WO2018129922A1 - 白色有机电致发光器件及其制备方法 - Google Patents

白色有机电致发光器件及其制备方法 Download PDF

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WO2018129922A1
WO2018129922A1 PCT/CN2017/098010 CN2017098010W WO2018129922A1 WO 2018129922 A1 WO2018129922 A1 WO 2018129922A1 CN 2017098010 W CN2017098010 W CN 2017098010W WO 2018129922 A1 WO2018129922 A1 WO 2018129922A1
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organic
layer
mass
energy
fluorescent material
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周亮
张洪杰
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Priority to EP17891345.5A priority patent/EP3570341B1/en
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Definitions

  • the invention belongs to the field of organic electroluminescence technology, and in particular relates to a white 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.
  • organic electroluminescence technology has attracted extensive attention and active participation in the scientific and industrial circles, and the performance of organic electroluminescent devices has been rapidly developed in the past ten years.
  • white organic electroluminescent devices have become a research hotspot due to their application prospects in full color display and high-end lighting.
  • transition metal complexes are considered 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 white organic electroluminescent devices in order to meet the needs of industrialization.
  • white organic electroluminescent devices based on transition metal complexes are often accompanied by lower operating life, lower color stability, or higher fabrication costs. Therefore, more and more research teams tend to use fluorescent materials instead of transition metal complexes to obtain fully fluorescent white organic electroluminescent devices.
  • fluorescent materials generally have lower luminous efficiency; in addition, the conductivity and thermal stability of fluorescent materials are generally poor, eventually resulting in imbalance of carrier injection, transport and distribution, thus resulting in a white fluorescent device having Lower luminous efficiency, higher Operating voltage and low operating stability.
  • the technical problem to be solved by the present invention is to provide a white 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 white organic electroluminescent device comprising:
  • An anode layer disposed on the substrate
  • a first luminescent layer disposed on the anode layer; the first luminescent layer being formed of a red organic fluorescent material, a first organic energy sensitizing material, and a first hole type organic host material; the red organic fluorescent material
  • the mass is 0.1% to 1.0% of the mass of the first hole type organic host material; the mass of the first organic energy sensitizing material is 8.0% to 25.0% of the mass of the first hole type organic host material;
  • the organic energy sensitizing material is a blue organic fluorescent material with energy level matching;
  • the second luminescent layer disposed on the first luminescent layer; the second luminescent layer being formed of a green organic fluorescent material, a second organic energy sensitizing material, and a second hole type organic host material; the green organic fluorescent
  • the mass of the material is 0.1% to 2.0% of the mass of the second hole type organic host material; the mass of the second organic energy sensitizing material is 8.0% to 25.0% of the mass of the second hole type organic host material;
  • Second The organic energy sensitizing material is a blue organic fluorescent material with energy level matching;
  • the red organic fluorescent material is rubrene and/or 4-dicyanomethyl-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidine-4 -vinyl)-4H-pyran;
  • the green organic fluorescent material is N,N'-dimethyl-quinacridone and/or 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H-10-(2-benzothiazolyl)-quinolizolo[9,9A,1GH]coumarin.
  • the first organic energy sensitizing material and the second organic energy sensitizing material are 2,2'-(9,10-fluorenyldi-4,1-phenylene)bis[6-methyl -benzothiazole].
  • the first hole type organic host material and the second hole type organic host material are each independently 4,4'-bis(9-carbazolyl)biphenyl, 1,3-dicarbazole- 9-ylbenzene, 9,9'-(5-(triphenylsilyl)-1,3-phenyl)di-9H-carbazole, 1,3,5-tris(9-oxazolyl)benzene
  • the first luminescent layer has a thickness of 5 to 10 nm; and the second luminescent layer has a thickness of 2 to 5 nm.
  • an anode interface layer is further disposed between the anode layer and the first light-emitting layer; the anode interface layer has a thickness of 2-10 nm.
  • a hole transport layer or an electron block layer is further disposed between the anode layer and the first light-emitting layer; and the hole transport layer or the electron block layer has a thickness of 40-60 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 second light emitting layer and the cathode layer; and the hole blocking layer or the electron transport 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 white organic electroluminescent device, comprising the following steps:
  • the first luminescent layer is formed of a red organic fluorescent material, a first organic energy sensitizing material, and a first hole type organic host material; a quality of the red organic fluorescent material Is a mass of the first hole type organic host material: 0.1% to 1.0%; the mass of the first organic energy sensitizing material is 8.0% to 25.0% of the mass of the first hole type organic host material;
  • the energy sensitizing material is a blue organic fluorescent material with energy level matching;
  • the second luminescent layer is composed of a green organic fluorescent material
  • the second organic energy sensitizing material is formed with the second hole type organic host material; the mass of the green organic fluorescent material is 0.2% to 2.0% of the mass of the second hole type organic host material; The mass of the energy sensitizing material is 8.0% to 25.0% of the mass of the second hole type organic host material; the second organic energy sensitizing material is a blue organic fluorescent material with energy level matching;
  • a cathode is formed on the second light-emitting layer to obtain a white organic electroluminescent device.
  • the present invention provides a white organic electroluminescent device comprising: a substrate; an anode layer disposed on the substrate; a first light emitting layer disposed on the anode layer; the first light emitting layer being red
  • the organic fluorescent material, the first organic energy sensitizing material is formed with the first hole type organic host material; the mass of the red organic fluorescent material is 0.1% to 1.0% of the mass of the first hole type organic host material; The mass of the organic energy sensitizing material is 8.0% to 25.0% of the mass of the first hole type organic host material; the first organic energy sensitizing material is an energy level matching blue organic fluorescent material; a second luminescent layer on the first luminescent layer; the second luminescent layer is formed of a green organic fluorescent material, a second organic energy sensitizing material and a second hole type organic host material; the quality of the green organic fluorescent material is 0.2% to 2.0% by mass of the second hole type organic host material; the second organic energy sensitizing material has a mass of 8.0% to 25.0% of the mass of the second
  • the invention adopts a blue organic fluorescent material as a luminescent material and an energy sensitizing material, and can effectively transfer photon energy to a red organic fluorescent material or a green organic fluorescent material, and the blue organic fluorescent material also has Superior electron transport capability, high doping concentration in the light-emitting layer, can function as an electronic host material, is beneficial to balance the distribution of holes and electrons in the light-emitting interval, and can also limit the recombination of holes and electrons to light.
  • the narrow region of the layer can effectively balance the distribution of carriers in the light-emitting layer; in addition, the device provided by the invention has simple structure, low cost, and good thermal stability of the material, which is beneficial to improving the life of the device.
  • FIG. 1 is a schematic structural view of a white organic electroluminescent device provided by the present invention.
  • Example 2 is a graph showing voltage-current density-luminance characteristics of a white 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's starting voltage 3.3 volts, at a voltage of 10.9 volts and a current density of 557.86 milliamps per square centimeter (mA/cm 2 ), the device achieves a maximum brightness of 11315 candelas per square meter (cd/m 2 );
  • Example 3 is a current density-power efficiency of a white organic electroluminescent device obtained in Example 1 of the present invention. Rate-current efficiency characteristic graph; the maximum current efficiency of the device is 13.17 candelas per amp (cd/A), and the maximum power efficiency is 11.82 lumens per watt (lm/W);
  • Example 4 is a spectrum diagram of a white 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 (0.366, 0.413);
  • Example 5 is a graph showing voltage-current density-luminance characteristics of a white 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's starting voltage 3.2 V, at a voltage of 10.2 V and a current density 559.44mA / cm 2 the device for maximum brightness 8738cd / m 2;
  • Example 6 is a graph showing current density-power efficiency-current efficiency characteristics of a white organic electroluminescent device obtained in Example 2 of the present invention; the maximum current efficiency of the device was 12.80 cd/A, and the maximum power efficiency was 11.80 lm/W.
