CN111416047B - Fluorescence/phosphorescence mixed white light organic light emitting diode and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of organic photoelectric devices, and discloses a fluorescence/phosphorescence mixed white light organic light emitting diode and a preparation method thereof. The light emitting layer of the fluorescence/phosphorescence mixed white light organic light emitting diode comprises a yellow phosphorescence light emitting layer and a blue fluorescence light emitting layer; the blue light fluorescence luminescent layer comprises a heterojunction double layer consisting of a hole-transport type blue light fluorescence material and an electron-transport type blue light fluorescence material, and a blue light material layer with triplet state-triplet state annihilation up-conversion luminescence characteristics. According to the invention, by introducing a blue light emitting thin layer with TTA characteristics, triplet excitons in the heterojunction blue layer of the device under high brightness can be effectively utilized by transferring energy to a TTA host material. The device structure skillfully utilizes the triplet exciton to inhibit the quenching of the triplet exciton of the device under high brightness, reduces the energy loss of the exciton, improves the efficiency roll-off and finally optimizes the overall performance of the device.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric devices, and particularly relates to a fluorescence/phosphorescence mixed white light organic light emitting diode and a preparation method thereof.
Background
White Organic Light-Emitting Diodes (abbreviated as WOLEDs) have the advantages of planar Light emission, lightness, thinness, low power consumption, large area, flexibility and flexibility, so that the White Organic Light-Emitting Diodes are of great interest in displaying and illuminating with great application potential. Before the widespread use of white organic light emitting diode technology, the efficiency roll-off of the device at high brightness and the lifetime of the device remain major problems that must be overcome. In the fluorescent/phosphorescent mixed white organic light emitting diode, due to the inclusion of the phosphorescent light emitting layer, the predictable serious efficiency reduction of the device under high brightness is usually caused by triplet-triplet annihilation and triplet-polaron quenching effect, and how to reduce the quenching is an important topic for the research of the fluorescent/phosphorescent mixed white organic light emitting diode. The biggest challenge faced at present is how to utilize excitons to the maximum extent, further improve efficiency, eliminate efficiency roll-off of the device under high brightness, and simultaneously consider stability, so that a fluorescent/phosphorescent mixed white-light organic light-emitting diode with high efficiency, low efficiency roll-off, good spectral stability and excellent comprehensive performance of long service life is prepared, and the requirements of lighting application are met.
Disclosure of Invention
In view of the above problems in the prior art, a primary object of the present invention is to provide a fluorescent/phosphorescent hybrid white organic light emitting diode.
The invention also aims to provide a preparation method of the fluorescence/phosphorescence mixed white organic light emitting diode.
The purpose of the invention is realized by the following technical scheme:
a fluorescence/phosphorescence mixed white light organic light emitting diode comprises a yellow phosphorescence emitting layer and a blue fluorescence emitting layer; the blue light fluorescence luminescent layer comprises a heterojunction double layer consisting of a hole-transport type blue light fluorescence material and an electron-transport type blue light fluorescence material, and a blue light material layer with triplet state-triplet state annihilation up-conversion luminescence characteristics; the yellow light phosphorescence emitting layer is made of a layer of yellow light phosphorescence material.
Further, the blue light material layer with triplet-triplet annihilation up-conversion luminescence characteristics is composed of a host material with triplet-triplet annihilation (TTA) characteristics and a blue light fluorescence guest material through doping.
Further, the singlet state energy level and the triplet state energy level of the hole-transport type blue light fluorescent material are respectively lower than those of the electron-transport type blue light fluorescent material; the triplet state energy level of the yellow phosphorescent material is lower than the singlet state and triplet state energy levels of the hole-transport blue fluorescent material; the triplet energy level of the host material having triplet-triplet annihilation (TTA) characteristics is lower than the singlet and triplet energy levels of the electron-transporting blue fluorescent material.
