CN116615044A - Doped material, preparation method thereof, light emitting diode and display device - Google Patents
Doped material, preparation method thereof, light emitting diode and display device Download PDFInfo
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Abstract
The application discloses a doped material, a preparation method thereof, a light emitting diode and a display device. The doping material comprises an aromatic diimide compound and a conjugated amine polymer doped with the aromatic diimide compound. An electrode modification layer is added between the cathode of the light-emitting diode and the electron transport layer, and the material of the electrode modification layer is selected from doping materials. By introducing the weak n-type doped electrode modification layer, the electron transmission performance of the aluminum electrode is improved, and meanwhile, the erosion of the electron transmission layer to the cathode is reduced.
Description
Technical Field
The application relates to the technical field of display, in particular to a doped material, a preparation method thereof, a light emitting diode and a display device.
Background
The Quantum Dot (QD) is a semiconductor cluster with a size of 1-10 nm, has an adjustable band gap photoelectron property due to Quantum size effect, and can be applied to the fields of light emitting diodes, solar cells, biological fluorescent markers and the like. The light emission of the required specific wavelength is realized by regulating the size of the quantum dot, and the quantum dot elements can be divided into II-VI group quantum dots (such as CdSe, cdS, cdTe, znSe, znS, etc.), III-V group quantum dots (such as GaAs, inAs, inP, etc.), carbon quantum dots and silicon quantum dots. CdSe QDs are currently being studied in many ways, with emission wavelength tuning ranging from blue to red. In the conventional inorganic electroluminescent device, electrons and holes are injected from a cathode and an anode, respectively, and then are recombined in a light emitting layer to form exciton light emission. Conduction band electrons in a wide bandgap semiconductor can be accelerated under a high electric field to obtain high enough energy to strike QDs to cause them to emit light. The semiconductor quantum dot material is used as a novel inorganic semiconductor fluorescent material and has important commercial application value.
The materials currently used as cathodes in quantum dot light emitting diode (Quantum Dot Light Emitting Diodes, QLED) devices are mainly metal electrodes with low work functions, such as silver (Ag), aluminum (Al), agMg alloys, etc. Al is used as a cathode material, so that the cost is low, and on the premise of ensuring the performance, the production cost of the electrode is reduced as much as possible, so that the commercialization of the QLED is realized. However, al still has a certain difference in electron transport properties from Ag. Meanwhile, al is relatively active and is easily influenced by environmental water oxygen and hydroxyl on the surface of the ZnO of the electron transport layer, for example, the surface of an Al material is easily oxidized in the air to form an Al2O3 compact layer, so that electron transport is influenced. Thus, the solution using Al as the cathode material still has room for improvement.
Disclosure of Invention
The application provides a doping material, a preparation method thereof, a light emitting diode and a display device, wherein the doping material is introduced between a cathode and an electron transport layer, so that the problem of lower electron transport performance of an aluminum electrode is solved.
The application provides a doping material, which comprises an aromatic diimide compound and a conjugated amine polymer doped with the aromatic diimide compound.
Alternatively, in some embodiments of the application, the aromatic diimide compound comprises a naphthalene diimide or a perylene diimide.
Alternatively, in some embodiments of the application, the conjugated amine polymer comprises polyaniline, polyethoxyethyleneimine, or polyaminoanthraquinone.
Alternatively, in some embodiments of the application, the conjugated amine polymer has an average molecular weight in the range of 10000 to 200000.
Alternatively, in some embodiments of the present application, the doping material is composed of an aromatic diimide compound and a conjugated amine-type polymer doped into the aromatic diimide compound.
Alternatively, in some embodiments of the application, the molar ratio of aromatic diimide compound to conjugated amine polymer is 1 to 10:1.
Correspondingly, the application also provides a preparation method of the doping material, which comprises the following steps: adding an aromatic diimide compound into an organic solvent to form an aromatic diimide compound solution, adding a conjugated amine polymer, and mixing to obtain the doped material.