  • the present invention provides a white organic electroluminescent device comprising:
  • An anode layer disposed on the substrate
  • a first luminescent layer disposed on the anode layer; the first luminescent layer being formed of a red organic fluorescent material, a first organic energy sensitizing material, and a first hole type organic host material; the red organic fluorescent material
  • the mass is 0.1% to 1.0% of the mass of the first hole type organic host material; the mass of the first organic energy sensitizing material is 8.0% to 25.0% of the mass of the first hole type organic host material;
  • the organic energy sensitizing material is a blue organic fluorescent material with energy level matching;
  • the second luminescent layer disposed on the first luminescent layer; the second luminescent layer being formed of a green organic fluorescent material, a second organic energy sensitizing material, and a second hole type organic host material; the green organic fluorescent
  • the mass of the material is 0.2% to 2.0% of the mass of the second hole type organic host material; the mass of the second organic energy sensitizing material is 8.0% to 25.0% of the mass of the second hole type organic host material;
  • the second organic energy sensitizing material is a blue organic fluorescent material with energy level matching;
  • 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 50 to 60 nm, still more preferably 50 nm; and the hole transport layer or electron blocking layer is a hole transport layer or an electron blocking layer which is well known to those skilled in the art.
  • the present invention preferably consists of 4,4'-cyclohexyl bis[N,N-bis(4-methylphenyl)aniline] (abbreviated as TAPC), 4,4'-two [N- (p-tolyl)-N-phenyl-amino]diphenyl (TPD for short) and N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-di Forming one or more of phenyl-4,4'-diamine (abbreviated as NPB), the molecular structural formula is as follows:
  • a first light emitting layer is disposed on the hole transport layer or the electron blocking layer; the first light emitting layer is formed of a red organic fluorescent material, a first organic energy sensitizing material and a first hole type organic host material;
  • the thickness of the first light-emitting layer is preferably 5 to 10 nm, more preferably 7 to 10 nm; and the mass of the red organic fluorescent material is 0.1% to 1.0%, preferably 0.1%, of the mass of the first hole-type organic host material.
  • the red organic fluorescent material may be a red organic fluorescent material well known to those skilled in the art, and is not particularly limited, in the present invention Preferred is rubrene (Rubrene, formula I) and/or 4-dicyanomethyl-2-tert-butyl-6-(1,1,7,7-tetramethyljuronidine) -4-vinyl)-4H-pyran (abbreviated as DCJTB, the molecular formula is as shown in formula II);
  • the mass of the first organic energy sensitizing material is 8.0% to 25.0% of the mass of the first hole type organic host material Preferably, it is 10.0% to 25.0%, more preferably 15.0% to 20.0%, still more preferably 16.0% to 18.0%;
  • the first organic energy sensitizing material is an energy level matching blue organic fluorescent material, which is The blue organic fluorescent material well known to those skilled in the art is not particularly limited as long as the energy and energy levels are matched.
  • the organic energy sensitizing material with energy and energy level can effectively transfer photon energy to green and red organic fluorescent materials, and has superior electron transport capability.
  • a basic principle of energy matching is: from the host material to the sensitizing material, and then from the sensitizing material to the luminescent material, the energy can be effectively transmitted, which requires the excited state energy of the host material > the excited state energy of the sensitized material > The excited state energy of the luminescent material;
  • a basic principle of energy level matching is that the bulk material has a wide energy gap and can effectively include the energy gap of the luminescent material to facilitate carrier trapping.
  • the energy level of the sensitizing material in the present invention should be favorable for the electron injection into the light-emitting interval and at the same time function as an electron-type auxiliary host material. Therefore, in the present invention, the first organic energy-sensitizing material is preferably 2, 2'- (9,10-decanediyldi-4-,1-phenylene)bis[6-methyl-benzothiazole] (DBzA for short, the formula is as shown in formula III). DBzA has high luminous efficiency and color purity, good thermal stability, and the function of energy sensitizing material, which can effectively transfer photon energy to red organic light-emitting material Rubrene, DCJTB or green organic light-emitting materials C545T and DMQA.
  • DBzA 2, 2'- (9,10-decanediyldi-4-,1-phenylene)bis[6-methyl-benzothiazole]
  • the first hole organic host material is not limited to the hole organic host material well known to those skilled in the art, and is preferably 4,4'-bis(9-carbazolyl)biphenyl in the present invention.
  • CBP the molecular formula is shown in formula IV
  • mCP 1,3-dioxazole-9-ylbenzene
  • mCP 1,3-dioxazole-9-ylbenzene
  • TCP 1,3,5-tris(9-carbazolyl)benzene
  • TcTa 4,4'-bis(triphenylsilyl)biphenyl
  • BSB 4,4'-bis(triphenylsilyl)biphenyl
  • a second light emitting layer is disposed on the first light emitting layer; the thickness of the second light emitting layer is preferably 2 to 5 nm, more preferably 2 to 4 nm, still more preferably 2 to 3 nm; and the second light emitting layer is made of green Organic fluorescent material
  • the second organic energy sensitizing material is formed with the second hole type organic host material; the green organic fluorescent material has a mass of 0.1% to 2.0%, preferably 0.1% by mass of the second hole type organic host material. 1.5%, more preferably 0.1% to 1.0%, still more preferably 0.1% to 0.5%, and most preferably 0.1% to 0.2%; the green organic fluorescent material may be a green organic fluorescent material well known to those skilled in the art.
  • N,N'-dimethyl-quinacridone ablecular formula is represented by Formula X
  • Formula X 2,3,6,7-tetrahydro-1, 1,7,7-tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)-quinazo[9,9A,1GH]coumarin
  • C545T for short, the formula is as shown in formula XI
  • the mass of the second organic energy sensitizing material is 8.0% to 25.0%, preferably 10.0% to 25.0%, more preferably 15.0% to 20.0%, and still more preferably the mass of the second hole type organic host material.
  • the second organic energy sensitizing material is a blue organic fluorescent material with energy level matching, which can be a blue organic fluorescent material well known to those skilled in the art. There are no special restrictions, as long as the energy and energy levels match.
  • DBzA 2,2'-(9,10-fluorenyldi-4,1-phenylene)bis[6-methyl-benzothiazole]
  • DBzA 2,2'-(9,10-fluorenyldi-4,1-phenylene)bis[6-methyl-benzothiazole]
  • Blue organic fluorescent material DBzA has high luminous efficiency and color purity, good thermal stability, and has the function of energy sensitizing material, which can effectively transfer photon energy to red organic fluorescent material or green organic fluorescent material; blue
  • the color organic fluorescent material DBzA has excellent electron transporting ability, and its doping concentration is large and has the function of an electronic host material, which can effectively balance the distribution of carriers in the light emitting layer.
  • the second hole organic host material is not limited to the hole organic host material well known to those skilled in the art, and is preferably 4,4'-bis(9-carbazolyl)biphenyl in the present invention.