Further, the yellow phosphorescent material is YDD001 (commercial material of Orleder company, Shi C, Sun N, Wu Z, et al. high performance phosphor thin organic light-emitting diodes used a novel interface detector [ J ]. Journal of materials Chemistry C, 2018,6) with a film thickness of 0.4. + -. 0.1 nm; the hole-transport blue-light fluorescent material is 4P-NPD, the film thickness is 5 +/-1 nanometers, the electron-transport blue-light fluorescent material is Bepp2, and the film thickness is 11 +/-1 nanometers; the host material with triplet-triplet annihilation (TTA) characteristic is MADN (Baluschiev, S, Miteva, T, Yakutkin, V, and the like. Up-Conversion Fluorescence: non-coherent Excitation by Sunlight [ J ] Physical Review Letters,97(14):143903), the blue-light Fluorescence guest material is DSA-ph, the doping concentration of the blue-light Fluorescence guest material is 3 + -1%, and the thickness of the blue-light material layer with triplet-triplet annihilation Up-Conversion luminescence characteristic is 3 + -1 nm. The structural formula of the material is as follows:
further, the structure of the fluorescent/phosphorescent mixed white organic light emitting diode sequentially comprises a conductive glass ITO (indium tin oxide) anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and an aluminum cathode from bottom to top.
Furthermore, the conductive glass ITO anode is transparent indium tin oxide sputtered on glass, and the square resistance is less than 10 ohms; the hole injection layer is made of HATCN, and the film thickness of the hole injection layer is 15 +/-5 nanometers; the hole transport layer is made of TAPC, and the film thickness of the hole transport layer is 65 +/-5 nanometers; the material of the electron barrier layer is 4P-NPD, and the film thickness is 5 +/-1 nanometer; the electron transport layer is made of Bepp2, and the film thickness is 47 +/-5 nanometers; the material of the electron injection layer is LiF, and the film thickness is 1 +/-0.25 nm; the thickness of the aluminum cathode is 120 +/-20 nanometers.
The preparation method of the fluorescence/phosphorescence mixed white organic light emitting diode comprises the following steps:
and transferring the pretreated ITO glass into a vacuum coating system, and sequentially evaporating and coating a hole injection layer, a hole transport layer, an electron barrier layer, a luminescent layer, an electron transport layer, an electron injection layer and an aluminum cathode on the ITO layer to obtain the fluorescence/phosphorescence mixed white light organic light-emitting diode.
Further, the glass ITO is pretreated as follows: firstly, performing ultrasonic treatment on the glass ITO for 60-90 minutes, then cleaning the glass ITO by using deionized water, and drying the glass ITO by using nitrogen; then baking the mixture in a vacuum oven at 120 ℃ for 30-60 minutes, and then treating the mixture for 6 +/-1 minutes by using ultraviolet ozone plasma.
Further, the degree of vacuum of the vapor deposition was 1 × 10-5～5×10-5And (6) handkerchief.
Further, the evaporation rate of the materials of the hole injection layer and the electron injection layer is controlled to be 0.03-0.05 nm/s; the evaporation rate of the hole transport layer, the electron blocking layer, the blue light fluorescence luminescent layer and the electron transport layer is controlled to be 0.05-0.1 nanometer/second; the evaporation rate of the yellow phosphorescent light-emitting layer is controlled to be 0.001-0.01 nm/s; the evaporation rate of the aluminum cathode is controlled to be 0.5-1 nm/s.
The key of the fluorescence/phosphorescence mixed white light organic light emitting diode is that a blue light fluorescence emitting layer not only comprises a heterojunction double layer consisting of a hole transmission type blue light fluorescence material and an electron transmission type blue light fluorescence material, but also introduces a TTA blue light emitting thin layer with triplet state-triplet state annihilation up-conversion luminescence characteristics, so that triplet state excitons in the heterojunction blue light layer of the device under high brightness can be effectively utilized by transferring energy to a TTA main body material. The device structure skillfully utilizes the triplet exciton to inhibit the quenching of the triplet exciton of the device under high brightness, reduces the energy loss of the exciton, improves the efficiency roll-off and finally optimizes the overall performance of the device.
The device of the invention has the following advantages and beneficial effects:
the fluorescent/phosphorescent mixed white organic light emitting diode not only has the characteristics of simplifying the structure of the device and being beneficial to reducing the preparation cost of the device, but also has the important points of reasonable energy level arrangement and optimization of the positions and the thicknesses of the yellow ultrathin phosphorescent layer and the TTA blue light emitting thin layer, finally realizes effective regulation and control of an exciton recombination region and energy transfer, reduces energy loss in the exciton transfer process, improves the utilization rate of excitons, ensures that the prepared fluorescent/phosphorescent mixed white organic light emitting diode has the advantages of high efficiency, low efficiency roll-off, good spectral stability and long service life, and shows potential application value in the field of future solid state lighting.
