,h]quinoxaline) At least one of (acetylacetone) ruthenium and tris(2-phenylpyridine) ruthenium;
  • the hole transporting material is selected from the group consisting of 1,1-di[4-[N,N'-bis(p-tolyl)amino]phenyl] Cyclohexane, N, N'-bis(3-methylphenyl)-N, N'-diphenyl-4,4'-biphenyldiamine, 4,4',4''-tris( ⁇ Azole-9-yl) a triphenylamine and one of N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-biphenyldiamine;
  • the electron transporting material is selected from the group consisting of 2-(4-biphenyl)-5-(4-tert-butyl)phenyl-1,3,4-oxadiazole, One of 8-hydroxyquinoline aluminum, 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative, and N-arylbenzimidazole.
  • the material of the electron injecting layer is selected from the group consisting of barium carbonate, azide, and lithium fluoride.
  • the material of the cathode is selected from the group consisting of silver, aluminum, platinum, and gold.
  • a method for preparing a polymer electroluminescent device comprising the steps of:
  • a hole injecting layer, a hole transporting layer, an electron blocking layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode are sequentially vacuum-deposited on the anode conductive substrate to obtain the polymer electroluminescent device;
  • the material of the electron blocking layer is selected from one of lithium fluoride, lithium carbonate, lithium oxide, and lithium chloride.
  • the surface treatment of the anode conductive substrate includes the step of using an oxygen plasma treatment, and the processing time is 2-15. Minutes, the power is 10 ⁇ 50W.
  • the polymer electroluminescent device is prepared by using a lithium compound as an inorganic electron blocking layer, which is low in material cost, simple in source, and most importantly, has a low work function of about 2.0 eV, and can be formed between the light emitting layer and the light emitting layer. 1.0eV
  • the transition barrier can make the electrons reconcile as much as possible with the holes in the light-emitting layer, thereby effectively blocking electrons from entering the hole transport layer, increasing the recombination probability of the excitons, thereby improving the light emission of the polymer electroluminescent device. effectiveness.
  • FIG. 1 is a schematic structural view of a polymer electroluminescent device according to an embodiment
  • FIG. 2 is a schematic view showing a preparation flow of a polymer electroluminescent device according to an embodiment
  • Example 3 is a device level diagram of the inorganic electron blocking layer of Example 1;
  • Figure 4 is the embodiment 1 A plot of brightness versus lumen efficiency for a polymer electroluminescent device versus a comparative polymer electroluminescent device.
  • a polymer electroluminescent device 100 of an embodiment includes an anode conductive substrate 110 which is sequentially stacked.
  • the anode conductive substrate 110 is preferably indium tin oxide glass (ITO), fluorine-doped tin oxide glass (FTO), or aluminum-doped zinc oxide glass (AZO) and a type of indium-doped zinc oxide glass (IZO).
  • ITO indium tin oxide glass
  • FTO fluorine-doped tin oxide glass
  • AZO aluminum-doped zinc oxide glass
  • IZO indium-doped zinc oxide glass
  • the material of the hole injection layer 120 is preferably one of molybdenum oxide (MoO 3 ), tungsten trioxide (WO 3 ), and vanadium pentoxide (V 2 O 5 ), and the thickness is preferably 20 to 80 nm. Further preferably, the material of the hole injection layer 120 is MoO 3 and has a thickness of 40 nm.
  • MoO 3 molybdenum oxide
  • WO 3 tungsten trioxide
  • V 2 O 5 vanadium pentoxide
  • the material of the hole transport layer 130 is preferably 1,1-di[4-[N,N'-bis(p-tolyl)amino] Phenyl]cyclohexane (TAPC), N, N'-bis(3-methylphenyl)-N, N'-diphenyl-4,4'-biphenyldiamine (TPD), 4,4',4''-tris(carbazol-9-yl)triphenylamine (TCTA) and N,N'-(1-naphthyl)-N, N'-diphenyl-4,4'- One of biphenyldiamine (NPB) preferably has a thickness of 20-60 nm. Further preferably, the material of the hole transport layer 130 is NPB and has a thickness of 40 nm.
  • the material of the electron blocking layer 140 is preferably one of lithium fluoride (LiF), lithium carbonate (Li 2 CO 3 ), lithium oxide (Li 2 O ), and lithium chloride (LiF ), and the thickness is preferably 0.7 to 5 nm.
  • Light emitting layer 150 The material is an organic light-emitting material; or the organic light-emitting material is doped as a guest material in a mixed material composed of a host material, and the doping mass ratio of the guest material is 1%-20%. .
  • the host material is one or both of a hole transporting material and an electron transporting material.
  • the thickness of the light-emitting layer 150 is preferably 2 to 50 nm.
  • the organic light-emitting material is selected from the group consisting of 4-(dinitylmethyl)-2-butyl-6-(1,7,7-tetramethyljuroxidine-9-vinyl)-4H-pyran (DCJTB), 8-hydroxyquinoline aluminum (Alq 3 ), bis( 4,6-difluorophenylpyridine-N,C 2 )pyridine hydrazide (FIrpic), bis(2-methyl-diphenyl) At least one of aryl [f,h]quinoxaline)(acetylacetonate) ruthenium (Ir(MDQ) 2 (acac)) and tris(2-phenylpyridine) ruthenium (Ir(ppy) 3 );
  • the hole transporting material is selected from the group consisting of 1,1-bis[4-[N,N'-bis(p-tolyl)amino]phenyl]cyclohexane (TAPC), N, N'-bis(3-methyl) Phenyl)
  • the material of the light-emitting layer 150 is Alq 3 and has a thickness of 30 nm.
