WO2018129921A1 - 一种蓝色有机电致发光器件及其制备方法 - Google Patents

一种蓝色有机电致发光器件及其制备方法 Download PDF

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WO2018129921A1
WO2018129921A1 PCT/CN2017/098005 CN2017098005W WO2018129921A1 WO 2018129921 A1 WO2018129921 A1 WO 2018129921A1 CN 2017098005 W CN2017098005 W CN 2017098005W WO 2018129921 A1 WO2018129921 A1 WO 2018129921A1
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layer
blue organic
hole
electroluminescent device
organic electroluminescent
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PCT/CN2017/098005
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English (en)
French (fr)
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周亮
张洪杰
赵学森
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中国科学院长春应用化学研究所
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Priority to EP17891195.4A priority Critical patent/EP3570340A4/en
Priority to JP2019559136A priority patent/JP6825137B2/ja
Priority to US16/477,282 priority patent/US10854820B2/en
Publication of WO2018129921A1 publication Critical patent/WO2018129921A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—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
    • 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

Definitions

  • the invention belongs to the field of organic electroluminescence technology, and in particular relates to a blue organic electroluminescent device and a preparation method thereof.
  • the organic light-emitting device is a self-luminous device, and when charges are injected into an organic film between an electron injecting electrode (anode) and a hole injecting electrode (cathode), electrons and holes are combined and then quenched, thereby generating light.
  • organic electroluminescent displays have adjustable color, active illumination, high brightness, high efficiency, wide viewing angle, low power consumption, and simple preparation process. It can produce a series of excellent characteristics such as curved flexible display, and has broad application prospects in the field of large flat panel full color display. It is widely regarded as the most competitive new generation display technology.
  • Transition metal complexes are regarded as ideal organic electroluminescent materials by academics and industry because of their high luminous efficiency and adjustable color of light.
  • Many research teams at home and abroad have started from material synthesis and device optimization, and strive to improve the comprehensive performance of blue organic electroluminescent devices in order to meet the needs of industrialization.
  • blue organic electroluminescent devices based on transition metal complexes are generally accompanied by lower color purity, lower operating life, or lower luminous efficiency. Therefore, more and more research teams tend to use blue fluorescent materials instead of blue transition metal complexes to obtain pure blue fluorescent organic electroluminescent devices.
  • pure blue fluorescent materials generally have lower luminous efficiency; in addition, the relatively wide energy gap of pure blue fluorescent materials brings great inconvenience to the screening of host materials, eventually leading to carrier injection, transmission and distribution. Unbalanced, thus making the blue light device It has low luminous efficiency and high operating voltage.
  • the resulting device has a low luminous efficiency, which limits its wide application in the field of illumination and display.
  • Ma Yuguang and others from South China University of Technology reported the new dark blue fluorescent material developed in Laser Photonics Reviews magazine and obtained excellent deep blue light-emitting device devices.
  • the obtained dark blue device has excellent color purity and color stability, its high operating voltage not only directly leads to low power efficiency of the device, but also indirectly reduces the operational stability of the device. It can be seen that the comprehensive properties such as color purity, luminous efficiency and working stability of the pure blue organic electroluminescent device have not been substantially improved.
  • the technical problem to be solved by the present invention is to provide a blue organic electroluminescent device and a preparation method thereof, which are simple in structure and have high efficiency, brightness and work stability.
  • the present invention provides a blue organic electroluminescent device comprising:
  • An anode layer disposed on the substrate
  • the light-emitting layer disposed on the anode layer; the light-emitting layer is formed of a blue organic fluorescent material and a hole-type organic host material; the quality of the blue organic fluorescent material is 8.0% of the mass of the hole-type organic host material ⁇ 25.0%; the excited state energy of the blue organic fluorescent material is smaller than the excited state energy of the hole type organic host material;
  • the blue organic fluorescent material is 2,2'-(9,10-fluorenyldi-4,1-phenylene)bis[6-methyl-benzothiazole].
  • the hole-type organic host material is 4,4'-bis(9-carbazolyl)biphenyl 1,3-dioxazole-9-ylbenzene, 9,9'-(5-(three Phenylsilyl)-1,3-phenyl)di-9H-carbazole, 1,3,5-tris(9-oxazolyl)benzene, 4,4',4"-tris(carbazole-9 One or more of triphenylamine and 4,4'-bis(triphenylsilyl)biphenyl.
  • the luminescent layer has a thickness of 5 to 20 nm.
  • an anode interface layer is further disposed between the anode layer and the light-emitting layer; the anode interface layer has a thickness of 2-10 nm.
  • a hole transport layer or an electron blocking layer is further disposed between the anode layer and the light emitting layer; and the hole transport layer or the electron blocking layer has a thickness of 40 to 60 nm.
  • a hole transport layer or an electron blocking layer is disposed between the anode interface layer and the light emitting layer.
  • a hole blocking layer or an electron transport layer is further disposed between the light emitting layer and the cathode layer; and the hole blocking layer or the electron transporting layer has a thickness of 40 to 60 nm.
  • a buffer layer is further disposed between the hole blocking layer or the electron transport layer and the cathode layer; the buffer layer has a thickness of 0.8 to 1.2 nm.
  • the invention also provides a preparation method of a blue organic electroluminescent device, comprising the following steps:
  • the light-emitting layer is formed of a blue organic fluorescent material and a hole-type organic host material; and the mass of the blue organic fluorescent material is 8.0% of the mass of the hole-type organic host material. 25.0%; the excited state energy of the blue organic fluorescent material is smaller than the excited state energy of the hole type organic host material;
  • a cathode is formed on the light-emitting layer to obtain a blue organic electroluminescent device.
  • the present invention provides a blue organic electroluminescent device comprising: a substrate; an anode layer disposed on the substrate; a light emitting layer disposed on the anode layer; the light emitting layer is composed of blue organic fluorescent
  • the material is formed with a hole type organic host material; the mass of the blue organic fluorescent material is 8.0% to 25.0% of the mass of the hole type organic host material; and the excited state energy of the blue organic fluorescent material is smaller than the hole type organic An excited state energy of the host material; and a cathode layer disposed on the light emitting layer.
  • the invention adopts a blue organic fluorescent material with an excited state energy smaller than that of the hole type organic host material as a luminescent material, which has high luminous efficiency and color purity, and good thermal stability, thereby ensuring the device.
  • the color purity and efficiency, while the blue organic fluorescent material also has superior electron transport capability, and the doping concentration is higher in the light-emitting layer, which can combine the functions of the host material and the blue light material, and is advantageous for balancing holes and electrons in the light-emitting interval.
  • the distribution can also limit the recombination of holes and electrons in a narrow region of the luminescent layer, and can effectively balance the distribution of carriers in the luminescent layer.
  • the device provided by the invention has a simple structure, low cost, and materials. Good thermal stability helps to improve the life of the device.
  • FIG. 1 is a schematic structural view of a blue organic electroluminescent device provided by the present invention.
  • Example 2 is a graph showing voltage-current density-luminance characteristics of a blue organic electroluminescent device obtained in Example 1 of the present invention; brightness of the device increases as current density and driving voltage increase, and the device is brightened.
  • Example 3 is a graph showing current density-power efficiency-current efficiency characteristics of a blue organic electroluminescent device obtained in Example 1 of the present invention; maximum current efficiency of the device is 6.41 cd per amp (cd/A), maximum power efficiency 6.71 lumens per watt (lm/W);
  • Example 4 is a spectrum diagram of a blue organic electroluminescent device obtained in Example 1 of the present invention at a luminance of 1000 cd/m 2 , and a color coordinate of the device is (0.135, 0.138);
  • Example 5 is a graph showing voltage-current density-luminance characteristics of a blue organic electroluminescent device obtained in Example 2 of the present invention; brightness of the device increases as current density and driving voltage increase, and the device is brightened.
  • Example 6 is a graph showing current density-power efficiency-current efficiency characteristics of a blue organic electroluminescent device obtained in Example 2 of the present invention; the maximum current efficiency of the device is 6.19 cd/A, and the maximum power efficiency is 6.51 lm/W. .
  • the present invention provides a blue organic electroluminescent device comprising:
  • An anode layer disposed on the substrate
  • the light-emitting layer disposed on the anode layer; the light-emitting layer is formed of a blue organic fluorescent material and a hole-type organic host material; the quality of the blue organic fluorescent material is 8.0% of the mass of the hole-type organic host material ⁇ 25.0%; the excited state energy of the blue organic fluorescent material is smaller than the excited state energy of the hole type organic host material;
  • the present invention has no particular requirements on the substrate, and is a substrate well known to those skilled in the art, preferably a plastic substrate, a polymer substrate, a silicon-based substrate or a glass substrate, more preferably a glass substrate.