Drawings
Fig. 1 is a schematic structural view of a fluorescence/phosphorescence hybrid white organic light emitting diode according to the present invention. Wherein 1 is a conductive glass ITO anode, 2 is a hole injection layer, 3 is a hole transport layer, 4 is an electron blocking layer, 5 is a luminescent layer, and the luminescent layer comprises an ultrathin yellow light phosphorescence luminescent layer Y and a hole transport type blue light fluorescent material luminescent layer B1Electron-transporting blue-light fluorescent material luminescent layer B2TTA blue light thin layer B with triplet-triplet annihilation up-conversion luminescence characteristic 36 is an electron transport layer, 7 is an electron injection layer, and 8 is an aluminum cathode.
Fig. 2 is a schematic diagram of exciton energy transfer and electroluminescence process in the light emitting layer of the fluorescence/phosphorescence mixed white organic light emitting diode according to the embodiment of the invention.
Fig. 3 is a graph showing electroluminescence characteristics of a fluorescence/phosphorescence hybrid white organic light emitting diode according to an embodiment of the present invention. Wherein (a) is a current density-luminance-voltage characteristic curve of the device; (b) is a current efficiency-power efficiency-current efficiency-brightness characteristic curve of the device; (c) is the electroluminescence spectrum chart of the device under different voltages, and the color coordinate and the color temperature of the device under different brightness are shown in the chart.
Fig. 4 is a schematic structural diagram of a comparative white light device for comparison in an embodiment of the present invention.
Fig. 5 is a graph showing the electroluminescent characteristics of the fluorescence/phosphorescence hybrid white organic light emitting diode according to the embodiment of the present invention and a comparative white light emitting device. Wherein,(a) normalizing an external quantum efficiency-brightness characteristic curve of the device; (b) the initial luminance of the device normalized luminance decay characteristic curve along with the working time is 1000cd/m2。
FIG. 6 is a graph showing the electroluminescence spectra at different brightnesses of a comparative white light device used for comparison in an example of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The structure of the fluorescent/phosphorescent mixed white organic light emitting diode of this embodiment is schematically shown in fig. 1, and includes a conductive glass ITO anode 1, a hole injection layer 2, a hole transport layer 3, an electron blocking layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and an aluminum cathode 8, where the light emitting layer 5 includes an ultra-thin yellow phosphorescent light emitting layer Y, a hole transport blue fluorescent material light emitting layer B, and a blue fluorescent material light emitting layer Y1Electron-transporting blue-light fluorescent material luminescent layer B2TTA blue light fluorescence luminescent thin layer B with triplet state-triplet state annihilation up-conversion luminescent characteristic3And (4) forming. In the device, the material of the hole injection layer 2 is HATCN, and the film thickness of the hole injection layer is 15 +/-5 nanometers; the material of the hole transport layer 3 is TAPC, and the film thickness of the hole transport layer is 65 +/-5 nanometers; the material of the electron blocking layer is 4P-NPD, and the film thickness of the electron blocking layer is 5 +/-1 nanometers; the material of the electron transport layer is Bepp2, and the film thickness of the electron transport layer is 47 +/-5 nanometers; the material of the electron injection layer is LiF, and the film thickness of the electron injection layer is 1 +/-0.25 nm; the aluminum cathode is 120 +/-20 nanometers thick; the yellow phosphorescent light-emitting layer in the light-emitting layer is made of YDD001, and the thickness of the film is 0.4 +/-0.1 nm; the blue light fluorescence luminescent layer is made of a hole transmission type blue light fluorescence material 4P-NPD with the film thickness of 5 +/-1 nanometers and an electron transmission type blue light fluorescence material Bepp2 with the film thickness of 11 +/-1 nanometers of a heterojunction double layer and a blue light fluorescence thin layer which is formed by doping a host material MADN with triplet-triplet up-conversion (TTA) characteristic with blue fluorescence guest material DSA-ph with the mass concentration of 3 +/-1 percent, and the film thickness is 3 +/-1 nanometers.