  • the material of the electron transport layer 160 is preferably 2-(4-biphenyl)-5-(4-tert-butyl)phenyl-1,3,4- One of oxadiazole, 8-hydroxyquinoline aluminum, 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and N-arylbenzimidazole,
  • the thickness is preferably 40-80 nm .
  • the material of the electron transport layer 160 is Bphen and has a thickness of 60 nm.
  • the material of the electron injection layer 170 is preferably one of cesium carbonate (Cs 2 CO 3 ), azide ruthenium (CsN 3 ), and lithium fluoride (LiF ), and has a thickness of 0.5 to 10 nm. Further preferably, the material of the electron injecting layer 170 is CsN 3 and has a thickness of 5 nm.
  • the material of the cathode 180 is preferably one of silver (Ag), aluminum (Al), platinum (Pt) and gold (Au), and the thickness is preferably 80-250nm. Further preferably, the material of the cathode 180 is selected from Ag and has a thickness of 100 nm.
  • the polymer electroluminescent device is prepared by using a lithium compound as an inorganic electron blocking layer, which is low in material cost, simple in source, and most importantly, has a low work function of about 2.0 eV, and can be formed between the light emitting layer and the light emitting layer.
  • the transition barrier of 1.0eV can make the electrons recombine as much as possible in the luminescent layer and improve the recombination probability of the excitons, thereby improving the luminescence efficiency and greatly improving the device preparation efficiency.
  • the embodiment also provides a method for preparing a polymer electroluminescent device, as shown in FIG. 2, comprising the following steps:
  • Step S1 An anode conductive substrate is provided and subjected to surface treatment.
  • the anode conductive substrate provided may be ultrasonically washed with detergent, deionized water, acetone, ethanol and isopropanol for a period of time to remove impurities on the surface of the substrate, and then the anode conductive substrate after cleaning.
  • Surface treatment such as oxygen plasma treatment, etc., oxygen plasma treatment time can be For 2 to 15 minutes, the power is 10 to 50 W, and the anode conductive substrate is preferably treated with an oxygen plasma of 35 W for 5 minutes.
  • Step S2 sequentially depositing a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode on an anode conductive substrate to obtain the polymer electroluminescent device; wherein, the electron
  • the material of the barrier layer is selected from one of lithium fluoride, lithium carbonate, lithium oxide, and lithium chloride.
  • the preparation process has the advantages of simple principle, easy availability of raw materials, high preparation efficiency, and wide application.
  • the instruments used in the following examples are as follows: high vacuum coating equipment (Shenyang Scientific Instrument Development Center Co., Ltd., pressure ⁇ 1 ⁇ 10 -3 Pa), current-voltage tester (Keithly, USA, model: 2602), electroluminescence Spectrometer (American photo research company, model: PR650) and screen brightness meter (Beijing Normal University, model: ST-86LA).
  • Example 1 ITO/MoO 3 /NPB /LiF/Alq 3 /Bphen/CsN 3 /Ag
  • ITO glass substrate cut into a suitable shape, and then ultrasonically use detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes. , removing the impurities on the surface of the substrate, cleaning it and then performing oxygen plasma treatment for 5 minutes, the power is 35W;
  • the hole injection layer was prepared by vacuum evaporation, and the material was MoO 3 with a thickness of 40 nm.
  • the hole transport layer was prepared by vacuum evaporation, and the material was NPB with a thickness of 40 nm.
  • An electron blocking layer was prepared by vacuum evaporation, and the material was LiF with a thickness of 1.5 nm.
  • the luminescent layer was prepared by vacuum evaporation, and the material was Alq 3 with a thickness of 30 nm.
  • the electron transport layer was prepared by vacuum evaporation, and the material was Bphen with a thickness of 60 nm.
  • the electron injecting layer was prepared by vacuum evaporation, and the material was CsN 3 and the thickness was 5 nm.
  • the cathode was prepared by vacuum evaporation, and the material was Ag, and the thickness was 100 nm to obtain the polymer electroluminescent device.
  • image 3 A device level diagram of the electron blocking layer of the present embodiment.
  • the solid line is an energy level structure in which an electron blocking layer is formed using a conventional organic material, and the broken line is added to the LiF electron blocking layer of the present embodiment.
  • the energy level improvement the energy level is from the bottom to the top, the value becomes smaller
  • the barrier of electrons crossing the barrier layer is greatly increased, which can limit the electrons in the light-emitting layer and recombine with the holes.
  • Luminescence improve luminous efficiency.
  • Example 2 IZO/WO 3 /TPD/Li 2 CO 3 /DCJTB/PBD/Cs 2 CO 3 /Al
  • IZO glass substrate is provided, cut into a suitable shape, and then ultrasonicated with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes. , removing the impurities on the surface of the substrate, cleaning it and then performing oxygen plasma treatment for 2 minutes, the power is 50W;
  • the hole injection layer was prepared by vacuum evaporation, and the material was selected from WO 3 and the thickness was 20 nm.
  • the hole transport layer was prepared by vacuum evaporation, and the material was TPD with a thickness of 50 nm.
  • An electron blocking layer was prepared by vacuum evaporation, and the material was Li 2 CO 3 and the thickness was 5 nm.
