WO2016065677A1 - 一种红色有机电致发光器件及其制备方法 - Google Patents

一种红色有机电致发光器件及其制备方法 Download PDF

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WO2016065677A1
WO2016065677A1 PCT/CN2014/091779 CN2014091779W WO2016065677A1 WO 2016065677 A1 WO2016065677 A1 WO 2016065677A1 CN 2014091779 W CN2014091779 W CN 2014091779W WO 2016065677 A1 WO2016065677 A1 WO 2016065677A1
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layer
bis
electron
light
ruthenium
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French (fr)
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周亮
张洪杰
冯婧
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中国科学院长春应用化学研究所
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Priority to EP14904828.2A priority Critical patent/EP3214665B1/en
Priority to JP2017523398A priority patent/JP6385575B2/ja
Priority to US15/522,581 priority patent/US10355230B2/en
Publication of WO2016065677A1 publication Critical patent/WO2016065677A1/zh

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Definitions

  • the invention relates to the field of organic electroluminescence technology, in particular to a red organic electroluminescent device and a preparation method thereof.
  • An organic electroluminescent device is a self-luminous device whose principle of illumination is that when an electric charge is injected into an organic layer between a hole injecting electrode and an electron injecting electrode, electrons and holes meet, combine, and then annihilate, thereby generating Light.
  • Organic electroluminescent devices have characteristics such as low voltage, high brightness, and wide viewing angle, and thus organic electroluminescent devices have been rapidly developed in recent years. Among them, the red organic electroluminescent device has become a research hotspot because of its broad application prospects in monochrome display and white light modulation.
  • the trivalent europium complex has been regarded as an ideal organic electroluminescent material by academics and industry because of its high luminous efficiency and adjustable color of light.
  • Many research teams at home and abroad have started from material synthesis and device optimization to improve the comprehensive performance of red organic electroluminescent devices to meet the needs of industrialization.
  • SRForrest et al. of Princeton University in the United States used a ruthenium complex btp 2 Ir(acac) having a standard red emission as a luminescent material to prepare an organic electroluminescent device by doping.
  • the device exhibits very good red light emission, unbalanced carrier injection results in lower efficiency and brightness of the device, and the device operates at a higher voltage.
  • red platinum complexes as luminescent materials, designed and optimized the structure of dual luminescent layer devices, and obtained organic electroluminescent devices with pure red light emission.
  • the device's efficiency attenuation is greatly alleviated, but the device still has the problem of high operating voltage and low brightness. It can be seen that the overall performance of the red organic electroluminescent device such as luminous efficiency, brightness, spectral stability and working life has not been effectively improved.
  • the technical problem to be solved by the present invention is to provide a red organic electroluminescent device with high comprehensive performance and a preparation method thereof.
  • red organic electroluminescent device comprising:
  • the electron-dominated light-emitting layer is composed of an organic sensitizing material, a red organic light-emitting material and an electronic type organic host material;
  • the organic sensitizing material is selected from one or two of tris(dibenzoylmethane) phenanthroline ruthenium and tris(thiophene trifluoroacetone) phenanthroline ruthenium;
  • the organic sensitizing material is from 0.1% by weight to 0.5% by weight of the electronic type organic host material.
  • the content of the red organic light-emitting material is 2% by weight to 5% by weight of the electronic organic organic material.
  • the red organic light-emitting material is selected from the group consisting of bis(2-phenylquinoline)-(2,2,6,6-tetramethyl-3,5-heptanedionate) ruthenium, di(2-) Oxazole [b]2-thienylpyridine) acetylacetonate ruthenium, tris(1-benzene Isoquinoline), bis(1-phenylisoquinoline)(acetylacetonate) ruthenium, bis[1-(9,9-dimethyl-9H-indol-2-yl)-isoquinoline (acetylacetone) ruthenium, bis[2-(9,9-dimethyl-9H-indol-2-yl)quinoline](acetylacetone) ruthenium, bis(2-phenylquinoline) (2 -(3-methylphenyl)pyridine) ruthenium, tris[2-phenyl-4-methylquinoline] ruthenium, bis(2-phen
  • the electronic organic host material is selected from the group consisting of 2,6-bis[3-(9H-9-carbazolyl)phenyl]pyridine, 1,4-bis(triphenylsilyl)benzene, 2, 2'-bis(4-(9-carbazolyl)phenyl)biphenyl, [2,4,6-trimethyl-3-(3-pyridyl)phenyl]borane, 1,3,5 -Tris[(3-pyridyl)-3-phenyl]benzene, 1,3-bis[3,5-bis(3-pyridyl)phenyl]benzene, 1,3,5-tris(1-phenyl -1H-benzimidazol-2-yl)benzene, 9-(4-t-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole and 9-(8-diphenyl) One or more of p-phosphoryl)-diazo
  • the hole-priming light-emitting layer is composed of a red organic light-emitting material and a hole-type organic host material; the red organic light-emitting material is 2.0 wt% to 5.0 wt% of the hole type organic host material;
  • the red organic light-emitting material is selected from the group consisting of bis(2-phenylquinoline)-(2,2,6,6-tetramethyl-3,5-heptanedionate) ruthenium, bis(2-benzoazole [ b] 2-thienylpyridine) acetylacetonate ruthenium, tris(1-phenylisoquinoline) ruthenium, bis(1-phenylisoquinoline)(acetylacetonate) ruthenium, two [1-(9, 9-Dimethyl-9H-indol-2-yl)-isoquinoline](acetylacetone) ruthenium, bis[2-(9,9-dimethyl-9H-indol-2-yl)quinoline] (acetylacetone) ruthenium, bis(2-phenylquinoline)(2-(3-methylphenyl)pyridine) ruthenium, tris[2-phenyl-4-methylquinoline] ruthenium
  • the hole-type organic host material is selected from the group consisting of 4,4'-N, N'-dicarbazole diphenyl, 1,3-dioxazole-9-ylbenzene, 9,9'-(5-(three Phenylsilyl)-1,3-phenyl)di-9H-carbazole, 1,3,5-tris(9-carbazolyl)benzene, 4,4',4"-tris (carbazole-9) One or more of triphenylamine and 1,4-bis(triphenylsilyl)biphenyl.
  • the material of the hole transporting-electron blocking layer is selected from the group consisting of 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline], dipyrazine [2,3-f :2',3'-h]quinoxaline-2,3,6,7,10,11- Hexaonitrile, N4, N4'-bis(naphthalen-1-yl)-N4, N4'-bis(4-vinylphenyl)biphenyl-4,4'-diamine, N,N'-bis ( 3-methylphenyl)-N,N'-bis(phenyl)-2,7-diamine-9,9-spirobifluorene, N,N,N',N'-tetra-(3-A Phenyl)-3-3'-dimethyl-p-diaminobiphenyl, 2,2'-bis(3-(N,N-di-p-tolylamino)phenyl
  • the material of the hole blocking-electron transport layer is selected from the group consisting of tris[2,4,6-trimethyl-3-(3-pyridyl)phenyl]borane, 1,3,5-tri [ (3-pyridine)-3-phenyl]benzene, 1,3-bis[3,5-di(3-pyridyl)phenyl]benzene and 1,3,5-tris(1-phenyl-1H One or more of - benzimidazol-2-yl)benzene.
  • the anode modification layer has a thickness of 1 to 10 nm
  • the hole transport-electron barrier layer has a thickness of 30 to 60 nm
  • the hole-dominant light-emitting layer has a thickness of 5 to 20 nm.
  • the thickness of the layer is 5 to 20 nm
  • the thickness of the hole blocking-electron transport layer is 30 to 60 nm
  • the thickness of the cathode modification layer is 0.8 to 1.2 nm
  • the thickness of the cathode layer is 90 to 300 nm.
  • the application also provides a method for preparing a red organic electroluminescent device, comprising:
  • the anode layer on the substrate is etched, and after drying, the anode modification layer, the hole transport-electron barrier layer, the hole-dominant light-emitting layer, the electron-dominated light-emitting layer, and the hole blocking are sequentially deposited on the anode layer.
  • the electron-dominated light-emitting layer is composed of an organic sensitizing material, a red organic light-emitting material and an electronic type organic host material;
  • the organic sensitizing material is selected from one or two of tris(dibenzoylmethane) phenanthroline ruthenium and tris(thiophene trifluoroacetone) phenanthroline ruthenium;
  • the organic sensitizing material is from 0.1% by weight to 0.5% by weight of the electronic type organic host material.
  • the evaporation rate of the anode modification layer is 0.01-0.05 nm/s
  • the host material in the hole transport-electron blocking layer, the hole-dominant light-emitting layer, the electron-dominated light-emitting layer and the hole blocking-electron transport layer The evaporation rate of the organic sensitizing material in the electron-dominated luminescent layer is 0.00005-0.0005 nm/s, and the red luminescence in the electron-dominated luminescent layer and the hole-dominant luminescent layer
  • the evaporation rate of the material is 0.001 to 0.005 nm/s
  • the evaporation rate of the cathode modification layer is 0.005 to 0.05 nm/s
  • the evaporation rate of the cathode layer is 0.5 to 2.0 nm/s.
  • the present application provides a red organic electroluminescent device comprising a substrate, an anode layer, an anode modification layer, a hole transport-electron barrier layer, a hole-dominant light-emitting layer, an electron-dominated light-emitting layer, hole blocking-electron transport Layer, cathode modification layer and cathode layer.
  • the luminescent material of the present application is a red luminescent material. When electrons and holes are respectively injected into the luminescent layer, electrons and holes will meet and recombine, thereby generating an exciton, and the excitons will transfer energy to the red in the luminescent layer.
  • the molecules of the luminescent material excite an electron to an excited state, and the excited state electrons return to the ground state by a radiation transition to generate a red photon, thereby causing the organic electroluminescent device to emit red light.
  • the present application relates to organic sensitization by adding one or two of tris(dibenzoylmethane) phenanthroline ruthenium and tris(thiophene trifluoroacetone) phenanthroline ruthenium to an electron-dominated light-emitting layer.
  • the material matches the energy level and the triplet energy with the energy content of the host material, the luminescent material and the triplet energy, so that the organic sensitizing material plays a deep carrier center and energy transfer step in the electroluminescence process.
  • the function not only can improve the energy transfer from the host material to the luminescent material, but also balance the distribution of electrons and holes in the light-emitting interval, thereby improving the luminous efficiency of the organic electroluminescent device, improving the spectral stability of the device, and reducing the work of the device. Voltage, delays the efficiency of the device, and increases the operating life of the device.
  • FIG. 1 is a schematic structural view of a red organic electroluminescent device of the present invention
  • Example 2 is a graph showing voltage-current density-luminance characteristics of a red organic electroluminescent device prepared in Example 1 of the present invention
  • Example 3 is a graph showing current density-power efficiency-current efficiency characteristics of a red organic electroluminescent device prepared in Example 1 of the present invention
  • Example 4 is a spectrum diagram of a red organic electroluminescent device prepared in Example 1 of the present invention at a luminance of 20,000 cd/m 2 .
  • the embodiment of the invention discloses a red organic electroluminescent device, comprising:
  • the electron-dominated light-emitting layer is composed of an organic sensitizing material, a red organic light-emitting material and an electronic type organic host material;
  • the organic sensitizing material is selected from one or two of tris(dibenzoylmethane) phenanthroline ruthenium and tris(thiophene trifluoroacetone) phenanthroline ruthenium;
  • the organic sensitizing material is from 0.1% by weight to 0.5% by weight of the electronic type organic host material.
  • OLED organic electroluminescent device
  • the principle of luminescence of an organic electroluminescent device is that under the driving of an external voltage, electrons and holes injected by the electrodes meet in the organic matter, and the energy is transmitted to the organic luminescent molecules to be excited to transition from the ground state to the ground state.
  • the excited state when the excited molecule returns from the excited state to the ground state, the radiation transitions to produce luminescence.
  • the present application provides a red organic electroluminescent device that emits red light because the luminescent material used is a red luminescent material, when electrons and holes are separately injected. When entering the luminescent layer, electrons and holes will meet and recombine, and then an exciton is generated.
  • the excitons transfer energy to the molecules of the red luminescent material in the luminescent layer, exciting an electron to an excited state, and the excited state electrons pass.