The fluorescence/phosphorescence mixed white light lamp of the embodiment hasThe organic light emitting diode is prepared by the following method: firstly, carrying out ultrasonic treatment on the ITO glass for 60-90 minutes, then cleaning the ITO glass by using deionized water, and then drying the ITO glass by using nitrogen; then baking the film in a vacuum oven at 120 ℃ for 30-60 minutes, treating the film for 6 +/-1 minutes by using ultraviolet ozone plasma, and then transferring the film into a vacuum coating system; when the vacuum degree reaches 1 multiplied by 10-5To 5X 10-5And when the ITO layer is coated with the hole injection layer, the hole transport layer, the electron blocking layer, the luminescent layer, the electron transport layer, the electron injection layer and the aluminum cathode in sequence. Wherein, the evaporation rate of the materials of the hole injection layer and the electron injection layer is controlled to be 0.03-0.05 nm/s; the evaporation rates of the materials of the hole transport layer, the electron blocking layer, the blue light fluorescence luminescent layer and the electron transport layer are controlled to be 0.05-0.1 nm/s; the evaporation rate of the yellow phosphorescent light-emitting layer is controlled to be 0.001-0.01 nm/s; the evaporation rate of the aluminum cathode is controlled to be 0.5-1 nm/s. The effective area of the device is the cross area of the ITO anode and the Al electrode, and is 4 mm multiplied by 4 mm.
The exciton energy transfer and electroluminescence process in the light emitting layer of the fluorescence/phosphorescence mixed white organic light emitting diode of the embodiment is schematically shown in fig. 2. It can be seen that, because the triplet energy level of the yellow phosphorescent material is lower than the singlet and triplet energy levels of 4P-NPD, and the triplet energy level of MADN is lower than the singlet and triplet energy levels of Bepp2, it is important that the singlet and triplet energy levels of the blue fluorescent material 4P-NPD are respectively lower than the Bepp2, so that by controlling the position and thickness of the ultra-thin phosphorescent layer and the TTA blue light emitting thin layer with triplet-triplet annihilation up-conversion luminescence property, in a low voltage range, singlet excitons in the heterojunction blue light layer recombination region are used for blue light fluorescence emission, and triplet exciton energy is transferred to phosphorescent molecules to realize phosphorescent emission, and finally white light is realized; at higher voltage, due to the fact that the concentration of triplet excitons in the heterojunction blue light layer is increased, except that part of energy of the triplet excitons is transferred to phosphorescent molecules to achieve yellow light phosphorescence emission, the surplus triplet excitons can be transferred to MADN which is a TTA host material through energy, then two MADN molecules are polymerized into a high-energy singlet exciton, and finally the energy is transferred to DSA-ph which is a blue light fluorescence guest material to form blue light emission, the roll-off of the efficiency of the prepared white light device is improved.
Fig. 3 shows the electroluminescent characteristics of the fluorescence/phosphorescence hybrid white organic light emitting diode of the present embodiment. It can be seen that the turn-on voltage of the device is as low as 2.6 volts and the maximum luminance exceeds 50000cd/m2The maximum Current Efficiency (CE), External Quantum Efficiency (EQE) and Power Efficiency (PE) were 57.3cdA, respectively-123.6%, and 68.8lmW-1At 1000cd/m2The brightness of the LED still keeps 43.6cdA-118.3%, and 38.1lmW-1Due to the introduction of a TTA light-emitting layer with excellent efficiency roll-off characteristics, at 5000cd/m2And 10000 cd/m2At brightness of (d), EQEs were still as high as 17.1% and 15.6%, showing very low efficiency roll-off. In addition, the device also showed very stable white light emission from 500cd/m2Up to 20000cd/m2The spectrum is almost constant in the luminance range. At 1000cd/m2The chromaticity coordinates CIE (0.49,0.38) at luminance, the color temperature CCT of 2127K, are very good warm white emission.
In order to prove the excellent comprehensive performance of the fluorescence/phosphorescence mixed white organic light emitting diode prepared by the invention, a contrast white light device is prepared on the basis of the structure (the structure is shown in figure 4). The contrast white light device has the same overall structure parameters as the white light device of the invention, and the difference is that only the ultrathin yellow phosphorescent light-emitting layer Y' and the hole-transport blue fluorescent material light-emitting layer B in the light-emitting layer of the contrast white light device1Electron transport blue light emitting material layer B2However, there is no TTA blue light emitting thin layer having triplet-triplet annihilation up-conversion emission characteristics. As shown in FIG. 5, they show completely different roll-off efficiency and device lifetime, and the fluorescent/phosphorescent mixed white organic light emitting diode of the present invention is 1000cd/m2The half-life at initial luminance reached nearly 600 hours, far exceeding that of the contrast device by less than 350 hours, and the spectrum of the contrast device also varied with luminance (as shown in FIG. 6), further demonstrating that the fluorescence/phosphorescence mixture of the present inventionThe excellent performance of the combined white organic light emitting diode.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A fluorescence/phosphorescence mixed white organic light emitting diode is characterized in that: the light emitting layer of the fluorescence/phosphorescence mixed white light organic light emitting diode comprises a yellow phosphorescence light emitting layer and a blue fluorescence light emitting layer; the blue light fluorescence luminescent layer comprises a heterojunction double layer consisting of a hole-transport type blue light fluorescence material and an electron-transport type blue light fluorescence material, and a blue light material layer with triplet state-triplet state annihilation up-conversion luminescence characteristics; the yellow phosphorescent light-emitting layer is made of a layer of yellow phosphorescent material;
the blue light material layer with the triplet-triplet annihilation up-conversion luminescence characteristic is formed by doping a host material with TTA characteristic and a blue light fluorescence guest material;
the singlet state energy level and the triplet state energy level of the hole transmission type blue light fluorescent material are respectively lower than those of the electron transmission type blue light fluorescent material; the triplet state energy level of the yellow phosphorescent material is lower than the singlet state and triplet state energy levels of the hole-transport blue fluorescent material; the triplet energy level of the host material having TTA characteristics is lower than the singlet and triplet energy levels of the electron transporting blue fluorescent material.