  • the luminescent layer was prepared by vacuum evaporation, and the material was DCJTB with a thickness of 50 nm.
  • the electron transport layer was prepared by vacuum evaporation, and the material was PBD with a thickness of 80 nm.
  • the electron injecting layer was prepared by vacuum evaporation, and the material was Cs 2 CO 3 and the thickness was 10 nm.
  • the cathode was prepared by vacuum evaporation, and Al was used as the material, and the thickness was 250 nm to obtain the polymer electroluminescent device.
  • Example 3 AZO/V 2 O 5 /TAPC/Li 2 O/ TPBI : Ir(ppy) 3 /TAZ/ CsN 3 /Au
  • AZO glass substrate cut into appropriate shape, and then ultrasonically use detergent, deionized water, acetone, ethanol, isopropanol for 15min. , removing the impurities on the surface of the substrate, cleaning it and then performing oxygen plasma treatment for 15 minutes, the power is 10W;
  • the hole injection layer was prepared by vacuum evaporation, and the material was V 2 O 5 and the thickness was 60 nm.
  • the hole transport layer was prepared by vacuum evaporation, and the material was selected from TAPC with a thickness of 60 nm.
  • An electron blocking layer was prepared by vacuum evaporation, and the material was Li 2 O and the thickness was 2 nm.
  • the luminescent layer was prepared by vacuum evaporation.
  • the material was selected from TPBI: Ir(ppy) 3 and the thickness was 10 nm.
  • the doping mass percentage of Ir(ppy) 3 in the luminescent layer was 15%.
  • the electron transport layer was prepared by vacuum evaporation, and the material was selected from TAZ with a thickness of 40 nm.
  • the electron injecting layer was prepared by vacuum evaporation, and the material was CsN 3 and the thickness was 5 nm.
  • the cathode was prepared by vacuum evaporation, and the material was Au, and the thickness was 80 nm to obtain the polymer electroluminescent device.
  • Example 4 FTO/V 2 O 5 /TAPC/LiF/ TPBI : Ir(MDQ) 2 (acac)/ TPBI/ Cs 2 CO 3 /Au
  • FTO glass substrate cut into appropriate shape, and then ultrasonically use detergent, deionized water, acetone, ethanol, isopropanol for 15min. , removing the impurities on the surface of the substrate, cleaning it and then performing oxygen plasma treatment for 10 min, the power is 30 W;
  • the hole injection layer was prepared by vacuum evaporation, and the material was V 2 O 5 and the thickness was 40 nm.
  • the hole transport layer was prepared by vacuum evaporation, and the material was selected from TAPC with a thickness of 60 nm.
  • the electron blocking layer was prepared by vacuum evaporation, and the material was LiF with a thickness of 0.5 nm.
  • the luminescent layer was prepared by vacuum evaporation.
  • the material was TPBI: Ir(MDQ) 2 (acac) and the thickness was 2 nm.
  • the doping mass percentage of Ir(MDQ) 2 (acac) in the luminescent layer was 1%.
  • the electron transport layer was prepared by vacuum evaporation, and the material was TPBI with a thickness of 50 nm.
  • the electron injecting layer was prepared by vacuum evaporation, and the material was Cs 2 CO 3 with a thickness of 0.5 nm.
  • the cathode was prepared by vacuum evaporation, and the material was Au, and the thickness was 80 nm to obtain the polymer electroluminescent device.
  • Example 5 ITO/ MoO 3 /TCTA/LiCl/TPBI : Firpic/ Alq 3 / CsN 3 /Pt
  • ITO glass substrate Provide ITO glass substrate, cut into a suitable shape, and then ultrasonically use detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes. Remove the impurities on the surface of the substrate, clean it and then perform oxygen plasma treatment for 8 minutes, the power is 40W;
  • the hole injection layer was prepared by vacuum evaporation, and the material was MoO 3 with a thickness of 80 nm.
  • the hole transport layer was prepared by vacuum evaporation, and the material was TCTA with a thickness of 30 nm.
  • the electron blocking layer was prepared by vacuum evaporation, and the material was LiCl with a thickness of 4 nm.
  • the light-emitting layer was prepared by vacuum evaporation, and the material was selected from TPBI: Firpic with a thickness of 25 nm, of which, Firpic The doping mass percentage in the luminescent layer is 20%;
  • the electron transport layer was prepared by vacuum evaporation, and the material was Alq 3 with a thickness of 35 nm.
  • the electron injecting layer was prepared by vacuum evaporation, and the material was CsN 3 and the thickness was 7 nm.
  • the cathode was prepared by vacuum evaporation, and the material was selected to be Pt and the thickness was 80 nm to obtain the polymer electroluminescent device.
  • ITO glass substrate cut into a suitable shape, and then ultrasonically use detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes. , removing the impurities on the surface of the substrate, cleaning it and then performing oxygen plasma treatment for 5 minutes, the power is 35W;
  • the hole injection layer was prepared by vacuum evaporation, and the material was MoO 3 with a thickness of 40 nm.
  • the hole transport layer was prepared by vacuum evaporation, and the material was NPB with a thickness of 40 nm.
  • the luminescent layer was prepared by vacuum evaporation, and the material was Alq 3 with a thickness of 30 nm.
  • the electron transport layer was prepared by vacuum evaporation, and the material was Bphen with a thickness of 60 nm.