  • the transition mode returns to the ground state, a red photon is generated, thereby realizing the red light of the organic electroluminescent device.
  • the red organic electroluminescent device of the present application comprises a substrate, an anode layer, an anode modification layer, a hole transport-electron barrier layer, a hole-dominant light-emitting layer, an electron-dominated light-emitting layer, a hole blocking-electron transport layer, and a cathode modification.
  • the layer and the cathode layer are sequentially connected to each other.
  • the hole-bearing light-emitting layer and the electron-based light-emitting layer are light-emitting layers of a red organic electron-emitting device.
  • the electronic dominant light-emitting layer of the invention is composed of an organic sensitizing material, a red organic light-emitting material and an electronic organic organic material, wherein the organic sensitizing material plays a sensitizing role in the electroluminescence process to improve the light from the host material to the light-emitting material.
  • the energy of the material transfers and balances the distribution of electrons and holes in the light-emitting interval; the molecules of the red organic light-emitting material are dispersed in the electron-dominated light-emitting layer as a light-emitting center; the electronic-type organic host material acts as a matrix to provide electron transport capability.
  • the energy level and the triplet energy of the organic sensitizing material need to match the energy level of the host material, the luminescent material, and the triplet energy to balance the distribution of electrons and holes in the light-emitting interval and accelerate
  • the energy transfer from the host material to the luminescent material gives the red organic electroluminescent device a better overall performance. Therefore, the present application selects a rare earth complex selected from the group consisting of tris(dibenzoylmethane) phenanthroline ruthenium (Eu(DBM)) by selecting a luminescent material. 3 phen) and one or both of tris(thiophene trifluoroacetone) phenanthroline ruthenium (Eu(TTA) 3 phen) having the structure of formula (X);
  • the doping concentration of the organic sensitizing material in the electron-based light-emitting layer of the present invention affects the performance of the organic electroluminescent device. If the doping concentration of the organic sensitizing material is too low, the sensitizing effect is unsatisfactory, and if the doping concentration is too high, the overall performance of the organic electroluminescent device is lowered. Therefore, the organic sensitizing material is from 0.1% by weight to 0.5% by weight, preferably from 0.2% by weight to 0.3% by weight, of the electronic type organic host material.
  • the red organic light-emitting material in the electron-based light-emitting layer is a light-emitting material well known to those skilled in the art, and the present application is not particularly limited, but in order to make the light-emitting effect better, the red organic light-emitting material is preferentially selected.
  • the doping concentration of the red organic light-emitting material also affects the overall performance of the red organic electroluminescent device. If the doping concentration of the red organic light-emitting material is too low, the device efficiency is low, and the color purity is not ideal. If the doping concentration is too high, the luminescent material molecules are agglomerated to form quenching molecules, and finally the device is integrated. performance. Therefore, the red organic light-emitting material in the electron-based light-emitting layer is preferably from 2.0 wt% to 5.0 wt%, more preferably from 2.5 wt% to 4.5 wt%, of the electron-type organic host material.
  • the electronic type host material functions as a matrix in the electron-dominated light-emitting layer to provide electron transport capability, and the electronic type host material is a material well known to those skilled in the art, and as a preferred embodiment, the electronic type host material is preferentially selected.
  • the hole-preferred light-emitting layer described in the present application is composed of a red organic light-emitting material and a hole-type organic host material, wherein molecules of the red organic light-emitting material are dispersed in the hole-dominant light-emitting layer as a light-emitting center.
  • the red organic light-emitting material is preferably 2.0 wt% to 5.0 wt%, more preferably 2.5 wt% to 4.5 wt% of the hole type organic host material in the hole-cavity light-emitting layer; the red organic light-emitting If the doping concentration of the material is too low, the device efficiency is low and the color purity is not ideal.
  • the hole-type host material functions as a matrix to provide hole transporting ability.
  • the red organic light-emitting material in the hole-priming light-emitting layer described in the present application is preferably selected from the group consisting of bis(2-phenylquinoline)-(2,2,6,6-tetramethyl) having the structure of the formula (II 1 ).
  • the hole-type organic host material is preferably selected from the group consisting of 4,4'-N,N'-dicarbazole diphenyl (CBP) having the structure of the formula (III) and 1,3-di having the structure of the formula (IV) Carbazole-9-ylbenzene (mCP), 9,9'-(5-(triphenylsilyl)-1,3-phenyl)di-9H-carbazole (SimCP) having the structure of formula (V) , 1,3,5-tris(9-carbazolyl)benzene (TCP) having the structure of formula (VI), 4,4',4"-tris(carbazol-9-yl) having the structure of formula (VII) One or more of triphenylamine (TcTa) and 1,4-bis(triphenylsilyl)biphenyl (BSB) having the structure of formula (VIII);
  • CBP 4,4'-N,N'-dicarbazole diphenyl
  • mCP
  • the substrate may be a glass substrate, a quartz substrate, a polycrystalline silicon substrate, a single crystal silicon substrate or a graphene film substrate, which is not particularly limited in the present application.
  • the anode layer is preferably selected from indium tin oxide (ITO), and its surface resistance is preferably 5 to 25 ⁇ .
  • ITO indium tin oxide
  • the anode modification layer can lower the driving voltage and accelerate the injection of holes, and the anode modification layer is preferably molybdenum oxide (MoO 3 ).
  • the hole transport-electron blocking layer described in this application functions to transport holes and block electrons.
  • the material of the hole transport-electron barrier layer is preferably selected from 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline] (TAPC) having the structure of formula (I 1 ) Dipyrazine [2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile group (HAT-CN) having the structure of formula (I 2 ) N4,N4'-bis(naphthalen-1-yl)-N4,N4'-bis(4-vinylphenyl)biphenyl-4,4'-diamine (VNPB) having the structure of formula (I 3 ) N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-2,7-diamine-9,9-spirobiguanidine having the structure of formula (I 4 )
  • the hole blocking-electron transporting layer functions to block holes and transport electrons to promote electron injection.
  • the material of the hole blocking-electron transport layer is preferably selected from tris[2,4,6-trimethyl-3-(3-pyridyl)phenyl]borane (3TPYMB) having the structure of the formula (XIV), 1,3,5-tris[(3-pyridyl)-3-phenyl]benzene (TmPyMB) having the structure (XV), 1,3-bis[3,5-di ((3,5-di) having the structure of formula (XVI) 3-pyridyl)phenyl]benzene (BmPyPhB) and one of 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi) having the structure of formula (XVII) Species or more;
  • the function of the cathode modification layer described in the present application is to lower the driving voltage and accelerate the injection of electrons, and the cathode modification layer is preferably lithium fluoride.
  • the cathode layer is preferably aluminum.
  • the source of the material of the hole transporting-electron blocking layer, the red organic light emitting material, the hole type organic host material, the organic sensitizing material, the electronic type organic host material, and the hole blocking-electron transport layer Without particular limitation, it can be obtained by preparation in a manner well known to those skilled in the art.
  • the anode layer and the cathode layer intersect each other to form a light-emitting region of the device.
  • the thickness of each layer in the red organic electroluminescent device of the present application has a great influence on the device, if the thickness is low. This will result in faster device efficiency degradation. If the thickness is higher, the device will operate at a higher voltage and have a lower lifetime.
  • the thickness of the anode modification layer is preferably from 1 to 10 nm
  • the thickness of the hole transport-electron barrier layer is preferably from 30 to 60 nm
  • the thickness of the hole-preferred light-emitting layer is preferably from 5 to 20 nm
  • the thickness of the electron-dominated light-emitting layer is preferably 5 to 20 nm
  • the thickness of the hole blocking-electron transport layer is preferably 30 to 60 nm
  • the thickness of the cathode modified layer is preferably 0.8 to 1.2 nm
  • the thickness of the cathode layer is preferably 90 to 300 nm.
  • the application also provides a preparation method of the red organic electroluminescent device, comprising:
  • the anode layer on the substrate is etched, and after drying, the anode modification layer, the hole transport-electron barrier layer, the hole-dominant light-emitting layer, the electron-dominated light-emitting layer, and the hole blocking are sequentially deposited on the anode layer.
  • the hole-dominant light-emitting layer is composed of a red organic light-emitting material and a hole-type organic host material;
  • the electron-dominated light-emitting layer is composed of an organic sensitizing material, a red organic light-emitting material and an electronic type organic host material;
  • the organic sensitizing material is selected from the group consisting of tris(dibenzoylmethane)phenanthroline ruthenium having the structure of formula (IX) and tris(thiophene trifluoroacetone) phenanthroline having the structure of formula (X) One or two of the mergers;
  • the organic sensitizing material is 0.1 wt% to 0.5 wt% of the electronic type organic host material
  • the preparation method of the red organic electroluminescent device is specifically:
  • the anode layer on the substrate is laser etched into strip electrodes, and then ultrasonically washed with washing liquid and deionized water for 10-20 min and placed in an oven for drying;
  • the dried substrate is placed in a pretreatment vacuum chamber, and subjected to a low pressure plasma treatment for 1 to 10 minutes under a vacuum of 8 to 15 Pa in an atmosphere of 350 to 500 V, and then transferred to an organic vapor deposition chamber;
  • the anode modification layer, the hole transport-electron barrier layer, the hole-dominant light-emitting layer, the electron-dominated light-emitting layer, and the hole blocking-electron transport are sequentially deposited on the anode layer.
  • the unfinished device was transferred to a metal deposition chamber, and the cathode modified layer and the metal cathode layer were sequentially evaporated in a vacuum atmosphere of 4 to 6 ⁇ 10 -5 Pa.
  • the present application achieves deposition of a material by controlling the evaporation rate.
  • the evaporation rate of the anode modification layer is controlled to be 0.01 to 0.05 nm/s, and the host material in the hole transport-electron blocking layer, the hole-dominant light-emitting layer, the electron-dominated light-emitting layer, and the hole blocking-electron transport layer
  • the evaporation rate is controlled at 0.05-0.1 nm/s
  • the evaporation rate of the organic sensitizing material is controlled at 0.00005-0.0005 nm/s
  • the evaporation rate of the red organic luminescent material is controlled at 0.001-0.005 nm/s.
  • the evaporation rate control of the cathode modified layer is controlled. At 0.005 to 0.015 nm/s, the evaporation rate of the metal cathode layer is controlled to be 0.5 to 2.0 nm/s. Where the vapor-emitting holes dominate the light-emitting layer, wherein the red organic light-emitting material and the hole-type organic host material are simultaneously evaporated in different evaporation sources, and the doped red organic light-emitting materials and holes are controlled by controlling the evaporation rates of the two materials.
  • the weight ratio of the organic host material is controlled between 2.0% and 5.0%; when the electron-emitting electron dominates the light-emitting layer, the organic sensitizing material, the red organic light-emitting material, and the electronic organic host material are simultaneously evaporated in different evaporation sources.
  • the mass ratio of the doped organic sensitizing material and the electronic organic organic material is controlled to be between 0.1% and 0.5%, so that the doped red organic luminescent material and the electronic organic organic material are The mass ratio is controlled between 2.0% and 5.0%.
  • the present application provides a red organic electroluminescent device in which a rare earth complex having a matching energy level distribution, such as Eu(DBM) 3 phen or Eu, is selected among electron-dominated light-emitting layers in the red organic electroluminescent device.
  • TTA) 3 phen acts as an organic sensitizing material, which acts as an electron deep-binding center, which is beneficial to balance the distribution of carriers and broaden the light-emitting interval of the device, thereby improving the luminous efficiency of the device, reducing the operating voltage of the device, and delaying the device.
  • the efficiency is attenuated, and the working life of the device is improved; and the organic sensitizing material has matched triplet energy, functions as an energy transfer step, accelerates energy transfer from the host material to the luminescent material, and relieves the current carrying of the luminescent material.
  • the problem of luminescence of the host material caused by insufficient subcapture ability, thereby improving the spectral stability of the device and reducing the dependence of device performance on the doping concentration of the luminescent material.
  • FIG. 1 is a schematic structural view of a red organic electroluminescent device according to the present invention, wherein 1 is a glass substrate, 2 is an anode layer, 3 is an anode modification layer, and 4 is a hole transport-electron blocking layer, 5 The hole is the luminescent layer, 6 is the electron-dominated luminescent layer, 7 is the hole blocking-electron transport layer, 8 is the cathode modified layer, and 9 is the metal cathode layer.
