CN113851592A - Organic light-emitting device and application thereof - Google Patents
Organic light-emitting device and application thereof Download PDFInfo
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- CN113851592A CN113851592A CN202111118072.2A CN202111118072A CN113851592A CN 113851592 A CN113851592 A CN 113851592A CN 202111118072 A CN202111118072 A CN 202111118072A CN 113851592 A CN113851592 A CN 113851592A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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Abstract
The invention discloses an organic light emitting device, comprising: the light-emitting diode comprises an anode, a cathode and at least three light-emitting layers which are positioned between the anode and the cathode in a laminated manner; the at least three light-emitting layers comprise a first light-emitting layer and a second light-emitting layer; in the at least three luminescent layers, the layers close to the anode and the cathode are both first luminescent layers, and the first luminescent layers and the second luminescent layers are alternately arranged. Compared with the prior art, the invention partially separates the triplet excitons in the luminescent layer into the singlet excitons and the singlet excitons which are transferred to the doping material, thereby ensuring that the responsibility of the functional layer of the device is more definite, and further improving the efficiency and the photochromic purity of the device; furthermore, the luminescent layer in the organic luminescent device provided by the invention is symmetrically distributed, so that the luminescent color of the device does not change after the device works for a long time.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an organic light-emitting device and application thereof.
Background
Organic electroluminescent materials (OLEDs), as a new generation display technology, have the advantages of being ultra-thin, self-luminescent, wide viewing angle, fast response, high luminous efficiency, good temperature adaptability, simple production process, low driving voltage, low energy consumption, and the like, and have been widely used in the industries of flat panel display, flexible display, solid state lighting, vehicle-mounted display, and the like.
According to the light emitting mechanism, the materials used for the light emitting layer of the OLED mainly include four materials, i.e., a fluorescent material, a phosphorescent material, a triplet-triplet annihilation (TTA) material, and a Thermally Activated Delayed Fluorescence (TADF) material. Among them, TADF materials have a low single triplet energy level difference, and triplet excitons in the emissive layer can be converted into singlet excitons through the TADF materials under thermal disturbance. A light emitting device employing the principle of TADF can achieve internal quantum efficiency of 100% in theory. However, due to the characteristics of TADF materials, the separated HOMO and LUMO energy levels result in a wider spectrum, and currently, a method of simultaneously doping a light-emitting layer with a highly efficient fluorescent dye is generally adopted to improve color purity, which is referred to as super-fluorescence in the industry.
Disclosure of Invention
The present invention provides an organic light emitting device comprising: the light-emitting diode comprises an anode, a cathode and at least three light-emitting layers which are positioned between the anode and the cathode in a laminated manner;
the at least three light-emitting layers comprise a first light-emitting layer and a second light-emitting layer;
in the at least three luminescent layers, the layers close to the anode and the cathode are first luminescent layers, and the first luminescent layers and the second luminescent layers are alternately arranged;
the first type of light-emitting layer comprises a host material, a guest material and a light-emitting doping material; the second type of light-emitting layer comprises a main body material and a light-emitting doping material; the doping concentration of the luminescent doping material in the first luminescent layer is less than that of the luminescent doping material in the second luminescent layer;
the guest material in the first type of light-emitting layer is selected from thermally activated delayed fluorescence materials;
the light emitting doping material in the first type light emitting layer and the light emitting doping material in the second type light emitting layer are respectively and independently selected from fluorescent materials.
Preferably, the at least three light-emitting layers include a first light-emitting layer, a second light-emitting layer and a third light-emitting layer which are sequentially arranged;
the first light-emitting layer comprises a first host material, a first guest material and a first light-emitting doped material; the doping concentration of the first luminescent doping material in the first luminescent layer is less than 1%;
the second luminescent layer comprises a second host material and a second luminescent doping material; the doping concentration of the second luminescent doping material in the second luminescent layer is more than 1 percent;
the third luminescent layer comprises a third host material, a second guest material and a third luminescent doping material; the doping concentration of the third luminescent doping material in the third luminescent layer is less than 1%;
the first guest material and the second guest material are respectively and independently thermal activation delayed fluorescence materials;
the first luminescent doping material, the second luminescent doping material and the third luminescent doping material are respectively and independently fluorescent materials.
