WO2012040926A1 - 有机电致发光器件及其制备方法 - Google Patents

有机电致发光器件及其制备方法 Download PDF

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WO2012040926A1
WO2012040926A1 PCT/CN2010/077505 CN2010077505W WO2012040926A1 WO 2012040926 A1 WO2012040926 A1 WO 2012040926A1 CN 2010077505 W CN2010077505 W CN 2010077505W WO 2012040926 A1 WO2012040926 A1 WO 2012040926A1
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layer
hole injection
metal oxide
poly
injection layer
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PCT/CN2010/077505
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English (en)
French (fr)
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周明杰
王平
黄辉
冯小明
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海洋王照明科技股份有限公司
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Priority to US13/823,044 priority Critical patent/US9123906B2/en
Priority to EP10857689.3A priority patent/EP2624324A4/en
Priority to CN2010800683499A priority patent/CN103038907A/zh
Priority to JP2013530520A priority patent/JP2013543654A/ja
Priority to PCT/CN2010/077505 priority patent/WO2012040926A1/zh
Publication of WO2012040926A1 publication Critical patent/WO2012040926A1/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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • 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
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene

Definitions

  • the present invention relates to an organic electroluminescent device and a method of fabricating the same.
  • the hole injection layer of the conventional organic electroluminescent device generally adopts small organic molecules, which are easily oxidized and unstable, thereby affecting the service life and efficiency of the organic electroluminescent device.
  • An organic electroluminescent device comprising an anode base layer, a hole injection layer on the anode base layer, a light-emitting layer on the hole injection layer, and a cathode electrode layer on the light-emitting layer, wherein the hole injection layer
  • the material is a metal oxide or a thiophene compound.
  • the metal oxide is at least one of zinc oxide, magnesium oxide and vanadium pentoxide
  • the thiophene compound is poly-3-hexylthiophene, poly 3- At least one of methylthiophene, poly-3-octyloxythiophene, and poly-3-dodecylthiophene.
  • the method further includes a hole transport layer between the hole injection layer and the light emitting layer, an electron transport layer between the light emitting layer and the cathode electrode layer, and an electron injecting layer between the electron transport layer and the cathode electrode layer. At least one layer.
  • the hole injecting layer formed of a metal oxide or a thiophene compound has a feature of increasing the recombination probability of electron-holes and is not easily oxidized, thereby enhancing the efficiency of the organic electroluminescent device and prolonging its service life.
  • the metal oxide is zinc oxide, magnesium oxide, vanadium pentoxide, etc.
  • the thiophene compound is poly-3-hexylthiophene, poly 3- Methylthiophene, poly-3-octyloxythiophene or poly-3-dodecylthiophene, etc., are less susceptible to oxidation than conventionally used small organic molecules, and are stable for a long period of time and have strong hole injecting ability.
  • Metal oxide materials have a large absorption in the range of ultraviolet light, which can shield ultraviolet rays, and ultraviolet irradiation has great influence on the stability of the device.
  • the selection of metal oxide materials can effectively improve the stability of the device and Slow down the aging of the device.
  • the thiophene of the polyalkylthiophene polymer has a certain length of side chain groups, and these alkyl side chains increase the distance between the chains, restricting the transport of holes to the main chain, thereby increasing electron-holes.
  • the probability of recombination can effectively enhance the luminous intensity and luminance of the device.
  • a method for preparing an organic electroluminescent device comprising the steps of:
  • the configuration of the metal oxide sol comprises the steps of dissolving the metal oxide in a solvent and configuring the concentration to be 10 ⁇ 35% metal oxide sol.
  • the metal oxide is zinc oxide or magnesium oxide
  • the solvent is a volume percentage 1:2 a mixed solution of water and acetic acid; or the metal oxide is vanadium pentoxide, and the solvent is ammonia water.
  • the rotation speed during the spin coating process is 500-2000 rpm / In minutes, the spin time is 30 seconds; the drying temperature is 50-200 ° C, and the drying time is 15-60 minutes.
  • step S1 the configuration of the thiophene compound sol comprises the following steps:
  • the thiophene compound is dissolved in an organic solvent to prepare a thiophene compound sol having a density of 1 ⁇ 10 -3 -1 ⁇ 10 -2 g/L.
  • the thiophene compound is poly-3-hexylthiophene, poly-3-methylthiophene, poly-3-octyloxythiophene or poly-3- Dodecylthiophene;
  • the organic solvent is at least one of chlorobenzene, xylene, tetrahydrofuran, chloroform or dichloromethane.
  • the rotation speed during the spin coating is 500-2500 rpm / In minutes, the spin time is 30 seconds; during drying, the temperature is 50-200 ° C, and the drying time is 15-100 minutes.
  • the hole injection layer is prepared by spin-coating a metal oxide material or a thiophene compound material, the process is simple, the equipment condition is not high, the operation is simple, and the manufacturing cost of the device can be greatly reduced. .
  • FIG. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment
  • FIG. 2 is a schematic structural view of an organic electroluminescent device according to another embodiment
  • Example 3 is a structure in which the hole injection layer of Example 2 and Example 8 is ITO (indium tin oxide) / hole injection layer / NPB (N , N ' - ( 1-naphthyl) - N , N '-Diphenyl-4,4'-biphenyldiamine) / Alq 3 (8-hydroxyquinoline aluminum) /LiF/Al film structure organic electroluminescent device and Example 10 without hole injection layer
  • the structure is a graph of the relationship between Luminance (in cd/m 2 ) and voltage (voltage, unit V) of ITO/NPB/Alq 3 /LiF/Al.