  • the ITO anode layer on the ITO glass was first laser etched into strip electrodes, which were then ultrasonically cleaned with cleaning solution and deionized water for 15 min and placed in an oven for drying. Next, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to low pressure plasma treatment for 3 minutes under a vacuum of 10 Pa in an atmosphere of 400 V, and then transferred to an organic vapor deposition chamber. In an organic vapor deposition chamber having a degree of vacuum of 1 to 2 ⁇ 10 -5 Pa, a 3 nm-thick MoO 3 anode modification layer 3 and a 40 nm-thick TAPC hole-transport-electron barrier layer 4, 10 nm are sequentially deposited on the ITO layer.
  • Thick PQ 2 Ir(dpm) doped TcTa hole-dominated luminescent layer 5 10 nm thick Tb(acac) 3 phen and PQ 2 Ir(dpm) co-doped CzSi electron-dominated luminescent layer 6 and 40 nm thick TmPyPB hole Block-electron transport layer 7.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF cathode modification layer 8 was evaporated in a vacuum atmosphere of 4 to 6 ⁇ 10 -5 Pa, and finally passed through a special mask on the LiF layer.
  • a 120 nm thick metal Al cathode layer 9 was deposited to prepare a structure of ITO/MoO 3 /TAPC/PQ 2 Ir(dpm) (4%): TcTa/Eu(TTA) 3 phen(0.2%): PQ 2 Ir( Dpm) (4%): an organic electroluminescent device of CzSi/TmPyPB/LiF/Al.
  • the evaporation rate of MoO 3 in the anode modification layer 3 is controlled at 0.01 nm/s
  • the evaporation rate of TAPC in the hole transport-electron blocking layer 4 is controlled at 0.05 nm/s
  • the evaporation rates of TcTa and TcTa are controlled at 0.002 nm/s and 0.05 nm/s, respectively.
  • the evaporation rates of Eu(TTA) 3 phen, PQ 2 Ir(dpm) and CzSi in the electron-dominated luminescent layer 6 are controlled at 0.0001 nm/s, respectively.
  • the evaporation rate of TmPyPB in the hole blocking-electron transport layer 7 is controlled at 0.05 nm/s
  • the evaporation rate of LiF in the cathode modified layer 8 is controlled at 0.005 nm/s
  • the metal cathode layer 9 The evaporation rate of Al in the middle is controlled at 1.0 nm/s.
  • FIG. 2 is a voltage-current density-luminance characteristic curve of the red organic electroluminescent device prepared in the present embodiment.
  • the curve ⁇ in FIG. 2 is the current density-voltage curve of the device, and the curve ⁇ is the brightness of the device.
  • - voltage curve according to Figure 2, the brightness of the device increases with the increase of current density and driving voltage, the device's starting voltage is 2.9 volts, the voltage is 9.8 volts, and the current density is 438.91 mA per square centimeter. (mA/cm 2 ) The device achieved a maximum brightness of 72,933 candelas per square meter (cd/m 2 ).
  • FIG. 3 is a current density-power efficiency-current efficiency characteristic curve of the red organic electroluminescent device prepared in the embodiment.
  • the maximum current efficiency of the device is 65.73 cd/A, and the maximum power is obtained.
  • the efficiency is 71.17 lm / W.
  • FIG. 4 is a spectrum diagram of a red organic electroluminescent device provided by the present invention at a luminance of 20,000 cd/m 2 .
  • the main peak of the spectrum is located at 592 nm.
  • the color coordinates of the device are (0.592, 0.377).
  • the ITO anode layer on the ITO glass was first laser etched into strip electrodes, which were then ultrasonically cleaned with cleaning solution and deionized water for 15 min and placed in an oven for drying. Next, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to low pressure plasma treatment for 3 minutes under a vacuum of 10 Pa in an atmosphere of 400 V, and then transferred to an organic vapor deposition chamber. In an organic vapor deposition chamber having a degree of vacuum of 1 to 2 ⁇ 10 -5 Pa, a 3 nm-thick MoO 3 anode modification layer 3 and a 40 nm-thick TAPC hole-transport-electron barrier layer 4, 10 nm are sequentially deposited on the ITO layer.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF cathode modification layer 8 was evaporated in a vacuum atmosphere of 4 to 6 ⁇ 10 -5 Pa, and finally passed through a special mask on the LiF layer.
  • a 120 nm thick metal Al cathode layer 9 was deposited to prepare a structure of ITO/MoO 3 /TAPC/PQ 2 Ir(dpm) (4%): mCP/Eu(TTA) 3 phen(0.2%): PQ 2 Ir( Dpm) (4%): an organic electroluminescent device of 26DCzPPy/TmPyPB/LiF/Al.
  • the evaporation rate of MoO 3 in the anode modification layer 3 is controlled at 0.01 nm/s
  • the evaporation rate of TAPC in the hole transport-electron blocking layer 4 is controlled at 0.05 nm/s
  • the evaporation rates of mCP and mCP are controlled at 0.002 nm/s and 0.05 nm/s, respectively, and the evaporation rates of Eu(TTA) 3 phen, PQ 2 Ir(dpm) and 26DCzPPy in the electron-dominated luminescent layer 6 are controlled at 0.0001 nm/s, respectively.
  • the evaporation rate of TmPyPB in the hole blocking-electron transport layer 7 is controlled at 0.05 nm/s
  • the evaporation rate of LiF in the cathode modified layer 8 is controlled at 0.005 nm/s
  • the metal cathode layer 9 The evaporation rate of Al in the middle is controlled at 1.0 nm/s.
  • the performance of the red organic electroluminescent device prepared in this example was tested.
  • the experimental results show that the device emits red light at about 592 nm under the driving of a DC power source.
  • the color coordinate of the device is (0.596, 0.378); as the operating voltage changes, the color coordinates of the device are almost unchanged.
  • the device has a starting voltage of 3.0 volts and a maximum brightness of the device of 70528 cd/m 2 .
  • the device has a maximum current efficiency of 64.92 cd/A and a maximum power efficiency of 67.95 lm/W.
  • the ITO anode layer on the ITO glass was first laser etched into strip electrodes, which were then ultrasonically cleaned with cleaning solution and deionized water for 15 min and placed in an oven for drying. Next, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to low pressure plasma treatment for 3 minutes under a vacuum of 10 Pa in an atmosphere of 400 V, and then transferred to an organic vapor deposition chamber. In an organic vapor deposition chamber having a degree of vacuum of 1 to 2 ⁇ 10 -5 Pa, a 3 nm-thick MoO 3 anode modification layer 3 and a 40 nm-thick TAPC hole-transport-electron barrier layer 4, 10 nm are sequentially deposited on the ITO layer.
  • Thick PQ 2 Ir(dpm) doped TcTa hole-dominated luminescent layer 5 10 nm thick Eu(DBM) 3 phen and PQ 2 Ir(dpm) co-doped 26DCzPPy electron-dominated luminescent layer 6 and 40 nm thick TmPyPB hole Block-electron transport layer 7.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF cathode modification layer 8 was evaporated in a vacuum atmosphere of 4 to 6 ⁇ 10 -5 Pa, and finally passed through a special mask on the LiF layer.
  • a 120 nm thick metal Al cathode layer 9 was deposited to prepare a structure of ITO/MoO 3 /TAPC/PQ 2 Ir(dpm) (4%): TcTa/Eu(DBM) 3 phen (0.3%): PQ 2 Ir( Dpm) (4%): an organic electroluminescent device of 26DCzPPy/TmPyPB/LiF/Al.
  • the evaporation rate of MoO 3 in the anode modification layer 3 is controlled at 0.01 nm/s
  • the evaporation rate of TAPC in the hole transport-electron blocking layer 4 is controlled at 0.05 nm/s
  • the evaporation rates of TcTa and TcTa are controlled at 0.003 nm/s and 0.05 nm/s, respectively.
  • the evaporation rates of Eu(DBM) 3 phen, PQ 2 Ir(dpm) and 26DCzPPy in the electron-dominated luminescent layer 6 are controlled at 0.0003 nm/s, respectively.
  • the evaporation rate of TmPyPB in the hole blocking-electron transport layer 7 is controlled at 0.05 nm/s
  • the evaporation rate of LiF in the cathode modified layer 8 is controlled at 0.005 nm/s
  • the metal cathode layer 9 The evaporation rate of Al in the middle is controlled at 1.0 nm/s.
  • the performance of the red organic electroluminescent device prepared in this example was tested.
  • the experimental results show that the device emits red light at about 592 nm under the driving of a DC power source.
  • the color coordinate of the device is (0.590, 0.381); as the operating voltage changes, the color coordinates of the device are almost unchanged.
  • the device has a starting voltage of 3.0 volts and a maximum brightness of the device of 69,864 cd/m 2 .
  • the device has a maximum current efficiency of 63.75 cd/A and a maximum power efficiency of 66.73 lm/W.
  • the ITO anode layer on the ITO glass was first laser etched into strip electrodes, which were then ultrasonically cleaned with cleaning solution and deionized water for 15 min and placed in an oven for drying. Next, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to low pressure plasma treatment for 3 minutes under a vacuum of 10 Pa in an atmosphere of 400 V, and then transferred to an organic vapor deposition chamber.
  • a 5 nm-thick MoO 3 anode-modified layer 3 and a 30 nm-thick TAPC hole-transport-electron-blocking layer 4 15 nm were sequentially deposited on the ITO layer.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.1 nm thick LiF cathode modification layer 8 was evaporated in a vacuum atmosphere of 4 to 6 ⁇ 10 -5 Pa, and finally passed through a special mask on the LiF layer.
  • a 250 nm thick metal Al cathode layer 9 was deposited to prepare a structure of ITO/MoO 3 /TAPC/Ir(dmpq) 3 (acac) (2%): mCP/Eu(DBM) 3 phen(0.1%): Ir ( Dmpq) 3 (acac) (3%): an organic electroluminescent device of 26DCzPPy/3TPYMB/LiF/Al.
  • the evaporation rate of MoO 3 in the anode modification layer 3 is controlled at 0.01 nm/s
  • the evaporation rate of TAPC in the hole transport-electron blocking layer 4 is controlled at 0.06 nm/s
  • the evaporation rates of acac) and mCP were controlled at 0.002 nm/s and 0.1 nm/s, respectively.
  • the evaporation rates of Eu(DBM) 3 phen, Ir(dmpq) 3 (acac) and 26DCzPPy in the electron-dominated luminescent layer 6 were controlled at 0.0001, respectively.
  • the evaporation rate of 3TPYMB in the hole blocking-electron transport layer 7 is controlled at 0.08 nm/s
  • the evaporation rate of LiF in the cathode modified layer 8 is controlled at 0.01 nm/s.
  • the evaporation rate of Al in the metal cathode layer 9 was controlled at 0.9 nm/s.
  • the performance of the red organic electroluminescent device prepared in this example was tested.
  • the experimental results show that the device emits red light at about 592 nm under the driving of a DC power source.
  • the brightness is 20000 cd/m 2
  • the color coordinates of the device are (0.588, 0.379); as the operating voltage changes, the color coordinates of the device are almost unchanged.
  • the device has a starting voltage of 3.1 volts and a maximum brightness of 64572 cd/m 2 .
  • the device has a maximum current efficiency of 60.11 cd/A and a maximum power efficiency of 60.89 lm/W.
  • the ITO anode layer on the ITO glass was first laser etched into strip electrodes, which were then ultrasonically cleaned with cleaning solution and deionized water for 15 min and placed in an oven for drying. Next, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to low pressure plasma treatment for 3 minutes under a vacuum of 10 Pa in an atmosphere of 400 V, and then transferred to an organic vapor deposition chamber. In an organic vapor deposition chamber having a degree of vacuum of 1 to 2 ⁇ 10 -5 Pa, a 6 nm-thick MoO 3 anode modification layer 3 and a 50 nm-thick TAPC hole-transport-electron barrier layer 4, 12 nm are sequentially deposited on the ITO layer.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.1 nm thick LiF cathode modification layer 8 was evaporated in a vacuum atmosphere of 4 to 6 ⁇ 10 -5 Pa, and finally passed through a special mask on the LiF layer.