Compared with the prior art, the invention partially separates the triplet excitons in the luminescent layer into the singlet excitons and the singlet excitons which are transferred to the doping material, thereby ensuring that the responsibility of the functional layer of the device is more definite, and further improving the efficiency and the photochromic purity of the device; furthermore, the luminescent layer in the organic luminescent device provided by the invention is symmetrically distributed, so that the luminescent color of the device does not change after the device works for a long time.
Drawings
Fig. 1 is a schematic structural diagram of an organic light emitting device provided by the present invention.
Fig. 2 is a schematic view of a light emitting mechanism of an organic light emitting device provided by the present invention;
fig. 3 is a schematic view of a light emitting mechanism of an organic light emitting device provided by the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. A
The inventor researches and discovers that: since the TADF material has a close single triplet energy level, the triplet energy level is often higher, so that under the condition of higher fluorescent dye doping, triplet excitons of the TADF material may be transferred to the fluorescent dye, and the triplet excitons of the fluorescent dye cannot emit light, thereby reducing the efficiency of the whole device. Although lower fluorescent dye doping can reduce the transfer of triplet excitons to the fluorescent dye, it also reduces the transfer of singlet excitons, making it difficult to obtain optimal color purity. Therefore, the technical problem to be solved by the present invention is to provide an organic light emitting device and an application thereof, wherein the organic light emitting device has good device efficiency and color purity, and the organic light emitting device has a structure with good stability and no light emitting color drift after long-time operation.
In view of the above, the second type light emitting layer is disposed between the two first type light emitting layers to form a system in which two layers of super-fluorescence are mixed with one layer of fluorescence, so that two processes of converting triplet excitons in the light emitting layer into singlet excitons and transferring the singlet excitons to the doping material are partially separated, thereby making the responsibility of the device function layer more definite, and improving the efficiency and the photochromic purity of the device, specifically as follows:
the present invention provides an organic light emitting device comprising: the light-emitting diode comprises an anode, a cathode and at least three light-emitting layers which are positioned between the anode and the cathode in a laminated manner;
the at least three light-emitting layers comprise a first light-emitting layer and a second light-emitting layer;
in the at least three luminescent layers, the layers close to the anode and the cathode are first luminescent layers, and the first luminescent layers and the second luminescent layers are alternately arranged;
the first type of light-emitting layer comprises a host material, a guest material and a light-emitting doping material; the second type of light-emitting layer comprises a main body material and a light-emitting doping material; the doping concentration of the luminescent doping material in the first luminescent layer is less than that of the luminescent doping material in the second luminescent layer;
the guest material in the first type of light-emitting layer is selected from thermally activated delayed fluorescence materials;
the light emitting doping material in the first type light emitting layer and the light emitting doping material in the second type light emitting layer are respectively and independently selected from fluorescent materials.
In addition, the organic light emitting device provided by the invention comprises an anode; the anode material thereof may be selected from metals such as copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof; may also be selected from metal oxides such as indium oxide, zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; the anode material may also be selected from conductive polymers such as polyaniline, polypyrrole, poly (3-methylthiophene), and the like. In addition, the anode material may also be selected from materials that facilitate hole injection in addition to the anode materials listed above, and combinations thereof, including known materials suitable for use as anodes. The cathode material in the organic light emitting device provided by the present invention may be selected from metals such as aluminum, magnesium, silver, indium, tin, titanium, etc., and alloys thereof. The cathode material may also be selected from multi-layered metallic materials such as LiF/Al, LiO2/Al、BaF2Al, etc. In addition to the cathode materials listed above, the cathode materials can also be materials that facilitate electron injection and combinations thereof, including materials known to be suitable as cathodes.
At least three layers of luminous layers are arranged between the anode and the cathode in a laminated manner; in the invention, the light-emitting layer comprises a first type light-emitting layer and a second type light-emitting layer; wherein, the luminescent layers close to the anode and the cathode are the first luminescent layers, and the two luminescent layers are alternately arranged; namely, the first type of light-emitting layer is at least two layers, and is positioned at the uppermost layer and the lowermost layer of the light-emitting layer.