Alternatively, in some embodiments of the application, the molar ratio of aromatic diimide compound to conjugated amine polymer is 1 to 10:1.
Alternatively, in some embodiments of the application, the concentration of the aromatic diimide solution is 0.01 to 0.1mol/L.
Alternatively, in some embodiments of the application, the organic solvent comprises at least one of N, N-dimethylformamide or dimethylsulfoxide.
In addition, the application also provides a light-emitting diode, which comprises an anode, a light-emitting layer, an electron transmission layer, an electrode modification layer and a cathode which are sequentially stacked; the electrode modification layer is made of the doped material or the electrode modification layer is made of the doped material prepared by the preparation method.
Alternatively, in some embodiments of the application, the thickness of the electrode modifying layer is 5 to 10nm.
Alternatively, in some embodiments of the application, the material of the cathode is selected from aluminum.
Alternatively, in some embodiments of the application, the light emitting layer is a quantum dot light emitting layer.
Alternatively, in some embodiments of the present application, the material of the electron transport layer includes at least one of ZnO, snO2, tiO 2.
Optionally, in some embodiments of the present application, the light emitting layer is a quantum dot light emitting layer, and a quantum dot material of the quantum dot light emitting layer includes at least one of CdS, cdSe, cdTe, znO, znS, znSe, znTe, gaAs, gaP, gaSb, hgS, hgSe, hgTe, inAs, inP, inSb, alAs, alP, cuInS or CuInSe.
Alternatively, in some embodiments of the application, the material of the anode comprises at least one of Au, ITO, IZO, al, pt or Si.
The application also provides a display device which comprises the light emitting diode.
The application has the following beneficial effects by introducing doping materials between the cathode and the electron transport layer:
the conjugated amine polymer is doped into the aromatic diimide compound, and the electron donating group on the conjugated amine polymer has a certain weak n-type doping effect on the aromatic diimide compound, so that the doping material can enhance electron injection and transmission relative to the aromatic diimide compound.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method of preparing a dopant material;
FIG. 2 is a block diagram of a front-mounted LED;
fig. 3 is a block diagram of an inverted light emitting diode.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
The application provides a doped material, a preparation method thereof, a light emitting diode and a display device. The following will describe in detail. The following description of the embodiments is not intended to limit the preferred embodiments.
In the present application, an aromatic group refers to a hydrocarbon group containing at least one aromatic ring.
In the application, conjugated refers to electron delocalization of molecular orbitals, so that the bond length of single bonds and double bonds between adjacent atoms is averaged, and the molecular energy is reduced.
The embodiment of the application provides a doping material, which comprises an aromatic diimide compound and a conjugated amine polymer doped into the aromatic diimide compound. Because the electron donating group on the conjugated amine polymer has a certain weak n-type doping effect on the aromatic diimide compound, compared with the aromatic diimide compound, the doping material can enhance electron injection and transmission; the doping material is introduced between the aluminum electrode and the electron transport layer, and the conjugated amine polymer plays a role of smoothing the electron transport layer, so that the film formation is more uniform and the film formation quality is better when the electrode is evaporated, thereby reducing the defect recombination of excitons and improving the efficiency of the device.
In some embodiments of the application, the aromatic diimide compound comprises a naphthalene diimide or a perylene diimide. Aromatic diimide is a common organic semiconductor material, has good photoelectric properties, and is widely applied to multifunctional photoelectric devices. However, most of the aromatic diimide compounds at present do not exhibit the desired electron transporting property.
In some embodiments of the application, the conjugated amine polymer is a weak n-type conjugated polymer, and the conjugated amine polymer comprises polyaniline, polyethoxyethyleneimine, or polyaminoanthraquinone. The conjugated amine polymer has high electron mobility, simple synthesis method, high interfacial efficiency in injecting and collecting electrons, and powerful stability under the conditions of material processing and production process. N-type material refers to a material whose conductivity is dominated by electrons.