  • CBP 1,3-dioxazole-9-ylbenzene
  • mCP 1,3-dioxazole-9-ylbenzene
  • mCP 9,9'-(5-(triphenylsilyl) )-1,3-phenyl)di-9H-carbazole
  • TCP 1,3,5-tris(9-carbazolyl)benzene
  • TcTa 4,4'-bis(triphenylsilyl)biphenyl
  • BSB 4,4'-bis(triphenylsilyl)biphenyl
  • the second luminescent layer is preferably further provided with a hole blocking layer or an electron transport layer;
  • the thickness of the layer or electron transport layer is preferably 40 to 60 nm, more preferably 45 to 55 nm. Further preferably, it is 50 nm; the hole blocking layer or the electron transporting layer may be a hole blocking layer or an electron transporting layer which is well known to those skilled in the art, and is not particularly limited.
  • the present invention is preferably three [2, 4, 6-trimethyl-3-(3-pyridyl)phenyl]borane (abbreviated as 3TPYMB), 1,3,5-tris[(3-pyridyl)-3-phenyl]benzene (abbreviated as TmPyPB), 1 , 3-bis[3,5-bis(3-pyridyl)phenyl]benzene (abbreviated as BmPyPhB), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene ( One or more of TPBi) and 1,3,5-tris ⁇ 6-[3-(pyridin-3-yl)phenyl]pyridin-2-yl ⁇ benzene (Tm3PyP26PyB for short), the molecular formula is XII, XIII, XIV, XV and XVI are shown.
  • 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.
  • the buffer layer is provided with a cathode layer; the cathode layer preferably has a thickness of 90 to 150 nm, more preferably 100 to 140 nm, still more preferably 110 to 130 nm, and most preferably 120 nm; and the cathode layer is a person skilled in the art.
  • the well-known cathode layer is not particularly limited, and is preferably formed of metal aluminum, magnesium silver alloy or silver in the present invention.
  • FIG. 1 The schematic diagram of the structure of the white 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 a A light-emitting layer, 6 is a second light-emitting layer, 7 is a hole blocking layer/electron transport layer, 8 is a buffer layer, and 9 is a cathode layer.
  • the white organic electroluminescent device has an anode and a cathode interdigitated to form a light-emitting region thereof, and when a forward voltage is applied between the two electrodes, the device emits white light covering 410 to 650 nm.
  • the invention adopts a blue organic fluorescent material as a luminescent material and an energy sensitizing material, and can effectively transfer photon energy to a red organic fluorescent material or a green organic fluorescent material, and the blue organic fluorescent material also has superior electron transporting ability, and emits light.
  • the doping concentration in the layer is high, which can function as an electron-type host material, which is advantageous for balancing the distribution of holes and electrons in the light-emitting interval, and also capable of confining the combination of holes and electrons in a narrow region of the light-emitting layer, which is effective.
  • the distribution of the carriers in the luminescent layer is balanced; in addition, the device provided by the invention has a simple structure, a low cost, and the materials have good thermal stability, which is beneficial to improving the life of the device.
  • the invention also provides a preparation method of the above white organic electroluminescent device, comprising the following steps Step:
  • the first luminescent layer is formed of a red organic fluorescent material, a first organic energy sensitizing material, and a first hole type organic host material; a quality of the red organic fluorescent material Is a mass of the first hole type organic host material: 0.1% to 1.0%; the mass of the first organic energy sensitizing material is 8.0% to 25.0% of the mass of the first hole type organic host material;
  • the energy sensitizing material is a blue organic fluorescent material with energy level matching;
  • the second luminescent layer is formed of a green organic fluorescent material, a second organic energy sensitizing material, and a second hole type organic host material; the green organic fluorescent material
  • the mass of the second hole type organic host material is 0.2% to 2.0%; the mass of the second organic energy sensitizing material is 8.0% to 25.0% of the mass of the second hole type organic host material;
  • the second organic energy sensitizing material is a blue organic fluorescent material with energy level matching;
  • a cathode is formed on the second light-emitting layer to obtain a white 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 first luminescent layer is formed on the hole transport layer or the electron blocking layer; the first luminescent 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 red organic fluorescent material in vacuum evaporation is preferably 0.00005 to 0.001 nm/s; the evaporation rate of the first organic sensitizing energy material is preferably 0.004 to 0.025 nm/s; the first hole type organic host material
  • the evaporation rate is preferably from 0.05 to 0.1 nm/s.
  • the red organic fluorescent material, the first organic sensitizing energy material and the first hole type organic host material in the organic mixed material are simultaneously evaporated in different evaporation sources, and the quality of the red organic fluorescent material is controlled by regulating the evaporation rate of the three materials.
  • the mass of the first organic energy sensitizing material is 8.0% to 25.0% of the mass of the first hole type organic host material, which is 0.1% to 1.0% by mass of the first hole type organic host material.
  • a second luminescent layer is formed on the first luminescent layer; the second luminescent layer is the same as described above, and details are not described herein again.
  • 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 green organic fluorescent material in the vacuum evaporation is preferably 0.0001 to 0.002 nm/s; the evaporation rate of the second organic sensitizing energy material is preferably 0.004 to 0.025 nm/s; the second hole type organic body
  • the evaporation rate of the material is preferably from 0.05 to 0.1 nm/s.
  • the green organic fluorescent material, the second organic sensitizing energy material and the second hole type organic host material in the organic mixed material are simultaneously evaporated in different evaporation sources, and the quality of the green organic fluorescent material is controlled by regulating the evaporation rate of the three materials. It is 0.1% to 2.0% by mass of the second hole type organic host material, and the mass of the second organic energy sensitizing material is 8.0% to 25.0% of the mass of the second hole type organic host material.
  • a hole blocking layer or an electron transport layer is preferably formed on the second light-emitting layer; the hole blocking layer or the electron transport layer is the same as described above, and is not described herein again;
  • the method which is well known to the person is not particularly limited, 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 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 white 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 white organic electroluminescent device provided by the invention has a simple structure and is advantageous for simplifying the preparation of the device.
  • the various functional materials selected generally have a relatively low price, which is beneficial to reduce the manufacturing cost of the device; and the selected materials have good thermal stability, which is beneficial to improve the life of the device.
  • 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 spectral stability 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.
  • Electron barrier layer 4 8 nm thick DCJTB, DBzA doped TcTa first luminescent layer 5, 2 nm thick C545T, DBzA doped TcTa second luminescent layer 6, 50 nm thick Tm3PyP26PyB hole blocking layer/electron transport layer 7.
  • a 120 nm thick metal Al electrode was prepared to have a structure of ITO/MoO 3 /TAPC/DCJTB (0.1%): DBzA (16 wt%): TcTa/C545T (0.2%): DBzA (20 wt%): TcTa/Tm3PyP26PyB/LiF /Al white organic electroluminescent device.
  • the evaporation rates of DCJTB, DBzA and TcTa in the first luminescent layer 5 are controlled at 0.00005 nm/sec, 0.008 nm/sec and 0.05 nm/sec, and the evaporation rates of C545T, DBzA and TcTa in the second luminescent layer 6 are controlled at 0.0001 nm/ Seconds, 0.01 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and Tm3PyP26PyB is controlled at 0.05 nm/sec, the evaporation rate of MoO 3 is controlled at 0.01 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec. The evaporation rate was controlled at 0.5 nm/sec.