  • a 240 nm thick metal Al cathode layer 9 was deposited to prepare a structure of ITO/MoO 3 /TAPC/Ir(MDQ) 2 (acac) (3%): TCP/Eu(DBM) 3 phen (0.3%): Ir ( MDQ) 2 (acac) (3%): Organic electroluminescent device of UGH2/BmPyPhB/LiF/Al.
  • the evaporation rate of MoO 3 in the anode modification layer 3 is controlled at 0.01 nm/s
  • the evaporation rate of TAPC in the hole transport-electron blocking layer 4 is controlled at 0.08 nm/s
  • the evaporation rates of acac) and TCP are controlled at 0.003 nm/s and 0.1 nm/s, respectively.
  • the evaporation rates of Eu(DBM) 3 phen, Ir(MDQ) 2 (acac) and UGH2 in the electron-dominated luminescent layer 6 are controlled at 0.0003, respectively.
  • the evaporation rate of BmPyPhB in the hole blocking-electron transport layer 7 is controlled at 0.09 nm/s
  • the evaporation rate of LiF in the cathode modified layer 8 is controlled at 0.012 nm/s.
  • the evaporation rate of Al in the metal cathode layer 9 was controlled at 1.2 nm/s.
  • the performance of the red organic electroluminescent device prepared in this example was tested.
  • the experimental results show that the device emits red light at about 592 nm under the driving of a DC power source.
  • the luminance is 20000 cd/m 2
  • the color coordinates of the device are (0.592, 0.378); as the operating voltage changes, the color coordinates of the device hardly change.
  • the device has a starting voltage of 3.1 volts and a maximum brightness of 60782 cd/m 2 .
  • the device has a maximum current efficiency of 62.34 cd/A and a maximum power efficiency of 63.14 lm/W.
  • the ITO anode layer on the ITO glass was first laser etched into strip electrodes, which were then ultrasonically cleaned with cleaning solution and deionized water for 15 min and placed in an oven for drying. Next, the dried substrate was placed in a pretreatment vacuum chamber, and the ITO anode was subjected to low pressure plasma treatment for 3 minutes under a vacuum of 10 Pa in an atmosphere of 400 V, and then transferred to an organic vapor deposition chamber. In an organic vapor deposition chamber having a degree of vacuum of 1 to 2 ⁇ 10 -5 Pa, a 3 nm-thick MoO 3 anode modification layer 3 and a 40 nm-thick TAPC hole-transport-electron barrier layer 4, 10 nm are sequentially deposited on the ITO layer.
  • the unfinished device was transferred to a metal deposition chamber, and a 1.0 nm thick LiF cathode modification layer 8 was evaporated in a vacuum atmosphere of 4 to 6 ⁇ 10 -5 Pa, and finally passed through a special mask on the LiF layer.
  • a 120 nm thick metal Al cathode layer 9 was deposited to prepare a structure of ITO/MoO 3 /TAPC/Ir(dpm)(piq) 2 (4%): BSB/Eu(TTA) 3 phen(0.3%): Ir ( Dpm) (piq) 2 (4%): Organic electroluminescent device of BCBP/TPBi/LiF/Al.
  • the evaporation rate of MoO 3 in the anode modification layer 3 is controlled at 0.02 nm/s
  • the evaporation rate of TAPC in the hole transport-electron blocking layer 4 is controlled at 0.08 nm/s
  • the holes dominate the luminescent layer 5
  • the evaporation rates of 2 and BSB are controlled at 0.004 nm/s and 0.1 nm/s, respectively.
  • the evaporation rates of Ir(dpm)(piq) 2 , Eu(TTA) 3 phen and BCBP in the electron-dominated luminescent layer 6 are controlled at 0.004, respectively.
  • the evaporation rate of TPBi in the hole blocking-electron transport layer 7 is controlled at 0.08 nm/s
  • the evaporation rate of LiF in the cathode modified layer 8 is controlled at 0.005 nm/s.
  • the evaporation rate of Al in the metal cathode layer 9 was controlled at 1.5 nm/s.
  • the performance of the red organic electroluminescent device prepared in this example was tested.
  • the experimental results show that the device emits red light at about 592 nm under the driving of a DC power source.
  • the color coordinate of the device is (0.592, 0.380); as the operating voltage changes, the color coordinates of the device are almost unchanged.
  • the device has a light-emitting voltage of 3.0 volts and a maximum brightness of the device of 63110 cd/m 2 .
  • the device has a maximum current efficiency of 61.71 cd/A and a maximum power efficiency of 64.59 lm/W.

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Abstract

一种红色有机电致发光器件，其由衬底（1）、阳极层（2）、阳极修饰层（3）、空穴传输-电子阻挡层（4）、空穴主导发光层（5）、电子主导发光层（6）、空穴阻挡-电子传输层（7）、阴极修饰层（8）与阴极层（9）依次设置而成；其中所述电子主导发光层（6）由有机敏化材料、红色有机发光材料与电子型有机主体材料组成。通过选择能级能量匹配的稀土配合物，例如Eu（DBM） 3phen或者Eu（TTA） 3phen作为有机敏化材料，将其微量掺入电子主导发光层（6）中，起到载流子深束缚中心及能量传递阶梯的作用，从而提高器件的发光效率、提高器件的光谱稳定性、降低器件的工作电压、延缓器件的效率衰减以及提高器件的工作寿命。

Description

一种红色有机电致发光器件及其制备方法
本申请要求于2014年10月30日提交中国专利局、申请号为201410605638.8、发明名称为“一种红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，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及有机电致发光技术领域，尤其涉及一种红色有机电致发光器件及其制备方法。
背景技术
有机电致发光器件是一种自发光器件，其发光原理是：当电荷被注入到空穴注入电极和电子注入电极之间的有机层时，电子和空穴相遇、结合并随后湮灭，因而产生光。有机电致发光器件具有低电压、高亮度、宽视角等特性，因此有机电致发光器件近年来得到了迅猛的发展。其中，红色有机电致发光器件由于在单色显示、白光调制等方面具有广阔的应用前景，因此成为研究的热点。
一直以来，三价铱配合物由于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，欲提高红色有机电致发光器件的综合性能，以满足产业化的需要。例如，2001年美国普林斯顿大学的S.R.Forrest等人采用具有标准红色发射的铱配合物btp2Ir(acac)作为发光材料，通过掺杂的方法制得有机电致发光器件。虽然该器件显示非常理想的红光发射，然而不平衡的载流子注入导致器件的效率和亮度较低，另外器件的工作电压较高。