  • the electron injecting layer was prepared by vacuum evaporation, and the material was CsN 3 and the thickness was 5 nm.
  • the cathode was prepared by vacuum evaporation, and the material was Ag, and the thickness was 100 nm to obtain the polymer electroluminescent device.
  • Figure 4 is a graph showing the relationship between brightness and lumen efficiency, wherein curve 1 is the embodiment 1 A plot of brightness versus lumen efficiency for the resulting device; curve 2 is a plot of brightness versus lumen efficiency for a device made in proportion.
  • Example 1 The lumen efficiency is greater than the proportional ratio, with a maximum lumen efficiency of 13.7 lm/W and a comparison of only 10.3 lm/W. It is shown that when the inorganic electron blocking layer is used, the electrons can be restrained as much as possible in the light-emitting layer to recombine with the holes, thereby increasing the recombination probability of the excitons, thereby improving the luminous efficiency and improving the light-emitting efficiency.

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Abstract

本发明涉及一种聚合物电致发光器件及其制备方法，该器件包括依次层叠设置的阳极导电基板、空穴注入层、空穴传输层、电子阻挡层、发光层、电子传输层、电子注入层及阴极，电子阻挡层的材料选自氟化锂、碳酸锂、氧化锂及氯化锂中的一种。该聚合物电致发光器件通过制备锂化合物作为无机电子阻挡层，材料价格低廉、来源简单，最重要的是，其功函数较低，达到了2.0eV左右，与发光层之间可以形成约1.0eV的跃迁势垒，可以使电子尽可能的限制在发光层中与空穴进行复合，提高了激子的复合几率，进而提高聚合物电致发光器件的发光效率。

Description

一种聚合物电致发光器件及其制备方法
【技术领域】
本发明涉及一种聚合物电致发光器件及其制备方法。
【背景技术】
1987 年，美国 Eastman Kodak 公司的 C.W.Tang 和 VanSlyke 报道利用超薄薄膜技术制备出了高亮度，高效率的聚合物电致发光器件（ OLED ）。在该 OLED 中， 10V 下亮度达到 1000 cd/m2 ，其发光效率为 1.51 lm/W ，使用寿命大于 100 小时。
OLED 的发光原理是基于在外加电场的作用下，电子从阴极注入到有机物的最低未占有分子轨道（ LUMO ），而空穴从阳极注入到有机物的最高占有轨道（ HOMO ）。电子和空穴在发光层相遇、复合、形成激子，激子在电场作用下迁移，将能量传递给发光材料，并激发电子从基态跃迁到激发态，激发态能量通过辐射失活，产生光子，释放光能。
在传统的电致发光器件中，一般用高 LUMO 能级的有机材料作为电子阻挡层，空穴的传输路径为阳极 - 空穴传输层 - 发光层，而电子的传输路径为阴极 - 电子传输层 - 发光层，当空穴和电子到达发光层之后，进行复合，形成激子发光。而如果发光层与空穴传输层之间的 LUMO 能级势垒较低，会使电子从发光层中穿越到空穴传输层，造成电子与空穴不能有效复合，发光效率低下。传统的用来阻挡电子的方法是在发光层与空穴传输层之间蒸镀一层高 LUMO 能级（约 3.2eV ）的有机材料，用来阻挡电子，将电子限制在发光层。一般电子阻挡层与发光层之间的 LUMO 势垒约在 0.5ev 左右才能有效阻挡，但是传统使用的材料的 LUMO 能级大多是与发光层（发光层的 LUMO 能级为 3.5eV 左右）相差甚小，阻挡效果不明显。
【发明内容】
基于此，有必要提供一种能有效阻挡电子进入空穴传输层的聚合物电致发光器件及其制备方法。
一种聚合物电致发光器件，包括依次层叠设置的阳极导电基板、空穴注入层、空穴传输层、电子阻挡层、发光层、电子传输层、电子注入层及阴极，所述电子阻挡层的材料选自氟化锂、碳酸锂、氧化锂及氯化锂中的一种。