  • the white organic electroluminescent device obtained in Example 1 was driven by a direct current voltage to display a white light emission covering from 410 nm to 650 nm; as the operating voltage was changed, the color coordinates of the device were stabilized from (0.307, 0.316) to ( Within the range of 0.425, 0.454). When the luminance was 1000 cd/m 2 , the color coordinates of the device were (0.366, 0.413).
  • Example 2 is a graph showing the voltage-current density-luminance characteristic of the white organic electroluminescent device obtained in Example 1. As shown in FIG. 2, the device has a starting voltage of 3.3 V, a voltage of 10.9 volts, and a current density of 557.86 mA. At /m 2 , the maximum brightness of the device is 11315 cd/m 2 .
  • FIG. 3 is a graph showing current density-power efficiency-current efficiency characteristics of the white organic electroluminescent device obtained in Example 1.
  • FIG. 3 the maximum current efficiency of the device is 13.17 cd/A, and the maximum power efficiency is 11.82 lm/W.
  • Example 4 is a spectrum diagram of a white organic electroluminescent device obtained in Example 1 at a luminance of 1000 cd/m 2 . As can be seen from Fig. 4, the color coordinates of the device are (0.366, 0.413).
  • 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 under a vacuum atmosphere of 3-5 ⁇ 10 -5 Pa.
  • a 120 nm thick metal Al electrode was prepared to have a structure of ITO/MoO 3 /TAPC/DCJTB (0.2%): DBzA (16 wt%): TcTa/C545T (0.1%): DBzA (20 wt%): TcTa/Tm3PyP26PyB/LiF /Al white organic electroluminescent device.
  • the evaporation rates of DCJTB, DBzA and TcTa in the first luminescent layer 5 are controlled at 0.00005 nm/sec, 0.008 nm/sec and 0.05 nm/sec, and the evaporation rates of C545T, DBzA and TcTa in the second luminescent layer 6 are controlled at 0.00005 nm/ Seconds, 0.01 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and Tm3PyP26PyB is controlled at 0.05 nm/sec, the evaporation rate of MoO 3 is controlled at 0.01 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec. The evaporation rate was controlled at 0.5 nm/sec.
  • the white organic electroluminescent device obtained in Example 2 was shown to cover white light emission from 410 nm to 650 nm under DC voltage driving; the color coordinate of the device was stable from (0.285, 0.301) to (as the operating voltage was changed). Within the range of 0.409, 0.413). When the luminance is 1000 cd/m 2 , the color coordinates of the device are (0.323, 0.365).
  • Example 5 is a graph showing voltage-current density-luminance characteristics of the white organic electroluminescent device obtained in Example 2. It can be seen from FIG. 5 that the luminance of the device increases as the current density and the driving voltage increase, and the device starts from The bright voltage was 3.2 V, and the maximum brightness of the device was 8738 cd/m 2 at a voltage of 10.2 V and a current density of 559.44 mA/m 2 .
  • Fig. 6 is a graph showing current density-power efficiency-current efficiency characteristics of the white organic electroluminescent device obtained in Example 2. As can be seen from Fig. 6, the maximum current efficiency of the device is 12.80 cd/A, and the maximum power efficiency is 11.80 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.
  • Electron barrier layer 4 8 nm thick DCJTB, DBzA doped TcTa first luminescent layer 5, 2 nm thick C545T, DBzA doped TcTa second luminescent layer 6, 50 nm thick Tm3PyP26PyB hole blocking layer/electron transport layer 7.
  • a 120 nm thick metal Al electrode was prepared to have a structure of ITO/MoO 3 /TAPC/DCJTB (0.1%): DBzA (18 wt%): TcTa/C545T (0.2%): DBzA (18 wt%): TcTa/Tm3PyP26PyB/LiF /Al white organic electroluminescent device.
  • the evaporation rates of DCJTB, DBzA, and TcTa in the first luminescent layer 5 are controlled at 0.00005 nm/sec, 0.009 nm/sec, and 0.05 nm/sec, and the evaporation rates of C545T, DBzA, and TcTa in the second luminescent layer 6 are controlled at 0.0001 nm/ Seconds, 0.009 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and Tm3PyP26PyB is controlled at 0.05 nm/sec, the evaporation rate of MoO 3 is controlled at 0.01 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec. The evaporation rate was controlled at 0.5 nm/sec.
  • the white organic electroluminescent device obtained in Example 3 was shown to cover white light emission from 410 nm to 650 nm under DC voltage driving; as the operating voltage was changed, the color coordinate of the device was stable from (0.303, 0.319) to ( Within the range of 0.432, 0.461).
  • the luminance is 1000 cd/m 2
  • the color coordinates of the device are (0.358, 0.411).
  • the device's starting voltage is 3.3V and the maximum brightness of the device is 11002cd/m 2 .
  • the device has a maximum current efficiency of 12.27 cd/A and a maximum power efficiency of 11.16 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 under a vacuum atmosphere of 3-5 ⁇ 10 -5 Pa.
  • Electron barrier layer 4 10 nm thick DCJTB, DBzA doped TcTa first luminescent layer 5, 2 nm thick C545T, DBzA doped TcTa second luminescent layer 6, 50 nm thick Tm3PyP26PyB hole blocking layer/electron transport layer 7.
  • a 120 nm thick metal Al electrode was prepared to have a structure of ITO/MoO 3 /TAPC/DCJTB (0.1%): DBzA (16 wt%): TcTa/C545T (0.2%): DBzA (20 wt%): TcTa/Tm3PyP26PyB/LiF /Al white organic electroluminescent device.
  • the evaporation rates of DCJTB, DBzA and TcTa in the first luminescent layer 5 are controlled at 0.00005 nm/sec, 0.008 nm/sec and 0.05 nm/sec, and the evaporation rates of C545T, DBzA and TcTa in the second luminescent layer 6 are controlled at 0.0001 nm/ Seconds, 0.01 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and Tm3PyP26PyB is controlled at 0.05 nm/sec, the evaporation rate of MoO 3 is controlled at 0.01 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec. The evaporation rate was controlled at 0.5 nm/sec.
  • the white organic electroluminescent device obtained in Example 4 was shown to cover white light emission from 410 nm to 650 nm under DC voltage driving; the color coordinate of the device was stable from (0.315, 0.322) to (as the operating voltage was changed). Within the range of 0.440, 0.462). When the luminance was 1000 cd/m 2 , the color coordinates of the device were (0.369, 0.421). The device's starting voltage is 3.3V and the maximum brightness of the device is 11996cd/m 2 . The device has a maximum current efficiency of 13.35 cd/A and a maximum power efficiency of 12.17 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 under a vacuum atmosphere of 3-5 ⁇ 10 -5 Pa.
  • Electron barrier layer 4 8 nm thick DCJTB, DBzA doped TcTa first luminescent layer 5, 3 nm thick C545T, DBzA doped TcTa second luminescent layer 6, 50 nm thick Tm3PyP26PyB hole blocking layer/electron transport layer 7.
  • a 120 nm thick metal Al electrode was prepared to have a structure of ITO/MoO 3 /TAPC/DCJTB (0.1%): DBzA (18 wt%): TcTa/C545T (0.2%): DBzA (18 wt%): TcTa/Tm3PyP26PyB/LiF /Al white organic electroluminescent device.