In some embodiments of the present application, the average molecular weight of the conjugated amine polymer may range from 10000 to 200000, from 50000 to 150000, and from 100000 ～ 130000.
In some embodiments of the application, the doping material consists of an aromatic diimide compound and a conjugated amine polymer doped with the aromatic diimide compound.
In some embodiments of the present application, the molar ratio of the aromatic diimide compound to the conjugated amine polymer may be 1 to 10:1, may be 3 to 7:1, or may be 4 to 6:1.
The doping material provided by the embodiment of the application can be prepared by the following method.
The embodiment of the application also provides a preparation method of the doped material, which comprises the following steps: adding an aromatic diimide compound into an organic solvent to form an aromatic diimide compound solution, adding a conjugated amine polymer, and mixing to obtain the doped material. The doping material is obtained by adopting a physical doping mode.
In some embodiments of the application, the molar ratio of aromatic diimide compound to conjugated amine polymer is 1-10:1, may be 3-7:1, and may be 4-6:1.
In some embodiments of the present application, the concentration of the aromatic diimide solution may be 0.01 to 0.1mol/L, may be 0.03 to 0.08mol/L, and may be 0.04 to 0.06mol/L.
In some embodiments of the application, the organic solvent comprises at least one of N, N-dimethylformamide or dimethylsulfoxide.
In some embodiments of the present application, as shown in fig. 1, a method for preparing a doped material includes:
s1: adding a proper amount of aromatic diamide compound into an organic solvent to form a solution with the total concentration of 0.01-0.1 mol/L;
s2: adding a certain amount of conjugated amine polymer (the molar ratio is aromatic diamide compound: conjugated amine polymer=1-10); stirring for 10-120 min at normal temperature to obtain the doped material.
The embodiment of the application also provides a light-emitting diode, which comprises an anode, a light-emitting layer, an electron transmission layer, an electrode modification layer and a cathode which are sequentially stacked; the electrode modification layer is made of the doped material or the electrode modification layer is made of the doped material prepared by the preparation method. When the doped material prepared by the preparation method is used as a raw material to form the electrode modification layer, a precursor film layer can be formed on the electron transport layer or the cathode by the doped material prepared by the preparation method, and the electrode modification layer is formed after drying and removing the organic solvent.
In some embodiments of the application, the light emitting layer is a quantum dot light emitting layer.
In some embodiments of the present application, a positive quantum dot light emitting diode is provided, as shown in fig. 1, and the materials of the positive quantum dot light emitting diode include, from bottom to top, a substrate 1, an anode 2, a hole transport layer 3, a quantum dot light emitting layer 4, an electron transport layer 5, an electrode modification layer 6, and a cathode 7, where the materials of the electrode modification layer 6 are selected from the above-mentioned doping materials.
In some embodiments of the present application, the thickness of the electrode modification layer 6 may be 5 to 10nm, or 6 to 9nm, or 7 to 8nm.
In some embodiments of the application, the material of the cathode 7 is selected from aluminum. Aluminum, although it is relatively low cost, has some difference in electron transport properties from Ag. Meanwhile, the metal is relatively active, and is easily influenced by environmental water oxygen and hydroxyl on the surface of ZnO, so that electron transmission is influenced. Therefore, the application aims at the aluminum electrode to increase the electrode modification layer and improve the electron transmission capacity of the aluminum electrode.
In some embodiments of the application, the thickness of the cathode 7 may be 60-100 nm, or 70-90 nm, or 80nm.
In some embodiments of the present application, the material of the anode 2 includes at least one of Au, indium doped tin oxide (ITO), indium doped zinc oxide (IZO), al, pt, or Si.