The thickness of each layer of the first type light-emitting layer is independently preferably 10nm or less; the thicknesses of all layers can be the same or different, in the invention, the thicknesses of the first type light-emitting layers at least positioned at the two outermost sides of the light-emitting layers are preferably the same, and the thicknesses of the first type light-emitting layers which are symmetrical by taking the second type light-emitting layer in the middle of the light-emitting layers as a center are more preferably the same, so that the whole light-emitting layers are symmetrically arranged, and the efficiency and the spectrum of the whole device can not be severely changed due to the change of a recombination center in the long-time operation process of the device.
The first type of light-emitting layer comprises a host material, an object material and a light-emitting doping material, and forms a super-fluorescent system light-emitting layer; the types of the host material, the guest material and the light-emitting doping material in each first type light-emitting layer can be the same or different, and are not particularly limited; the concentrations of the host material, the guest material and the luminescent doping material in the first luminescent layer can be the same or different, and are not limited; in the invention, most preferably, the types and concentrations of the host material, the guest material and the light-emitting doping material in each layer of the first type light-emitting layer are the same, so that the light-emitting device is symmetrical not only in structure but also in composition, the stability of the device is further improved, and the light-emitting color does not change after the light-emitting device is operated for a long time.
In the invention, optionally, the host material in the first light-emitting layer is one or more of arylamine compounds, arylphosphorus compounds, anthracene compounds, triazine compounds, carbazole compounds containing imine substituents and arylsilicon compounds, and more preferably one or more of formulas (I-1) to (I-8).
Optionally, the mass concentration of the guest material in the first type light-emitting layer is 10% -90%, or 20% -80%, or 30% -70%, or 30% -60%; in the embodiment provided by the invention, the mass concentration of the guest material in the first type light-emitting layer is specifically 30-50%; the difference in the singlet-triplet level of the guest material is preferably 0.3eV or less; it can be a single material or an exciplex formed from two materials; the above condition is satisfied, and optionally, the guest material is a compound represented by formula (II-1) and/or formula (II-2):
in the invention, the doping concentration of the luminescent doping material in each layer of the first luminescent layer is less than 1%, and is optionally 0.1-0.9%, or 0.2-0.7%, or 0.3-0.6%, or 0.4-0.6% independently; in the embodiment provided by the invention, the doping concentration of the light-emitting doping material in the first type light-emitting layer is specifically 0.5%; if the concentration of the doping material is less than 0.5%, the energy transfer is insufficient, and if the concentration of the doping material is more than 0.5%, the triplet excitons can also be transferred, so that the efficiency of the device can be optimized by the doping concentration of 0.5% in the embodiment of the invention; in the present invention, optionally, the types of the light emitting doping materials in each layer of the first type light emitting layer are respectively and independently one or more of an aromatic fused ring fluorescent material, a pyran fluorescent material, an aromatic amine fluorescent material, a resonance type delayed fluorescent material and a pyrromethene derivative fluorescent material, and more specifically, one or more of formulas (III-1) to (III-27).
Wherein, R in the formulas (III-7) to (III-18) is independently preferably one or more of hydrogen, halogen, cyano, C1-C10 alkyl, C2-C6 alkenyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C30 aryl and C3-C30 heteroaryl, more preferably one or more of hydrogen, halogen, cyano, C1-C6 alkyl, C2-C4 alkenyl, C1-C4 alkoxy, C1-C4 thioalkoxy, C6-C20 aryl and C3-C20 heteroaryl, and still more preferably one or more of hydrogen, chlorine, cyano, C1-C4 alkyl, C2-C72 alkenyl, C3 alkoxy, C3-C3 alkoxy, C8672-C3 thioalkoxy, C3-C3 alkoxy and C3-C3 heteroaryl.
The second type light-emitting layer in the light-emitting layers is positioned between two first type light-emitting layers, namely a second type light-emitting layer is arranged between every two first type light-emitting layers; the thickness of the second type light-emitting layer is preferably 20nm or less; when the organic light-emitting device provided by the invention comprises a plurality of second type light-emitting layers, the thicknesses of the layers can be the same or different, and are not particularly limited, and the thicknesses are preferably the same so that the whole light-emitting device is designed in a symmetrical structure; in the examples provided by the present invention, the thickness is specifically 10 nm.