  • An anode layer is disposed on the substrate; the anode layer is formed of a material that is easy to inject holes, preferably a conductive metal, a conductive metal oxide or graphene, more preferably an indium tin oxide, a gold electrode, a platinum electrode or
  • the graphene electrode is more preferably indium tin oxide; the surface resistance of the indium tin oxide is preferably 8 to 25 ohms.
  • the anode layer is preferably further provided with an anode interface layer; the anode interface layer preferably has a thickness of 2 to 10 nm, more preferably 2 to 8 nm, still more preferably 2 to 5 nm, and most preferably 3 nm;
  • the anode interface layer is preferably an anode interface layer well known to those skilled in the art, and is not particularly limited. In the present invention, molybdenum trioxide, lithium fluoride or sodium chloride is preferred.
  • the anode interface layer is preferably provided with a hole transport layer or an electron blocking layer;
  • the thickness of the electron blocking layer is preferably 40 to 60 nm, more preferably 40 to 50 nm;
  • the hole transport layer or the electron blocking layer may be a hole transport layer or an electron blocking layer well known to those skilled in the art, and there is no
  • the invention preferably consists of 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline] (abbreviated as TAPC), 4,4'-bis[N-(p-toluene).
  • NPB 4'-diamine
  • the hole transport layer or the electron blocking layer is provided with a light emitting layer;
  • the light emitting layer is formed of a blue organic fluorescent material and a hole type organic host material;
  • the thickness of the light emitting layer is preferably 5 to 20 nm, more preferably 5 to 15 nm, more preferably 8 to 12 nm, and most preferably 10 nm;
  • the mass of the blue organic fluorescent material is 8.0% to 25.0%, preferably 10.0% to 25.0%, of the mass of the hole type organic host material, Preferably, it is 15.0% to 20.0%, and more preferably 15.0% to 16.0%;
  • the blue organic fluorescent material is an energy level matching blue organic fluorescent material, which is an energy level matching blue well known to those skilled in the art.
  • the organic fluorescent material can be used without any particular limitation as long as the energy and energy levels are matched.
  • a basic principle of energy matching is that energy can be effectively transmitted from the host material to the luminescent material, which requires the excited state energy of the host material > the excited state energy of the luminescent material; a basic principle of energy level matching is: the energy of the host material The gap is wide enough to effectively include the energy gap of the luminescent material to facilitate carrier trapping.
  • the energy level of the blue organic fluorescent material in the present invention should facilitate the electron injection into the light-emitting interval while functioning as an electron-type auxiliary host material.
  • the blue organic fluorescent material is preferably 2, 2'- (9,10-nonyldiyl-2,1-phenylene)bis[6-methyl-benzothiazole] (DBzA for short, formula I).
  • the blue organic fluorescent material DBzA is selected as the luminescent material, which has high luminous efficiency and color purity, good thermal stability, and excellent electron transporting ability, and can effectively balance the distribution of carriers in the luminescent layer.
  • the hole organic host material may be a hole organic host material well known to those skilled in the art, and is not particularly limited.
  • CBP 4,4′-bis(9-carbazolyl)biphenyl
  • CBP 4,4′-bis(9-carbazolyl)biphenyl
  • mCP 1,3-dicarbazol-9-ylbenzene
  • TCP 9,9'-(5-(triphenylsilyl)- 1,3-phenyl)di-9H-carbazole
  • TCP 1,3,5-tris(9-carbazolyl)benzene
  • TCP 1,3,5-tris(9-carbazolyl)benzene
  • TCP 1,3,5-tris(9-carbazolyl)benzene
  • TCP 1,3,5-tris(9-carbazolyl)benzene
  • TCP 1,3,5-tris(9-carbazolyl)benzene
  • TCP 4,4',4"-tris(carbazol-9-yl)triphenylamine
  • TcTa 4,4'-bis(triphenylsilyl
  • the light-emitting layer is preferably further provided with a hole blocking layer or an electron transport layer;
  • the thickness of the electron transport layer is preferably 40 to 60 nm, more preferably 40 to 55 nm, still more preferably 40 to 50 nm; and the hole blocking layer or electron transport layer is a hole blocking layer or an electron transport layer well known to those skilled in the art.
  • TmPyPB 1,3,5- Tris[(3-pyridyl)-3-phenyl]benzene
  • BmPyPhB 1,3-bis[3,5-di(3-pyridyl)phenyl]benzene
  • TPBi 1,3,5 -Tris(1-phenyl-1H-benzimidazol-2-yl)benzene
  • TPBi 1,3,5-tris ⁇ 6-[3-(pyridin-3-yl)phenyl]pyridine-2
  • Tm3PyP26PyB One or more of -yl ⁇ benzene having the formulas shown in Formulas VIII, IX, X, XI and XI
  • a buffer layer is preferably further provided on the hole blocking layer or the electron transport layer; the thickness of the buffer layer is preferably 0.8 to 1.2 nm, more preferably 0.9 to 1.1.
  • the buffer layer is not particularly limited, and is preferably formed of lithium fluoride, sodium chloride or sodium carbonate in the present invention.
  • a cathode layer is disposed on the buffer layer; the cathode layer preferably has a thickness of 90 to 150 nm, more preferably It is 100 to 140 nm, more preferably 110 to 130 nm, and most preferably 120 nm; the cathode layer is a cathode layer well known to those skilled in the art, and is not particularly limited.
  • metal aluminum, magnesium silver alloy is preferred. Or silver formation.
  • FIG. 1 The schematic diagram of the structure of the blue organic electroluminescent device provided by the present invention is shown in FIG. 1 , wherein 1 is a substrate, 2 is an anode layer, 3 is an anode interface layer, 4 is a hole transport layer/electron blocking layer, and 5 is The light-emitting layer, 6 is a hole blocking layer/electron transport layer, 7 is a buffer layer, and 8 is a cathode layer.
  • the blue organic electroluminescent device has an anode and a cathode interdigitated to form a light-emitting region thereof. When a forward voltage is applied between the two electrodes, the device emits pure blue light having a main emission peak at about 462 nm.
  • the invention adopts a blue organic fluorescent material with an excited state energy smaller than that of the hole type organic host material as a luminescent material, which has high luminous efficiency and color purity, and good thermal stability, thereby ensuring color purity and efficiency of the device, and simultaneously
  • the blue organic fluorescent material also has superior electron transporting ability, and has a high doping concentration in the light emitting layer, and can function as both a host material and a blue light material, which is advantageous for balancing the distribution of holes and electrons in the light emitting interval, and can also be empty.
  • the combination of the holes and the electrons is limited to the narrow region of the light-emitting layer, and can effectively balance the distribution of carriers in the light-emitting layer.
  • the device provided by the invention has a simple structure, low cost, and good thermal stability of the materials. Help to improve the life of the device.
  • the invention also provides a preparation method of the above blue organic electroluminescent device, comprising the following steps:
  • the light-emitting layer is formed of a blue organic fluorescent material and a hole-type organic host material; and the mass of the blue organic fluorescent material is 8.0% of the mass of the hole-type organic host material. 25.0%; the excited state energy of the blue organic fluorescent material is smaller than the excited state energy of the hole type organic host material;
  • a cathode is formed on the light-emitting layer to obtain a blue organic electroluminescent device.
  • an anode layer is first formed on a substrate; the substrate and the anode layer are the same as described above, and will not be described herein.
  • the conductive metal, the conductive metal oxide or the graphene on the substrate is preferably etched to obtain an electrode.
  • the shape and size of the etched electrode are not particularly limited in the present invention, such as being 10 mm wide and 30 mm long. Strip electrode.
  • anode interface layer is then preferably formed on the anode layer; the anode interface layer is the same as described above and will not be described herein.
  • an anode interface layer is formed on the anode layer; the method of forming the anode interface layer is a method well known to those skilled in the art, and is not particularly limited.
  • the substrate for forming the anode layer after drying is subjected to a low-pressure oxygen plasma treatment under vacuum, and then the anode interface layer is vapor-deposited;
  • the vacuum condition of the vacuum condition is preferably 8 to 15 Pa;
  • the voltage of the low pressure oxygen plasma treatment is 350 to 500 volts;
  • the time of the low pressure oxygen plasma treatment is preferably 5 to 15 minutes;
  • the degree of vacuum of the vapor deposition is preferably 5 to 8 ⁇ 10 ⁇ 5 Pa.