为了解决这些问题，2009年，中国科学院长春应用化学研究所的马东阁等人选择高效率的铱配合物(fbi)2Ir(acac)作为红光染料，将其掺入优选的主体材料中制得了多层结构的红色有机电致发光器件。该器件具有较高的最大发光效率和最大亮度，然而器件的发光效率随着电流密度的提高迅速地衰减；另外，复杂的器件结构不但导致器件的制作成本较高而且不利 于降低器件的工作电压。2013年，香港大学支志明等人合成红色铂配合物作为发光材料，设计并优化双发光层器件结构，获得了具有纯正红光发射的有机电致发光器件。该器件的效率衰减得到大幅缓解，然而器件仍然存在工作电压较高、亮度较低的问题。由此可见，红色有机电致发光器件的发光效率、亮度、光谱稳定性和工作寿命等综合性能仍然没有得到有效改善。
发明内容
本发明解决的技术问题在于提供一种综合性能较高的红色有机电致发光器件及其制备方法。
有鉴于此，本申请提供了一种红色有机电致发光器件，包括：
衬底；
复合于所述衬底上的阳极层；
复合于所述阳极层上的阳极修饰层；
复合于所述阳极修饰层上的空穴传输-电子阻挡层；
复合于所述空穴传输-电子阻挡层上的空穴主导发光层；
复合于所述空穴主导发光层上的电子主导发光层；
复合于所述电子主导发光层上的空穴阻挡-电子传输层；
复合于所述空穴阻挡-电子传输层上的阴极修饰层；
复合于所述阴极修饰层上的阴极层；
所述电子主导发光层由有机敏化材料、红色有机发光材料与电子型有机主体材料组成；
所述有机敏化材料选自三(二苯甲酰甲烷)邻菲罗啉合铕和三(噻吩甲酰三氟丙酮)邻菲罗啉合铕中的一种或两种；
所述有机敏化材料为所述电子型有机主体材料的0.1wt％～0.5wt％。
优选的，所述红色有机发光材料的含量为所述电子型有机主体材料的2wt％～5wt％。
优选的，所述红色有机发光材料选自二(2-苯基喹啉)-(2,2,6,6-四甲基-3,5-庚二酮酸)合铱、二(2-苯唑[b]2-噻吩基吡啶)乙酰丙酮合铱、三(1-苯 基异喹啉)合铱、二(1-苯基异喹啉)(乙酰丙酮)合铱、二[1-(9,9-二甲基-9H-芴-2-基)-异喹啉](乙酰丙酮)合铱、二[2-(9,9-二甲基-9H-芴-2-基)喹啉](乙酰丙酮)合铱、二(2-苯基喹啉)(2-(3-甲基苯基)吡啶)合铱、三[2-苯基-4-甲基喹啉]合铱、双(苯基异喹啉)(2,2,6,6-四甲基己烷-3，5-二酮)合铱、二(2-甲基二苯唑[f,h]喹喔啉)(乙酰丙酮)合铱和二[2-(2-甲基苯基)-7-甲基-喹啉](乙酰丙酮)合铱中的一种或多种。
优选的，所述电子型有机主体材料选自2,6-二[3-(9H-9-咔唑基)苯基]吡啶、1,4-双(三苯基硅烷基)苯、2,2’-双(4-(9-咔唑基)苯基)联苯、[2,4,6-三甲基-3-(3-吡啶基)苯基]硼烷、1，3，5-三[(3-吡啶)-3-苯基]苯、1,3-双[3,5-二(3-吡啶基)苯基]苯、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯、9-(4-特丁基苯基)-3,6-双(三苯基硅基)-9H-咔唑和9-(8-二苯基磷酰基)-二苯唑[b,d]呋喃-9H-咔唑中的一种或多种。
优选的，所述空穴主导发光层由红色有机发光材料和空穴型有机主体材料组成；所述红色有机发光材料为所述空穴型有机主体材料的2.0wt％～5.0wt％；
所述红色有机发光材料选自二(2-苯基喹啉)-(2,2,6,6-四甲基-3,5-庚二酮酸)合铱、二(2-苯唑[b]2-噻吩基吡啶)乙酰丙酮合铱、三(1-苯基异喹啉)合铱、二(1-苯基异喹啉)(乙酰丙酮)合铱、二[1-(9,9-二甲基-9H-芴-2-基)-异喹啉](乙酰丙酮)合铱、二[2-(9,9-二甲基-9H-芴-2-基)喹啉](乙酰丙酮)合铱、二(2-苯基喹啉)(2-(3-甲基苯基)吡啶)合铱、三[2-苯基-4-甲基喹啉]合铱、双(苯基异喹啉)(2,2,6,6-四甲基己烷-3，5-二酮)合铱、二(2-甲基二苯唑[f,h]喹喔啉)(乙酰丙酮)合铱和二[2-(2-甲基苯基)-7-甲基-喹啉](乙酰丙酮)合铱中的一种或多种；
所述空穴型有机主体材料选自4，4’-N，N’-二咔唑二苯基、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)三苯胺和1,4-双(三苯基硅烷基)联苯中的一种或多种。
优选的，所述空穴传输-电子阻挡层的材料选自4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]、二吡嗪[2，3-f:2’,3’-h]喹喔啉-2，3，6，7，10，11- 六腈基、N4,N4'-二(萘-1-基)-N4,N4'-双(4-乙烯基苯基)联苯-4,4'-二胺、N,N'-双(3-甲基苯基)-N,N'-双(苯基)-2，7-二胺-9，9-螺双芴、N,N,N',N'-四-(3-甲基苯基)-3-3’-二甲基对二氨基联苯、2,2'-二(3-(N,N-二-对甲苯氨基)苯基)联苯、N,N'-二(萘-2-基)-N,N'-二(苯基)二氨基联苯、N,N'-二(萘-1基)-N,N'–二苯基-2，7-二氨基-9，9-螺双芴、N,N'-二(3-甲基苯基)-N,N'-二苯基-2,7-二氨基-9，9-二甲基芴、N,N'-二(萘-1-基)-N,N'-二苯基-2，7-二氨基-9，9-二甲基芴、N,N'–二(3-甲基苯基)-N,N'–二苯基-2，7-二氨基-9，9-二苯基芴、N,N'-二(萘-1-基)-N,N'-二苯基-2,7-二氨基-9,9-二苯基芴、N,N'-二(萘-1-基)-N,N'-二苯基-2,2’-二甲基二氨基联苯、2,2',7,7'-四(N,N-二苯基氨基)-2,7-二氨基-9,9-螺双芴、9,9-二[4-(N,N–二萘-2-基-氨基)苯基]-9H-芴、9，9-[4-(N-萘-1基-N-苯胺)-苯基]-9H-芴、2，2’-二[N,N-二(4-苯基)氨基]-9,9-螺双芴、2,2’-双(N,N-苯氨基)-9,9-螺双芴、N,N’-二苯基-N,N’-(1-萘基)-1，1’-联苯-4，4’-二胺和4，4’-二[N-(对-甲苯基)-N-苯基-氨基]二苯基中的一种或多种。
优选的，所述空穴阻挡-电子传输层的材料选自三[2,4,6-三甲基-3-(3-吡啶基)苯基]硼烷、1，3，5-三[(3-吡啶)-3-苯基]苯、1,3-双[3,5-二(3-吡啶基)苯基]苯和的1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯中的一种或多种。
优选的，所述阳极修饰层的厚度为1～10nm，所述空穴传输-电子阻挡层的厚度为30～60nm，所述空穴主导发光层的厚度为5～20nm，所述电子主导发光层的厚度为5～20nm，所述空穴阻挡-电子传输层的厚度为30～60nm，所述阴极修饰层的厚度为0.8～1.2nm，所述阴极层的厚度为90～300nm。
本申请还提供了一种红色有机电致发光器件的制备方法，包括：
将衬底上的阳极层进行刻蚀，烘干后在所述阳极层上依次蒸镀阳极修饰层、空穴传输-电子阻挡层、空穴主导发光层、电子主导发光层、空穴阻挡-电子传输层、阴极修饰层与阴极层；
所述电子主导发光层由有机敏化材料、红色有机发光材料与电子型有机主体材料组成；
所述有机敏化材料选自三(二苯甲酰甲烷)邻菲罗啉合铕和三(噻吩甲酰三氟丙酮)邻菲罗啉合铕中的一种或两种；
所述有机敏化材料为所述电子型有机主体材料的0.1wt％～0.5wt％。
优选的，所述阳极修饰层的蒸发速率为0.01～0.05nm/s，所述空穴传输-电子阻挡层、空穴主导发光层、电子主导发光层与空穴阻挡-电子传输层中主体材料的蒸发速率为0.05～0.1nm/s，所述电子主导发光层中的有机敏化材料的蒸发速率为0.00005～0.0005nm/s，所述电子主导发光层与空穴主导发光层中的红色发光材料的蒸发速率为0.001～0.005nm/s，所述阴极修饰层的蒸发速率为0.005～0.05nm/s，所述阴极层的蒸发速率为0.5～2.0nm/s。
本申请提供了一种红色有机电致发光器件，其包括衬底、阳极层、阳极修饰层、空穴传输-电子阻挡层、空穴主导发光层、电子主导发光层、空穴阻挡-电子传输层、阴极修饰层与阴极层。本申请的发光材料为红色发光材料，当电子和空穴分别注入到发光层时，电子和空穴会相遇并发生复合，进而产生一个激子，激子会把能量传递给发光层中的红色发光材料的分子，激发一个电子到激发态，激发态的电子通过辐射跃迁的方式回到基态时会产生一个红色的光子，从而使有机电致发光器件发红光。
本申请通过在电子主导发光层中加入三(二苯甲酰甲烷)邻菲罗啉合铕和三(噻吩甲酰三氟丙酮)邻菲罗啉合铕的一种或两种作为有机敏化材料，使其能级及三重态能量与主体材料、发光材料的能级及三重态能量相匹配，使有机敏化材料在电致发光过程中起到载流子深束缚中心及能量传递阶梯的作用，不仅能够提高从主体材料到发光材料的能量传递，也可平衡电子和空穴在发光区间的分布，从而提高有机电致发光器件的发光效率、提高器件的光谱稳定性、降低器件的工作电压、延缓器件的效率衰减、提高器件的工作寿命。
附图说明
图1为本发明红色有机电致发光器件的结构示意图；
图2为本发明实施例1制备的红色有机电致发光器件的电压-电流密度-亮度特性曲线图；
图3为本发明实施例1制备的红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；
图4为本发明实施例1制备的红色有机电致发光器件在亮度为20000cd/m2时的光谱图。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
本发明实施例公开了一种红色有机电致发光器件，包括：
衬底；
复合于所述衬底上的阳极层；
复合于所述阳极层上的阳极修饰层；
复合于所述阳极修饰层上的空穴传输-电子阻挡层；
复合于所述空穴传输-电子阻挡层上的空穴主导发光层；
复合于所述空穴主导发光层上的电子主导发光层；
复合于所述电子主导发光层上的空穴阻挡-电子传输层；
复合于所述空穴阻挡-电子传输层上的阴极修饰层；
复合于所述阴极修饰层上阴极层；
所述电子主导发光层由有机敏化材料、红色有机发光材料与电子型有机主体材料组成；
所述有机敏化材料选自三(二苯甲酰甲烷)邻菲罗啉合铕和三(噻吩甲酰三氟丙酮)邻菲罗啉合铕中的一种或两种；
所述有机敏化材料为电子型有机主体材料的0.1wt％～0.5wt％。
有机电致发光器件(OLED)的发光原理是在外界电压的驱动下，由电极注入的电子和空穴在有机物中相遇，并将能量传递给有机发光分子，使其受到激发，从基态跃迁到激发态，当受激发分子从激发态回到基态时辐射跃迁而产生发光的现象。本申请提供了一种红色有机电致发光器件，其发红光是由于所采用的发光材料是红色发光材料，当电子和空穴分别注 入到发光层时，电子和空穴会相遇并发生复合，进而产生一个激子，激子把能量传递给发光层中的红色发光材料的分子，激发一个电子到激发态，激发态的电子通过跃迁的方式回到基态时会产生一个红色的光子，从而实现有机电致发光器件发红光。
本申请所述红色有机电致发光器件由衬底、阳极层、阳极修饰层、空穴传输-电子阻挡层、空穴主导发光层、电子主导发光层、空穴阻挡-电子传输层、阴极修饰层与阴极层依次连接设置。其中空穴主导发光层与电子主导发光层是红色有机电子发光器件的发光层。
本发明的电子主导发光层由有机敏化材料、红色有机发光材料与电子型有机主体材料组成，其中有机敏化材料在电致发光过程中起到敏化的作用，以提高从主体材料到发光材料的能量传递并平衡电子和空穴在发光区间的分布；红色有机发光材料的分子分散在电子主导发光层中作为发光中心；电子型有机主体材料起到基质的作用，提供电子传输能力。在电子主导发光层中，所述有机敏化材料的能级及三重态能量需要与主体材料、发光材料的能级及三重态能量相匹配，才能平衡电子和空穴在发光区间的分布并加速从主体材料到发光材料的能量传递，使红色有机电致发光器件具有较好的综合性能。因此，本申请通过对发光材料的选取，所述有机敏化材料选择了稀土配合物，所述有机敏化材料选自三(二苯甲酰甲烷)邻菲罗啉合铕(Eu(DBM)3phen)和具有式(Ⅹ)结构的三(噻吩甲酰三氟丙酮)邻菲罗啉合铕(Eu(TTA)3phen)中的一种或两种；
Figure PCTCN2014091779-appb-000001
Figure PCTCN2014091779-appb-000002
本发明中所述有机敏化材料在所述电子主导发光层中的掺杂浓度对有机电致发光器件的性能造成影响。若所述有机敏化材料的掺杂浓度过低则会导致敏化效果不理想，若掺杂浓度过高则会降低有机电致发光器件的综合性能。因此，所述有机敏化材料为所述电子型有机主体材料的0.1wt％～0.5wt％，优选为0.2wt％～0.3wt％。