  • an organic electroluminescent device of an embodiment includes an anode base layer 110, a hole injection layer 120, and a light-emitting layer in this order. 130 and cathode electrode layer 140.
  • the anode base layer 110 may be an inorganic conductive material such as indium tin oxide (ITO), zinc oxide or tin oxide, or an organic conductive polymer such as polyaniline or the like.
  • ITO indium tin oxide
  • zinc oxide or tin oxide zinc oxide or tin oxide
  • organic conductive polymer such as polyaniline or the like.
  • Hole injection layer 120 Prepared using metal oxides or thiophenes.
  • metal oxides such as zinc oxide, magnesium oxide or vanadium pentoxide
  • thiophene compounds such as poly-3-hexylthiophene, poly-3-methylthiophene, poly-3-octyloxy Thiophene or poly-3-dodecylthiophene and the like.
  • the light-emitting layer 130 may be tetra-tert-butyl perylene (TBP), 4-(dinitylmethyl)-2-butyl-6-(1,7,7,7-tetramethyl sulphonium -9-vinyl) -4H-pyran (DCJTB), 9,10-di- ⁇ -naphthylene fluorene (AND), bis(2-methyl-8-hydroxyquinoline)-(4-diphenol Aluminum (BALQ), 4-(dinitrileyl)-2-isopropyl-6-( 1,1,7,7-tetramethyljuroxidine-9-vinyl) -4H-pyridyl Oral (DCJTI), dimethyl quinacridone (DMQA) or 8-hydroxyquinoline aluminum (Alq 3 ). Further, the light-emitting layer 130 may also employ a polymer polyparaphenylene acetylene and a derivative thereof (PVV).
  • PVV polymer polyparaphenylene acetylene and
  • the cathode electrode layer 140 may be aluminum, gold, magnesium silver alloy, aluminum magnesium alloy, aluminum calcium alloy or aluminum lithium alloy.
  • the hole injection layer 120 is prepared by using a metal oxide or an organic polymer, has strong oxidation resistance, can effectively enhance the stability and service life of the organic electroluminescent device, and at the same time, the metal oxide or the organic polymer can balance holes and electrons.
  • the transmission rate increases the probability of recombination of holes and electrons, and can effectively enhance the luminous intensity and luminance of the device.
  • the organic electroluminescent device may also employ, for example, an anode substrate layer / Hole injection layer / luminescent layer / electron injection layer / cathode electrode layer, anode base layer / hole injection layer / luminescent layer / electron transport layer / cathode electrode layer, anode base layer / hole injection layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode Electrode Layer, Anode Substrate Layer / Hole Injection Layer / Hole Transport Layer / Luminescent Layer / Electron Injection Layer / Cathode Electrode Layer, Anode Substrate Layer / Hole injection layer / hole transport layer / light-emitting layer / electron transport layer / cathode electrode layer, anode base layer / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / cathode electrode layer, anode base layer / hole injection layer / hole transport layer
  • Figure 2 shows an anode substrate layer 210 / hole injection layer 220 / hole transport layer 230 / light-emitting layer 240 / electron transport layer 250 / Electron injection layer 260 / cathode electrode layer 270 structure of the organic electroluminescent device structure.
  • the hole transport layer may be N, N'-bis(3-methylphenyl)-N, N'-diphenyl -4,4'-biphenyldiamine (TPD), polyparaphenylene acetylene and its derivatives (PPV), N, N'-(1-naphthyl)-N, N'-diphenyl-4,4 '- Biphenyldiamine (NPB), 1,3,5-triphenylbenzene (TDAPB), polyvinylcarbazole (PVK), copper phthalocyanine (CuPc) or P Preparation of materials such as doped inorganic semiconductors.
  • TPD N'-bis(3-methylphenyl)-N
  • PV polyparaphenylene acetylene and its derivatives
  • NPB N'-(1-naphthyl)-N
  • TDAPB 1,3,5-
  • the electron transport layer may be 2-(4-biphenyl)-5-(4-tert-butyl)phenyl-1,3,4-oxadiazole (PBD), 8-hydroxyquinoline aluminum (Alq 3 ) , 2,5-bis(1-naphthyl)-1,3,4-oxadiazole (BND), 1,2,4-triazole derivatives (such as TAZ), N-arylbenzimidazole (TPBI) Preparation of materials such as quinoxaline derivatives (TPQ) or n-type doped inorganic semiconductors.
  • PBD 2-(4-biphenyl)-5-(4-tert-butyl)phenyl-1,3,4-oxadiazole
  • Alq 3 8-hydroxyquinoline aluminum
  • BND 2,5-bis(1-naphthyl)-1,3,4-oxadiazole
  • TAZ 1,2,4-triazole derivatives
  • TPBI N-arylbenzimidazole
  • the electron injecting layer may be lithium fluoride (LiF), lithium oxide (LiO 2 ), cerium oxide (Cs 2 O ), aluminum oxide (Al 2 O 3 ), sodium fluoride (NaF), or cesium fluoride (CsF). ), calcium fluoride (CaF 2 ), magnesium fluoride (MgF 2 ), sodium chloride (NaCl), potassium chloride (KCl), barium chloride (RbCl), lithium metaborate (LiBO 2 ) or potassium silicate Preparation of materials such as (K 2 SiO 3 ).
  • the above has an anode base layer 110 / hole injection layer 120 / light emitting layer 130 / cathode electrode layer 140
  • a metal oxide sol or a thiophene compound sol is disposed; then an anode base layer 110 is provided, and the anode base layer 110 is provided.