2. The white OLED of claim 1, wherein: the yellow phosphorescent material is YDD001, and the film thickness of the yellow phosphorescent material is 0.4 +/-0.1 nm; the hole-transport blue-light fluorescent material is 4P-NPD, the film thickness is 5 +/-1 nanometers, the electron-transport blue-light fluorescent material is Bepp2, and the film thickness is 11 +/-1 nanometers; the host material with TTA characteristics is MADN, the blue light fluorescence object material is DSA-ph, the doping quality concentration of the blue light fluorescence object material is 3 +/-1%, and the thickness of the blue light material layer with triplet state-triplet state annihilation up-conversion luminescence characteristics is 3 +/-1 nm.
3. The fluorescence/phosphorescence hybrid white organic light emitting diode according to any one of claims 1 to 2, wherein: the structure of the fluorescence/phosphorescence mixed white light organic light emitting diode sequentially comprises a conductive glass ITO anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and an aluminum cathode from bottom to top.
4. The white OLED of claim 3, wherein: the conductive glass ITO anode is transparent indium tin oxide sputtered on glass, and the square resistance is less than 10 ohms; the hole injection layer is made of HATCN, and the film thickness of the hole injection layer is 15 +/-5 nanometers; the hole transport layer is made of TAPC, and the film thickness of the hole transport layer is 65 +/-5 nanometers; the material of the electron barrier layer is 4P-NPD, and the film thickness is 5 +/-1 nanometer; the electron transport layer is made of Bepp2, and the film thickness is 47 +/-5 nanometers; the material of the electron injection layer is LiF, and the film thickness is 1 +/-0.25 nm; the thickness of the aluminum cathode is 120 +/-20 nanometers.
5. The method of claim 3 or 4, wherein the method comprises the following steps:
and transferring the pretreated ITO glass into a vacuum coating system, and sequentially evaporating and coating a hole injection layer, a hole transport layer, an electron barrier layer, a luminescent layer, an electron transport layer, an electron injection layer and an aluminum cathode on the ITO layer to obtain the fluorescence/phosphorescence mixed white light organic light-emitting diode.
6. The method of claim 5, wherein the glass ITO is pre-treated by the following steps: firstly, performing ultrasonic treatment on the glass ITO for 60-90 minutes, then cleaning the glass ITO by using deionized water, and drying the glass ITO by using nitrogen; then baking the mixture in a vacuum oven at 120 ℃ for 30-60 minutes, and then treating the mixture for 6 +/-1 minutes by using ultraviolet ozone plasma.
7. The method of claim 5, wherein the step of preparing the fluorescence/phosphorescence hybrid white organic light emitting diode comprises: the vacuum degree of the vapor deposition is 1 × 10-5～5×10-5And (6) handkerchief.
8. The method of claim 5, wherein the step of preparing the fluorescence/phosphorescence hybrid white organic light emitting diode comprises: the evaporation rate of the materials of the hole injection layer and the electron injection layer is controlled to be 0.03-0.05 nm/s; the evaporation rate of the hole transport layer, the electron blocking layer, the blue light fluorescence luminescent layer and the electron transport layer is controlled to be 0.05-0.1 nanometer/second; the evaporation rate of the yellow phosphorescent light-emitting layer is controlled to be 0.001-0.01 nm/s; the evaporation rate of the aluminum cathode is controlled to be 0.5-1 nm/s.
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