在优选的实施方式中，所述阳极导电基板选自铟锡氧化物玻璃、掺氟氧化锡玻璃、掺铝氧化锌玻璃及掺铟氧化锌玻璃中的一种。
在优选的实施方式中，所述空穴注入层的材料选自氧化钼、三氧化钨及五氧化二钒中的一种。
在优选的实施方式中，所述空穴传输层的材料选自 1 ， 1- 二 [4-[N ， N′- 二 (p- 甲苯基 ) 氨基 ] 苯基 ] 环己烷、 N ， N'- 二（ 3- 甲基苯基） -N ， N'- 二苯基 -4,4'- 联苯二胺、 4,4',4''- 三 ( 咔唑 -9- 基 ) 三苯胺及 N ， N'- （ 1- 萘基） -N ， N'- 二苯基 -4,4'- 联苯二胺中的一种。
在优选的实施方式中，所述电子传输层的材料选自 2- （ 4- 联苯基） -5- （ 4- 叔丁基）苯基 -1,3,4- 恶二唑、 8- 羟基喹啉铝、 4,7- 二苯基 -1,10- 菲罗啉、 1,2,4- 三唑衍生物及 N- 芳基苯并咪唑中的一种。
在优选的实施方式中，所述发光层的材料为有机发光材料；或者所述有机发光材料作为客体材料掺杂在主体材料之中，组成的混合材料，且客体材料的掺杂质量比为 1%-20% ；所述主体材料为空穴传输材料与电子传输材料中的一种或两种；
其中，有机发光材料选自 4- （二腈甲基） -2- 丁基 -6- （ 1,1,7,7- 四甲基久洛呢啶 -9- 乙烯基） -4H- 吡喃、 8- 羟基喹啉铝，双（ 4,6- 二氟苯基吡啶 -N,C2 ）吡啶甲酰合铱、二（ 2- 甲基 - 二苯基 [f,h] 喹喔啉）（乙酰丙酮）合铱及三（ 2- 苯基吡啶）合铱中的至少一种；
所述空穴传输材料选自 1 ， 1- 二 [4-[N ， N′- 二 (p- 甲苯基 ) 氨基 ] 苯基 ] 环己烷、 N ， N'- 二（ 3- 甲基苯基） -N ， N'- 二苯基 -4,4'- 联苯二胺、 4,4',4''- 三 ( 咔唑 -9- 基 ) 三苯胺及 N ， N'- （ 1- 萘基） -N ， N'- 二苯基 -4,4'- 联苯二胺中的一种；
所述电子传输材料选自 2- （ 4- 联苯基） -5- （ 4- 叔丁基）苯基 -1,3,4- 恶二唑、 8- 羟基喹啉铝、 4,7- 二苯基 -1,10- 菲罗啉、 1,2,4- 三唑衍生物及 N- 芳基苯并咪唑中的一种。
在优选的实施方式中，所述电子注入层的材料选自碳酸铯、叠氮铯及氟化锂中的一种。
在优选的实施方式中，所述阴极的材料选自银、铝、铂及金中的一种。
一种聚合物电致发光器件的制备方法，包括如下步骤：
提供阳极导电基板，并对其进行表面处理；
在所述阳极导电基板上依次真空蒸镀空穴注入层、空穴传输层、电子阻挡层、发光层、电子传输层、电子注入层及阴极，得到所述聚合物电致发光器件；其中，所述电子阻挡层的材料选自氟化锂、碳酸锂、氧化锂及氯化锂中的一种。
在优选的实施方式中，对阳极导电基板进行表面处理包括使用氧等离子体处理的步骤，处理时间为 2~15 分钟，功率为 10~50W 。
该聚合物电致发光器件通过制备锂化合物作为无机电子阻挡层，材料价格低廉、来源简单，最重要的是，其功函数较低，达到了 2.0eV 左右，与发光层之间可以形成约 1.0eV 的跃迁势垒，可以使电子尽可能的限制在发光层中与空穴进行复合，从而有效阻挡电子进入空穴传输层，提高了激子的复合几率，进而提高聚合物电致发光器件的发光效率。
【附图说明】
图 1 为一实施方式的聚合物电致发光器件的结构示意图；
图 2 为一实施方式的聚合物电致发光器件的制备流程示意图；
图 3 为实施例 1 的无机电子阻挡层的器件能级图；
图 4 为实施例 1 的聚合物电致发光器件与对比例的聚合物电致发光器件的亮度与流明效率的关系曲线图。
【具体实施方式】
下面主要结合附图及具体实施例对聚合物电致发光器件及其制备方法作进一步详细的说明。
如图 1 所示，一实施方式的聚合物电致发光器件 100 包括依次层叠设置的阳极导电基板 110 、空穴注入层 120 、空穴传输层 130 、电子阻挡层 140 、发光层 150 、电子传输层 160 、电子注入层 170 及阴极 180 。
阳极导电基板 110 优选铟锡氧化物玻璃（ ITO ）、掺氟氧化锡玻璃（ FTO ）、掺铝氧化锌玻璃（ AZO ）及掺铟氧化锌玻璃中（ IZO ）的一种。
空穴注入层 120 的材料优选氧化钼（ MoO3 ）、三氧化钨（ WO3 ）及五氧化二钒（ V2O5 ）中的一种，厚度优选 20~80nm 。进一步优选的，空穴注入层 120 的材料选用 MoO3 ，厚度为 40nm 。
空穴传输层 130 的材料优选 1 ， 1- 二 [4-[N ， N′- 二 (p- 甲苯基 ) 氨基 ] 苯基 ] 环己烷（ TAPC ）、 N ， N'- 二（ 3- 甲基苯基） - N ， N'- 二苯基 -4,4'- 联苯二胺（ TPD ）、 4,4',4''- 三 ( 咔唑 -9- 基 ) 三苯胺（ TCTA ）及 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺（ NPB ）中的一种，厚度优选 20-60nm 。进一步优选的，空穴传输层 130 的材料选用 NPB ，厚度为 40nm 。