In some embodiments of the present application, the hole transport layer 3 may be made using hole transport materials conventional in the art, including, but not limited to, poly (9, 9-dioctylfluorene-co-N- (4-sec-ylphenyl) -diphenylamine) (TFB), polyvinylcarbazole (PVK), poly [ bis (4-phenyl) (4-butylphenyl) amine (Poly-TPD), tris (carbazole-9-yl) triphenylamine (TCTA), poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT: PSS), 4' -bis (9-Carbazole) Biphenyl (CBP), and the like, or mixtures of any combination thereof, as well as other high performance hole transport materials.
In some embodiments of the present application, the thickness of the hole transport layer 3 may be 20 to 40nm, 25 to 35nm, or 30nm.
In some embodiments of the present application, the quantum dots of the quantum dot light emitting layer 4 are one of red, green and blue. May be CdS, cdSe, cdTe, znO, znS, znSe, znTe, gaAs, gaP, gaSb, hgS, hgSe, hgTe, inAs, inP, inSb, alAs, alP, cuInS, cuInSe, and at least one of various core-shell structured quantum dots.
In some embodiments of the present application, the thickness of the quantum dot light emitting layer 4 may be 20 to 60nm, or 30 to 50nm, or 40nm.
In some embodiments of the present application, the material of the electron transport layer 5 includes at least one of ZnO, snO2, tiO 2.
In some embodiments of the present application, the thickness of the electron transport layer 5 may be 20 to 60nm, 30 to 50nm, or 40nm.
In some embodiments of the present application, an inverted quantum dot light emitting diode is provided, as shown in fig. 2, the substrate 11, the cathode 12, the electrode modification layer 13, the electron transport layer 14, the quantum dot light emitting layer 15, the hole transport layer 16, and the anode 17 are sequentially arranged from bottom to top, and the material of the electrode modification layer 13 is selected from the doping materials described above.
In some embodiments of the present application, the thickness of the electrode modification layer 13 may be 5 to 10nm, or 6 to 9nm, or 7 to 8nm.
The material selection and thickness of other layers are the same as those of the positive quantum dot light emitting diode, and are not repeated here.
The embodiment of the application also provides a display device which comprises the quantum dot light emitting diode.
The embodiment of the application also provides a preparation method of the light-emitting diode, which comprises the steps of sequentially forming a laminated light-emitting layer, an electron transmission layer, an electrode modification layer and a cathode on an anode, or sequentially forming the laminated electrode modification layer, the laminated electron transmission layer, the laminated light-emitting layer and the laminated anode on the cathode; the electrode modification layer material comprises the doping material, or the electrode modification layer raw material is selected from the doping material prepared by the preparation method.
In some embodiments of the present application, the electrode modification layer is prepared from the doped material by the preparation method, and the preparation method of the electrode modification layer includes: the doping material is prepared by the preparation method, a precursor film layer is formed by using the doping material, and the electrode modification layer is formed after heating for 10-60 minutes at 80-130 ℃ and removing the organic solvent.
In some embodiments of the present application, the preparation method of the positive quantum dot light emitting diode includes sequentially forming a hole transport layer 3, a quantum dot light emitting layer 4, an electron transport layer 5, an electrode modification layer 6 and a cathode 7 on an anode 2; the material of the electrode modification layer 6 includes the above-described doping material.
In some embodiments of the present application, a method for preparing a positive quantum dot light emitting diode includes:
(1) Providing a substrate 1 and forming an anode 2 on the substrate;
(2) Growing a hole transport layer 3 on the anode 2;
(3) Spin-coating a quantum dot light-emitting layer 4 on the hole transport layer 3;
(4) Spin-coating an electron transport layer 5 on the quantum dot light-emitting layer 4;
(5) Spin-coating a doping material on the electron transport layer 5 to form an electrode modification layer 6;
(6) Evaporating the cathode 7 to obtain the quantum dot light emitting diode.
In some embodiments of the present application, a method of fabricating an inverted quantum dot light emitting diode includes sequentially forming an electrode modification layer 13, an electron transport layer 14, a quantum dot light emitting layer 15, a hole transport layer 16, and an anode 17 on a cathode 12; the material of the electrode modification layer 13 is selected from the above-mentioned doping materials.