In the invention, the second type of light-emitting layer comprises a main material and a light-emitting doping material, and is a common fluorescent light-emitting layer; when the number of the second type light-emitting layers is greater than or equal to 2, the host material and the light-emitting doping material in each second type light-emitting layer may be the same or different, and are not particularly limited; in the present invention, when the second type light-emitting layer is a multilayer, the type and concentration of the host material and the light-emitting dopant material in each layer are preferably the same, so that the light-emitting device is also provided in a symmetrical structure in terms of composition.
When the triplet level of the host material in the second type of light-emitting layer is T1 and the triplet level of the light-emitting dopant material is T2, T1-T2 is preferably greater than 0.3 eV; the singlet energy level of the host material in the second type of light-emitting layer is preferably lower than the singlet energy level of the guest material in the first type of light-emitting layer; the triplet energy level of the host material in the light-emitting layer of the second type is preferably lower than the triplet energy level of the guest material. After the triplet excitons in the light-emitting layer are converted into singlet excitons through the arrangement of different material energy levels in the light-emitting layer, the excess singlet excitons can be consumed through the second type light-emitting layer, so that the efficiency and the photochromic purity of the device are improved.
In the present invention, the host material in the second type light-emitting layer is preferably one or more of arylamine compounds, arylphosphorus compounds, anthracene compounds, triazine compounds, carbazole compounds containing imine substituents and arylsilicon compounds, and more preferably one or more of formulas (I-1) to (I-8).
In the present invention, the doping concentration of the light emitting dopant in the second type of light emitting layer is greater than 1%, optionally greater than or equal to 2%, optionally 2% to 10%, optionally 3% to 10%, and if the doping concentration is less than 3%, singlet excitons cannot be transferred, and if the doping concentration is greater than 10%, the singlet excitons will have a solvation effect. In the embodiment provided by the invention, the concentration of the light-emitting doping material in the second type light-emitting layer is specifically 5% -10%. The kind of the luminescent doping material is preferably one or more of an aromatic condensed ring fluorescent material, a pyran fluorescent material, an aromatic amine fluorescent material, a resonance type delayed fluorescent material and a pyrromethene derivative fluorescent material, and more preferably one or more of formulas (III-1) to (III-27).
According to the invention, the number of the light-emitting layers which are arranged between the anode and the cathode in a laminated manner can be selected from 3, 5, 7 or 9, so that the upper, lower and outermost sides of the light-emitting layers are both first-class light-emitting layers, and the light-emitting layers are symmetrically arranged; taking an organic light-emitting device comprising three light-emitting layers as an example, the organic light-emitting device comprises an anode, a cathode, a first light-emitting layer, a second light-emitting layer and a third light-emitting layer, wherein the first light-emitting layer, the second light-emitting layer and the third light-emitting layer are sequentially arranged between the anode and the cathode; the first light-emitting layer comprises a first host material, a first guest material and a first light-emitting doped material; the doping concentration of the first luminescent doping material in the first luminescent layer is less than 1%; the second luminescent layer comprises a second host material and a second luminescent doping material; the doping concentration of the second luminescent doping material in the second luminescent layer is more than 1 percent; the third luminescent layer comprises a third host material, a second guest material and a third luminescent doping material; the doping concentration of the third luminescent doping material in the third luminescent layer is less than 1%; the first guest material and the second guest material are respectively and independently thermal activation delayed fluorescence materials; the first luminescent doping material, the second luminescent doping material and the third luminescent doping material are respectively and independently fluorescent materials.
The first light-emitting layer and the third light-emitting layer are first light-emitting layers which are all super-fluorescent system light-emitting layers; in the invention, the thicknesses of the optional first light-emitting layer and the third light-emitting layer are respectively and independently less than or equal to 10 nm; the thicknesses of the first light-emitting layer and the third light-emitting layer can be the same or different, and optionally, in the invention, the thickness of the first light-emitting layer is the same as that of the third light-emitting layer, so that the whole structure of the light-emitting layers is symmetrically arranged, and the light-emitting efficiency is more stable.