按照本发明，所述电子主导发光层中所述红色有机发光材料为本领域技术人员熟知的发光材料，本申请没有特别的限制，但是为了使发光效果更好，所述红色有机发光材料优先选自具有式(Ⅱ1)结构的二(2-苯基喹啉)-(2,2,6,6-四甲基-3,5-庚二酮酸)合铱(PQ2Ir(dpm))、具有式(Ⅱ2)结构的二(2-苯唑[b]2-噻吩基吡啶)乙酰丙酮合铱(Ir(btp)2(acac))、具有式(Ⅱ3)结构的三(1-苯基异喹啉)合铱(Ir(piq)3)、具有式(Ⅱ4)结构的二(1-苯基异喹啉)(乙酰丙酮)合铱(Ir(piq)2(acac))、具有式(Ⅱ5)结构的二[1-(9,9-二甲基-9H-芴-2-基)-异喹啉](乙酰丙酮)合铱(Ir(fliq)2(acac))、具有式(Ⅱ6)结构的二[2-(9,9-二甲基-9H-芴-2-基)喹啉](乙酰丙酮)合铱(Ir(flq)2(acac))、具有式(Ⅱ7)结构的二(2-苯基喹啉)(2-(3-甲基苯基)吡啶)合铱(Ir(phq)2tpy)、具有式(Ⅱ8)结构的三[2-苯基-4-甲基喹啉]合铱(Ir(Mphq)3)、具有式(Ⅱ9)结构的双(苯基异喹啉)(2,2,6,6-四甲基己烷-3，5-二酮)合铱(Ir(dpm)(piq)2)、具有式(Ⅱ10)结构的二(2-甲基二苯唑[f,h]喹喔啉)(乙酰丙酮)合铱(Ir(MDQ)2(acac))和具有式(Ⅱ11)结构的二[2-(2-甲基苯基)-7-甲基-喹啉](乙酰丙酮)合铱(Ir(dmpq)2(acac))中的一种或多种；
Figure PCTCN2014091779-appb-000003
Figure PCTCN2014091779-appb-000004
在电子主导发光层中，所述红色有机发光材料的掺杂浓度也会影响红色有机电致发光器件的综合性能。若所述红色有机发光材料的掺杂浓度过低，则会导致器件效率偏低、色纯度不理想，掺杂浓度过高则会导致发光材料分子团聚，形成淬灭分子，最终降低器件的综合性能。因此，所述电子主导发光层中所述红色有机发光材料优选为所述电子型有机主体材料的2.0wt％～5.0wt％，更优选为2.5wt％～4.5wt％。所述电子型主体材料在电子主导发光层中起到基质的作用，提供电子传输能力，所述电子型主体材料为本领域技术人员熟知的材料，作为优选方案，所述电子型主体材料优先选自具有式(XI)结构的2,6-二[3-(9H-9-咔唑基)苯基]吡啶(26DCzPPy)、具有式(XII)结构的1,4-双(三苯基硅烷基)苯(UGH2)、具有式(XIII)结构的2,2’-双(4-(9-咔唑基)苯基)联苯(BCBP)、具有式(XIV)结构的[2,4,6-三甲基-3-(3-吡啶基)苯基]硼烷(3TPYMB)、具有式(XV)结构的1,3,5-三[(3-吡啶)-3-苯基]苯(TmPyPB)、具有式 (XVI)结构的1,3-双[3,5-二(3-吡啶基)苯基]苯(BmPyPhB)、具有式(XVII)结构的1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBi)、具有式(XVIII)结构的9-(4-特丁基苯基)-3,6-双(三苯基硅基)-9H-咔唑(CzSi)和具有式(XIX)结构的9-(8-二苯基磷酰基)-二苯唑[b,d]呋喃-9H-咔唑(DFCzPO)中的一种或多种；
Figure PCTCN2014091779-appb-000005
Figure PCTCN2014091779-appb-000006
本申请中所述空穴主导发光层由红色有机发光材料和空穴型有机主体材料组成，其中红色有机发光材料的分子分散在空穴主导发光层中作为发光中心。所述红色有机发光材料在所述空穴主导发光层中优选为所述空穴型有机主体材料的2.0wt％～5.0wt％，更优选为2.5wt％～4.5wt％；所述红色有机发光材料的掺杂浓度过低，则会导致器件效率偏低、色纯度不理想，掺杂浓度过高则会导致发光材料分子团聚，形成淬灭分子，最终降低器件的综合性能。所述空穴型主体材料起到基质的作用，提供空穴传输能力。本申请中所述空穴主导发光层中所述红色有机发光材料优先选自具有式(Ⅱ1)结构的二(2-苯基喹啉)-(2,2,6,6-四甲基-3,5-庚二酮酸)合铱(PQ2Ir(dpm))、具有式(Ⅱ2)结构的二(2-苯唑[b]2-噻吩基吡啶)乙酰丙酮合铱(Ir(btp)2(acac))、具有式(Ⅱ3)结构的三(1-苯基异喹啉)合铱(Ir(piq)3)、具有式(Ⅱ4)结构的二(1-苯基异喹啉)(乙酰丙酮)合铱(Ir(piq)2(acac))、具有式(Ⅱ5)结构的二[1-(9,9-二甲基-9H-芴-2-基)-异喹啉](乙酰丙酮)合铱(Ir(fliq)2(acac))、具有式(Ⅱ6)结构的二[2-(9,9-二甲基-9H-芴-2-基)喹啉](乙酰丙酮)合铱(Ir(flq)2(acac))、具有式(Ⅱ7)结构的二(2-苯基喹啉)(2-(3-甲基苯基)吡啶)合铱(Ir(phq)2tpy)、具有式(Ⅱ8)结构的三[2-苯基-4-甲基喹啉]合铱(Ir(Mphq)3)、具有式(Ⅱ9)结构的双(苯基异喹啉)(2,2,6,6-四甲基己烷-3，5-二酮)合铱(Ir(dpm)(piq)2)、具有式(Ⅱ10)结构的二(2-甲基二苯唑[f,h]喹喔啉)(乙酰丙酮)合铱(Ir(MDQ)2(acac))和具有式(Ⅱ11)结构的二[2-(2-甲基苯基)-7-甲基-喹啉](乙酰丙酮)合铱(Ir(dmpq)2(acac))中的一种或多种；
所述空穴型有机主体材料优先选自具有式(III)结构的4，4’-N，N’-二咔唑二苯基(CBP)、具有式(IV)结构的1,3-二咔唑-9-基苯(mCP)、具有式(V)结构的9,9'-(5-(三苯基硅烷基)-1,3-苯基)二-9H-咔唑(SimCP)、 具有式(VI)结构的1,3,5-三(9-咔唑基)苯(TCP)、具有式(VII)结构的4,4',4″-三(咔唑-9-基)三苯胺(TcTa)和具有式(VIII)结构的1,4-双(三苯基硅烷基)联苯(BSB)中的一种或多种；
Figure PCTCN2014091779-appb-000007
Figure PCTCN2014091779-appb-000008
Figure PCTCN2014091779-appb-000009
按照本发明，所述红色有机电致发光器件中，所述衬底可以为玻璃衬底、石英衬底、多晶硅衬底、单晶硅衬底或石墨烯薄膜衬底，本申请没有特别的限制。所述阳极层优先选自铟锡氧化物(ITO)，其面阻优选为5～25Ω。所述阳极修饰层能够降低驱动电压，加速空穴的注入，所述阳极修饰层优选采用氧化钼(MoO3)。
本申请中所述空穴传输-电子阻挡层的作用是传输空穴并阻挡电子。所述空穴传输-电子阻挡层层的材料优先选自具有式(Ⅰ1)结构的4,4'-环己基二[N,N–二(4-甲基苯基)苯胺](TAPC)、具有式(Ⅰ2)结构的二吡嗪[2，3-f:2’,3’-h]喹喔啉-2，3，6，7，10，11-六腈基(HAT-CN)、具有式(Ⅰ3)结构的N4,N4'-二(萘-1-基)-N4,N4'-双(4-乙烯基苯基)联苯 -4,4'-二胺(VNPB)、具有式(Ⅰ4)结构的N,N'-双(3-甲基苯基)-N,N'-双(苯基)-2，7-二胺-9，9-螺双芴(Spiro-TPD)、具有式(Ⅰ5)结构的N,N,N',N'-四-(3-甲基苯基)-3-3’-二甲基对二氨基联苯(HMTPD)、具有式(Ⅰ6)结构的2,2'-二(3-(N,N-二-对甲苯氨基)苯基)联苯(3DTAPBP)、具有式(Ⅰ7)结构的N,N'-二(萘-2-基)-N,N'-二(苯基)二氨基联苯(β-NPB)、具有式(Ⅰ8)结构的N,N'-二(萘-1基)-N,N'-二苯基-2，7-二氨基-9，9-螺双芴(Spiro-NPB)、具有式(Ⅰ9)结构的N,N'-二(3-甲基苯基)-N,N'-二苯基-2,7-二氨基-9，9-二甲基芴(DMFL-TPD)、具有式(Ⅰ10)结构的N,N'-二(萘-1-基)-N,N'-二苯基-2，7-二氨基-9，9-二甲基芴(DMFL-NPB)、具有式(Ⅰ11)结构的N,N'-二(3-甲基苯基)-N,N'-二苯基-2，7-二氨基-9，9-二苯基芴(DPFL-TPD)、具有式(Ⅰ12)结构的N,N'-二(萘-1-基)-N,N'-二苯基-2,7-二氨基-9,9-二苯基芴(DPFL-NPB)、具有式(Ⅰ13)结构的N,N'-二(萘-1-基)-N,N'-二苯基-2,2’-二甲基二氨基联苯(α-NPD)、具有式(Ⅰ14)结构的2,2',7,7'-四(N,N-二苯基氨基)-2,7-二氨基-9,9-螺双芴(Spiro-TAD)、具有式(Ⅰ15)结构的9,9-二[4-(N,N–二萘-2-基-氨基)苯基]-9H-芴(NPAPF)、具有式(Ⅰ16)结构的9，9-[4-(N-萘-1基-N-苯胺)-苯基]-9H-芴(NPBAPF)、具有式(Ⅰ17)结构的2，2’-二[N,N-二(4-苯基)氨基]-9,9-螺双芴(2,2'-Spiro-DBP)、具有式(Ⅰ18)结构的2,2’-双(N,N-苯氨基)-9,9-螺双芴(Spiro-BPA)、具有式(Ⅰ19)结构的N,N’-二苯基-N,N’-(1-萘基)-1，1’-联苯-4，4’-二胺(NPB)和具有式(Ⅰ20)结构的4，4’-二[N-(对-甲苯基)-N-苯基-氨基]二苯基(TPD)中的一种或多种；
Figure PCTCN2014091779-appb-000010
Figure PCTCN2014091779-appb-000011
Figure PCTCN2014091779-appb-000012
按照本发明所述空穴阻挡-电子传输层的作用是阻挡空穴并传输电子，促进电子的注入。所述空穴阻挡-电子传输层的材料优先选自具有式(XIV)结构的三[2,4,6-三甲基-3-(3-吡啶基)苯基]硼烷(3TPYMB)、具有式(XV)结构的1，3，5-三[(3-吡啶)-3-苯基]苯(TmPyMB)、具有式(XVI)结构的1,3-双[3,5-二(3-吡啶基)苯基]苯(BmPyPhB)和具有式(XVII)结构的1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBi)中的一种或多种；
Figure PCTCN2014091779-appb-000013
本申请中所述阴极修饰层的作用是降低驱动电压，加速电子的注入，所述阴极修饰层优选为氟化锂。所述阴极层优选为铝。
本申请对所述空穴传输-电子阻挡层的材料、红色有机发光材料、空穴型有机主体材料、有机敏化材料、电子型有机主体材料以及空穴阻挡-电子传输层的材料的来源均没有特别的限制，按照本领域技术人员熟知的方式制备即可得到。
本申请中所述阳极层与所述阴极层相互交叉形成器件的发光区，本申请所述红色有机电致发光器件中每层的厚度对所述器件的影响也是很大的，若厚度偏低则会导致器件效率衰减加快，若厚度偏高则会导致器件工作电压高、寿命低。因此所述阳极修饰层的厚度优选为1～10nm，空穴传输-电子阻挡层的厚度优选为30～60nm，空穴主导发光层的厚度优选为5～20nm，电子主导发光层的厚度优选为5～20nm，空穴阻挡-电子传输层的厚度优选为30～60nm，阴极修饰层的厚度优选为0.8～1.2nm，阴极层的厚度优选为90～300nm。
本申请还提供了所述红色有机电致发光器件的制备方法，包括：
将衬底上的阳极层进行刻蚀，烘干后在所述阳极层上依次蒸镀阳极修饰层、空穴传输-电子阻挡层、空穴主导发光层、电子主导发光层、空穴阻挡-电子传输层、阴极修饰层与阴极层；
所述空穴主导发光层由红色有机发光材料与空穴型有机主体材料组成；
所述电子主导发光层由有机敏化材料、红色有机发光材料与电子型有机主体材料组成；
所述有机敏化材料选自具有式(Ⅸ)结构的三(二苯甲酰甲烷)邻菲罗啉合铕和具有式(Ⅹ)结构的三(噻吩甲酰三氟丙酮)邻菲罗啉合铕中的一种或两种；
所述有机敏化材料为所述电子型有机主体材料的0.1wt％～0.5wt％；
Figure PCTCN2014091779-appb-000014
按照本发明，所述红色有机电致发光器件的制备方法具体为：
先将衬底上的阳极层激光刻蚀成条状的电极，然后依次用清洗液、去离子水超声清洗10～20min并放入烘箱烘干；
将烘干后的衬底放入预处理真空室，在真空度为8～15Pa的氛围下用350～500V的电压对其进行1～10min的低压等离子处理后把它转移到有机蒸镀室；
待真空度达到1～2×10-5Pa时，依次在阳极层上蒸镀阳极修饰层、空穴传输-电子阻挡层、空穴主导发光层、电子主导发光层、空穴阻挡-电子传输层；未完成的器件被转移到金属蒸镀室，在4～6×10-5Pa的真空氛围下依次蒸镀阴极修饰层和金属阴极层。