  • the evaporation rates of DCJTB, DBzA, and TcTa in the first luminescent layer 5 are controlled at 0.00005 nm/sec, 0.009 nm/sec, and 0.05 nm/sec, and the evaporation rates of C545T, DBzA, and TcTa in the second luminescent layer 6 are controlled at 0.0001 nm/ Seconds, 0.009 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and Tm3PyP26PyB is controlled at 0.05 nm/sec, the evaporation rate of MoO 3 is controlled at 0.01 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec. The evaporation rate was controlled at 0.5 nm/sec.
  • the white organic electroluminescent device obtained in Example 5 was shown to cover white light emission from 410 nm to 650 nm under DC voltage driving; the color coordinate of the device stabilized from (0.311, 0.318) to (as the operating voltage changes). Within the range of 0.433, 0.465). When the luminance was 1000 cd/m 2 , the color coordinates of the device were (0.349, 0.421). The device's starting voltage is 3.2V and the maximum brightness of the device is 12618cd/m 2 . The device has a maximum current efficiency of 12.78 cd/A and a maximum power efficiency of 11.45 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 under a vacuum atmosphere of 3-5 ⁇ 10 -5 Pa.
  • Electron barrier layer 4 10 nm thick DCJTB, DBzA doped TcTa first luminescent layer 5, 2 nm thick C545T, DBzA doped TcTa second luminescent layer 6, 50 nm thick Tm3PyP26PyB hole blocking layer/electron transport layer 7.
  • a 120 nm thick metal Al electrode was prepared to have a structure of ITO/MoO 3 /TAPC/DCJTB (0.1%): DBzA (18 wt%): TcTa/C545T (0.2%): DBzA (20 wt%): TcTa/Tm3PyP26PyB/ A white organic electroluminescent device of LiF/Al.
  • the evaporation rates of DCJTB, DBzA and TcTa in the first luminescent layer 5 are controlled at 0.00005 nm/sec, 0.008 nm/sec and 0.05 nm/sec, and the evaporation rates of C545T, DBzA and TcTa in the second luminescent layer 6 are controlled at 0.0001 nm/ Seconds, 0.01 nm/sec and 0.05 nm/sec, the evaporation rate of TAPC and Tm3PyP26PyB is controlled at 0.05 nm/sec, the evaporation rate of MoO 3 is controlled at 0.01 nm/sec, and the evaporation rate of LiF is controlled at 0.005 nm/sec. The evaporation rate was controlled at 0.5 nm/sec.
  • the white organic electroluminescent device obtained in Example 6 was shown to cover white light emission from 410 nm to 650 nm under DC voltage driving; the color coordinate of the device was stable from (0.316, 0.334) to (as the operating voltage was changed). Within the range of 0.455, 0.465). When the luminance is 1000 cd/m 2 , the color coordinates of the device are (0.377, 0.432). The device's starting voltage is 3.3V and the maximum brightness of the device is 12963cd/m 2 . The device has a maximum current efficiency of 13.02 cd/A and a maximum power efficiency of 11.70 lm/W.

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Abstract

一种白色有机电致发光器件，包括：衬底；阳极层；第一发光层；所述第一发光层由红色有机荧光材料、第一有机能量敏化材料与第一空穴型有机主体材料形成；第二发光层；所述第二发光层由绿色有机荧光材料、第二有机能量敏化材料与第二空穴型有机主体材料形成；阴极层。与现有技术相比，采用蓝色有机荧光材料作为发光材料与能量敏化材料，能够有效地将光子能量传递给红色有机荧光材料或绿色有机荧光材料，同时其也具有优越电子传输能力，在发光层中掺杂浓度较高，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。

Description

[根据细则37.2由ISA制定的发明名称]　白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201710032344.4、发明名称为“一种白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，尤其涉及一种白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，白色有机电致发光器件由于在全彩显示、高端照明等方面的应用前景，已经成为目前的研究热点。
一直以来，高性能、高品质白色有机电致发光器件的研发设计始终是该领域的重点及热点。因为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，努力提高白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白色有机电致发光器件通常伴随着较低的工作寿命、较低的色稳定性或者较高的制作成本。因此，越来越多的研究团队倾向于采用荧光发光材料取代过渡金属配合物，获得全荧光白色有机电致发光器件。然而，荧光材料普遍具有较低的发光效率；另外，荧光材料的导电性能和热稳定性普遍较差，最终导致载流子注入、传输及分布的不均衡，因而使得所制得白色荧光器件具有较低的发光效率、较高的 工作电压和较低的工作稳定性。
为了解决这些问题，国内外的研发团队纷纷致力于新型荧光材料的设计和白色器件结构的优化。例如，2009年中国科学院长春应用化学研究所马东阁等人在Organic Electronics杂志发表研究论文，通过将红、绿、蓝三种颜色的有机荧光材料掺杂到不同的发光层中，获得了优越的全荧光白光器件。所得器件具有较高的效率、亮度和色恢复系数，然而复杂的器件结构不仅导致复杂的制备工艺流程，还导致器件的光谱稳定性较差；另外，器件的工作电压较高，不利于器件工作稳定性的提高。2014年，香港城市大学Chun-Sing Lee等人在Organic Electronics杂志发表研究论文，通过将橙光材料掺杂到天蓝色发光材料中形成发光层，极大地简化了器件的结构，获得了白光器件。虽然所得白光器件具有较低的工作电压，有利于提高工作稳定性；然而，器件过于简单的发光层设计导致其色恢复系数较低并且光谱稳定性较差。由此可见，白色有机电致发光器件的发光效率、亮度、色恢复系数、光谱稳定性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白色有机电致发光器件及其制备方法，该白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。
本发明提供了一种白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第一发光层；所述第一发光层由红色有机荧光材料、第一有机能量敏化材料与第一空穴型有机主体材料形成；所述红色有机荧光材料的质量为第一空穴型有机主体材料质量的0.1％～1.0％；所述第一有机能量敏化材料的质量为第一空穴型有机主体材料质量的8.0％～25.0％；所述第一有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
设置在所述第一发光层上的第二发光层；所述第二发光层由绿色有机荧光材料、第二有机能量敏化材料与第二空穴型有机主体材料形成；所述绿色有机荧光材料的质量为第二空穴型有机主体材料质量的0.1％～2.0％；所述第二有机能量敏化材料的质量为第二空穴型有机主体材料质量的8.0％～25.0％；所述第二 有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