  • the surface is pretreated; finally, a metal oxide sol or a thiophene sol is coated on the surface pretreated anode substrate 110 by spin coating to form a hole injection layer 120; 120 is coated with a light-emitting layer 130, and a cathode electrode layer 140 is coated on the light-emitting layer 130, and dried to obtain an organic electroluminescent device.
  • the pretreatment of the surface of the anode base layer 110 may be oxygen plasma treatment or ultraviolet-ozone treatment. , hydrogen peroxide immersion cleaning or acid immersion cleaning.
  • the raw material of the hole injection layer 120 is specifically a deionized water/acetate sol of zinc oxide or magnesium oxide having a mass fraction of 10-35%, wherein the volume ratio of deionized water to acetic acid is 1:2; or the mass fraction is 10- 35% aqueous solution of vanadium pentoxide; or poly-3-hexylthiophene, poly-3-methylthiophene, poly-3-octyloxythiophene or 1 ⁇ 10 -3 -1 ⁇ 10 -2 g/L An organic solvent sol of poly-3-dodecylthiophene.
  • the rotation speed during the spin coating process is 500-2000.
  • the transfer time is 30 seconds for the transfer/minute; the temperature is 50-200 ° C during the drying process, and the drying time is 15-60 minutes.
  • the hole injection layer 120 is made of poly-3-hexylthiophene, poly-3-methylthiophene, poly-3-octyloxythiophene or poly 3-
  • the rotation speed is 500-2500 rpm
  • the spin coating time is 30 seconds
  • the drying temperature is 50-200 ° C
  • the drying time is 15-100. Minutes.
  • the organic solvent is at least one of chlorobenzene, xylene, tetrahydrofuran, chloroform or dichloromethane.
  • the above preparation process further includes spin coating, evaporation, sputtering, sputtering or chemical vapor deposition in the hole injection layer and the light emitting layer. a step of depositing a hole transport layer, or depositing an electron transport layer on the light-emitting layer by spin coating, evaporation, sputtering, sputtering or chemical vapor deposition, and depositing an electron injection layer between the electron transport layer and the cathode electrode layer Wait for steps.
  • the hole injection layer is prepared by spin-coating a metal oxide material or an organic polymer material, the process is simple, the equipment conditions are not required, the operation is simple, and the manufacturing cost of the device can be greatly reduced.
  • Example 1 The indium tin oxide glass was photolithographically processed, cut into the required light-emitting area, and then ultrasonically washed with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes, respectively, and cleaned. It is surface treated with oxygen plasma, the oxygen plasma treatment time is 5-15 minutes, and the power is 10-50W. Its main function is to reduce the roughness and contact angle of the surface of the anode base layer, so as to improve the wetness of the surface of the anode base layer.
  • the adsorption and the surface treatment can further remove the organic pollutants on the surface of the anode base layer, enhance the combination with the organic layer, and increase the surface work function of the anode base layer, thereby improving the hole injection ability.
  • Example 2 The indium tin oxide glass was photolithographically processed, cut into a desired light-emitting area, and then ultrasonically washed with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes, respectively, and cleaned. It is subjected to oxygen plasma treatment, and the oxygen plasma treatment time is 5-15 minutes, and the power is 10-50 W. Dissolve a mixed solution of zinc oxide (ZnO) and deionized water/acetic acid ratio of 1:2 into a solution with a mass fraction of 25%, and drop the prepared solution onto the homogenizer at a spin coating speed of 500-2000 rpm.
  • ZnO zinc oxide
  • deionized water/acetic acid ratio of 1:2 into a solution with a mass fraction of 25%
  • a hole transport layer and a light-emitting layer were prepared by thermal evaporation, followed by evaporation of the electron injection layer and the cathode electrode layer.
  • the relationship between the luminance and voltage of the organic electroluminescent device prepared is shown in Fig. 3.
  • Example 3 The indium tin oxide glass was photolithographically processed, cut into a desired light-emitting area, and then ultrasonically washed with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes in sequence, and then cleaned. It is UV-ozone treated with a processing time of 15-30 minutes and a power of 10-30W. Dissolve a mixed solution of zinc oxide (ZnO) and deionized water/acetic acid ratio of 1:2 into a solution with a mass fraction of 35%, and drip the prepared solution onto a homogenizer at a spin coating speed of 500-2000 rpm.
  • ZnO zinc oxide
  • deionized water/acetic acid ratio of 1:2 into a solution with a mass fraction of 35%
  • a hole transport layer, a light-emitting layer, and an electron transport layer were prepared by thermal evaporation, followed by evaporation of the electron injection layer and the cathode electrode layer.
  • Example 4 The indium tin oxide glass was photolithographically processed, cut into a desired light-emitting area, and then ultrasonically washed with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes in sequence, and then cleaned. It is UV-ozone treated with a processing time of 15-30 minutes and a power of 10-30W.
  • the zinc oxide (ZnO) of Example 1 was changed into a mixed solution of magnesium oxide (MgO) and deionized water/acetic acid ratio of 1:2 to prepare a solution having a mass fraction of 10%, and the solution was placed on a homogenizer.
  • the spin coating speed of 500-5000 rpm was spin-coated on the anode base layer, the spin coating time was 30 seconds, and then calcined in a muffle furnace at 450 ° C for 30 minutes, and dried to obtain a hole injection layer. Then, a hole transport layer, a light-emitting layer, and an electron transport layer were prepared by thermal evaporation, followed by evaporation of the electron injection layer and the cathode electrode layer.
  • Example 5 The indium tin oxide glass was photolithographically processed, cut into a desired light-emitting area, and then ultrasonically washed with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes, respectively, and cleaned. It is subjected to oxygen plasma treatment in which the oxygen plasma treatment time is 5-15 minutes and the power is 10-50 W.