In the present invention, the first host material and the third host material are each independently preferably one or more of an arylamine compound, an arylphosphorus compound, an anthracene compound, a triazine compound, a carbazole compound containing an imine substituent, and an arylsilicon compound, and optionally, each independently is one or more of formulas (I-1) to (I-8).
Optionally, the mass concentration of the first guest material in the first light-emitting layer is 10% to 90%, or 20% to 80%, or 30% to 70%, or 40% to 60%; in the embodiment provided by the present invention, the mass concentration of the first guest material in the first light emitting layer is specifically 50%; optionally, the mass concentration of the second guest material in the third light-emitting layer is 10% to 90%, or 20% to 80%, or 30% to 70%, or 30% to 60%, or 30% to 50%; the difference in the singlet-triplet level between the first guest material and the second guest material is preferably 0.3eV or less independently of each other; the first guest material and the second guest material can be a single material or an exciplex formed by two materials; in the invention, optionally, the first guest material and the second guest material are each independently a compound represented by formula (II-1) and/or formula (II-2).
In the invention, the doping concentration of the first luminescent doping material in the first luminescent layer is less than 1%, and further 0.1% to 0.9%, or 0.2% to 0.7%, or 0.3% to 0.6%, or 0.4% to 0.6%; in the embodiments provided by the present invention, the doping concentration of the first luminescent material in the first luminescent layer is specifically 0.5%; the doping concentration of the third luminescent doping material in the third luminescent layer is less than 1%, and further optionally, the doping concentration is 0.1% -0.9%, or 0.2% -0.7%, or 0.3% -0.6%, or 0.4% -0.6%; in the embodiment provided by the invention, the doping concentration is specifically 0.5%; the first luminescent doping material and the third luminescent doping material can be the same or different in type, and can be selected as the same doping material in the invention; the doping materials are the same in type and concentration, so that the whole light-emitting layer is structurally and compositionally symmetrical, and the light-emitting efficiency and purity of the device are further ensured; the first luminescent doping material and the third luminescent doping material are preferably one or more of an aromatic fused-ring fluorescent material, a pyran fluorescent material, an aromatic amine fluorescent material, a resonance-type delayed fluorescent material and a pyrromethene derivative fluorescent material, and are optionally one or more of formulas (III-1) to (III-27) independently.
A second light-emitting layer is arranged between the first light-emitting layer and the third light-emitting layer; the second light-emitting layer is a second light-emitting layer, the thickness of the second light-emitting layer is preferably less than or equal to 20nm, and the thickness of the second light-emitting layer is optionally 5-20 nm or 5-15 nm; in the embodiments provided by the present invention, the thickness of the second light emitting layer is specifically 10 nm.
The second luminescent layer comprises a second main material and a second luminescent doping material, and is a common fluorescent luminescent layer; in the present invention, the singlet energy level of the second host material is preferably lower than the singlet energy level of the thermally activated delayed fluorescence material, that is, lower than the singlet energy levels of the first guest material and the second guest material; the triplet energy level of the second host material is preferably lower than the triplet energy level of the thermally activated delayed fluorescence material, i.e. lower than the triplet energy levels of the first guest material and the second guest material; optionally, the material of the second main body is one or more of arylamine compounds containing carbazole substituent groups, aryl phosphorus compounds, anthracene compounds, triazine compounds, carbazole compounds containing imine substituent groups and aryl silicon compounds, and further may be one or more of formulas (I-1) to (I-8).
The doping concentration of the second luminescent doping material in the second luminescent layer is more than 1%, optionally more than or equal to 2%, further optionally 2% -10%, or 3% -10%, or even 4% -10%; in the embodiment provided by the invention, the doping concentration of the second luminescent doping material is specifically 5% -10%; assuming that the triplet level of the second host material in the second light emitting layer is T1 and the triplet level of the second light emitting dopant material is T2, T1-T2 are preferably greater than 0.3 eV; in the present invention, the second light-emitting doped material satisfying the above conditions may be one or more selected from an aromatic fused-ring fluorescent material, a pyran fluorescent material, an aromatic amine fluorescent material, a resonance-type delayed fluorescent material and a pyrromethene derivative fluorescent material, and further may be one or more selected from formulas (III-1) to (III-27).