与设置在所述第二发光层上的阴极层。
优选的，所述红色有机荧光材料为红荧烯和/或4-二氰甲烯基-2-叔丁基-6-(1,1,7,7-四甲基久洛尼定-4-乙烯基)-4H-吡喃；
所述绿色有机荧光材料为N,N'-二甲基-喹吖啶酮和/或2,3,6,7-四氢-1,1,7,7-四甲基-1H,5H,11H-10-(2-苯并噻唑基)-喹嗪并[9,9A,1GH]香豆素。
优选的，所述第一有机能量敏化材料与第二有机能量敏化材料为2,2'-(9,10-蒽二基二-4,1-亚苯基)二[6-甲基-苯并噻唑]。
优选的，所述第一空穴型有机主体材料与第二空穴型有机主体材料各自独立地为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，所述第一发光层的厚度为5～10nm；所述第二发光层的厚度为2～5nm。
优选的，所述阳极层与第一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，所述阳极层与第一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，所述第二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白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第一发光层；所述第一发光层由红色有机荧光材料、第一有机能量敏化材料与第一空穴型有机主体材料形成；所述红色有机荧光材料的质量为第一空穴型有机主体材料质量的0.1％～1.0％；所述第一有机能量敏化材料的质量为第一空穴型有机主体材料质量的8.0％～25.0％；所述第一有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
在所述第一发光层上形成第二发光层；所述第二发光层由绿色有机荧光材 料、第二有机能量敏化材料与第二空穴型有机主体材料形成；所述绿色有机荧光材料的质量为第二空穴型有机主体材料质量的0.2％～2.0％；所述第二有机能量敏化材料的质量为第二空穴型有机主体材料质量的8.0％～25.0％；所述第二有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
在所述第二发光层上形成阴极，得到白色有机电致发光器件。
本发明提供了一种白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第一发光层；所述第一发光层由红色有机荧光材料、第一有机能量敏化材料与第一空穴型有机主体材料形成；所述红色有机荧光材料的质量为第一空穴型有机主体材料质量的0.1％～1.0％；所述第一有机能量敏化材料的质量为第一空穴型有机主体材料质量的8.0％～25.0％；所述第一有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；设置在所述第一发光层上的第二发光层；所述第二发光层由绿色有机荧光材料、第二有机能量敏化材料与第二空穴型有机主体材料形成；所述绿色有机荧光材料的质量为第二空穴型有机主体材料质量的0.2％～2.0％；所述第二有机能量敏化材料的质量为第二空穴型有机主体材料质量的8.0％～25.0％；所述第二有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；与设置在所述第二发光层上的阴极层。与现有技术相比，本发明采用蓝色有机荧光材料作为发光材料与能量敏化材料，能够有效地将光子能量传递给红色有机荧光材料或绿色有机荧光材料，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，可以起到电子型主体材料的功能，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是本发明提供的白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中得到的白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3.3伏，在电压为10.9伏、电流密度为557.86毫安每平方厘米(mA/cm2)时器件获得最大亮度11315坎德拉每平方米(cd/m2)；
图3是本发明实施例1中得到的白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13.17坎德拉每安培(cd/A)，最大功率效率为11.82流明每瓦特(lm/W)；
图4是本发明实施例1中得到的白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(0.366,0.413)；
图5是本发明实施例2中得到的白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3.2伏，在电压为10.2伏、电流密度为559.44mA/cm2时器件获得最大亮度8738cd/m2；
图6是本发明实施例2中得到的白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12.80cd/A，最大功率效率为11.80lm/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。
本发明提供了一种白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第一发光层；所述第一发光层由红色有机荧光材料、第一有机能量敏化材料与第一空穴型有机主体材料形成；所述红色有机荧光材料的质量为第一空穴型有机主体材料质量的0.1％～1.0％；所述第一有机能量敏化材料的质量为第一空穴型有机主体材料质量的8.0％～25.0％；所述第一有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
设置在所述第一发光层上的第二发光层；所述第二发光层由绿色有机荧光材料、第二有机能量敏化材料与第二空穴型有机主体材料形成；所述绿色有机荧光材料的质量为第二空穴型有机主体材料质量的0.2％～2.0％；所述第二有机能量敏化材料的质量为第二空穴型有机主体材料质量的8.0％～25.0％；所述第二有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
与设置在所述第二发光层上的阴极层。
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50～60nm，再优选为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 PCTCN2017098010-appb-000001
所述空穴传输层或电子阻挡层上设置有第一发光层；所述第一发光层由红色有机荧光材料、第一有机能量敏化材料与第一空穴型有机主体材料形成；所 述第一发光层的厚度优选为5～10nm，更优选为7～10nm；所述红色有机荧光材料的质量为第一空穴型有机主体材料质量的0.1％～1.0％，优选为0.1％～0.8％，更优选为0.1％～0.5％，再优选为0.1％～0.2％；所述红色有机荧光材料为本领域技术人员熟知的红色有机荧光材料即可，并无特殊的限制，本发明中优选为红荧烯(Rubrene，分子式如式I所示)和/或4-二氰甲烯基-2-叔丁基-6-(1,1,7,7-四甲基久洛尼定-4-乙烯基)-4H-吡喃(简称DCJTB，分子式如式II所示)；所述第一有机能量敏化材料的质量为第一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16.0％～18.0％；所述第一有机能量敏化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。能量与能级匹配的有机能量敏化材料，能够有效将光子能量传递给绿色及红色有机荧光材料，并且具有优越的电子传输能力。其中，能量匹配的一个基本原则是：从主体材料到敏化材料，再从敏化材料到发光材料，能量能够有效传递，这就要求主体材料的激发态能量>敏化材料的激发态能量>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。而本发明中敏化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，在本发明中所述第一有机能量敏化材料优选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III所示)。DBzA具有高的发光效率和色纯度，热稳定性能好，并且兼具能量敏化材料的功能，能够有效地将光子能量传递给红色有机发光材料Rubrene、DCJTB或者绿色有机发光材料C545T、DMQA。所述第一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IV所示)、1,3-二咔唑-9-基苯(简称mCP，分子式如式V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VI所示)、1,3,5-三(9-咔唑基)苯(简称TCP，分子式如式VII所示)、4,4',4”–三(咔唑-9-基)三苯胺(简称TcTa，分子式如式VIII所示)与4,4’-双(三苯基硅烷基)联苯(简称BSB，分子式如式IX所示)。
Figure PCTCN2017098010-appb-000002