  • the zinc oxide (ZnO) of Example 1 was changed into a mixed solution of magnesium oxide (MgO) and deionized water/acetic acid ratio of 1:2 to prepare a solution having a mass fraction of 30%, and the solution was placed on a homomixer.
  • the spin coating speed of 500-5000 rpm was spin-coated on the anode base layer, the spin coating time was 30 seconds, and then calcined in a muffle furnace at 450 ° C for 30 minutes, and dried to obtain a hole injection layer. Then, a hole transport layer, a light-emitting layer, and an electron transport layer were prepared by thermal evaporation, followed by evaporation of the electron injection layer and the cathode electrode layer.
  • Example 6 The indium tin oxide glass was photolithographically processed, cut into a desired light-emitting area, and then ultrasonically washed with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes, respectively, and cleaned. It is subjected to oxygen plasma treatment in which the oxygen plasma treatment time is 5-15 minutes and the power is 10-50 W.
  • the zinc oxide (ZnO) of Example 1 was changed into a mixed solution of magnesium oxide (MgO) and deionized water/acetic acid ratio of 1:2 to prepare a solution having a mass fraction of 20%, and the solution was placed on a homomixer.
  • the spin coating speed of 500-5000 rpm was spin-coated on the anode base layer, the spin coating time was 30 seconds, and then calcined in a muffle furnace at 450 ° C for 30 minutes, and dried to obtain a hole injection layer. Then, a hole transport layer, a light-emitting layer, and an electron transport layer were prepared by thermal evaporation, followed by evaporation of the electron injection layer and the cathode electrode layer.
  • Example 7 The indium tin oxide glass was photolithographically processed, cut into a desired light-emitting area, and then ultrasonically washed with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes in sequence, and then cleaned. It is subjected to oxygen plasma treatment in which the oxygen plasma treatment time is 5-15 minutes and the power is 10-50 W.
  • the zinc oxide (ZnO) of Example 1 was replaced with poly-3-hexylthiophene and chlorobenzene to prepare a solution having a density of 1 ⁇ 10 -3 g/L, and the solution was placed on a homogenizer at 500-2500 rpm.
  • the spin coating speed was spin-coated on the anode base layer, the spin coating time was 30 seconds, and then baked in a 200 ° C oven for 30 minutes, and after drying, a hole injection layer was obtained. Then, a hole transport layer, a light-emitting layer, and an electron transport layer were prepared by thermal evaporation, followed by evaporation of the electron injection layer and the cathode electrode layer.
  • Example 8 The indium tin oxide glass was photolithographically processed, cut into a desired light-emitting area, and then ultrasonically washed with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes in sequence, and then cleaned. It is subjected to oxygen plasma treatment in which the oxygen plasma treatment time is 5-15 minutes and the power is 10-50 W.
  • the zinc oxide (ZnO) of Example 1 was replaced with poly-3-hexylthiophene and chlorobenzene to prepare a solution having a density of 5 ⁇ 10 -3 g/L, and the solution was placed on a homogenizer at 500-2500 rpm.
  • the spin coating speed was spin-coated on the anode base layer, the spin coating time was 30 seconds, and then baked in a 200 ° C oven for 30 minutes, and after drying, a hole injection layer was obtained. Then, a hole transport layer and a light-emitting layer were prepared by thermal evaporation, followed by evaporation of the electron injection layer and the cathode electrode layer.
  • the relationship between the luminance and voltage of the organic electroluminescent device prepared is shown in Fig. 3.
  • Example 9 The indium tin oxide glass was photolithographically processed, cut into a desired light-emitting area, and then ultrasonically washed with detergent, deionized water, acetone, ethanol, and isopropanol for 15 minutes, respectively, and cleaned. It is UV-ozone treated with a processing time of 15-30 minutes and a power of 10-30W.
  • the zinc oxide (ZnO) of Example 1 was replaced with poly-3-hexylthiophene and chlorobenzene to prepare a solution having a density of 1 ⁇ 10 -2 g/L, and the solution was placed on a homogenizer at 500-2500 rpm.
  • the spin coating speed was spin-coated on the anode base layer, the spin coating time was 30 seconds, and then baked in a 200 ° C oven for 30 minutes, and after drying, a hole injection layer was obtained. Then, a hole transport layer, a light-emitting layer, and an electron transport layer were prepared by thermal evaporation, followed by evaporation of the electron injection layer and the cathode electrode layer.
  • Example 10 Comparative device without hole injection layer: The indium tin oxide glass was photolithographically processed, cut into a desired light-emitting area, and then sequentially washed with detergent, deionized water, acetone, ethanol, and isopropyl The alcohol was sonicated for 15 minutes, and then cleaned and then subjected to oxygen plasma treatment, wherein the oxygen plasma treatment time was 5-15 minutes, and the power was 10-50 W. No hole injection layer was added. The hole transport layer and the light-emitting layer were prepared by direct thermal evaporation, followed by evaporation of the electron injection layer and the cathode electrode layer.