  • a hole transport layer or an electron blocking layer is then preferably formed on the anode interface layer; the hole transport layer or the electron blocking layer is the same as described above and will not be described herein.
  • the method of forming is not limited to the method well known to those skilled in the art, and the present invention is preferably vacuum evaporation; the degree of vacuum of the vapor deposition is preferably from 1 to 3 ⁇ 10 -5 Pa; The evaporation rate of the organic matter in vacuum evaporation is preferably 0.05 to 0.1 nm/s.
  • a light-emitting layer is formed on the hole transport layer or the electron blocking layer; the light-emitting layer is the same as described above, and details are not described herein again.
  • the method of forming is not limited to the method known to those skilled in the art, and the present invention is preferably vacuum evaporation; the degree of vacuum of the vapor deposition is preferably 1-3 ⁇ 10 ⁇ 5 Pa; The evaporation rate of the blue organic fluorescent material in vacuum evaporation is preferably 0.004 to 0.025 nm/s; and the evaporation rate of the hole type organic host material is preferably 0.05 to 0.1 nm/s.
  • the blue organic fluorescent material in the organic mixed material and the hole-type organic host material are simultaneously evaporated in different evaporation sources, and the quality of the blue organic fluorescent material is the quality of the hole-type organic host material by controlling the evaporation rate of the two materials. 8.0% to 25.0%.
  • a hole blocking layer or an electron transporting layer is preferably formed on the light-emitting layer; the hole blocking layer or the electron transporting layer is the same as described above and will not be described herein; the method of forming is well known to those skilled in the art.
  • the method is not particularly limited, and the present invention is preferably vacuum vapor deposition; the degree of vacuum of the vapor deposition is preferably from 1 to 3 ⁇ 10 -5 Pa.
  • the evaporation rate of the organic matter in the vacuum evaporation is preferably 0.05 to 0.1 nm/s.
  • a buffer layer is formed on the hole blocking layer or the electron transport layer; the buffer layer is the same as described above and will not be described herein; the method of forming is a method well known to those skilled in the art, and there is no special In the present invention, vacuum evaporation is preferred; the degree of vacuum of the vacuum evaporation is preferably 5 to 8 ⁇ 10 -5 Pa; and the evaporation rate is preferably 0.5 to 1.5 nm/s.
  • a cathode layer is formed on the buffer layer to obtain a blue organic electroluminescent device.
  • the cathode layer is the same as described above, and is not described herein again; the method for forming is a method well known to those skilled in the art, and is not particularly limited.
  • vacuum evaporation is preferred; the vacuum evaporation is performed.
  • the degree of vacuum is preferably 5 to 8 ⁇ 10 -5 Pa.
  • the blue organic electroluminescent device provided by the invention has a simple structure and is advantageous for simplifying the preparation process of the device, and at the same time, various functional materials selected generally have relatively low price, which is beneficial to reducing the manufacturing cost of the device; The materials have good thermal stability, which is beneficial to improve the life of the device. Life.
  • the invention simplifies the device structure and the preparation process by optimizing the design of the device structure, improves the efficiency, brightness and working stability of the device and reduces the manufacturing cost of the device under the premise of ensuring that the color purity of the device is not reduced.
  • the ITO anode layer on the ITO glass was first laser etched into a patterned electrode, which was then ultrasonically cleaned with a cleaning solution, deionized water for 15 minutes, and placed in an oven for drying. Then, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to a low-pressure oxygen plasma treatment for 10 minutes under a vacuum of 10 Pa for 10 minutes, and then transferred to a metal deposition chamber.
  • the 3 nm MoO 3 anode interface layer 3 was vapor-deposited in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa.
  • the unfinished device is transferred to the organic vapor deposition chamber, and a 40 nm thick TAPC hole transport layer is sequentially evaporated on the anode interface layer 3 under a vacuum atmosphere of a vacuum of 1 to 3 ⁇ 10 -5 Pa.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF buffer layer was evaporated in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa, and finally deposited on the LiF layer through a special mask.
  • a 120 nm thick metal Al electrode was prepared into a blue organic electroluminescent device having a structure of ITO/MoO 3 /TAPC/DBzA (16 wt%): TcTa/TmPyPB/LiF/Al.
  • the evaporation rates of DBzA and TcTa in the luminescent layer 5 were controlled at 0.008 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and TmPyPB was controlled at 0.05 nm/sec, and the evaporation rate of MoO 3 was controlled at 0.01 nm/sec.
  • the rate was controlled at 0.005 nm/sec, and the evaporation rate of Al was controlled at 0.5 nm/sec.
  • the blue organic electroluminescent device obtained in Example 1 is driven by a direct current voltage, and shows a pure blue light emission with a main peak at 462 nm; the color coordinate of the device is stable from (0.131, 0.133) to (0.146) as the operating voltage changes. , within the range of 0.142).
  • the luminance is 1000 cd/m 2
  • the color coordinates of the device are (0.135, 0.138).
  • Example 2 is a voltage-current density-luminance curve of the blue organic electroluminescent device obtained in Example 1. As can be seen from FIG. 2, the device has a light-emitting voltage of 3.0 volts and a maximum luminance of the device of 10384 cd/m 2 .
  • Example 3 is a graph showing current density-power efficiency-current efficiency characteristics of the blue organic electroluminescent device obtained in Example 1. As can be seen from FIG. 3, the maximum current efficiency of the device is 6.41 cd/A, and the maximum power efficiency is obtained. The rate is 6.71 lm/W.
  • Example 4 is a spectrum diagram when the luminance of the blue organic electroluminescence device obtained in Example 1 was 1000 cd/m 2 , and the color coordinates of the device were (0.135, 0.138).
  • the ITO anode layer on the ITO glass was first laser etched into a patterned electrode, which was then ultrasonically cleaned with a cleaning solution, deionized water for 15 minutes, and placed in an oven for drying. Then, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to a low-pressure oxygen plasma treatment for 10 minutes under a vacuum of 10 Pa for 10 minutes, and then transferred to a metal deposition chamber.
  • the 3 nm MoO 3 anode interface layer 3 was vapor-deposited in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa.
  • the unfinished device is transferred to the organic vapor deposition chamber, and a 40 nm thick TAPC hole transport layer is sequentially evaporated on the anode interface layer 3 under a vacuum atmosphere of a vacuum of 1 to 3 ⁇ 10 -5 Pa.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF buffer layer was evaporated in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa, and finally deposited on the LiF layer through a special mask.
  • a 120 nm thick metal Al electrode was prepared into a blue organic electroluminescent device having a structure of ITO/MoO 3 /TAPC/DBzA (15 wt%): TcTa/Tm3PyP26PyB/LiF/Al.
  • the evaporation rates of DBzA and TcTa in the luminescent layer 5 were controlled at 0.0075 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and TmPyPB was controlled at 0.05 nm/sec, and the evaporation rate of MoO 3 was controlled at 0.01 nm/sec.
  • the rate was controlled at 0.005 nm/sec, and the evaporation rate of Al was controlled at 0.5 nm/sec.
  • the blue organic electroluminescent device obtained in Example 2 is driven by a direct current voltage and exhibits a pure blue light emission with a main peak at 462 nm; the color coordinate of the device is stable from (0.133, 0.132) to (0.144) as the operating voltage changes. , within the range of 0.143). When the luminance is 1000 cd/m 2 , the color coordinates of the device are (0.136, 0.134).
  • Example 5 is a voltage-current density-luminance curve of the blue organic electroluminescent device obtained in Example 2; as can be seen from FIG. 5, the luminance of the device increases as the current density and the driving voltage increase, and the device The starting voltage was 2.8 volts and the maximum brightness of the device was 10937 cd/m 2 .
  • Example 6 is a graph showing current density-power efficiency-current efficiency characteristics of the blue organic electroluminescent device obtained in Example 2; as can be seen from FIG. 6, the maximum current efficiency of the device is 6.19 cd/A, and the maximum power efficiency is 6.51. Lm/W.
  • the ITO anode layer on the ITO glass was first laser etched into a patterned electrode, which was then ultrasonically cleaned with a cleaning solution, deionized water for 15 minutes, and placed in an oven for drying. Then, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to a low-pressure oxygen plasma treatment for 10 minutes under a vacuum of 10 Pa for 10 minutes, and then transferred to a metal deposition chamber.
  • the 3 nm MoO 3 anode interface layer 3 was vapor-deposited in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa.