In some embodiments of the application, a method of fabricating an inverted quantum dot light emitting diode includes:
(1) Providing a substrate 11, and forming a cathode 12 on the substrate;
(2) Spin-coating an electrode modification layer 13 on the cathode 12;
(3) Spin-coating an electron transport layer 14 on the electrode modification layer 13;
(3) Forming a quantum dot light emitting layer 15 on the electron transport layer 14;
(4) Spin-coating a hole transport layer 16 on the quantum dot light emitting layer 15;
(6) An anode 17 is formed on the hole transport layer 16.
The following description is made with reference to specific embodiments.
Example 1
The method for preparing the quantum dot light emitting diode of the embodiment comprises the following steps:
the ITO substrate needs to be subjected to a pretreatment process, and basically specific treatment steps comprise: and cleaning the ITO conductive glass with a cleaning agent to preliminarily remove stains on the surface, sequentially and respectively ultrasonically cleaning the ITO conductive glass in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min to remove impurities on the surface, and finally drying the ITO conductive glass with high-purity nitrogen to obtain the ITO positive electrode.
Hole transport layer: placing an ITO substrate on a spin coater, and spin-coating a film by using a prepared solution of a hole transport material TFB; the film thickness is controlled by adjusting the concentration of the solution, spin-coating speed and spin-coating time, and then thermally annealed at an appropriate temperature. Spin coating conditions were 3000rpm,30s; the annealing condition is 150 ℃ for 30min. The thickness was 30nm.
Preparation of a quantum dot luminescent layer: placing the substrate on which the hole transport layer is spin-coated on a spin coater, spin-coating the prepared luminescent substance solution with a certain concentration to form a film, controlling the thickness of the luminescent layer by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and drying at a proper temperature. Spin coating conditions were 3000rpm,30s; the annealing condition was 80℃for 30min. The thickness was 40nm.
Preparation of an electron transport layer: the electron transport layer is a ZnO nano material film, a substrate on which the quantum dot luminescent layer is spin-coated is placed on a spin-coating instrument, zinc oxide composite material solution with a certain concentration is prepared to be spin-coated into a film, the thickness of the electron transport layer is controlled by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then annealing is performed to form the film. Spin coating conditions were 3000rpm,30s; the annealing condition was 80℃for 30min. The thickness was 40nm.
Preparation of electrode modification layer: the doping material is spin-coated onto the electron transport layer and then annealed. Spin coating conditions: 2000rpm,20s; annealing conditions: 80 ℃ for 15min. The thickness was 8nm.
Preparation of a cathode: the cathode material of this embodiment is metallic aluminum. And placing the substrate on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of 80nm metal aluminum serving as a cathode through a mask plate.
And (3) packaging: and packaging the obtained QLED device by adopting a common machine. In the packaging environment, the oxygen content and the water content are both lower than 0.1ppm so as to ensure the stability of the device.
The preparation method of the doping material in the step (5) comprises the following steps:
an appropriate amount of naphthalimide was added to 5ml of N, N-Dimethylformamide (DMF) to form a solution having a total concentration of 0.05M;
0.01M polyaniline (naphthalimide and polyaniline molar ratio=5) was added. Stirring for 1h at normal temperature to obtain the doped material.
The quantum dot light emitting diode structure prepared in this embodiment is: an ITO anode/a TFB hole transport layer/a QD quantum dot layer/a ZnO electron transport layer/an electrode modification layer of a doping material/an Al cathode.
Example two
The method for preparing the quantum dot light emitting diode of the embodiment comprises the following steps:
the ITO substrate needs to be subjected to a pretreatment process, and basically specific treatment steps comprise: and cleaning the ITO conductive glass with a cleaning agent to preliminarily remove stains on the surface, sequentially and respectively ultrasonically cleaning the ITO conductive glass in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min to remove impurities on the surface, and finally drying the ITO conductive glass with high-purity nitrogen to obtain the ITO positive electrode.