电子阻挡层 140 的材料优选氟化锂（ LiF ）、碳酸锂（ Li2CO3 ）、氧化锂（ Li2O ）及氯化锂（ LiF ）中的一种，厚度优选 0.7-5nm 。
发光层 150 的材料为有机发光材料；或者有机发光材料作为客体材料掺杂在主体材料之中组成的混合材料，且客体材料的掺杂质量比为 1%-20% 。主体材料为空穴传输材料与电子传输材料中的一种或两种。发光层 150 的厚度优选为 2-50nm 。
其中，有机发光材料选自 4- （二腈甲基） -2- 丁基 -6- （ 1,1,7,7- 四甲基久洛呢啶 -9- 乙烯基） -4H- 吡喃（ DCJTB ）、 8- 羟基喹啉铝（ Alq3 ），双（ 4,6- 二氟苯基吡啶 -N,C2 ）吡啶甲酰合铱（ FIrpic ）、二（ 2- 甲基 - 二苯基 [f,h] 喹喔啉）（乙酰丙酮）合铱（ Ir(MDQ)2(acac) ）及三（ 2- 苯基吡啶）合铱 (Ir(ppy)3) 中的至少一种；空穴传输材料选自 1 ， 1- 二 [4-[N ， N′- 二 (p- 甲苯基 ) 氨基 ] 苯基 ] 环己烷（ TAPC ）、 N ， N'- 二（ 3- 甲基苯基） - N ， N'- 二苯基 -4,4'- 联苯二胺（ TPD ）、 4,4',4''- 三 ( 咔唑 -9- 基 ) 三苯胺（ TCTA ）及 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺（ NPB ）中的一种；电子传输材料选自 2- （ 4- 联苯基） -5- （ 4- 叔丁基）苯基 -1,3,4- 恶二唑（ PBD ）、 8- 羟基喹啉铝（ Alq3 ）、 4,7- 二苯基 -1,10- 菲罗啉（ Bphen ）、 1,2,4- 三唑衍生物（如 TAZ ）或 N- 芳基苯并咪唑（ TPBI ）中的一种。
进一步优选的，发光层 150 的材料选用 Alq3 ，厚度为 30nm 。
电子传输层 160 的材料优选 2- （ 4- 联苯基） -5- （ 4- 叔丁基）苯基 -1,3,4- 恶二唑、 8- 羟基喹啉铝、 4,7- 二苯基 -1,10- 菲罗啉、 1,2,4- 三唑衍生物及 N- 芳基苯并咪唑中的一种，厚度优选 40-80nm 。进一步优选的，电子传输层 160 的材料选用 Bphen ，厚度为 60nm 。
电子注入层 170 的材料优选碳酸铯（ Cs2CO3 ）、叠氮铯（ CsN3 ）及氟化锂（ LiF ）中的一种，厚度为 0.5-10nm 。进一步优选的，电子注入层 170 的材料选用 CsN3 ，厚度为 5nm 。
阴极 180 的材料优选银（ Ag ）、铝（ Al ）、铂（ Pt ）及金（ Au ）中的一种，厚度优选 80-250nm 。进一步优选的，阴极 180 的材料选用 Ag ，厚度为 100nm 。
该聚合物电致发光器件通过制备锂化合物作为无机电子阻挡层，材料价格低廉、来源简单，最重要的是，其功函数较低，达到了 2.0eV 左右，与发光层之间可以形成约 1.0eV 的跃迁势垒，可以使电子尽可能的限制在发光层中与空穴进行复合，提高了激子的复合几率，进而提高发光效率，可大大提高器件制备效率。
本实施方式还提供了一种聚合物电致发光器件的制备方法，如图 2 所示，包括如下步骤：
步骤 S1 ：提供阳极导电基板，并对其进行表面处理。
优选的，首先可以对提供的阳极导电基板依次用洗洁精、去离子水、丙酮、乙醇及异丙醇各超声一段时间，以去除基板表面的杂物，然后再对清洗后的阳极导电基板进行表面处理，如可以使用氧等离子体处理等，氧等离子体处理的时间可以为 2~15 分钟，功率为 10~50W ，优选采用 35W 功率的氧等离子体对阳极导电基板进行处理 5 分钟。
步骤 S2 ：在阳极导电基板上依次真空蒸镀空穴注入层、空穴传输层、电子阻挡层、发光层、电子传输层、电子注入层及阴极，得到所述聚合物电致发光器件；其中，电子阻挡层的材料选自氟化锂、碳酸锂、氧化锂及氯化锂中的一种。
该制备过程原理简单，原料易得，制备效率高，可以广泛推广应用。
以下为具体实施例部分：
以下各实施例使用的仪器如下：高真空镀膜设备（沈阳科学仪器研制中心有限公司，压强 <1×10-3Pa ）、电流 - 电压测试仪（美国 Keithly 公司，型号： 2602 ）、电致发光光谱测试仪（美国 photo research 公司，型号： PR650 ）以及屏幕亮度计（北京师范大学，型号： ST-86LA ）。
实施例 1 ： ITO/MoO3/NPB /LiF/Alq3/Bphen/CsN3/Ag
提供 ITO 玻璃基板，裁剪成合适的形状后，依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15min ，去除基板表面的杂物，清洗干净后对其进行氧等离子体处理 5min ，功率为 35W ；
真空蒸镀制备空穴注入层，材料选用 MoO3 ，厚度为 40nm ；
真空蒸镀制备空穴传输层，材料选用 NPB ，厚度为 40nm ；
真空蒸镀制备电子阻挡层，材料为 LiF ，厚度为 1.5nm ；
真空蒸镀制备发光层，材料选用 Alq3 ，厚度为 30nm ；
真空蒸镀制备电子传输层，材料选用 Bphen ，厚度为 60nm ；