  • the unfinished device is transferred to the organic vapor deposition chamber, and a 50 nm thick TAPC hole transport layer is sequentially evaporated on the anode interface layer 3 under a vacuum atmosphere of a vacuum of 1 to 3 ⁇ 10 -5 Pa.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF buffer layer was evaporated in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa, and finally deposited on the LiF layer through a special mask.
  • a 120 nm thick metal Al electrode was prepared into a blue organic electroluminescent device having a structure of ITO/MoO 3 /TAPC/DBzA (16 wt%): TcTa/TmPyPB/LiF/Al.
  • the evaporation rates of DBzA and TcTa in the luminescent layer 5 were controlled at 0.008 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and TmPyPB was controlled at 0.05 nm/sec, and the evaporation rate of MoO 3 was controlled at 0.01 nm/sec.
  • the rate was controlled at 0.005 nm/sec, and the evaporation rate of Al was controlled at 0.5 nm/sec.
  • the blue organic electroluminescent device obtained in Example 3 is driven by a direct current voltage and exhibits a pure blue light emission with a main peak at 462 nm; the color coordinate of the device is stable from (0.135, 0.136) to (0.141) as the operating voltage changes. , within the range of 0.149).
  • the luminance was 1000 cd/m 2
  • the color coordinates of the device were (0.137, 0.140).
  • the device has a starting voltage of 3.1 volts and a maximum brightness of the device of 11056 cd/m 2 .
  • the device has a maximum current efficiency of 6.46 cd/A and a maximum power efficiency of 6.54 lm/W.
  • the ITO anode layer on the ITO glass was first laser etched into a patterned electrode, which was then ultrasonically cleaned with a cleaning solution, deionized water for 15 minutes, and placed in an oven for drying. Then, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to a low-pressure oxygen plasma treatment for 10 minutes under a vacuum of 10 Pa for 10 minutes, and then transferred to a metal deposition chamber.
  • the 3 nm MoO 3 anode interface layer 3 was vapor-deposited in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa.
  • the unfinished device is transferred to the organic vapor deposition chamber, and a 50 nm thick TAPC hole transport layer is sequentially evaporated on the anode interface layer 3 under a vacuum atmosphere of a vacuum of 1 to 3 ⁇ 10 -5 Pa.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF buffer layer was evaporated in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa, and finally deposited on the LiF layer through a special mask.
  • a 120 nm thick metal Al electrode was prepared into an organic electroluminescent device having a structure of ITO/MoO 3 /TAPC/DBzA (16 wt%): TcTa/TmPyPB/LiF/Al.
  • the evaporation rates of DBzA and TcTa in the luminescent layer 5 were controlled at 0.008 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and TmPyPB was controlled at 0.05 nm/sec, and the evaporation rate of MoO 3 was controlled at 0.01 nm/sec.
  • the rate was controlled at 0.005 nm/sec, and the evaporation rate of Al was controlled at 0.5 nm/sec.
  • the blue organic electroluminescent device obtained in Example 4 is driven by a direct current voltage, and shows a pure blue light emission with a main peak at 462 nm; the color coordinate of the device is stable from (0.131, 0.130) to (0.145) as the operating voltage changes. , within the range of 0.141).
  • the luminance is 1000 cd/m 2
  • the color coordinates of the device are (0.132, 0.137).
  • the device has a starting voltage of 3.0 volts and a maximum brightness of 11296 cd/m 2 .
  • the device has a maximum current efficiency of 6.23 cd/A and a maximum power efficiency of 6.52 lm/W.
  • the ITO anode layer on the ITO glass was first laser etched into a patterned electrode, which was then ultrasonically cleaned with a cleaning solution, deionized water for 15 minutes, and placed in an oven for drying. Then, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to a low-pressure oxygen plasma treatment for 10 minutes under a vacuum of 10 Pa for 10 minutes, and then transferred to a metal deposition chamber.
  • the 3 nm MoO 3 anode interface layer 3 was vapor-deposited in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa.
  • the unfinished device is transferred to the organic vapor deposition chamber, and a 40 nm thick TAPC hole transport layer is sequentially evaporated on the anode interface layer 3 under a vacuum atmosphere of a vacuum of 1 to 3 ⁇ 10 -5 Pa.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF buffer layer was evaporated in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa, and finally deposited on the LiF layer through a special mask.
  • a 120 nm thick metal Al electrode was prepared into a blue organic electroluminescent device having a structure of ITO/MoO 3 /TAPC/DBzA (16 wt%): TcTa/TmPyPB/LiF/Al.
  • the evaporation rates of DBzA and TcTa in the luminescent layer 5 were controlled at 0.008 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and TmPyPB was controlled at 0.05 nm/sec, and the evaporation rate of MoO 3 was controlled at 0.01 nm/sec.
  • the rate was controlled at 0.005 nm/sec, and the evaporation rate of Al was controlled at 0.5 nm/sec.
  • the blue organic electroluminescent device obtained in Example 5 is driven by a direct current voltage, and shows a pure blue light emission with a main peak at 462 nm; the color coordinate of the device is stable from (0.135, 0.133) to (0.148) as the operating voltage changes. , within the range of 0.146).
  • the luminance was 1000 cd/m 2
  • the color coordinates of the device were (0.139, 0.141).
  • the device has a starting voltage of 2.9 volts and a maximum brightness of the device of 9885 cd/m 2 .
  • the device has a maximum current efficiency of 6.32 cd/A and a maximum power efficiency of 6.84 lm/W.
  • the ITO anode layer on the ITO glass was first laser etched into a patterned electrode, which was then ultrasonically cleaned with a cleaning solution, deionized water for 15 minutes, and placed in an oven for drying. Then, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to a low-pressure oxygen plasma treatment for 10 minutes under a vacuum of 10 Pa for 10 minutes, and then transferred to a metal deposition chamber.
  • the 3 nm MoO 3 anode interface layer 3 was vapor-deposited in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa.
  • the unfinished device is transferred to the organic vapor deposition chamber, and a 50 nm thick TAPC hole transport layer is sequentially evaporated on the anode interface layer 3 under a vacuum atmosphere of a vacuum of 1 to 3 ⁇ 10 -5 Pa.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF buffer layer was evaporated in a vacuum atmosphere of 3 to 5 ⁇ 10 -5 Pa, and finally deposited on the LiF layer through a special mask.
  • a 120 nm thick metal Al electrode was prepared into an organic electroluminescent device having a structure of ITO/MoO 3 /TAPC/DBzA (15 wt%): TcTa/TmPyPB/LiF/Al.
  • the evaporation rates of DBzA and TcTa in the luminescent layer 5 were controlled at 0.0075 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and TmPyPB was controlled at 0.05 nm/sec, and the evaporation rate of MoO 3 was controlled at 0.01 nm/sec.
  • the rate was controlled at 0.005 nm/sec, and the evaporation rate of Al was controlled at 0.5 nm/sec.
  • the blue organic electroluminescent device obtained in Example 6 is driven by a direct current voltage and exhibits a pure blue light emission with a main peak at 462 nm; the color coordinate of the device is stable from (0.130, 0.135) to (0.142) as the operating voltage changes. , within the range of 0.148).
  • the luminance was 1000 cd/m 2
  • the color coordinates of the device were (0.137, 0.143).
  • the device has a light-emitting voltage of 3.0 volts and a maximum brightness of the device of 10,656 cd/m 2 .
  • the device has a maximum current efficiency of 6.28 cd/A and a maximum power efficiency of 6.57 lm/W.