Hole transport layer: placing an ITO substrate on a spin coater, and spin-coating a film by using a prepared solution of a hole transport material TFB; the film thickness is controlled by adjusting the concentration of the solution, spin-coating speed and spin-coating time, and then thermally annealed at an appropriate temperature. Spin coating conditions were 3000rpm,30s; the annealing condition is 150 ℃ for 30min. The thickness was 30nm.
Preparation of a quantum dot luminescent layer: placing the substrate on which the hole transport layer is spin-coated on a spin coater, spin-coating the prepared luminescent substance solution with a certain concentration to form a film, controlling the thickness of the luminescent layer by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and drying at a proper temperature. Spin coating conditions were 3000rpm,30s; the annealing condition was 80℃for 30min. The thickness was 40nm.
Preparation of an electron transport layer: the electron transport layer is a ZnO nano material film, a substrate on which the quantum dot luminescent layer is spin-coated is placed on a spin-coating instrument, zinc oxide composite material solution with a certain concentration is prepared to be spin-coated into a film, the thickness of the electron transport layer is controlled by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then annealing is performed to form the film. Spin coating conditions were 3000rpm,30s; the annealing condition was 80℃for 30min. The thickness was 40nm.
Preparation of electrode modification layer: the doping material is spin-coated onto the electron transport layer and then annealed. Spin coating conditions: 2000rpm,20s; annealing conditions: 80 ℃ for 15min. The thickness was 8nm.
Preparation of a cathode: the cathode material of this embodiment is metallic aluminum. And placing the substrate on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of 80nm metal aluminum serving as a cathode through a mask plate.
And (3) packaging: and packaging the obtained QLED device by adopting a common machine. In the packaging environment, the oxygen content and the water content are both lower than 0.1ppm so as to ensure the stability of the device.
The preparation method of the doping material in the step (5) comprises the following steps:
a proper amount of naphthalimide is added into 5ml of DMF to form a solution with the total concentration of 0.05M;
0.01M polyethoxyethyleneimine (molar ratio of naphthalimide to polyethoxyethyleneimine=5) was added. Stirring for 1h at normal temperature to obtain the doped material.
The quantum dot light emitting diode structure prepared in this embodiment is: an ITO anode/a TFB hole transport layer/a QD quantum dot layer/a ZnO electron transport layer/an electrode modification layer of a doping material/an Al cathode.
Example III
The method for preparing the quantum dot light emitting diode of the embodiment comprises the following steps:
(1) The ITO substrate needs to be subjected to a pretreatment process, and basically specific treatment steps comprise: and cleaning the ITO conductive glass with a cleaning agent to preliminarily remove stains on the surface, sequentially and respectively ultrasonically cleaning the ITO conductive glass in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min to remove impurities on the surface, and finally drying the ITO conductive glass with high-purity nitrogen to obtain the ITO positive electrode.
(2) Hole transport layer: placing an ITO substrate on a spin coater, and spin-coating a film by using a prepared solution of a hole transport material TFB; the film thickness is controlled by adjusting the concentration of the solution, spin-coating speed and spin-coating time, and then thermally annealed at an appropriate temperature. Spin coating conditions were 3000rpm,30s; the annealing condition is 150 ℃ for 30min. The thickness was 30nm.
(3) Preparation of a quantum dot luminescent layer: placing the substrate on which the hole transport layer is spin-coated on a spin coater, spin-coating the prepared luminescent substance solution with a certain concentration to form a film, controlling the thickness of the luminescent layer by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and drying at a proper temperature. Spin coating conditions were 3000rpm,30s; the annealing condition was 80℃for 30min. The thickness was 40nm.