The organic electroluminescent device provided by the invention can optionally comprise one or more layers of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer besides the luminescent layer.
The organic electroluminescent device may be fabricated according to a method known in the art and will not be described in detail herein. In the present invention, the organic electroluminescent device can be fabricated by: an anode is formed on a transparent or opaque smooth substrate, a light-emitting layer is formed on the anode, and a cathode is formed on the light-emitting layer. The light-emitting layer can be formed by a known film formation method such as evaporation, sputtering, spin coating, dipping, ion plating, or the like.
Specifically, referring to fig. 1, fig. 1 is a schematic structural diagram of an organic light emitting device provided by the present invention; wherein 1 is an anode, 2 is a hole injection layer and/or a hole transmission layer, 3 is a first luminescent layer, 4 is a second luminescent layer, 5 is a first luminescent layer, 6 is an electron injection layer and/or an electron transmission layer, 7 is a cathode, and 8-10 are luminescent doping materials.
Referring to fig. 2 and 3, fig. 2 and 3 are schematic views illustrating a light emitting mechanism of an organic light emitting device according to the present invention.
The invention partially separates the two processes of converting the triplet excitons in the luminescent layer into the singlet excitons and transferring the singlet excitons to the doping material, thereby ensuring that the responsibility of the functional layer of the device is more definite, and further improving the efficiency and the photochromic purity of the device; furthermore, the luminescent layer in the organic luminescent device provided by the invention is symmetrically distributed, so that the luminescent color of the device does not change after the device works for a long time.
The invention also provides a display device comprising the display panel. In the invention, the display device can be a mobile phone display screen, a computer display screen, a television display screen, an intelligent watch display screen, an intelligent automobile display screen, a VR or AR helmet display screen, display screens of various intelligent devices and the like.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention adopts a mode of testing the performance of an OLED device to illustrate the effect of the invention, the structure of the OLED device is ITO (150)/HIL (10)/HTL (95)/EBL (10)/EML (30)/HBL (5)/ETL (30)/LiF (1)/Al (1000), and the unit of the film thickness is nm. HIL is an english abbreviation of hole injection layer. HTL is an english abbreviation of hole transport layer. EBL is an english abbreviation for electron blocking layer. EML is an english abbreviation of light emitting layer. HBL is an english abbreviation for hole blocking layer. ETL is an english abbreviation of electron transport layer. LiF and Al are abbreviations for lithium fluoride and aluminum, respectively.
The general preparation steps of the OLED device are as follows:
(1) and (3) carrying out ultrasonic treatment on the patterned ITO substrate in isopropanol and deionized water for 30min, and drying. Before being placed into a cavity, the ITO substrate is treated in ultraviolet ozone equipment for 10 min; the vacuum degree of the cavity reaches 2 multiplied by 10-5At Pa, vapor deposition is started.
(2) The compound HATCN was vacuum-evaporated onto the ITO anode layer to a thickness of 10nm as HIL. (ii) a
(3) Evaporating a compound NPB as HTL on the HIL, wherein the thickness is 95 nm;
(4) evaporating 2-TNATA on HTL to form EBL with thickness of 10nm
(5) The EML is vapor-deposited on the EBL as a non-common step, and the specific manufacturing method will be described later.
(6) Evaporating a compound TPBI on EML in vacuum to serve as HBL, wherein the thickness is 5 nm;
(7) evaporating a compound Bphen on HBL in vacuum to be used as ETL, wherein the thickness is 30 nm;
(8) aluminum was evaporated onto the ETL to a thickness of 100 nm.
Device example 1
The first light-emitting layer structure in the light-emitting layer is MCP:4CZIPN: TTPA (30%, 0.5%, 10), the second light-emitting layer structure is MCP: TTPA (5%, 10), and the third light-emitting layer structure is MCP:4CZIPN: TTPA (30%, 0.5%, 10). First, a first light-emitting layer is evaporated, wherein the MCP rate is 0.065nm/s, the 4CZIPN rate is 0.03nm/s, the TTPA rate is 0.005nm/s, and the film thickness is 10 nm. And evaporating a second light-emitting layer on the first light-emitting layer, wherein the MCP rate is 0.095nm/s, the TTPA rate is 0.005nm/s, and the thickness is 10 nm. And evaporating a third light-emitting layer on the second light-emitting layer, wherein the MCP rate is 0.065nm/s, the 4CZIPN rate is 0.03nm/s, the TTPA rate is 0.005nm/s, and the thickness is 10 nm.