Description

有机电致发光器件及其制备方法
【技术领域】
本发明涉及一种有机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 报道了有机电致发光研究中的突破性进展。利用真空镀膜技术制备出了高亮度、高效率的双层小分子有机电致发光器件。 1990 年，英国剑桥大学的 R.H.Friend 小组制备了第一个高分子发光二极管。自此，有机发光二极管（ Organic Light-Emitting Diode ， OLED ）在短短的十几年内已发展到应用阶段。
但传统的有机电致发光器件的空穴注入层普遍采用有机小分子，易被氧化而不稳定，从而影响有机电致发光器件的使用寿命和效率。
【发明内容】
基于此，有必要提供一种使用寿命较长，性能较好的有机电致发光器件。
一种有机电致发光器件，包括阳极基底层、位于阳极基底层上的空穴注入层、位于空穴注入层上的发光层及位于发光层上的阴极电极层，其中，空穴注入层的材质为金属氧化物或噻吩类化合物。
优选的，金属氧化物为氧化锌、氧化镁和五氧化二钒中的至少一种；噻吩类化合物为聚 3- 己基噻吩、聚 3- 甲基噻吩、聚 3- 辛氧基噻吩和聚 3- 十二烷基噻吩中的至少一种 。
优选的，还包括位于空穴注入层及发光层之间的空穴传输层、位于发光层及阴极电极层之间的电子传输层及位于电子传输层与阴极电极层之间的电子注入层中的至少一层。
金属氧化物或噻吩类化合物形成的空穴注入层具有提高电子-空穴的复合几率，且不易被氧化的特点，从而增强了有机电致发光器件的效率并延长了其使用寿命。
进一步，金属氧化物采用氧化锌、氧化镁、五氧化二钒等，噻吩类化合物采用聚 3- 己基噻吩、聚 3- 甲基噻吩、聚 3- 辛氧基噻吩或聚 3- 十二烷基噻吩等，相比较传统使用的有机小分子，不易被氧化，能长期稳定存在且空穴注入能力较强。
金属氧化物材料在紫外光的范围内有较大的吸收，可以起到了屏蔽紫外线的作用，而紫外的照射对于器件的稳定性影响很大，选择金属氧化物材料能有效提高器件的稳定性和减缓器件老化程度。
聚烷基噻吩类聚合物的噻吩上具有一定长度的侧链基团，而这些烷基侧链会使链间距离增长，使空穴的传输限制在主链上，从而提高了电子-空穴复合的几率，能有效的增强器件的发光强度和发光亮度。
此外，还有必要提供一种使用寿命较长的有机电致发光器件的制备方法。
一种有机电致发光器件的制备方法，其特征在于，包括如下步骤：
S1 、配置金属氧化物溶胶或噻吩类化合物溶胶；
S2 、提供阳极基底层，对阳极基底层表面进行预处理；
S3 、采用旋涂技术，将金属氧化物溶胶或噻吩类化合物溶胶涂覆在表面预处理后的阳极基底层上，形成一层空穴注入层；然后在空穴注入层上涂覆一层发光层，以及在发光层上涂覆一层阴极电极层，烘干，即得到有机电致发光器件。
优选的，步骤 S1 中，金属氧化物溶胶的配置包括如下步骤：将金属氧化物溶于溶剂中，配置成浓度为 10~35% 的金属氧化物溶胶。
优选的，金属氧化物为氧化锌或氧化镁，溶剂为体积百分比 1:2 的水和醋酸的混合溶液；或金属氧化物为五氧化二钒，溶剂为氨水。
优选的，当形成空穴注入层的原料为金属氧化物溶胶时，旋涂过程中转速为 500-2000 转 / 分钟，旋涂时间为 30 秒；干燥过程中温度为 50-200℃，干燥时间为15-60 分钟。
优选的，步骤 S1 中，噻吩类化合物溶胶的配置包括如下步骤：
将噻吩类化合物溶于有机溶剂中，配置成密度为 1 × 10-3-1 × 10-2g/L 的 噻吩类化合物溶胶。
优选的，噻吩类化合物为聚 3- 己基噻吩、聚 3- 甲基噻吩、聚 3- 辛氧基噻吩或聚 3- 十二烷基噻吩；有机溶剂为氯苯、二甲苯、四氢呋喃、三氯甲烷或二氯甲烷中的至少一种。
优选的，当形成空穴注入层的原料为噻吩类化合物溶胶时，旋涂过程中转速为 500-2500 转 / 分钟，旋涂时间为 30 秒；干燥过程中温度为 50-200℃，干燥时间为15-100 分钟。
上述有机电致发光器件的制备方法，通过旋涂金属氧化物材料或噻吩类化合物材料来制备空穴注入层，工序简单，对设备条件要求不高，操作简易，可大大的降低器件的制作成本。
【附图说明】
图 1 为一实施方式的有机电致发光器件的结构示意图；
图 2 为另一实施方式的有机电致发光器件的结构示意图；
图 3 为采用了实施例 2 、实施例 8 的空穴注入层的结构为 ITO （铟锡氧化物） / 空穴注入层 /NPB （ N ， N ' - （ 1- 萘基） - N ， N ' - 二苯基 -4,4'- 联苯二胺） / Alq3 （ 8- 羟基喹啉铝） /LiF/Al 膜层结构的有机电致发光器件以及实施例 10 没有采用空穴注入层的结构为 ITO/ NPB/ Alq3/LiF/Al 的的发光亮度（ Luminance ，单位 cd/m2 ）与电压（ Voltage ，单位 V ）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有机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，一实施方式的有机电致发光器件依次包括阳极基底层 110 、空穴注入层 120 、发光层 130 及阴极电极层 140 。
阳极基底层110可以采用无机导电材料，如铟锡氧化物（ITO）、氧化锌或氧化锡等，或者有机导电聚合物，如聚苯胺等。