真空蒸镀制备电子注入层，材料选用 CsN3 ，厚度为 5nm ；
真空蒸镀制备阴极，材料选用 Ag ，厚度为 100nm ，得到所述聚合物电致发光器件。
图 3 为本实施例的电子阻挡层的器件能级图。实线为使用传统有机材料制作电子阻挡层的能级结构，虚线为加入了本实施例的 LiF 电子阻挡层后 LUMO 能级提升的结果（能级从下往上，数值变小），当能级提升后，电子穿越到阻挡层的势垒大大增大，这就可以将电子限制在发光层中与空穴复合发光，提高发光效率。
实施例 2 ： IZO/WO3/TPD/Li2CO3/DCJTB/PBD/Cs 2CO3/Al
提供 IZO 玻璃基板，裁剪成合适的形状后，依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15min ，去除基板表面的杂物，清洗干净后对其进行氧等离子体处理 2min ，功率为 50W ；
真空蒸镀制备空穴注入层，材料选用 WO3 ，厚度为 20nm ；
真空蒸镀制备空穴传输层，材料选用 TPD ，厚度为 50nm ；
真空蒸镀制备电子阻挡层，材料为 Li2CO3 ，厚度为 5nm ；
真空蒸镀制备发光层，材料选用 DCJTB ，厚度为 50nm ；
真空蒸镀制备电子传输层，材料选用 PBD ，厚度为 80nm ；
真空蒸镀制备电子注入层，材料选用 Cs2CO3 ，厚度为 10nm ；
真空蒸镀制备阴极，材料选用 Al ，厚度为 250nm ，得到所述聚合物电致发光器件。
实施例 3 ： AZO/V2O5/TAPC/Li2O/ TPBI : Ir(ppy)3/TAZ/ CsN3/Au
提供 AZO 玻璃基板，裁剪成合适的形状后，依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15min ，去除基板表面的杂物，清洗干净后对其进行氧等离子体处理 15min ，功率为 10W ；
真空蒸镀制备空穴注入层，材料选用 V2O5 ，厚度为 60nm ；
真空蒸镀制备空穴传输层，材料选用 TAPC ，厚度为 60nm ；
真空蒸镀制备电子阻挡层，材料为 Li2O ，厚度为 2nm ；
真空蒸镀制备发光层，材料选用 TPBI : Ir(ppy)3 ，厚度为 10nm ，其中， Ir(ppy)3 在发光层的掺杂质量百分比为 15% ；
真空蒸镀制备电子传输层，材料选用 TAZ ，厚度为 40nm ；
真空蒸镀制备电子注入层，材料选用 CsN3 ，厚度为 5nm ；
真空蒸镀制备阴极，材料选用 Au ，厚度为 80nm ，得到所述聚合物电致发光器件。
实施例 4 ： FTO/ V2O5/TAPC/LiF/ TPBI : Ir(MDQ)2(acac)/ TPBI/ Cs2CO3/Au
提供 FTO 玻璃基板，裁剪成合适的形状后，依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15min ，去除基板表面的杂物，清洗干净后对其进行氧等离子体处理 1 ０ min ，功率为３ 0W ；
真空蒸镀制备空穴注入层，材料选用 V2O5 ，厚度为 40nm ；
真空蒸镀制备空穴传输层，材料选用 TAPC ，厚度为 60nm ；
真空蒸镀制备电子阻挡层，材料为 LiF ，厚度为 0.5nm ；
真空蒸镀制备发光层，材料选用 TPBI : Ir(MDQ)2(acac) ，厚度为 2nm ，其中， Ir(MDQ)2(acac) 在发光层的掺杂质量百分比为 1% ；
真空蒸镀制备电子传输层，材料选用 TPBI ，厚度为 50nm ；
真空蒸镀制备电子注入层，材料选用 Cs2CO3 ，厚度为 0.5nm ；
真空蒸镀制备阴极，材料选用 Au ，厚度为 80nm ，得到所述聚合物电致发光器件。
实施例 5 ： ITO/ MoO3/TCTA/LiCl/TPBI : Firpic/ Alq3/ CsN3/Pt
提供 ITO 玻璃基板，裁剪成合适的形状后，依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15min ，去除基板表面的杂物，清洗干净后对其进行氧等离子体处理 8min ，功率为 40W ；
真空蒸镀制备空穴注入层，材料选用 MoO3 ，厚度为 80nm ；
真空蒸镀制备空穴传输层，材料选用 TCTA ，厚度为 30nm ；
真空蒸镀制备电子阻挡层，材料为 LiCl ，厚度为 4nm ；
真空蒸镀制备发光层，材料选用 TPBI : Firpic ，厚度为 25nm ，其中， Firpic 在发光层的掺杂质量百分比为 20% ；
真空蒸镀制备电子传输层，材料选用 Alq3 ，厚度为 35nm ；
真空蒸镀制备电子注入层，材料选用 CsN3 ，厚度为 7nm ；
真空蒸镀制备阴极，材料选用 Pt ，厚度为 80nm ，得到所述聚合物电致发光器件。
对比例 ITO/MoO3/NPB/Alq3/Bphen/CsN3/Ag
提供 ITO 玻璃基板，裁剪成合适的形状后，依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15min ，去除基板表面的杂物，清洗干净后对其进行氧等离子体处理 5min ，功率为 35W ；