Device example 2
The first light-emitting layer structure in the light-emitting layer is MCP:4CZIPN: TTPA (30%, 0.5%, 10), the second light-emitting layer structure is MCP: TTPA (10%, 10), and the third light-emitting layer structure is MCP:4CZIPN: TTPA (30%, 0.5%, 10). First, a first light-emitting layer is evaporated, wherein the MCP rate is 0.065nm/s, the 4CZIPN rate is 0.03nm/s, the TTPA rate is 0.005nm/s, and the film thickness is 10 nm. And evaporating a second light-emitting layer on the first light-emitting layer, wherein the MCP rate is 0.09nm/s, the TTPA rate is 0.01nm/s, and the thickness is 10 nm. And evaporating a third light-emitting layer on the second light-emitting layer, wherein the MCP rate is 0.065nm/s, the 4CZIPN rate is 0.03nm/s, the TTPA rate is 0.005nm/s, and the thickness is 10 nm.
Comparative device example 1
The first light-emitting layer structure in the light-emitting layer is MCP:4CZIPN: TTPA (30%, 0.5%, 15), the second light-emitting layer structure is MCP: TTPA (5%, 15), the first light-emitting layer is evaporated, the MCP rate is 0.06nm/s, the 4CZIPN rate is 0.03nm/s, the TTPA rate is 0.01nm/s, and the film thickness is 15 nm. And evaporating a second light-emitting layer on the first light-emitting layer, wherein the MCP rate is 0.095nm/s, the TTPA rate is 0.005nm/s, and the thickness is 15 nm.
Comparative device example 2
The light-emitting layer was MCP 4CZIPN TTPA (30%, 0.5%, 30), the MCP rate was 0.0695nm/s, the 4CZIPN rate was 0.03nm/s, the TTPA rate was 0.0005nm/s, and the film thickness was 30 nm.
Comparative device example 3
The light-emitting layer was MCP 4CZIPN TTPA (30%, 5%, 30), the MCP rate was 0.065nm/s, the 4CZIPN rate was 0.03nm/s, the TTPA rate was 0.005nm/s, and the film thickness was 30 nm.
The above devices were lighted and tested using a spectroradiometer and a programmable power supply, and the test results are shown in table 1.
TABLE 1 results of device Performance test
As can be seen from examples 1 and 2, the concentration of the fluorescent dopant in the intermediate layer is increased, and the efficiency of the device can be kept stable thanks to the lower doping concentration of the superfluorescence.
Comparing example 1 with comparative example 1, comparative example 1 shows that recombination centers of devices change due to long-time lighting, and color coordinates shift after long-time lighting due to asymmetric distribution of light emitting layers. Examples since the light emitting layer exhibited a symmetrical distribution, the spectrum hardly changed after long-time lighting.
Comparing example 1 with comparative example 2, comparative example 2 is a structure of super fluorescence, energy cannot be sufficiently transferred to a fluorescent dopant due to low fluorescent doping, and color coordinates of a device are not pure.
Comparing example 1 with comparative example 3, comparative example 3 is a super-fluorescent structure, and due to the higher fluorescence doping concentration, the energy transfer efficiency based on dexter is greatly increased, and the fluorescent material cannot convert triplet state energy into light, so that the efficiency of the device is obviously reduced.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (16)
1. An organic light-emitting device, comprising: the light-emitting diode comprises an anode, a cathode and at least three light-emitting layers which are positioned between the anode and the cathode in a laminated manner;
the at least three light-emitting layers comprise a first light-emitting layer and a second light-emitting layer;
in the at least three luminescent layers, the layers close to the anode and the cathode are both first luminescent layers, and the first luminescent layers and the second luminescent layers are alternately arranged;
the first type of light-emitting layer comprises a host material, a guest material and a light-emitting doping material; the second type of light-emitting layer comprises a main body material and a light-emitting doping material; the doping concentration of the light-emitting doping material in the first type light-emitting layer is smaller than that of the light-emitting doping material in the second type light-emitting layer;
the guest material in the first type of light-emitting layer is selected from thermally activated delayed fluorescence materials;
the light-emitting doping material in the first type light-emitting layer and the light-emitting doping material in the second type light-emitting layer are respectively and independently selected from fluorescent materials.