空穴注入层 120 采用金属氧化物或噻吩类化合物制备。其中，金属氧化物如氧化锌、氧化镁或五氧化二钒等；噻吩类化合物如聚 3- 己基噻吩、聚 3- 甲基噻吩、聚 3- 辛氧 基噻吩或聚 3- 十二烷基噻吩等。
发光层 130 可以采用四 - 叔丁基二萘嵌苯（ TBP ）、 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 ）、 9,10- 二 - β - 亚萘基蒽（ AND ）、二（ 2- 甲基 -8- 羟基喹啉） - （ 4- 联苯酚）铝（ BALQ ）、 4- （二腈甲烯基） -2- 异丙基 -6- （ 1,1,7,7- 四甲基久洛呢啶 -9- 乙烯基） -4H- 吡喃（ DCJTI ）、二甲基喹吖啶酮（ DMQA ）或 8- 羟基喹啉铝（ Alq3 ）。此外，发光层 130 还可以采用聚合物聚对苯乙炔及其衍生物（ PPV ）。
阴极电极层 140 可以采用铝、金、镁银合金、铝镁合金、铝钙合金或铝锂合金等。
空穴注入层120采用金属氧化物或有机聚合物制备，抗氧化能力强，可以有效增强有机电致发光器件的稳定性和使用寿命，同时，金属氧化物或有机聚合物可以平衡空穴和电子的传输速率，提高空穴-电子的复合几率，能有效增强器件的发光强度和发光亮度。
此外，为进一步增强有机电致发光器件的空穴 - 电子的传输速率，有机电致发光器件还可以采用诸如阳极基底层 / 空穴注入层 / 发光层 / 电子注入层 / 阴极电极层、阳极基底层 / 空穴注入层 / 发光层 / 电子传输层 / 阴极电极层、阳极基底层 / 空穴注入层 / 发光层 / 电子传输层 / 电子注入层 / 阴极电极层、阳极基底层 / 空穴注入层 / 空穴传输层 / 发光层 / 电子注入层 / 阴极电极层、阳极基底层 / 空穴注入层 / 空穴传输层 / 发光层 / 电子传输层 / 阴极电极层、阳极基底层 / 空穴注入层 / 空穴传输层 / 发光层 / 电子传输层 / 电子注入层 / 阴极电极层等结构。图 2 所示为依次具有阳极基底层 210/ 空穴注入层 220/ 空穴传输层 230/ 发光层 240/ 电子传输层 250/ 电子注入层 260/ 阴极电极层 270 结构的有机电致发光器件的结构示意图。
其中， 空穴传输层可以采用 N ， N'- 二（ 3- 甲基苯基） - N ， N'- 二苯基 -4,4'- 联苯二胺（ TPD ）、聚对苯乙炔及其衍生物（ PPV ）、 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺（ NPB ）、 1 , 3 ,5- 三苯基苯（ TDAPB ）、聚乙烯基咔唑（ PVK ）、酞菁铜（ CuPc ）或 P 型掺杂无机半导体等材料制备。
电子传输层可以采用 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 ）、 2,5- 二 (1- 萘基 )-1,3,4- 二唑（ BND ）、 1,2,4- 三唑衍生物（如 TAZ ）、 N- 芳基苯并咪唑（ TPBI ）、喹喔啉衍生物（ TPQ ）或 n 型掺杂无机半导体等材料制备。
电子注入层可以采用氟化锂（ LiF ）、氧化锂（ LiO2 ）、氧化铯（ Cs2O ）、三氧化二铝（ Al2O3 ）、氟化钠（ NaF ）、氟化铯（ CsF ）、氟化钙（ CaF2 ）、氟化镁（ MgF2 ）、氯化钠（ NaCl ）、氯化钾（ KCl ）、氯化铷（ RbCl ）、偏硼酸锂（ LiBO2 ）或硅酸钾（ K2SiO3 ）等材料制备。
上述具有阳极基底层 110/ 空穴注入层 120/ 发光层 130/ 阴极电极层 140 结构的有机电致发光器件的制备过程中，首先配置金属氧化物溶胶或噻吩类化合物溶胶；然后提供阳极基底层 110 ，并对阳极基底层 110 表面进行预处理；最后采用旋涂技术，将金属氧化物溶胶或噻吩类化合物溶胶涂覆在表面预处理后的阳极基底层 110 上，形成一层空穴注入层 120 ；再在空穴注入层 120 上涂覆一层发光层 130 ，以及在发光层 130 上涂覆一层阴极电极层 140 ，烘干，即得到有机电致发光器件。
其中，对阳极基底层 110 表面进行的预处理可以为氧等离子处理、紫外 - 臭氧处理 、过氧化氢浸泡清洗或酸浸泡清洗等。
空穴注入层 120 的原料具体是质量分数为 10-35% 的氧化锌或氧化镁的去离子水 / 醋酸溶胶，其中去离子水与醋酸的体积比为 1:2 ；或质量分数为 10-35% 的五氧化二钒的氨水溶胶；或密度为 1 × 10-3-1 × 10-2g/L 的 聚 3- 己基噻吩、聚 3- 甲基噻吩、聚 3- 辛氧基噻吩或聚 3- 十二烷基噻吩的有机溶剂溶胶。
当空穴注入层 120 的原料为含氧化锌、氧化镁或五氧化二钒的溶胶时，旋涂过程中转速为 500-2000 转 / 分钟，旋涂时间为 30 秒；干燥过程中温度为 50-200℃，干燥时间为15-60 分钟。
当空穴注入层 120 的原料为聚 3- 己基噻吩、聚 3- 甲基噻吩、聚 3- 辛氧基噻吩或聚 3- 十二烷基噻吩的有机溶剂溶胶时，旋涂过程中转速为 500-2500 转 / 分钟，旋涂时间为 30 秒；干燥过程中温度为 50-200℃，干燥时间为15-100 分钟。其中，有机溶剂为氯苯、二甲苯、四氢呋喃、三氯甲烷或二氯甲烷中的至少一种。