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Abstract

一种蓝色有机电致发光器件，包括：衬底（1）；设置在衬底上的阳极层（2）；设置在阳极层上的发光层（5）；发光层由蓝色有机荧光材料与空穴型有机主体材料形成；蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％；设置在发光层上的阴极层（8）。采用激发态能量小于空穴型有机主体材料的蓝色有机荧光材料作为发光材料，兼具较高的发光效率与色纯度，热稳定性能好，同时也具有优越电子传输能力，在发光层中掺杂浓度较高，可以兼具主体材料和蓝光材料的功能，有利于平衡空穴和电子在发光区间的分布，也能够将空穴和电子的复合限制在发光层的狭窄区域，能够有效平衡载流子在发光层的分布。

Description

一种蓝色有机电致发光器件及其制备方法
本申请要求2017年1月16日提交中国专利局、申请号为201710032259.8、发明名称为“一种蓝色有机电致发光器件及其制备方法”的中国专利申请的优先权，该专利申请的全部内容通过引用结合在此。
技术领域
本发明属于有机电致发光技术领域，尤其涉及一种蓝色有机电致发光器件及其制备方法。
背景技术
有机发光器件是一种自发光器件，当电荷被注入到电子注入电极(阳极)和空穴注入电极(阴极)之间的有机膜时，电子和空穴结合并随后湮灭，因而产生光。与其他平面显示技术如液晶显示器、等离子体显示器件、场发射显示器相比，有机电致发光显示具有发光颜色可调、主动发光、高亮度、高效率、宽视角、低能耗、制备工艺简单、可制备弯曲柔性显示屏等一系列优异特性，而且在大平面平板全色显示器领域中具有广阔的应用前景，被普遍认为是最具竞争力的新一代显示技术。因此，有机电致发光技术的研究吸引了科学界和工业界的广泛关注和积极参与，使得有机电致发光器件的性能在过去的十多年中得到了迅速的发展。其中，蓝色有机电致发光器件由于在单色显示、白光调制等方面的应用前景，已经成为目前的研究热点。
一直以来，高性能、高品质纯蓝色有机电致发光器件的研发设计始终是该领域的重点及难点。过渡金属配合物因为具有发光效率高和发光颜色可调等优点而被学术界和产业界视为理想的有机电致发光材料。国内外的许多研究团队从材料合成和器件优化方面着手，努力提高蓝色有机电致发光器件的综合性能，以期满足产业化的需要。然而，基于过渡金属配合物所得的蓝色有机电致发光器件通常伴随着较低的色纯度、较低的工作寿命或者较低的发光效率。因此，越来越多的研究团队倾向于采用蓝色荧光发光材料取代蓝色过渡金属配合物，获得纯蓝色的荧光有机电致发光器件。然而，纯蓝色荧光材料普遍具有较低的发光效率；另外，纯蓝色荧光材料相对较宽的能隙给主体材料的筛选带了很大不便，最终导致载流子注入、传输及分布的不均衡，因而使得所制得蓝光器件 具有较低的发光效率和较高的工作电压。
为了解决这些问题，国内外的研发团队纷纷致力于新型纯蓝色发光材料的设计和蓝光器件结构的优化。例如，2010年中国科学院长春应用化学研究所周亮等人在Journal of Luminescence杂志发表研究论文，通过将微量的电子传输材料8–羟基喹啉铝(简称AlQ)掺入发射纯蓝色光的空穴传输材料N，N′-双(1-萘基)-N，N′-二苯基-1，1′-二苯基-4，4′-二胺(简称NPB)中，获得了较为稳定的纯蓝色发光器件。然而，所得器件的发光效率较低，限制了其在照明及显示领域的广泛应用。2014年，华南理工大学马於光等人在Laser Photonics Reviews杂志报道了所研制的新型深蓝色荧光材料，并获得了优异的深蓝色发光器件器件。虽然所得深蓝色器件的色纯度和色稳定性非常优异，然而其较高的工作电压不仅直接导致了器件的低功率效率，还间接降低了器件的工作稳定性。由此可见，纯蓝色有机电致发光器件的色纯度、发光效率和工作稳定性等综合性能仍然没有得到实质性改善。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种蓝色有机电致发光器件及其制备方法，该蓝色有机电致发光器件结构简单且具有较高的效率、亮度与工作稳定性。
本发明提供了一种蓝色有机电致发光器件，包括：
衬底；
设置在所述衬底上的阳极层；
设置在所述阳极层上的发光层；所述发光层由蓝色有机荧光材料与空穴型有机主体材料形成；所述蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％；所述蓝色有机荧光材料的激发态能量小于空穴型有机主体材料的激发态能量；
与设置在所述发光层上的阴极层。
优选的，所述蓝色有机荧光材料为2,2'-(9,10-蒽二基二-4,1-亚苯基)二[6-甲基-苯并噻唑]。
优选的，所述空穴型有机主体材料为4，4'-二(9-咔唑基)联苯1,3-二咔唑-9-基苯、9,9'-(5-(三苯基硅烷基)-1,3-苯基)二-9H-咔唑、1,3,5-三(9-咔唑基)苯、4,4',4”–三(咔唑-9-基)三苯胺与4,4’-双(三苯基硅烷基)联苯中的一种或多种。
优选的，所述发光层的厚度为5～20nm。
优选的，所述阳极层与发光层之间还设置有阳极界面层；所述阳极界面层的厚度为2～10nm。
优选的，所述阳极层与发光层之间还设置有空穴传输层或电子阻挡层；所述空穴传输层或电子阻挡层的厚度为40～60nm。在存在阳极界面层的情况下，空穴传输层或电子阻挡层设置在阳极界面层与发光层之间。
优选的，所述发光层与阴极层之间还设置有空穴阻挡层或电子传输层；所述空穴阻挡层或电子传输层的厚度为40～60nm。
优选的，所述空穴阻挡层或电子传输层与阴极层之间还设置有缓冲层；所述缓冲层的厚度为0.8～1.2nm。
本发明还提供了一种蓝色有机电致发光器件的制备方法，包括以下步骤：
在衬底上形成阳极层；
在所述阳极层上形成发光层；所述发光层由蓝色有机荧光材料与空穴型有机主体材料形成；所述蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％；所述蓝色有机荧光材料的激发态能量小于空穴型有机主体材料的激发态能量；
在所述发光层上形成阴极，得到蓝色有机电致发光器件。
本发明提供了一种蓝色有机电致发光器件，包括：衬底；设置在所述衬底上的阳极层；设置在所述阳极层上的发光层；所述发光层由蓝色有机荧光材料与空穴型有机主体材料形成；所述蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％；所述蓝色有机荧光材料的激发态能量小于空穴型有机主体材料的激发态能量；与设置在所述发光层上的阴极层。与现有技术相比，本发明采用激发态能量小于空穴型有机主体材料的蓝色有机荧光材料作为发光材料，兼具较高的发光效率与色纯度，热稳定性能好，从而可保证器件的色纯度和效率，同时蓝色有机荧光材料也具有优越电子传输能力，在发光层中掺杂浓度较高，可以兼具主体材料和蓝光材料的功能，有利于平衡空穴和电子在发光区间的分布，也能够将空穴和电子的复合限制在发光层的狭窄区域，能够有效平衡载流子在发光层的分布；另外，本发明提供的器件结构简单，成本较低，且材料均具有良好的热稳定性，有利于提高器件的寿命。
附图说明
图1是本发明提供的蓝色有机电致发光器件的结构示意图；
图2是本发明实施例1中得到的蓝色有机电致发光器件的电压-电流密度-亮度特性曲线图；器件的亮度随着电流密度和驱动电压的升高而升高，器件的起亮电压为3.0伏，在电压为8.4伏、电流密度为657.78毫安每平方厘米(mA/cm2)时器件获得最大亮度10384坎德拉每平方米(cd/m2)；
图3是本发明实施例1中得到的蓝色有机电致发光器件的电流密度-功率效率-电流效率特性曲线图；器件的最大电流效率为6.41坎德拉每安培(cd/A)，最大功率效率为6.71流明每瓦特(lm/W)；
图4是本发明实施例1中得到的蓝色有机电致发光器件在亮度为1000cd/m2时的光谱图，器件色坐标为(0.135,0.138)；
图5是本发明实施例2中得到的蓝色有机电致发光器件的电压-电流密度-亮度特性曲线图；器件的亮度随着电流密度和驱动电压的升高而升高，器件的起亮电压为2.8伏，在电压为8.0伏、电流密度为910.09mA/cm2时器件获得最大亮度10937cd/m2；
图6是本发明实施例2中得到的蓝色有机电致发光器件的电流密度-功率效率-电流效率特性曲线图；器件的最大电流效率为6.19cd/A，最大功率效率为6.51lm/W。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种蓝色有机电致发光器件，包括：
衬底；
设置在所述衬底上的阳极层；