2. The organic light-emitting device according to claim 1, wherein the doping concentration of the light-emitting dopant material in the first type light-emitting layer is less than 1%; the doping concentration of the luminescent doping material in the second type luminescent layer is more than 1%.
3. The organic light-emitting device according to claim 2, wherein the at least three light-emitting layers include a first light-emitting layer, a second light-emitting layer, and a third light-emitting layer, which are provided in this order;
the first light-emitting layer comprises a first host material, a first guest material and a first light-emitting doped material; the doping concentration of the first luminescent doping material in the first luminescent layer is less than 1%;
the second luminescent layer comprises a second host material and a second luminescent doping material; the doping concentration of the second luminescent doping material in the second luminescent layer is more than 1%;
the third light-emitting layer comprises a third host material, a second guest material and a third light-emitting doped material; the doping concentration of a third luminescent doping material in the third luminescent layer is less than 1%;
the first guest material and the second guest material are each independently a thermally activated delayed fluorescence material;
the first luminescent doping material, the second luminescent doping material and the third luminescent doping material are respectively and independently fluorescent materials.
4. The organic light-emitting device of claim 3, wherein the triplet energy level of the second host material is T1; the triplet energy level of the second light emitting dopant material is T2; T1-T2 is greater than 0.3 eV.
5. The organic light-emitting device according to claim 3, wherein the singlet state energy level of the second host material is lower than the singlet state energy level of the thermally-activated delayed fluorescence material; the triplet energy level of the second host material is lower than the triplet energy level of the thermally activated delayed fluorescence material.
6. The organic light-emitting device according to claim 3, wherein the doping concentration of the second light-emitting dopant material in the second light-emitting layer is greater than 2%.
7. The organic light-emitting device of claim 3, wherein the first and third emissive dopant materials are the same.
8. The organic light-emitting device according to claim 3, wherein the first light-emitting layer and the third light-emitting layer each independently have a thickness of 10nm or less;
the thickness of the second light-emitting layer is less than or equal to 20 nm.
9. The organic light-emitting device according to claim 3, wherein the thickness of the first light-emitting layer is the same as the thickness of the third light-emitting layer.
10. The organic light-emitting device according to claim 3, wherein the mass concentration of the first guest material in the first light-emitting layer is 10% to 90%;
the mass concentration of the second guest material in the third light-emitting layer is 10-90%.
11. The organic light-emitting device according to claim 3, wherein the first host material, the second host material and the third host material are each independently selected from one or more of arylamine compounds containing carbazole substituents, arylphosphorus compounds, anthracene compounds, triazine compounds, carbazole compounds containing imine substituents and arylsilicon compounds.
12. The organic light-emitting device according to claim 3, wherein the first host material, the second host material and the third host material are each independently selected from one or more of formulas (I-1) to (I-8):
13. the organic light-emitting device according to claim 3, wherein the difference in the singlet triplet level of the first guest material and the second guest material is each independently 0.3eV or less; the first guest material and the second guest material are single materials or exciplex formed by two materials.
14. The organic light-emitting device according to claim 3, wherein the first guest material and the second guest material are each independently selected from compounds represented by formula (II-1) and/or formula (II-2):
15. the organic light-emitting device according to claim 3, wherein the first light-emitting doped material, the second light-emitting doped material and the third light-emitting doped material are each independently one or more of an aromatic fused-ring fluorescent material, a pyran fluorescent material, an aromatic amine fluorescent material, a resonance-type delayed fluorescent material and a pyrromethene derivative fluorescent material.
16. A display device comprising the organic light-emitting device according to any one of claims 1 to 15.
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| CN110854279A (en) * | 2019-10-22 | 2020-02-28 | 深圳市华星光电技术有限公司 | OLED display panel and display device |
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| CN110854279A (en) * | 2019-10-22 | 2020-02-28 | 深圳市华星光电技术有限公司 | OLED display panel and display device |
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