此外，为进一步增强有机电致发光器件的空穴-电子的传输速率，上述制备过程还包括采用旋涂、蒸镀、溅射、喷镀或化学蒸发沉积方式在空穴注入层及发光层之间沉积空穴传输层的步骤，或者采用旋涂、蒸镀、溅射、喷镀或化学蒸发沉积方式在发光层上沉积电子传输层及在电子传输层与阴极电极层之间沉积电子注入层等步骤。
通过旋涂金属氧化物材料或有机聚合物材料来制备空穴注入层，工序简单，对设备条件要求不高，操作简易，可大大的降低器件的制作成本。
以下为具体实施例部分：
实施例1 ：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其使用氧等离子进行表面处理，氧等离子处理时间为 5-15 分钟，功率为 10-50W ，其主要作用是减小阳极基底层表面的粗糙度和接触角，以利于改善阳极基底层表面的湿润性和吸附性，而且通过表面处理后能够进一步去除阳极基底层表面的有机污染物，增强其与有机层的结合，使阳极基底层表面功函数增加，从而提高空穴注入能力。将氧化锌（ ZnO ）与去离子水 / 醋酸比例为 1:2 的混合溶液配置成质量分数为 10% 的溶液，将所配溶液滴在匀胶机上以 500-2000 转 / 分钟的旋涂速度旋涂在阳极基底层上，旋涂时间为 30 秒，然后在 150℃ 烘箱中烘烤 30 分钟，干燥后得到空穴注入层。然后热蒸镀制备空穴传输层、发光层和电子传输层，接着再蒸镀电子注入层和阴极电极层。
实施例2 ：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其进行氧等离子处理，氧等离子处理时间为 5-15 分钟，功率为 10-50W 。将氧化锌（ ZnO ）与去离子水 / 醋酸比例为 1:2 的混合溶液配置成质量分数为 25% 的溶液，将所配溶液滴在匀胶机上以 500-2000 转 / 分钟的旋涂速度旋涂在阳极基底层上，旋涂时间为 30 秒，然后在 150℃ 烘箱中烘烤 30 分钟，干燥后得到空穴注入层。然后热蒸镀制备空穴传输层和发光层，接着再蒸镀电子注入层和阴极电极层。制备得到有机电致发光器件的发光亮度与电压的关系曲线如图 3 所示。
实施例3 ：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其进行 紫外 - 臭氧处理 ，处理时间为 15-30 分钟，功率为 10-30W 。将氧化锌（ ZnO ）与去离子水 / 醋酸比例为 1:2 的混合溶液配置成质量分数为 35% 的溶液，将所配溶液滴在匀胶机上以 500-2000 转 / 分钟的旋涂速度旋涂在阳极基底层上，旋涂时间为 30 秒，然后在 150℃ 烘箱中烘烤 30 分钟，干燥后得到空穴注入层。然后热蒸镀制备空穴传输层、发光层和电子传输层，接着再蒸镀电子注入层和阴极电极层。
实施例4 ：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其进行 紫外 - 臭氧处理 ，处理时间为 15-30 分钟，功率为 10-30W 。将实施例 1 的氧化锌（ ZnO ）换成氧化镁（ MgO ）与去离子水 / 醋酸比例为 1:2 的混合溶液配置成质量分数为 10% 的溶液，将所配溶液在匀胶机上以 500-5000 转 / 分钟的旋涂速度旋涂在阳极基底层上，旋涂时间为 30 秒，然后在 450℃ 的马弗炉中煅烧 30 分钟，干燥后得到空穴注入层。然后热蒸镀制备空穴传输层、发光层和电子传输层，接着再蒸镀电子注入层和阴极电极层。
实施例5 ：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其进行氧等离子处理，其中氧等离子处理时间为 5-15 分钟，功率为 10-50W 。将实施例 1 的氧化锌（ ZnO ）换成氧化镁（ MgO ）与去离子水 / 醋酸比例为 1:2 的混合溶液配置成质量分数为 30% 的溶液，将所配溶液在匀胶机上以 500-5000 转 / 分钟的旋涂速度旋涂在阳极基底层上，旋涂时间为 30 秒，然后在 450℃ 的马弗炉中煅烧 30 分钟，干燥后得到空穴注入层。然后热蒸镀制备空穴传输层、发光层和电子传输层，接着再蒸镀电子注入层和阴极电极层。
实施例6 ：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其进行氧等离子处理，其中氧等离子处理时间为 5-15 分钟，功率为 10-50W 。将实施例 1 的氧化锌（ ZnO ）换成氧化镁（ MgO ）与去离子水 / 醋酸比例为 1:2 的混合溶液配置成质量分数为 20% 的溶液，将所配溶液在匀胶机上以 500-5000 转 / 分钟的旋涂速度旋涂在阳极基底层上，旋涂时间为 30 秒，然后在 450℃ 的马弗炉中煅烧 30 分钟，干燥后得到空穴注入层。然后热蒸镀制备空穴传输层、发光层和电子传输层，接着再蒸镀电子注入层和阴极电极层。