设置在所述阳极层上的发光层；所述发光层由蓝色有机荧光材料与空穴型有机主体材料形成；所述蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％；所述蓝色有机荧光材料的激发态能量小于空穴型有机主体材料的激发态能量；
与设置在所述发光层上的阴极层。
本发明对所述衬底没有特殊的要求，为本领域技术人员熟知的衬底即可，优选为塑料衬底、聚合物衬底、硅基衬底或玻璃衬底，更优选玻璃衬底。
所述衬底上设置有阳极层；所述阳极层由易于空穴注入的材料形成，优选为导电金属、导电金属氧化物或石墨烯，更优选为铟锡氧化物、金电极、铂电极或石墨烯电极，再优选为铟锡氧化物；所述铟锡氧化物的面阻优选为8～25欧姆。
按照本发明，所述阳极层上优选还设置有阳极界面层；所述阳极界面层的厚度优选为2～10nm，更优选为2～8nm，再优选为2～5nm，最优选为3nm；所述阳极界面层为本领域技术人员熟知的阳极界面层即可，并无特殊的限制，本发明中优选为三氧化钼、氟化锂或氯化钠。
为提高空穴的传输能力，同时阻隔电子的传输，进而减小器件的损耗，提高器件的效率，所述阳极界面层上优选设置有空穴传输层或电子阻挡层；所述空穴传输层或电子阻挡层的厚度优选为40～60nm，更优选为40～50nm，；所述空穴传输层或电子阻挡层为本领域技术人员熟知的空穴传输层或电子阻挡层即可，并无特殊的限制，本发明优选由4,4'–环己基二[N,N–二(4–甲基苯基)苯胺](简称TAPC)、4，4'–二[N-(对-甲苯基)-N-苯基-氨基]二苯基(简称TPD)与N，N'-双(1-萘基)-N，N'-二苯基-1，1'-二苯基-4，4'-二胺(简称NPB)中的一种或多种形成，其分子结构式如下所示：
Figure PCTCN2017098005-appb-000001
所述空穴传输层或电子阻挡层上设置有发光层；所述发光层由蓝色有机荧光材料与空穴型有机主体材料形成；所述发光层的厚度优选为5～20nm，更优选 为5～15nm，再优选为8～12nm，最优选为10nm；所述蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％，优选为10.0％～25.0％，更优选为15.0％～20.0％，再优选为15.0％～16.0％；所述蓝色有机荧光材料为能级能量匹配的蓝色有机荧光材料，其为本领域技术人员熟知的能级能量匹配的蓝色有机荧光材料即可，并无特殊的限制，只要能量及能级匹配即可。能量匹配的一个基本原则是：从主体材料到发光材料，能量能够有效传递，这就要求主体材料的激发态能量>发光材料的激发态能量；能级匹配的一个基本原则是：主体材料的能隙较宽，能够有效地将发光材料的能隙包含在内，以便促进载流子的俘获。而本发明中蓝色有机荧光材料的能级应该有利于电子注入发光区间，同时起到电子型辅助主体材料的作用，因此，在本发明中所述蓝色有机荧光材料优选2,2'-(9,10-蒽二基二-4,1-亚苯基)二[6-甲基-苯并噻唑](简称DBzA，分子式如式I所示)。选择蓝色有机荧光材料DBzA作为发光材料，其兼具高的发光效率和色纯度，热稳定性能好，同时兼具优越的电子传输能力，能够有效平衡载流子在发光层的分布。所述空穴有机主体材料为本领域技术人员熟知的空穴有机主体材料即可，并无特殊的限制，本发明中优选为4，4'-二(9-咔唑基)联苯(简称CBP，分子式如式II所示)、1,3-二咔唑-9-基苯(简称mCP，分子式如式III所示)、9,9'-(5-(三苯基硅烷基)-1,3-苯基)二-9H-咔唑(简称SimCP，分子式如式IV所示)、1,3,5-三(9-咔唑基)苯(简称TCP，分子式如式V所示)、4,4',4”–三(咔唑-9-基)三苯胺(简称TcTa，分子式如式VI所示)与4,4’-双(三苯基硅烷基)联苯(简称BSB，分子式如式VII所示)。
Figure PCTCN2017098005-appb-000002
Figure PCTCN2017098005-appb-000003
为了提高电子的传输能力，同时阻隔空穴的传输，进而减少器件的损耗，提高器件的效率，所述发光层上优选还设置有空穴阻挡层或电子传输层；所述空穴阻挡层或电子传输层的厚度优选为40～60nm，更优选为40～55nm，再优选为40～50nm；所述空穴阻挡层或电子传输层为本领域技术人员熟知的空穴阻挡层或电子传输层即可，并无特殊的限制，本发明中优选由三[2,4,6-三甲基-3-(3-吡啶基)苯基]硼烷(简称3TPYMB)、1，3，5-三[(3-吡啶)-3-苯基]苯(简称TmPyPB)、1,3-双[3,5-二(3-吡啶基)苯基]苯(简称BmPyPhB)、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(简称TPBi)与1,3,5-三{6-[3-(吡啶-3-基)苯基]吡啶-2-基}苯(简称Tm3PyP26PyB)中的一种或多种，其分子式如式VIII、IX、X、XI与XII所示。
Figure PCTCN2017098005-appb-000004
为了增进电子的注入效率，进而提高器件的效率，所述空穴阻挡层或电子传输层上优选还设置有缓冲层；所述缓冲层的厚度优选为0.8～1.2nm，更优选为0.9～1.1nm，再优选为1nm；所述缓冲层为本领域技术人员熟知的缓冲层即可，并无特殊的限制，本发明中优选由氟化锂、氯化钠或碳酸钠形成。
所述缓冲层上设置有阴极层；所述阴极层的厚度优选为90～150nm，更优选 为100～140nm，再优选为110～130nm，最优选为120nm；所述阴极层为本领域技术人员熟知的阴极层即可，并无特殊的限制，本发明中优选由金属铝、镁银合金或银形成。
本发明提供的蓝色有机电致发光器件的结构示意图如图1所示，其中1为衬底，2为阳极层，3为阳极界面层，4为空穴传输层/电子阻挡层，5为发光层，6为空穴阻挡层/电子传输层，7为缓冲层，8为阴极层。蓝色有机电致发光器件阳极与阴极相互交叉形成其发光区，当在两个电极之间施加正向电压时，该器件就会发出主发射峰位于462纳米左右的纯蓝色光。
本发明采用激发态能量小于空穴型有机主体材料的蓝色有机荧光材料作为发光材料，兼具较高的发光效率与色纯度，热稳定性能好，从而可保证器件的色纯度和效率，同时蓝色有机荧光材料也具有优越电子传输能力，在发光层中掺杂浓度较高，可以兼具主体材料和蓝光材料的功能，有利于平衡空穴和电子在发光区间的分布，也能够将空穴和电子的复合限制在发光层的狭窄区域，能够有效平衡载流子在发光层的分布；另外，本发明提供的器件结构简单，成本较低，且材料均具有良好的热稳定性，有利于提高器件的寿命。
本发明还提供了一种上述蓝色有机电致发光器件的制备方法，包括以下步骤：
在衬底上形成阳极层；
在所述阳极层上形成发光层；所述发光层由蓝色有机荧光材料与空穴型有机主体材料形成；所述蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％；所述蓝色有机荧光材料的激发态能量小于空穴型有机主体材料的激发态能量；
在所述发光层上形成阴极，得到蓝色有机电致发光器件。
按照本发明，首先在衬底上形成阳极层；所述衬底与阳极层均同上所述，在此不再赘述。在本发明中，优选将衬底上的导电金属、导电金属氧化物或石墨烯腐蚀得到电极，本发明对腐蚀的电极的形状和大小没有特殊的限制，如可以腐蚀成10mm宽、30mm长的条状电极。
然后优选在阳极层上形成阳极界面层；所述阳极界面层同上所述，在此不再赘述。本发明优选将形成阳极层的衬底清洗烘干后，再在阳极层上形成阳极界面层；所述形成阳极界面层的方法为本领域技术人员熟知的方法即可，并无特殊的限制，本发明中优选为将烘干后的形成阳极层的衬底先在真空条件下进 行低压氧等离子处理后，再蒸镀上阳极界面层；所述真空条件的真空度优选为8～15帕；所述低压氧等离子处理的电压为350～500伏；所述低压氧等离子处理的时间优选为5～15min；所述蒸镀的真空度优选为5～8×10-5帕。
然后优选在阳极界面层上形成空穴传输层或电子阻挡层；所述空穴传输层或电子阻挡层同上所述，在此不再赘述。所述形成的方法为本领域技术人员熟知的方法即可，并没有特殊的限制，本发明优选为真空蒸镀；所述蒸镀的真空度优选为1～3×10-5帕；所述真空蒸镀中有机物的蒸发速率优选为0.05～0.1nm/s。
然后在空穴传输层或电子阻挡层上形成发光层；所述发光层同上所述，在此不再赘述。所述形成的方法为本领域技术人员熟知的方法即可，并无特殊的限制，本发明优选为真空蒸镀；所述蒸镀的真空度优选为1～3×10-5帕；所述真空蒸镀中蓝色有机荧光材料的蒸发速率优选为0.004～0.025nm/s；所述空穴型有机主体材料的蒸发速率优选为0.05～0.1nm/s。有机混合材料中的蓝色有机荧光材料与空穴型有机主体材料在不同的蒸发源中同时蒸发，通过调控两种材料的蒸发速率使得蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％。