真空蒸镀制备空穴注入层，材料选用 MoO3 ，厚度为 40nm ；
真空蒸镀制备空穴传输层，材料选用 NPB ，厚度为 40nm ；
真空蒸镀制备发光层，材料选用 Alq3 ，厚度为 30nm ；
真空蒸镀制备电子传输层，材料选用 Bphen ，厚度为 60nm ；
真空蒸镀制备电子注入层，材料选用 CsN3 ，厚度为 5nm ；
真空蒸镀制备阴极，材料选用 Ag ，厚度为 100nm ，得到所述聚合物电致发光器件。
附图 4 为亮度与流明效率的关系图，其中，曲线 1 为实施例 1 制得的器件的亮度与流明效率的关系图；曲线 2 为对比例制得的器件的亮度与流明效率的关系图。从附图 4 上可以看到，在不同亮度下，实施例 1 的流明效率都比对比例的要大，最大的流明效率为 13.7 lm/W ，而对比例的仅为 10.3 lm/W ，表明当使用无机电子阻挡层时，可使电子尽可能的限制在发光层中与空穴进行复合，提高了激子的复合几率，进而提高发光效率，有利于提高出光效率。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种聚合物电致发光器件，包括依次层叠设置的阳极导电基板、空穴注入层、空穴传输层、电子阻挡层、发光层、电子传输层、电子注入层及阴极，其特征在于，所述电子阻挡层的材料选自氟化锂、碳酸锂、氧化锂及氯化锂中的一种。
  2. 如权利要求 1 所述的聚合物电致发光器件，其特征在于，所述阳极导电基板选自铟锡氧化物玻璃、掺氟氧化锡玻璃、掺铝氧化锌玻璃及掺铟氧化锌玻璃中的一种。
  3. 如权利要求 1 所述的聚合物电致发光器件，其特征在于，所述空穴注入层的材料选自氧化钼、三氧化钨及五氧化二钒中的一种。
  4. 如权利要求 1 所述的聚合物电致发光器件，其特征在于，所述空穴传输层的材料选自 1 ， 1- 二 [4-[N ， N′- 二 (p- 甲苯基 ) 氨基 ] 苯基 ] 环己烷、 N ， N'- 二（ 3- 甲基苯基） -N ， N'- 二苯基 -4,4'- 联苯二胺、 4,4',4''- 三 ( 咔唑 -9- 基 ) 三苯胺及 N ， N'- （ 1- 萘基） -N ， N'- 二苯基 -4,4'- 联苯二胺中的一种。
  5. 如权利要求 1 所述的聚合物电致发光器件，其特征在于，所述电子传输层的材料选自 2- （ 4- 联苯基） -5- （ 4- 叔丁基）苯基 -1,3,4- 恶二唑、 8- 羟基喹啉铝、 4,7- 二苯基 -1,10- 菲罗啉、 1,2,4- 三唑衍生物及 N- 芳基苯并咪唑中的一种。
  6. 如权利要求 1 所述的聚合物电致发光器件，其特征在于，所述发光层的材料为有机发光材料；或者所述有机发光材料作为客体材料掺杂在主体材料之中，组成的混合材料，且客体材料的掺杂质量比为 1%-20% ；所述主体材料为空穴传输材料与电子传输材料中的一种或两种；
    其中，有机发光材料选自 4- （二腈甲基） -2- 丁基 -6- （ 1,1,7,7- 四甲基久洛呢啶 -9- 乙烯基） -4H- 吡喃、 8- 羟基喹啉铝，双（ 4,6- 二氟苯基吡啶 -N,C2 ）吡啶甲酰合铱、二（ 2- 甲基 - 二苯基 [f,h] 喹喔啉）（乙酰丙酮）合铱及三（ 2- 苯基吡啶）合铱中的至少一种；
    所述空穴传输材料选自 1 ， 1- 二 [4-[N ， N′- 二 (p- 甲苯基 ) 氨基 ] 苯基 ] 环己烷、 N ， N'- 二（ 3- 甲基苯基） -N ， N'- 二苯基 -4,4'- 联苯二胺、 4,4',4''- 三 ( 咔唑 -9- 基 ) 三苯胺及 N ， N'- （ 1- 萘基） -N ， N'- 二苯基 -4,4'- 联苯二胺中的一种；
    所述电子传输材料选自 2- （ 4- 联苯基） -5- （ 4- 叔丁基）苯基 -1,3,4- 恶二唑、 8- 羟基喹啉铝、 4,7- 二苯基 -1,10- 菲罗啉、 1,2,4- 三唑衍生物及 N- 芳基苯并咪唑中的一种。
  7. 如权利要求 1 所述的聚合物电致发光器件，其特征在于，所述电子注入层的材料选自碳酸铯、叠氮铯及氟化锂中的一种。
  8. 如权利要求 1 所述的聚合物电致发光器件，其特征在于，所述阴极的材料选自银、铝、铂及金中的一种。
  9. 一种聚合物电致发光器件的制备方法，其特征在于，包括如下步骤：
    提供阳极导电基板，并对其进行表面处理；
    在所述阳极导电基板上依次真空蒸镀空穴注入层、空穴传输层、电子阻挡层、发光层、电子传输层、电子注入层及阴极，得到所述聚合物电致发光器件；其中，所述电子阻挡层的材料选自氟化锂、碳酸锂、氧化锂及氯化锂中的一种。
  10. 如权利要求 9 所述的聚合物电致发光器件的制备方法，其特征在于，对阳极导电基板进行表面处理包括使用氧等离子体处理的步骤，处理时间为 2~15 分钟，功率为
    10~50W 。
PCT/CN2011/083044 2011-11-28 2011-11-28 一种聚合物电致发光器件及其制备方法 Ceased WO2013078590A1 (zh)

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