所述第一发光层上设置有第二发光层；所述第二发光层的厚度优选为2～5nm，更优选为2～4nm，再优选为2～3nm；所述第二发光层由绿色有机荧光材 料、第二有机能量敏化材料与第二空穴型有机主体材料形成；所述绿色有机荧光材料的质量为第二空穴型有机主体材料质量的0.1％～2.0％，优选为0.1％～1.5％，再优选为0.1％～1.0％，再优选为0.1％～0.5％，最优选为0.1％～0.2％；所述绿色有机荧光材料为本领域技术人员熟知的绿色有机荧光材料即可，并无特殊限制，本发明中优选为N,N'-二甲基-喹吖啶酮(简称DMQA，分子式如式X所示)和/或2,3,6,7-四氢-1,1,7,7-四甲基-1H,5H,11H-10-(2-苯并噻唑基)-喹嗪并[9,9A,1GH]香豆素(简称C545T，分子式如式XI所示)；所述第二有机能量敏化材料的质量为第二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18.0％～20.0％；所述第二有机能量敏化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。本发明中优选为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III所示)；蓝色有机荧光材料DBzA具有高的发光效率和色纯度，热稳定性能好，并且兼具能量敏化材料的功能，能够有效地将光子能量传递给红色有机荧光材料或绿色有机荧光材料；蓝色有机荧光材料DBzA兼具优越的电子传输能力，其掺杂浓度较大兼具电子型主体材料的作用，能够有效平衡载流子在发光层的分布。所述第二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IV所示)、1,3-二咔唑-9-基苯(简称mCP，分子式如式V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VI所示)、1,3,5-三(9-咔唑基)苯(简称TCP，分子式如式VII所示)、4,4',4”–三(咔唑-9-基)三苯胺(简称TcTa，分子式如式VIII所示)与4,4’-双(三苯基硅烷基)联苯(简称BSB，分子式如式IX所示)。
Figure PCTCN2017098010-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，所述第二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45～55nm， 再优选为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XII、XIII、XIV、XV与XVI所示。
Figure PCTCN2017098010-appb-000004
Figure PCTCN2017098010-appb-000005
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。
本发明提供的白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为第一发光层，6为第二发光层，7为空穴阻挡层/电子传输层，8为缓冲层，9为阴极层。白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，该器件就会发出覆盖410～650nm的白色光。
本发明采用蓝色有机荧光材料作为发光材料与能量敏化材料，能够有效地将光子能量传递给红色有机荧光材料或绿色有机荧光材料，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，可以起到电子型主体材料的功能，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白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第一发光层；所述第一发光层由红色有机荧光材料、第一有机能量敏化材料与第一空穴型有机主体材料形成；所述红色有机荧光材料的质量为第一空穴型有机主体材料质量的0.1％～1.0％；所述第一有机能量敏化材料的质量为第一空穴型有机主体材料质量的8.0％～25.0％；所述第一有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
在所述第一发光层上形成第二发光层；所述第二发光层由绿色有机荧光材料、第二有机能量敏化材料与第二空穴型有机主体材料形成；所述绿色有机荧光材料的质量为第二空穴型有机主体材料质量的0.2％～2.0％；所述第二有机能量敏化材料的质量为第二空穴型有机主体材料质量的8.0％～25.0％；所述第二有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
在所述第二发光层上形成阴极，得到白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第一发光层；所述第一发光层同上所述，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； 所述真空蒸镀中红色有机荧光材料的蒸发速率优选为0.00005～0.001nm/s；第一有机敏化能量材料的蒸发速率优选为0.004～0.025nm/s；所述第一空穴型有机主体材料的蒸发速率优选为0.05～0.1nm/s。有机混合材料中的红色有机荧光材料、第一有机敏化能量材料与第一空穴型有机主体材料在不同的蒸发源中同时蒸发，通过调控三种材料的蒸发速率使得红色有机荧光材料的质量为第一空穴型有机主体材料质量的0.1％～1.0％，第一有机能量敏化材料的质量为第一空穴型有机主体材料质量的8.0％～25.0％。
在第一发光层上形成第二发光层；所述第二发光层同上所述，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。所述真空蒸镀中绿色有机荧光材料的蒸发速率优选为0.0001～0.002nm/s；第二有机敏化能量材料的蒸发速率优选为0.004～0.025nm/s；所述第二空穴型有机主体材料的蒸发速率优选为0.05～0.1nm/s。有机混合材料中的绿色有机荧光材料、第二有机敏化能量材料与第二空穴型有机主体材料在不同的蒸发源中同时蒸发，通过调控三种材料的蒸发速率使得绿色有机荧光材料的质量为第二空穴型有机主体材料质量的0.1％～2.0％，第二有机能量敏化材料的质量为第二空穴型有机主体材料质量的8.0％～25.0％。
按照本发明，优选在第二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，得到白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。
本发明所提供的白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，在保证器件光谱稳定性不降低的前提下，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白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50纳米厚的TAPC空穴传输层/电子阻挡层4、8纳米厚的DCJTB、DBzA掺杂TcTa第一发光层5、2纳米厚的C545T、DBzA掺杂TcTa第二发光层6、50纳米厚的Tm3PyP26PyB空穴阻挡层/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/DCJTB(0.1％)：DBzA(16wt％)：TcTa/C545T(0.2％)：DBzA(20wt％)：TcTa/Tm3PyP26PyB/LiF/Al的白色有机电致发光器件。第一发光层5中DCJTB、DBzA和TcTa的蒸发速率控制在0.00005纳米/秒、0.008纳米/秒和0.05纳米/秒，第二发光层6中C545T、DBzA和TcTa的蒸发速率控制在0.0001纳米/秒、0.01纳米/秒和0.05纳米/秒，TAPC和Tm3PyP26PyB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中得到的白色有机电致发光器件在直流电压驱动下，显示覆盖从410纳米到650纳米的白光发射；随着工作电压的变化，器件色坐标稳定在从(0.307,0.316)到(0.425,0.454)的范围内。当亮度为1000cd/m2时，器件色 坐标为(0.366,0.413)。
图2为实施例1中得到的白色有机电致发光器件的电压-电流密度-亮度特性曲线图，由图2可知器件的起亮电压为3.3V，在电压为10.9伏、电流密度为557.86mA/m2时，器件的最大亮度为11315cd/m2。
图3为实施例1中得到的白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13.17cd/A，最大功率效率为11.82lm/W。
图4为实施例1中得到的白色有机电致发光器件在亮度为1000cd/m2时的光谱图。由图4可知，器件色坐标为(0.366,0.413)。
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50纳米厚的TAPC空穴传输层/电子阻挡层4、7纳米厚的DCJTB、DBzA掺杂TcTa第一发光层5、3纳米厚的C545T、DBzA掺杂TcTa第二发光层6、50纳米厚的Tm3PyP26PyB空穴阻挡层/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/DCJTB(0.2％)：DBzA(16wt％)：TcTa/C545T(0.1％)：DBzA(20wt％)：TcTa/Tm3PyP26PyB/LiF/Al的白色有机电致发光器件。第一发光层5中DCJTB、DBzA和TcTa的蒸发速率控制在0.00005纳米/秒、0.008纳米/秒和0.05纳米/秒，第二发光层6中C545T、DBzA和TcTa的蒸发速率控制在0.00005纳米/秒、0.01纳米/秒和0.05纳米/秒，TAPC和Tm3PyP26PyB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中得到的白色有机电致发光器件在直流电压驱动下，显示覆盖从410纳米到650纳米的白光发射；随着工作电压的变化，器件色坐标稳定在从(0.285,0.301)到(0.409,0.413)的范围内。当亮度为1000cd/m2时，器件色 坐标为(0.323,0.365)。
图5为实施例2中得到的白色有机电致发光器件的电压-电流密度-亮度特性曲线图，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3.2V，在电压为10.2V、电流密度为559.44mA/m2时器件的最大亮度为8738cd/m2。