(4) Preparation of an electron transport layer: the electron transport layer is a ZnO nano material film, a substrate on which the quantum dot luminescent layer is spin-coated is placed on a spin-coating instrument, zinc oxide composite material solution with a certain concentration is prepared to be spin-coated into a film, the thickness of the electron transport layer is controlled by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then annealing is performed to form the film. Spin coating conditions were 3000rpm,30s; the annealing condition was 80℃for 30min. The thickness was 40nm.
(5) Preparation of electrode modification layer: the doping material is spin-coated onto the electron transport layer and then annealed. Spin coating conditions: 2000rpm,20s; annealing conditions: 80 ℃ for 15min. The thickness was 8nm.
(6) Preparation of a cathode: the cathode material of this embodiment is metallic aluminum. And placing the substrate on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of 80nm metal aluminum serving as a cathode through a mask plate.
(7) And (3) packaging: and packaging the obtained QLED device by adopting a common machine. In the packaging environment, the oxygen content and the water content are both lower than 0.1ppm so as to ensure the stability of the device.
The preparation method of the doping material in the step (5) comprises the following steps:
1) Adding a proper amount of perylene diimide to 5ml of DMF to form a solution with the total concentration of 0.05M;
2) 0.01M polyaminoanthraquinone (perylene diimide and polyaminoanthraquinone molar ratio=5) was added. Stirring for 1h at normal temperature to obtain the doped material.
The quantum dot light emitting diode structure prepared in this embodiment is: an ITO anode/a TFB hole transport layer/a QD quantum dot layer/a ZnO electron transport layer/an electrode modification layer of a doping material/an Al cathode.
The first comparative example is a quantum dot light emitting diode, the preparation process is the same as the third example, the difference is that the first comparative example is not added with an electrode modification layer, and the prepared quantum dot light emitting diode has the following structure: ITO anode/TFB hole transport layer/QD quantum dot layer/ZnO electron transport layer/Al cathode.
The second comparative example is a quantum dot light-emitting diode, the preparation process is the same as the third example, the difference is that the second comparative example is not added with an electrode modification layer, the cathode material of the second comparative example is Ag, and the prepared quantum dot light-emitting diode has the following structure: ITO anode/TFB hole transport layer/QD quantum dot layer/ZnO electron transport layer/Ag cathode.
The quantum dot light emitting diodes prepared in the examples and the comparative examples were subjected to performance test, and external quantum efficiency, turn-on voltage and device lifetime of the two were measured as follows.
TABLE 1
| EQE(％) | Open-up voltage (V) | T50@1K | |
| Comparative example one | 6.6 | 4.57 | 980 |
| Comparative example two | 12.5 | 2.71 | 1890 |
| Example 1 | 13.6 | 2.63 | 2204 |
| Example two | 14.8 | 2.22 | 2109 |
| Example III | 13.2 | 2.52 | 2022 |
Note that: EQE is the external quantum dot efficiency of the device; t50@1k is the time at 1000 nit for which the light emission luminance decays to 50%.
As can be seen from the results in the table, the examples have improved quantum efficiency, reduced turn-on voltage, and improved device lifetime over the comparative examples. In the embodiment, an electrode modification layer of doping material is added between an aluminum electrode and a ZnO electron transport layer, and in the comparative example, the electrode modification layer is not added. Therefore, the existence of the electrode modification layer of the doping material can enhance the electron injection performance and improve the efficiency and stability of the device. And compared with the second comparative example, the embodiment uses Ag as the cathode material, and the embodiment uses Al as the cathode material, but after the doping material is introduced, the device performance is obviously improved, and the device performance equivalent to that of an Ag electrode device can be obtained.
According to the application, the conjugated amine polymer is doped into the aromatic diimide compound to obtain the doped material, and the doped material is used as an electrode modification layer material, so that the electron injection performance of the aluminum electrode is enhanced, and meanwhile, the electrode modification layer film can smooth the electron transmission layer, so that the electron injection efficiency is improved, the damage of the ZnO electron transmission layer and external water oxygen to the electrode is reduced, and the device efficiency and stability are improved. Meanwhile, the Al electrode is adopted, so that the production cost is reduced, and the large-scale production can be realized.