在制备红色有机电致发光器件的过程中，本申请通过控制蒸发速率实现材料的沉积。按照本发明，所述阳极修饰层蒸发速率控制在0.01～0.05nm/s，空穴传输-电子阻挡层、空穴主导发光层、电子主导发光层、空穴阻挡-电子传输层中主体材料的蒸发速率控制在0.05～0.1nm/s，有机敏化材料的蒸发速率控制在0.00005～0.0005nm/s，红色有机发光材料的蒸发速率控制在0.001～0.005nm/s，阴极修饰层的蒸发速率控制在0.005～0.015nm/s，金属阴极层蒸发速率控制在0.5～2.0nm/s。其中蒸镀空穴主导发光层时，其中红色有机发光材料、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掺杂的红色有机发光材料和空穴型有机主体材料的重量比控制在2.0％～5.0％之间；蒸镀电子主导发光层时，其中有机敏化材料、红色有机发光材料、电子型有机主体材料在不同的蒸发源中同时蒸发，通过调控三种材料的蒸发速率使得掺杂的有机敏化材料和电子型有机主体材料的质量比控制在0.1％～0.5％之间，使得掺杂的红色有机发光材料和电子型有机主体材料的质量比控制在2.0％～5.0％之间。
本申请提供了一种红色有机电致发光器件，所述红色有机电致发光器件中的电子主导发光层中选择具有匹配的能级分布的稀土配合物，例如Eu(DBM)3phen或者Eu(TTA)3phen作为有机敏化材料，其起到电子深束缚中心的作用，有利于平衡载流子的分布、拓宽器件的发光区间，从而提高器件的发光效率、降低器件的工作电压、延缓器件的效率衰减、提高器件的工作寿命；并且，所述有机敏化材料具有匹配的三重态能量，起到能量传递阶梯的作用，能够加速从主体材料到发光材料的能量传递，缓解发光材料载流子俘获能力不足导致的主体材料发光问题，从而提高器件的光谱稳定性、降低器件性能对发光材料掺杂浓度的依赖。
为了进一步理解本发明，下面结合实施例对本发明提供的红色有机电 致发光器件及其制备方法进行详细说明，本发明的保护范围不受以下实施例的限制。
如图1所示，图1为本发明红色有机电致发光器件的结构示意图，其中1为玻璃衬底，2为阳极层，3为阳极修饰层，4为空穴传输-电子阻挡层，5为空穴主导发光层，6为电子主导发光层，7为空穴阻挡-电子传输层，8为阴极修饰层，9为金属阴极层。
实施例1
先将ITO玻璃上的ITO阳极层激光刻蚀成条状电极，然后依次用清洗液、去离子水超声清洗15min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10Pa的氛围下用400V的电压对ITO阳极进行3min的低压等离子处理后将其转移到有机蒸镀室。在真空度为1～2×10-5Pa的有机蒸镀室中，在ITO层上依次蒸镀3nm厚的MoO3阳极修饰层3、40nm厚的TAPC空穴传输-电子阻挡层4、10nm厚PQ2Ir(dpm)掺杂TcTa的空穴主导发光层5、10nm厚Tb(acac)3phen与PQ2Ir(dpm)共掺杂CzSi的电子主导发光层6和40nm厚的TmPyPB空穴阻挡-电子传输层7。接下来，未完成的器件被转移到金属蒸镀室，在4～6×10-5Pa的真空氛围下蒸镀1.0nm厚的LiF阴极修饰层8，最后通过特制的掩模版在LiF层上蒸镀120nm厚的金属Al阴极层9，制备成结构为ITO/MoO3/TAPC/PQ2Ir(dpm)(4％)：TcTa/Eu(TTA)3phen(0.2％)：PQ2Ir(dpm)(4％)：CzSi/TmPyPB/LiF/Al的有机电致发光器件。阳极修饰层3中MoO3的蒸发速率控制在0.01nm/s，空穴传输-电子阻挡层4中TAPC的蒸发速率控制在0.05nm/s，空穴主导发光层5中PQ2Ir(dpm)和TcTa的蒸发速率分别控制在0.002nm/s和0.05nm/s，电子主导发光层6中Eu(TTA)3phen、PQ2Ir(dpm)和CzSi的蒸发速率分别控制在0.0001nm/s、0.002nm/s和0.05nm/s，空穴阻挡-电子传输层7中TmPyPB的蒸发速率控制在0.05nm/s，阴极修饰层8中LiF的蒸发速率控制在0.005nm/s，金属阴极层9中Al的蒸发速率控制在1.0nm/s。
如图2所示，图2为本实施例制备的红色有机电致发光器件的电压-电流密度-亮度特性曲线，图2中○曲线为器件的电流密度-电压曲线，□ 曲线为器件的亮度-电压曲线，根据图2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2.9伏，在电压为9.8伏、电流密度为438.91毫安每平方厘米(mA/cm2)时器件获得最大亮度72933坎德拉每平方米(cd/m2)。
如图3所示，图3为本实施例制备的红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，根据图3可知，器件的最大电流效率为65.73cd/A，最大功率效率为71.17lm/W。
如图4所示，图4为本发明提供的红色有机电致发光器件在亮度为20000cd/m2时的光谱图，根据图4可知，光谱主峰位于592纳米。器件色坐标为(0.592，0.377)。
实施例2
先将ITO玻璃上的ITO阳极层激光刻蚀成条状电极，然后依次用清洗液、去离子水超声清洗15min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10Pa的氛围下用400V的电压对ITO阳极进行3min的低压等离子处理后将其转移到有机蒸镀室。在真空度为1～2×10-5Pa的有机蒸镀室中，在ITO层上依次蒸镀3nm厚的MoO3阳极修饰层3、40nm厚的TAPC空穴传输-电子阻挡层4、10nm厚PQ2Ir(dpm)掺杂mCP的空穴主导发光层5、10nm厚Eu(TTA)3phen与PQ2Ir(dpm)共掺杂26DCzPPy的电子主导发光层6和40nm厚的TmPyPB空穴阻挡-电子传输层7。接下来，未完成的器件被转移到金属蒸镀室，在4～6×10-5Pa的真空氛围下蒸镀1.0nm厚的LiF阴极修饰层8，最后通过特制的掩模版在LiF层上蒸镀120nm厚的金属Al阴极层9，制备成结构为ITO/MoO3/TAPC/PQ2Ir(dpm)(4％)：mCP/Eu(TTA)3phen(0.2％):PQ2Ir(dpm)(4％)：26DCzPPy/TmPyPB/LiF/Al的有机电致发光器件。阳极修饰层3中MoO3的蒸发速率控制在0.01nm/s，空穴传输-电子阻挡层4中TAPC的蒸发速率控制在0.05nm/s，空穴主导发光层5中PQ2Ir(dpm)和mCP的蒸发速率分别控制在0.002nm/s和0.05nm/s，电子主导发光层6中Eu(TTA)3phen、PQ2Ir(dpm)和26DCzPPy的蒸发速率分别控制在0.0001nm/s、0.002nm/s和0.05nm/s，空穴阻挡-电子 传输层7中TmPyPB的蒸发速率控制在0.05nm/s，阴极修饰层8中LiF的蒸发速率控制在0.005nm/s，金属阴极层9中Al的蒸发速率控制在1.0nm/s。
检测本实施例制备的红色有机电致发光器件的性能，实验结果表明，在直流电源驱动下，器件发射位于592纳米左右的红光。当亮度为20000cd/m2时，器件的色坐标为(0.596，0.378)；随着工作电压的变化，器件的色坐标几乎不变。器件的起亮电压为3.0伏，器件的最大亮度为70528cd/m2。器件的最大电流效率为64.92cd/A，最大功率效率为67.95lm/W。
实施例3
先将ITO玻璃上的ITO阳极层激光刻蚀成条状电极，然后依次用清洗液、去离子水超声清洗15min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10Pa的氛围下用400V的电压对ITO阳极进行3min的低压等离子处理后将其转移到有机蒸镀室。在真空度为1～2×10-5Pa的有机蒸镀室中，在ITO层上依次蒸镀3nm厚的MoO3阳极修饰层3、40nm厚的TAPC空穴传输-电子阻挡层4、10nm厚PQ2Ir(dpm)掺杂TcTa的空穴主导发光层5、10nm厚Eu(DBM)3phen与PQ2Ir(dpm)共掺杂26DCzPPy的电子主导发光层6和40nm厚的TmPyPB空穴阻挡-电子传输层7。接下来，未完成的器件被转移到金属蒸镀室，在4～6×10-5Pa的真空氛围下蒸镀1.0nm厚的LiF阴极修饰层8，最后通过特制的掩模版在LiF层上蒸镀120nm厚的金属Al阴极层9，制备成结构为ITO/MoO3/TAPC/PQ2Ir(dpm)(4％)：TcTa/Eu(DBM)3phen(0.3％):PQ2Ir(dpm)(4％)：26DCzPPy/TmPyPB/LiF/Al的有机电致发光器件。阳极修饰层3中MoO3的蒸发速率控制在0.01nm/s，空穴传输-电子阻挡层4中TAPC的蒸发速率控制在0.05nm/s，空穴主导发光层5中PQ2Ir(dpm)和TcTa的蒸发速率分别控制在0.003nm/s和0.05nm/s，电子主导发光层6中Eu(DBM)3phen、PQ2Ir(dpm)和26DCzPPy的蒸发速率分别控制在0.0003nm/s、0.004nm/s和0.1nm/s，空穴阻挡-电子传输层7中TmPyPB的蒸发速率控制在0.05nm/s，阴极修饰层8中LiF的蒸发速率控制在0.005nm/s，金属阴极层9中Al的蒸发速率控制在1.0 nm/s。
检测本实施例制备的红色有机电致发光器件的性能，实验结果表明，器件在直流电源驱动下，发射位于592纳米左右的红光。当亮度为20000cd/m2时，器件的色坐标为(0.590,0.381)；随着工作电压的变化，器件的色坐标几乎不变。器件的起亮电压为3.0伏，器件的最大亮度为69864cd/m2。器件的最大电流效率为63.75cd/A，最大功率效率为66.73lm/W。
实施例4
先将ITO玻璃上的ITO阳极层激光刻蚀成条状电极，然后依次用清洗液、去离子水超声清洗15min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10Pa的氛围下用400V的电压对ITO阳极进行3min的低压等离子处理后将其转移到有机蒸镀室。在真空度为1～2×10-5Pa的有机蒸镀室中，在ITO层上依次蒸镀5nm厚的MoO3阳极修饰层3、30nm厚的TAPC空穴传输-电子阻挡层4、15nm厚Ir(dmpq)3(acac)掺杂mCP的空穴主导发光层5、15nm厚Eu(DBM)3phen与Ir(dmpq)3(acac)共掺杂26DCzPPy的电子主导发光层6和35nm厚的3TPYMB空穴阻挡-电子传输层7。接下来，未完成的器件被转移到金属蒸镀室，在4～6×10-5Pa的真空氛围下蒸镀1.1nm厚的LiF阴极修饰层8，最后通过特制的掩模版在LiF层上蒸镀250nm厚的金属Al阴极层9，制备成结构为ITO/MoO3/TAPC/Ir(dmpq)3(acac)(2％)：mCP/Eu(DBM)3phen(0.1％)：Ir(dmpq)3(acac)(3％)：26DCzPPy/3TPYMB/LiF/Al的有机电致发光器件。阳极修饰层3中MoO3的蒸发速率控制在0.01nm/s，空穴传输-电子阻挡层4中TAPC的蒸发速率控制在0.06nm/s，空穴主导发光层5中Ir(dmpq)3(acac)和mCP的蒸发速率分别控制在0.002nm/s和0.1nm/s，电子主导发光层6中Eu(DBM)3phen、Ir(dmpq)3(acac)和26DCzPPy的蒸发速率分别控制在0.0001nm/s、0.003nm/s和0.1nm/s，空穴阻挡-电子传输层7中3TPYMB的蒸发速率控制在0.08nm/s，阴极修饰层8中LiF的蒸发速率控制在0.01nm/s，金属阴极层9中Al的蒸发速率控制在0.9nm/s。
检测本实施例制备的红色有机电致发光器件的性能，实验结果表明， 器件在直流电源驱动下，发射位于592纳米左右的红光。当亮度为20000cd/m2时，器件的色坐标为(0.588,0.379)；随着工作电压的变化，器件的色坐标几乎不变。器件的起亮电压为3.1伏，器件的最大亮度为64572cd/m2。器件的最大电流效率为60.11cd/A，最大功率效率为60.89lm/W。
实施例5