图6为实施例2中得到的白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12.80cd/A，最大功率效率为11.80lm/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、8纳米厚的DCJTB、DBzA掺杂TcTa第一发光层5、2纳米厚的C545T、DBzA掺杂TcTa第二发光层6、50纳米厚的Tm3PyP26PyB空穴阻挡层/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/DCJTB(0.1％)：DBzA(18wt％)：TcTa/C545T(0.2％)：DBzA(18wt％)：TcTa/Tm3PyP26PyB/LiF/Al的白色有机电致发光器件。第一发光层5中DCJTB、DBzA和TcTa的蒸发速率控制在0.00005纳米/秒、0.009纳米/秒和0.05纳米/秒，第二发光层6中C545T、DBzA和TcTa的蒸发速率控制在0.0001纳米/秒、0.009纳米/秒和0.05纳米/秒，TAPC和Tm3PyP26PyB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中得到的白色有机电致发光器件在直流电压驱动下，显示覆盖从410纳米到650纳米的白光发射；随着工作电压的变化，器件色坐标稳定在从(0.303,0.319)到(0.432,0.461)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.358,0.411)。器件的起亮电压为3.3V，器件的最大亮度为11002cd/m2。 器件的最大电流效率为12.27cd/A，最大功率效率为11.16lm/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DCJTB、DBzA掺杂TcTa第一发光层5、2纳米厚的C545T、DBzA掺杂TcTa第二发光层6、50纳米厚的Tm3PyP26PyB空穴阻挡层/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/DCJTB(0.1％)：DBzA(16wt％)：TcTa/C545T(0.2％)：DBzA(20wt％)：TcTa/Tm3PyP26PyB/LiF/Al的白色有机电致发光器件。第一发光层5中DCJTB、DBzA和TcTa的蒸发速率控制在0.00005纳米/秒、0.008纳米/秒和0.05纳米/秒，第二发光层6中C545T、DBzA和TcTa的蒸发速率控制在0.0001纳米/秒、0.01纳米/秒和0.05纳米/秒，TAPC和Tm3PyP26PyB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中得到的白色有机电致发光器件在直流电压驱动下，显示覆盖从410纳米到650纳米的白光发射；随着工作电压的变化，器件色坐标稳定在从(0.315,0.322)到(0.440,0.462)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.369,0.421)。器件的起亮电压为3.3V，器件的最大亮度为11996cd/m2。器件的最大电流效率为13.35cd/A，最大功率效率为12.17lm/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50纳米厚的TAPC空穴传输层/电子阻挡层4、8纳米厚的DCJTB、DBzA掺杂TcTa第一发光层5、3纳米厚的C545T、DBzA掺杂TcTa第二发光层6、50纳米厚的Tm3PyP26PyB空穴阻挡层/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/DCJTB(0.1％)：DBzA(18wt％)：TcTa/C545T(0.2％)：DBzA(18wt％)：TcTa/Tm3PyP26PyB/LiF/Al的白色有机电致发光器件。第一发光层5中DCJTB、DBzA和TcTa的蒸发速率控制在0.00005纳米/秒、0.009纳米/秒和0.05纳米/秒，第二发光层6中C545T、DBzA和TcTa的蒸发速率控制在0.0001纳米/秒、0.009纳米/秒和0.05纳米/秒，TAPC和Tm3PyP26PyB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中得到的白色有机电致发光器件在直流电压驱动下，显示覆盖从410纳米到650纳米的白光发射；随着工作电压的变化，器件色坐标稳定在从(0.311,0.318)到(0.433,0.465)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.349,0.421)。器件的起亮电压为3.2V，器件的最大亮度为12618cd/m2。器件的最大电流效率为12.78cd/A，最大功率效率为11.45lm/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DCJTB、DBzA掺杂TcTa第一发光层5、2纳米厚的C545T、DBzA掺杂TcTa第二发光层6、50纳米厚的Tm3PyP26PyB空穴阻挡层/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/DCJTB(0.1％)：DBzA(18wt％)：TcTa/C545T(0.2％)：DBzA(20 wt％)：TcTa/Tm3PyP26PyB/LiF/Al的白色有机电致发光器件。第一发光层5中DCJTB、DBzA和TcTa的蒸发速率控制在0.00005纳米/秒、0.008纳米/秒和0.05纳米/秒，第二发光层6中C545T、DBzA和TcTa的蒸发速率控制在0.0001纳米/秒、0.01纳米/秒和0.05纳米/秒，TAPC和Tm3PyP26PyB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中得到的白色有机电致发光器件在直流电压驱动下，显示覆盖从410纳米到650纳米的白光发射；随着工作电压的变化，器件色坐标稳定在从(0.316,0.334)到(0.455,0.465)的范围内。当亮度为1000cd/m2时，器件色坐标为(0.377,0.432)。器件的起亮电压为3.3V，器件的最大亮度为12963cd/m2。器件的最大电流效率为13.02cd/A，最大功率效率为11.70lm/W。

Claims (15)

  1. 一种白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第一发光层；所述第一发光层由红色有机荧光材料、第一有机能量敏化材料与第一空穴型有机主体材料形成；所述红色有机荧光材料的质量为第一空穴型有机主体材料质量的0.1％～1.0％；所述第一有机能量敏化材料的质量为第一空穴型有机主体材料质量的8.0％～25.0％；所述第一有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
    设置在所述第一发光层上的第二发光层；所述第二发光层由绿色有机荧光材料、第二有机能量敏化材料与第二空穴型有机主体材料形成；所述绿色有机荧光材料的质量为第二空穴型有机主体材料质量的0.1％～2.0％；所述第二有机能量敏化材料的质量为第二空穴型有机主体材料质量的8.0％～25.0％；所述第二有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
    与设置在所述第二发光层上的阴极层。
  2. 根据权利要求1所述的白色有机电致发光器件，其特征在于，所述红色有机荧光材料为红荧烯和/或4-二氰甲烯基-2-叔丁基-6-(1,1,7,7-四甲基久洛尼定-4-乙烯基)-4H-吡喃。
  3. 根据权利要求1所述的白色有机电致发光器件，其特征在于，所述绿色有机荧光材料为N,N'-二甲基-喹吖啶酮和/或2,3,6,7-四氢-1,1,7,7-四甲基-1H,5H,11H-10-(2-苯并噻唑基)-喹嗪并[9,9A,1GH]香豆素。
  4. 根据权利要求1所述的白色有机电致发光器件，其特征在于，所述第一有机能量敏化材料与第二有机能量敏化材料为2,2'-(9,10-蒽二基二-4,1-亚苯基)二[6-甲基-苯并噻唑]。
  5. 根据权利要求1所述的白色有机电致发光器件，其特征在于，所述第一空穴型有机主体材料与第二空穴型有机主体材料各自独立地为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。
  6. 根据权利要求1所述的白色有机电致发光器件，其特征在于，所述第一 发光层的厚度为5～10nm；所述第二发光层的厚度为2～5nm。
  7. 根据权利要求1所述的白色有机电致发光器件，其特征在于，所述阳极层与第一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。
  8. 根据权利要求1所述的白色有机电致发光器件，其特征在于，所述阳极层与第一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。
  9. 根据权利要求1所述的白色有机电致发光器件，其特征在于，所述第二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。
  10. 根据权利要求9所述的白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。
  11. 一种白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第一发光层；所述第一发光层由红色有机荧光材料、第一有机能量敏化材料与第一空穴型有机主体材料形成；所述红色有机荧光材料的质量为第一空穴型有机主体材料质量的0.1％～1.0％；所述第一有机能量敏化材料的质量为第一空穴型有机主体材料质量的8.0％～25.0％；所述第一有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
    在所述第一发光层上形成第二发光层；所述第二发光层由绿色有机荧光材料、第二有机能量敏化材料与第二空穴型有机主体材料形成；所述绿色有机荧光材料的质量为第二空穴型有机主体材料质量的0.2％～2.0％；所述第二有机能量敏化材料的质量为第二空穴型有机主体材料质量的8.0％～25.0％；所述第二有机能量敏化材料为能级能量匹配的蓝色有机荧光材料；
    在所述第二发光层上形成阴极，得到白色有机电致发光器件。
  12. 根据权利要求11所述的制备方法，其特征在于，所述红色有机荧光材料为红荧烯和/或4-二氰甲烯基-2-叔丁基-6-(1,1,7,7-四甲基久洛尼定-4-乙烯基)-4H-吡喃。
  13. 根据权利要求11所述的制备方法，其特征在于，所述绿色有机荧光材料为N,N'-二甲基-喹吖啶酮和/或2,3,6,7-四氢-1,1,7,7-四甲基-1H,5H,11H-10-(2-苯并噻唑基)-喹嗪并[9,9A,1GH]香豆素。
  14. 根据权利要求11所述的制备方法，其特征在于，所述第一有机能量敏化材料与第二有机能量敏化材料为2,2'-(9,10-蒽二基二-4,1-亚苯基)二[6-甲基-苯并噻唑]。
  15. 根据权利要求11所述的制备方法，其特征在于，所述第一空穴型有机主体材料与第二空穴型有机主体材料各自独立地为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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