实施例7 ：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其进行氧等离子处理，其中氧等离子处理时间为 5-15 分钟，功率为 10-50W 。将实施例 1 的氧化锌（ ZnO ）换成聚 3- 己基噻吩与氯苯配置成密度为 1×10-3g/L 的溶液，将所配溶液在匀胶机上以 500-2500 转 / 分钟的旋涂速度旋涂在阳极基底层上，旋涂时间为 30 秒，然后在 200℃ 烘箱中烘烤 30 分钟，干燥后得到空穴注入层。然后热蒸镀制备空穴传输层、发光层和电子传输层，接着再蒸镀电子注入层和阴极电极层。
实施例8 ：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其进行氧等离子处理，其中氧等离子处理时间为 5-15 分钟，功率为 10-50W 。将实施例 1 的氧化锌（ ZnO ）换成聚 3- 己基噻吩与氯苯配置成密度为 5×10-3g/L 的溶液，将所配溶液在匀胶机上以 500-2500 转 / 分钟的旋涂速度旋涂在阳极基底层上，旋涂时间为 30 秒，然后在 200℃ 烘箱中烘烤 30 分钟，干燥后得到空穴注入层。然后热蒸镀制备空穴传输层和发光层，接着再蒸镀电子注入层和阴极电极层。制备得到有机电致发光器件的发光亮度与电压的关系曲线如图 3 所示。
实施例9 ：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其进行 紫外 - 臭氧处理 ，处理时间为 15-30 分钟，功率为 10-30W 。将实施例 1 的氧化锌（ ZnO ）换成聚 3- 己基噻吩与氯苯配置成密度为 1×10-2g/L 的溶液，将所配溶液在匀胶机上以 500-2500 转 / 分钟的旋涂速度旋涂在阳极基底层上，旋涂时间为 30 秒，然后在 200℃ 烘箱中烘烤 30 分钟，干燥后得到空穴注入层。然后热蒸镀制备空穴传输层、发光层和电子传输层，接着再蒸镀电子注入层和阴极电极层。
实施例10 ：不采用空穴注入层的对比器件：将铟锡氧化物玻璃进行光刻处理，剪裁成所需要的发光面积，然后依次用洗洁精、去离子水、丙酮、乙醇、异丙醇各超声 15 分钟，清洗干净后对其进行氧等离子处理，其中氧等离子处理时间为 5-15 分钟，功率为 10-50W 。没有加入空穴注入层。直接热蒸镀制备空穴传输层和发光层，接着再蒸镀电子注入层和阴极电极层。
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. 一种有机电致发光器件，包括阳极基底层、位于所述阳极基底层上的空穴注入层、位于所述空穴注入层上的发光层及位于所述发光层上的阴极电极层，其特征在于，所述空穴注入层的材质为金属氧化物或噻吩类化合物。
  2. 如权利要求 1 所述的有机电致发光器件，其特征在于，所述金属氧化物为氧化锌、氧化镁和五氧化二钒中的至少一种；所述噻吩类化合物为聚 3-己基噻吩、聚 3- 甲基噻吩、聚 3- 辛氧基噻吩和聚 3- 十二烷基噻吩中的至少一种。
  3. 如权利要求 1 所述的有机电致发光器件，其特征在于，还包括位于所述空穴注入层及所述发光层之间的空穴传输层、位于所述发光层及所述阴极电极层之间的电子传输层及位于所述电子传输层与所述阴极电极层之间的电子注入层中的至少一层。
  4. 一种有机电致发光器件的制备方法，其特征在于，包括如下步骤：
    S1 、配置金属氧化物溶胶或噻吩类化合物溶胶；
    S2 、提供阳极基底层，对所述阳极基底层表面进行预处理；
    S3 、采用旋涂技术，将所述金属氧化物溶胶或噻吩类化合物溶胶涂覆在表面预处理后的所述阳极基底层上，形成一层空穴注入层；然后在所述空穴注入层上涂覆一层发光层，以及在所述发光层上涂覆一层阴极电极层，烘干，即得到所述有机电致发光器件。
  5. 如权利要求 4 所述的有机电致发光器件的制备方法，其特征在于，步骤 S1 中，金属氧化物溶胶的配置包括如下步骤：
    将金属氧化物溶于溶剂中，配置成浓度为 10~35% 的金属氧化物溶胶。
  6. 如权利要求 5 所述的有机电致发光器件的制备方法，其特征在于，所述金属氧化物为氧化锌或氧化镁，所述溶剂为体积百分比 1:2 的水和醋酸的混合溶液；或所述金属氧化物为五氧化二钒，所述溶剂为氨水。
  7. 如权利要求 4 或 6 所述的有机电致发光器件的制备方法，其特征在于，当形成所述空穴注入层的原料为金属氧化物溶胶时，旋涂过程中转速为 500-2000 转 / 分钟，旋涂时间为 30 秒；干燥程中温度为 50-200℃，干燥时间为15-60 分钟。
  8. 如权利要求 4 所述的有机电致发光器件的制备方法，其特征在于，步骤 S1 中，噻吩类化合物溶胶的配置包括如下步骤：
    将噻吩类化合物溶于有机溶剂中，配置成密度为1 × 10-3-1 × 10-2g/L 的 噻吩类化合物溶胶。
  9. 如权利要求8 所述的有机电致发光器件的制备方法，其特征在于，所述噻吩类化合物为聚 3-己基噻吩、聚 3-甲基噻吩、聚 3-辛氧基噻吩或聚 3-十二烷基噻吩；所述有机溶剂为氯苯、二甲苯、四氢呋喃、三氯甲烷或二氯甲烷中的至少一种。
  10. 如权利要求 4 或 9 所述的有机电致发光器件的制备方法，其特征在于，当形成所述空穴注入层的原料为噻吩类化合物溶胶时，旋涂过程中转速为 500-2500转 / 分钟，旋涂时间为 30秒；干燥过程中温度为 50-200℃，干燥时间为15-100分钟。
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