先将ITO玻璃上的ITO阳极层激光刻蚀成条状电极，然后依次用清洗液、去离子水超声清洗15min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10Pa的氛围下用400V的电压对ITO阳极进行3min的低压等离子处理后将其转移到有机蒸镀室。在真空度为1～2×10-5Pa的有机蒸镀室中，在ITO层上依次蒸镀6nm厚的MoO3阳极修饰层3、50nm厚的TAPC空穴传输-电子阻挡层4、12nm厚Ir(MDQ)2(acac)掺杂TCP的空穴主导发光层5、16nm厚Eu(DBM)3phen与Ir(MDQ)2(acac)共掺杂UGH2的电子主导发光层6和45nm厚的BmPyPhB空穴阻挡-电子传输层7。接下来，未完成的器件被转移到金属蒸镀室，在4～6×10-5Pa的真空氛围下蒸镀1.1nm厚的LiF阴极修饰层8，最后通过特制的掩模版在LiF层上蒸镀240nm厚的金属Al阴极层9，制备成结构为ITO/MoO3/TAPC/Ir(MDQ)2(acac)(3％)：TCP/Eu(DBM)3phen(0.3％)：Ir(MDQ)2(acac)(3％)：UGH2/BmPyPhB/LiF/Al的有机电致发光器件。阳极修饰层3中MoO3的蒸发速率控制在0.01nm/s，空穴传输-电子阻挡层4中TAPC的蒸发速率控制在0.08nm/s，空穴主导发光层5中Ir(MDQ)2(acac)和TCP的蒸发速率分别控制在0.003nm/s和0.1nm/s，电子主导发光层6中Eu(DBM)3phen、Ir(MDQ)2(acac)和UGH2的蒸发速率分别控制在0.0003nm/s、0.003nm/s和0.1nm/s，空穴阻挡-电子传输层7中BmPyPhB的蒸发速率控制在0.09nm/s，阴极修饰层8中LiF的蒸发速率控制在0.012nm/s，金属阴极层9中Al的蒸发速率控制在1.2nm/s。
检测本实施例制备的红色有机电致发光器件的性能，实验结果表明，器件在直流电源驱动下，发射位于592纳米左右的红光。当亮度为20000cd/m2时，器件的色坐标为(0.592,0.378)；随着工作电压的变化，器件的色 坐标几乎不变。器件的起亮电压为3.1伏，器件的最大亮度为60782cd/m2。器件的最大电流效率为62.34cd/A，最大功率效率为63.14lm/W。
实施例6
先将ITO玻璃上的ITO阳极层激光刻蚀成条状电极，然后依次用清洗液、去离子水超声清洗15min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10Pa的氛围下用400V的电压对ITO阳极进行3min的低压等离子处理后将其转移到有机蒸镀室。在真空度为1～2×10-5Pa的有机蒸镀室中，在ITO层上依次蒸镀3nm厚的MoO3阳极修饰层3、40nm厚的TAPC空穴传输-电子阻挡层4、10nm厚Ir(dpm)(piq)2掺杂BSB的空穴主导发光层5、10nm厚Tb(acac)3phen与Ir(dpm)(piq)2共掺杂BCBP的电子主导发光层6和40nm厚的TPBi空穴阻挡-电子传输层7。接下来，未完成的器件被转移到金属蒸镀室，在4～6×10-5Pa的真空氛围下蒸镀1.0nm厚的LiF阴极修饰层8，最后通过特制的掩模版在LiF层上蒸镀120nm厚的金属Al阴极层9，制备成结构为ITO/MoO3/TAPC/Ir(dpm)(piq)2(4％)：BSB/Eu(TTA)3phen(0.3％)：Ir(dpm)(piq)2(4％)：BCBP/TPBi/LiF/Al的有机电致发光器件。阳极修饰层3中MoO3的蒸发速率控制在0.02nm/s，空穴传输-电子阻挡层4中TAPC的蒸发速率控制在0.08nm/s，空穴主导发光层5中Ir(dpm)(piq)2和BSB的蒸发速率分别控制在0.004nm/s和0.1nm/s，电子主导发光层6中Ir(dpm)(piq)2、Eu(TTA)3phen和BCBP的蒸发速率分别控制在0.004nm/s、0.0003nm/s和0.1nm/s，空穴阻挡-电子传输层7中TPBi的蒸发速率控制在0.08nm/s，阴极修饰层8中LiF的蒸发速率控制在0.005nm/s，金属阴极层9中Al的蒸发速率控制在1.5nm/s。
检测本实施例制备的红色有机电致发光器件的性能，实验结果表明，器件在直流电源驱动下，发射位于592纳米左右的红光。当亮度为20000cd/m2时，器件的色坐标为(0.592,0.380)；随着工作电压的变化，器件的色坐标几乎不变。器件的起亮电压为3.0伏，器件的最大亮度为63110cd/m2。器件的最大电流效率为61.71cd/A，最大功率效率为64.59lm/W。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种红色有机电致发光器件，包括：
    衬底；
    复合于所述衬底上的阳极层；
    复合于所述阳极层上的阳极修饰层；
    复合于所述阳极修饰层上的空穴传输-电子阻挡层；
    复合于所述空穴传输-电子阻挡层上的空穴主导发光层；
    复合于所述空穴主导发光层上的电子主导发光层；
    复合于所述电子主导发光层上的空穴阻挡-电子传输层；
    复合于所述空穴阻挡-电子传输层上的阴极修饰层；
    复合于所述阴极修饰层上的阴极层；
    所述电子主导发光层由有机敏化材料、红色有机发光材料与电子型有机主体材料组成；
    所述有机敏化材料选自三(二苯甲酰甲烷)邻菲罗啉合铕和三(噻吩甲酰三氟丙酮)邻菲罗啉合铕中的一种或两种；
    所述有机敏化材料为所述电子型有机主体材料的0.1wt％～0.5wt％。
  2. 根据权利要求1所述的红色有机电致发光器件，其特征在于，所述红色有机发光材料的含量为所述电子型有机主体材料的2wt％～5wt％。
  3. 根据权利要求1或2所述的红色有机电致发光器件，其特征在于，所述红色有机发光材料选自二(2-苯基喹啉)-(2,2,6,6-四甲基-3,5-庚二酮酸)合铱、二(2-苯唑[b]2-噻吩基吡啶)乙酰丙酮合铱、三(1-苯基异喹啉)合铱、二(1-苯基异喹啉)(乙酰丙酮)合铱、二[1-(9,9-二甲基-9H-芴-2-基)-异喹啉](乙酰丙酮)合铱、二[2-(9,9-二甲基-9H-芴-2-基)喹啉](乙酰丙酮)合铱、二(2-苯基喹啉)(2-(3-甲基苯基)吡啶)合铱、三[2-苯基-4-甲基喹啉]合铱、双(苯基异喹啉)(2,2,6,6-四甲基己烷-3，5-二酮)合铱、二(2-甲基二苯唑[f,h]喹喔啉)(乙酰丙酮)合铱和二[2-(2-甲基苯基)-7-甲基-喹啉](乙酰丙酮)合铱中的一种或多种。
  4. 根据权利要求1所述的红色有机电致发光器件，其特征在于，所 述电子型有机主体材料选自2,6-二[3-(9H-9-咔唑基)苯基]吡啶、1,4-双(三苯基硅烷基)苯、2,2’-双(4-(9-咔唑基)苯基)联苯、[2,4,6-三甲基-3-(3-吡啶基)苯基]硼烷、1，3，5-三[(3-吡啶)-3-苯基]苯、1,3-双[3,5-二(3-吡啶基)苯基]苯、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯、9-(4-特丁基苯基)-3,6-双(三苯基硅基)-9H-咔唑和9-(8-二苯基磷酰基)-二苯唑[b,d]呋喃-9H-咔唑中的一种或多种。
  5. 根据权利要求1所述的红色有机电致发光器件，其特征在于，所述空穴主导发光层由红色有机发光材料和空穴型有机主体材料组成；所述红色有机发光材料为所述空穴型有机主体材料的2.0wt％～5.0wt％；
    所述红色有机发光材料选自二(2-苯基喹啉)-(2,2,6,6-四甲基-3,5-庚二酮酸)合铱、二(2-苯唑[b]2-噻吩基吡啶)乙酰丙酮合铱、三(1-苯基异喹啉)合铱、二(1-苯基异喹啉)(乙酰丙酮)合铱、二[1-(9,9-二甲基-9H-芴-2-基)-异喹啉](乙酰丙酮)合铱、二[2-(9,9-二甲基-9H-芴-2-基)喹啉](乙酰丙酮)合铱、二(2-苯基喹啉)(2-(3-甲基苯基)吡啶)合铱、三[2-苯基-4-甲基喹啉]合铱、双(苯基异喹啉)(2,2,6,6-四甲基己烷-3，5-二酮)合铱、二(2-甲基二苯唑[f,h]喹喔啉)(乙酰丙酮)合铱和二[2-(2-甲基苯基)-7-甲基-喹啉](乙酰丙酮)合铱中的一种或多种；
    所述空穴型有机主体材料选自4，4’-N，N’-二咔唑二苯基、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)三苯胺和1,4-双(三苯基硅烷基)联苯中的一种或多种。
  6. 根据权利要求1所述的红色有机电致发光器件，其特征在于，所述空穴传输-电子阻挡层的材料选自4,4′-环己基二[N,N-二(4-甲基苯基)苯胺]、二吡嗪[2，3-f:2’,3’-h]喹喔啉-2，3，6，7，10，11-六腈基、N4,N4′-二(萘-1-基)-N4,N4′-双(4-乙烯基苯基)联苯-4,4′-二胺、N,N′-双(3-甲基苯基)-N,N′-双(苯基)-2，7-二胺-9，9-螺双芴、N,N,N′,N′-四-(3-甲基苯基)-3-3’-二甲基对二氨基联苯、2,2′-二(3-(N,N-二-对甲苯氨基)苯基)联苯、N,N′-二(萘-2-基)-N,N′-二(苯基)二氨基联苯、N,N′-二(萘-1基)-N,N′–二苯基-2，7-二氨基-9，9-螺双芴、N,N′-二(3-甲基苯 基)-N,N′-二苯基-2,7-二氨基-9，9-二甲基芴、N,N′-二(萘-1-基)-N,N′-二苯基-2，7-二氨基-9，9-二甲基芴、N,N′–二(3-甲基苯基)-N,N′–二苯基-2，7-二氨基-9，9-二苯基芴、N,N′-二(萘-1-基)-N,N′-二苯基-2,7-二氨基-9,9-二苯基芴、N,N′-二(萘-1-基)-N,N′-二苯基-2,2’-二甲基二氨基联苯、2,2′,7,7′-四(N,N-二苯基氨基)-2,7-二氨基-9,9-螺双芴、9,9-二[4-(N,N–二萘-2-基-氨基)苯基]-9H-芴、9，9-[4-(N-萘-1基-N-苯胺)-苯基]-9H-芴、2，2’-二[N,N-二(4-苯基)氨基]-9,9-螺双芴、2,2’-双(N,N-苯氨基)-9,9-螺双芴、N,N’-二苯基-N,N’-(1-萘基)-1，1’-联苯-4，4’-二胺和4，4’-二[N-(对-甲苯基)-N-苯基-氨基]二苯基中的一种或多种。
  7. 根据权利要求1所述的红色有机电致发光器件，其特征在于，所述空穴阻挡-电子传输层的材料选自三[2,4,6-三甲基-3-(3-吡啶基)苯基]硼烷、1，3，5-三[(3-吡啶)-3-苯基]苯、1,3-双[3,5-二(3-吡啶基)苯基]苯和的1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯中的一种或多种。
  8. 根据权利要求1所述的红色有机电致发光器件，其特征在于，所述阳极修饰层的厚度为1～10nm，所述空穴传输-电子阻挡层的厚度为30～60nm，所述空穴主导发光层的厚度为5～20nm，所述电子主导发光层的厚度为5～20nm，所述空穴阻挡-电子传输层的厚度为30～60nm，所述阴极修饰层的厚度为0.8～1.2nm，所述阴极层的厚度为90～300nm。
  9. 一种红色有机电致发光器件的制备方法，包括：
    将衬底上的阳极层进行刻蚀，烘干后在所述阳极层上依次蒸镀阳极修饰层、空穴传输-电子阻挡层、空穴主导发光层、电子主导发光层、空穴阻挡-电子传输层、阴极修饰层与阴极层；
    所述电子主导发光层由有机敏化材料、红色有机发光材料与电子型有机主体材料组成；
    所述有机敏化材料选自三(二苯甲酰甲烷)邻菲罗啉合铕和三(噻吩甲酰三氟丙酮)邻菲罗啉合铕中的一种或两种；
    所述有机敏化材料为所述电子型有机主体材料的0.1wt％～0.5wt％。
  10. 根据权利要求9所述的制备方法，其特征在于，所述阳极修饰层的蒸发速率为0.01～0.05nm/s，所述空穴传输-电子阻挡层、空穴主导发光 层、电子主导发光层与空穴阻挡-电子传输层中主体材料的蒸发速率为0.05～0.1nm/s，所述电子主导发光层中的有机敏化材料的蒸发速率为0.00005～0.0005nm/s，所述电子主导发光层与空穴主导发光层中的红色发光材料的蒸发速率为0.001～0.005nm/s，所述阴极修饰层的蒸发速率为0.005～0.05nm/s，所述阴极层的蒸发速率为0.5～2.0nm/s。
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