按照本发明，优选在发光层上形成空穴阻挡层或电子传输层；所述空穴阻挡层或电子传输层同上所述，在此不再赘述；所述形成的方法为本领域技术人员熟知的方法即可，并无特殊的限制，本发明优选为真空蒸镀；所述蒸镀的真空度优选为1～3×10-5帕。所述真空蒸镀中有机物的蒸发速率优选为0.05～0.1nm/s。
再优选在空穴阻挡层或电子传输层上形成缓冲层；所述缓冲层同上所述，在此不再赘述；所述形成的方法为本领域技术人员熟知的方法即可，并无特殊的限制，本发明中优选为真空蒸镀；所述真空蒸镀的真空度优选为5～8×10-5帕；蒸发速率优选为0.5～1.5nm/s。
最后在所述缓冲层上形成阴极层，得到蓝色有机电致发光器件。所述阴极层同上所述，在此不再赘述；所述形成的方法为本领域技术人员熟知的方法即可，并无特殊的限制，本发明中优选为真空蒸镀；所述真空蒸镀的真空度优选为5～8×10-5帕。
本发明所提供的蓝色有机电致发光器件结构简单，有利于简化器件的制备过程，同时所选用的各种功能材料普遍具有相对低廉的价格，有利于降低器件的制作成本；另外所选用的材料都具有良好的热稳定性，有利于提高器件的寿 命。
本发明通过优化器件结构的设计，简化器件结构及制备流程，在保证器件色纯度不降低的前提下，提高器件的效率、亮度和工作稳定性，降低器件的制作成本。
为了进一步说明本发明，以下结合实施例对本发明提供的一种蓝色有机电致发光器件及其制备方法进行详细描述。
以下实施例中所用的试剂均为市售。
实施例1
先将ITO玻璃上的ITO阳极层激光刻蚀成图案化的电极，然后依次用清洗液、去离子水超声清洗15分钟并放入烘箱烘干。接着将烘干后的衬底放入预处理真空室，在真空度为10帕的氛围下用400伏的电压对ITO阳极进行10分钟的低压氧等离子处理后将其转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀3纳米MoO3阳极界面层3。然后，未完成的器件被转移到有机蒸镀室，在真空度为1～3×10-5帕的真空氛围下，在阳极界面层3上依次蒸镀40纳米厚的TAPC空穴传输层/电子阻挡层4、10纳米厚的DBzA掺杂TcTa发光层5、40纳米厚的TmPyPB空穴阻挡层/电子传输层6。接下来，未完成的器件被转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀1.0纳米厚的LiF缓冲层，最后通过特制的掩模版在LiF层上蒸镀120纳米厚的金属Al电极，制备成结构为ITO/MoO3/TAPC/DBzA(16wt％):TcTa/TmPyPB/LiF/Al的蓝色有机电致发光器件。发光层5中DBzA和TcTa的蒸发速率控制在0.008纳米/秒和0.05纳米/秒，TAPC和TmPyPB的蒸发速率控制在0.05纳米/秒，MoO3的蒸发速率控制在0.01纳米/秒，LiF的蒸发速率控制在0.005纳米/秒，Al的蒸发速率控制在0.5纳米/秒。
实施例1中得到的蓝色有机电致发光器件在直流电压驱动下，显示主峰位于462纳米的纯正蓝光发射；随着工作电压的变化，器件色坐标稳定在从(0.131,0.133)到(0.146,0.142)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.135,0.138)。
图2为实施例1中得到的蓝色有机电致发光器件的电压-电流密度-亮度曲线图；由图2可知，器件的起亮电压为3.0伏，器件的最大亮度为10384cd/m2。
图3为实施例1中得到的蓝色有机电致发光器件的电流密度-功率效率-电流效率特性曲线图；由图3可知，器件的最大电流效率为6.41cd/A，最大功率效 率为6.71lm/W。
图4为实施例1中得到的蓝色有机电致发光器件的亮度为1000cd/m2时的光谱图，器件色坐标为(0.135,0.138)。
实施例2
先将ITO玻璃上的ITO阳极层激光刻蚀成图案化的电极，然后依次用清洗液、去离子水超声清洗15分钟并放入烘箱烘干。接着将烘干后的衬底放入预处理真空室，在真空度为10帕的氛围下用400伏的电压对ITO阳极进行10分钟的低压氧等离子处理后将其转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀3纳米MoO3阳极界面层3。然后，未完成的器件被转移到有机蒸镀室，在真空度为1～3×10-5帕的真空氛围下，在阳极界面层3上依次蒸镀40纳米厚的TAPC空穴传输层/电子阻挡层4、10纳米厚的DBzA掺杂TcTa发光层5、40纳米厚的Tm3PyP26PyB空穴阻挡层/电子传输层6。接下来，未完成的器件被转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀1.0纳米厚的LiF缓冲层，最后通过特制的掩模版在LiF层上蒸镀120纳米厚的金属Al电极，制备成结构为ITO/MoO3/TAPC/DBzA(15wt％)：TcTa/Tm3PyP26PyB/LiF/Al的蓝色有机电致发光器件。发光层5中DBzA和TcTa的蒸发速率控制在0.0075纳米/秒和0.05纳米/秒，TAPC和TmPyPB的蒸发速率控制在0.05纳米/秒，MoO3的蒸发速率控制在0.01纳米/秒，LiF的蒸发速率控制在0.005纳米/秒，Al的蒸发速率控制在0.5纳米/秒。
实施例2中得到的蓝色有机电致发光器件在直流电压驱动下，显示主峰位于462纳米的纯正蓝光发射；随着工作电压的变化，器件色坐标稳定在从(0.133,0.132)到(0.144,0.143)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.136,0.134)。
图5为实施例2中得到的蓝色有机电致发光器件的电压-电流密度-亮度曲线图；由图5可知，器件的亮度随着电流密度和驱动电压的升高而升高，器件的起亮电压为2.8伏，器件的最大亮度为10937cd/m2。
图6为实施例2中得到的蓝色有机电致发光器件的电流密度-功率效率-电流效率特性曲线图；由图6可知，器件的最大电流效率为6.19cd/A，最大功率效率为6.51lm/W。
实施例3
先将ITO玻璃上的ITO阳极层激光刻蚀成图案化的电极，然后依次用清洗 液、去离子水超声清洗15分钟并放入烘箱烘干。接着将烘干后的衬底放入预处理真空室，在真空度为10帕的氛围下用400伏的电压对ITO阳极进行10分钟的低压氧等离子处理后将其转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀3纳米MoO3阳极界面层3。然后，未完成的器件被转移到有机蒸镀室，在真空度为1～3×10-5帕的真空氛围下，在阳极界面层3上依次蒸镀50纳米厚的TAPC空穴传输层/电子阻挡层4、10纳米厚的DBzA掺杂TcTa发光层5、50纳米厚的TmPyPB空穴阻挡层/电子传输层6。接下来，未完成的器件被转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀1.0纳米厚的LiF缓冲层，最后通过特制的掩模版在LiF层上蒸镀120纳米厚的金属Al电极，制备成结构为ITO/MoO3/TAPC/DBzA(16wt％):TcTa/TmPyPB/LiF/Al的蓝色有机电致发光器件。发光层5中DBzA和TcTa的蒸发速率控制在0.008纳米/秒和0.05纳米/秒，TAPC和TmPyPB的蒸发速率控制在0.05纳米/秒，MoO3的蒸发速率控制在0.01纳米/秒，LiF的蒸发速率控制在0.005纳米/秒，Al的蒸发速率控制在0.5纳米/秒。
实施例3中得到的蓝色有机电致发光器件在直流电压驱动下，显示主峰位于462纳米的纯正蓝光发射；随着工作电压的变化，器件色坐标稳定在从(0.135,0.136)到(0.141,0.149)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.137,0.140)。器件的起亮电压为3.1伏，器件的最大亮度为11056cd/m2。器件的最大电流效率为6.46cd/A，最大功率效率为6.54lm/W。
实施例4