The above description is made in detail of a doping material, a preparation method thereof, a light emitting diode and a display device provided by the embodiment of the present application, and specific examples are applied to illustrate the principles and embodiments of the present application, and the above description of the embodiment is only for helping to understand the method and core idea of the present application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, the present description should not be construed as limiting the present application.
Claims (10)
1. A doping material, the doping material comprising:
aromatic diimide compounds and conjugated amine polymers doped with the aromatic diimide compounds.
2. A doping material according to claim 1, wherein the aromatic diimide compound comprises naphthalene diimide or perylene diimide; and/or
The conjugated amine polymer comprises polyaniline, polyethoxyethyleneimine or polyaminoanthraquinone.
3. A doped material according to claim 1, wherein said conjugated amine polymer has an average molecular weight in the range of 10000 to 200000; and/or
The molar ratio of the aromatic diimide compound to the conjugated amine polymer is 1-10:1.
4. A doped material according to claim 1, wherein said doped material consists of an aromatic diimide compound and said conjugated amine-based polymer doped into said aromatic diimide compound.
5. A method of preparing a dopant material, comprising:
adding an aromatic diimide compound into an organic solvent to form an aromatic diimide compound solution, adding a conjugated amine polymer, and mixing to obtain the doped material.
6. The method for producing a doped material according to claim 5, wherein a molar ratio of said aromatic diimide compound to said conjugated amine polymer is 1 to 10:1; and/or
The concentration of the aromatic diimide compound solution is 0.01-0.1 mol/L; and/or
The organic solvent comprises at least one of N, N-dimethylformamide or dimethyl sulfoxide.
7. A light emitting diode, the light emitting diode comprising:
an anode, a light-emitting layer, an electron transport layer, an electrode modification layer and a cathode which are sequentially laminated;
wherein the material of the electrode modification layer is selected from the doping materials according to any one of claims 1 to 4, or the raw material of the electrode modification layer is selected from the doping materials prepared by the preparation method according to any one of claims 5 to 7.
8. The led of claim 7, wherein the electrode modification layer has a thickness of 5-10 nm.
9. The led of claim 7, wherein the cathode material is selected from aluminum; and/or
The material of the electron transport layer comprises at least one of ZnO, snO2 and TiO 2; and/or
The light-emitting layer is a quantum dot light-emitting layer, and the quantum dot material of the quantum dot light-emitting layer comprises at least one of CdS, cdSe, cdTe, znO, znS, znSe, znTe, gaAs, gaP, gaSb, hgS, hgSe, hgTe, inAs, inP, inSb, alAs, alP, cuInS or CuInSe; and/or
The material of the anode comprises at least one of Au, ITO, IZO, al, pt or Si.
10. A display device, characterized in that the display device comprises a light emitting diode according to any one of claims 7-9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210101237.3A CN116615044A (en) | 2022-01-27 | 2022-01-27 | Doped material, preparation method thereof, light emitting diode and display device |
| PCT/CN2022/128666 WO2023142570A1 (en) | 2022-01-27 | 2022-10-31 | Doping material and preparation method therefor, and light-emitting diode |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210101237.3A CN116615044A (en) | 2022-01-27 | 2022-01-27 | Doped material, preparation method thereof, light emitting diode and display device |
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| CN116615044A true CN116615044A (en) | 2023-08-18 |
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| JP2013023491A (en) * | 2011-07-26 | 2013-02-04 | Idemitsu Kosan Co Ltd | Aromatic amine derivative and organic electroluminescent element including the same |
| CN103554106B (en) * | 2013-11-14 | 2016-05-25 | 中国科学院化学研究所 | Amido/amine oxide is modified perylene diimides derivative, its preparation method and application |
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