先将ITO玻璃上的ITO阳极层激光刻蚀成图案化的电极，然后依次用清洗液、去离子水超声清洗15分钟并放入烘箱烘干。接着将烘干后的衬底放入预处理真空室，在真空度为10帕的氛围下用400伏的电压对ITO阳极进行10分钟的低压氧等离子处理后将其转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀3纳米MoO3阳极界面层3。然后，未完成的器件被转移到有机蒸镀室，在真空度为1～3×10-5帕的真空氛围下，在阳极界面层3上依次蒸镀50纳米厚的TAPC空穴传输层/电子阻挡层4、10纳米厚的DBzA掺杂TcTa发光层5、40纳米厚的TmPyPB空穴阻挡层/电子传输层6。接下来，未完成的器件被转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀1.0纳米厚的LiF缓冲层，最后通过特制的掩模版在LiF层上蒸镀120纳米厚的金属Al电极，制备成结构为ITO/MoO3/TAPC/DBzA(16wt％):TcTa/TmPyPB/LiF/Al的有机电致发光器件。发 光层5中DBzA和TcTa的蒸发速率控制在0.008纳米/秒和0.05纳米/秒，TAPC和TmPyPB的蒸发速率控制在0.05纳米/秒，MoO3的蒸发速率控制在0.01纳米/秒，LiF的蒸发速率控制在0.005纳米/秒，Al的蒸发速率控制在0.5纳米/秒。
实施例4中得到的蓝色有机电致发光器件在直流电压驱动下，显示主峰位于462纳米的纯正蓝光发射；随着工作电压的变化，器件色坐标稳定在从(0.131,0.130)到(0.145,0.141)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.132,0.137)。器件的起亮电压为3.0伏，器件的最大亮度为11296cd/m2。器件的最大电流效率为6.23cd/A，最大功率效率为6.52lm/W。
实施例5
先将ITO玻璃上的ITO阳极层激光刻蚀成图案化的电极，然后依次用清洗液、去离子水超声清洗15分钟并放入烘箱烘干。接着将烘干后的衬底放入预处理真空室，在真空度为10帕的氛围下用400伏的电压对ITO阳极进行10分钟的低压氧等离子处理后将其转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀3纳米MoO3阳极界面层3。然后，未完成的器件被转移到有机蒸镀室，在真空度为1～3×10-5帕的真空氛围下，在阳极界面层3上依次蒸镀40纳米厚的TAPC空穴传输层/电子阻挡层4、10纳米厚的DBzA掺杂TcTa发光层5、50纳米厚的TmPyPB空穴阻挡层/电子传输层6。接下来，未完成的器件被转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀1.0纳米厚的LiF缓冲层，最后通过特制的掩模版在LiF层上蒸镀120纳米厚的金属Al电极，制备成结构为ITO/MoO3/TAPC/DBzA(16wt％):TcTa/TmPyPB/LiF/Al的蓝色有机电致发光器件。发光层5中DBzA和TcTa的蒸发速率控制在0.008纳米/秒和0.05纳米/秒，TAPC和TmPyPB的蒸发速率控制在0.05纳米/秒，MoO3的蒸发速率控制在0.01纳米/秒，LiF的蒸发速率控制在0.005纳米/秒，Al的蒸发速率控制在0.5纳米/秒。
实施例5中得到的蓝色有机电致发光器件在直流电压驱动下，显示主峰位于462纳米的纯正蓝光发射；随着工作电压的变化，器件色坐标稳定在从(0.135,0.133)到(0.148,0.146)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.139,0.141)。器件的起亮电压为2.9伏，器件的最大亮度为9885cd/m2。器件的最大电流效率为6.32cd/A，最大功率效率为6.84lm/W。
实施例6
先将ITO玻璃上的ITO阳极层激光刻蚀成图案化的电极，然后依次用清洗 液、去离子水超声清洗15分钟并放入烘箱烘干。接着将烘干后的衬底放入预处理真空室，在真空度为10帕的氛围下用400伏的电压对ITO阳极进行10分钟的低压氧等离子处理后将其转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀3纳米MoO3阳极界面层3。然后，未完成的器件被转移到有机蒸镀室，在真空度为1～3×10-5帕的真空氛围下，在阳极界面层3上依次蒸镀50纳米厚的TAPC空穴传输层/电子阻挡层4、10纳米厚的DBzA掺杂TcTa发光层5、50纳米厚的TmPyPB空穴阻挡层/电子传输层6。接下来，未完成的器件被转移到金属蒸镀室，在3～5×10-5帕的真空氛围下蒸镀1.0纳米厚的LiF缓冲层，最后通过特制的掩模版在LiF层上蒸镀120纳米厚的金属Al电极，制备成结构为ITO/MoO3/TAPC/DBzA(15wt％):TcTa/TmPyPB/LiF/Al的有机电致发光器件。发光层5中DBzA和TcTa的蒸发速率控制在0.0075纳米/秒和0.05纳米/秒，TAPC和TmPyPB的蒸发速率控制在0.05纳米/秒，MoO3的蒸发速率控制在0.01纳米/秒，LiF的蒸发速率控制在0.005纳米/秒，Al的蒸发速率控制在0.5纳米/秒。
实施例6中得到的蓝色有机电致发光器件在直流电压驱动下，显示主峰位于462纳米的纯正蓝光发射；随着工作电压的变化，器件色坐标稳定在从(0.130,0.135)到(0.142,0.148)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.137,0.143)。器件的起亮电压为3.0伏，器件的最大亮度为10656cd/m2。器件的最大电流效率为6.28cd/A，最大功率效率为6.57lm/W。

Claims (11)

  1. 一种蓝色有机电致发光器件，其特征在于，包括：
    衬底；
    设置在所述衬底上的阳极层；
    设置在所述阳极层上的发光层；所述发光层由蓝色有机荧光材料与空穴型有机主体材料形成；所述蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％；所述蓝色有机荧光材料的激发态能量小于空穴型有机主体材料的激发态能量；
    与设置在所述发光层上的阴极层。
  2. 根据权利要求1所述的蓝色有机电致发光器件，其特征在于，所述蓝色有机荧光材料为2,2'-(9,10-蒽二基二-4,1-亚苯基)二[6-甲基-苯并噻唑]。
  3. 根据权利要求1所述的蓝色有机电致发光器件，其特征在于，所述空穴型有机主体材料为4，4'-二(9-咔唑基)联苯、1,3-二咔唑-9-基苯、9,9'-(5-(三苯基硅烷基)-1,3-苯基)二-9H-咔唑、1,3,5-三(9-咔唑基)苯、4,4′,4″–三(咔唑-9-基)三苯胺与4,4’-双(三苯基硅烷基)联苯中的一种或多种。
  4. 根据权利要求1所述的蓝色有机电致发光器件，其特征在于，所述发光层的厚度为5～20nm。
  5. 根据权利要求1所述的蓝色有机电致发光器件，其特征在于，所述阳极层与发光层之间还设置有阳极界面层；所述阳极界面层的厚度为2～10nm。
  6. 根据权利要求1所述的蓝色有机电致发光器件，其特征在于，所述阳极层与发光层之间还设置有空穴传输层或电子阻挡层；所述空穴传输层或电子阻挡层的厚度为40～60nm。
  7. 根据权利要求1所述的蓝色有机电致发光器件，其特征在于，所述发光层与阴极层之间还设置有空穴阻挡层或电子传输层；所述空穴阻挡层或电子传输层的厚度为40～60nm。
  8. 根据权利要求7所述的蓝色有机电致发光器件，其特征在于，所述空穴阻挡层或电子传输层与阴极层之间还设置有缓冲层；所述缓冲层的厚度为0.8～1.2nm。
  9. 一种蓝色有机电致发光器件的制备方法，其特征在于，包括以下步骤：
    在衬底上形成阳极层；
    在所述阳极层上形成发光层；所述发光层由蓝色有机荧光材料与空穴型有机主体材料形成；所述蓝色有机荧光材料的质量为空穴型有机主体材料质量的8.0％～25.0％；所述蓝色有机荧光材料的激发态能量小于空穴型有机主体材料的激发态能量；
    在所述发光层上形成阴极，得到蓝色有机电致发光器件。
  10. 根据权利要求9所述的制备方法，其特征在于，所述蓝色有机荧光材料为2,2'-(9,10-蒽二基二-4,1-亚苯基)二[6-甲基-苯并噻唑]。
  11. 根据权利要求1所述的制备方法，其特征在于，所述空穴型有机主体材料为4，4'-二(9-咔唑基)联苯、1,3-二咔唑-9-基苯、9,9'-(5-(三苯基硅烷基)-1,3-苯基)二-9H-咔唑、1,3,5-三(9-咔唑基)苯、4,4',4″–三(咔唑-9-基)三苯胺与4,4’-双(三苯基硅烷基)联苯中的一种或多种。
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