CN116234345A - Electroluminescent device, preparation method thereof and display device - Google Patents
Electroluminescent device, preparation method thereof and display device Download PDFInfo
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- CN116234345A CN116234345A CN202111460542.3A CN202111460542A CN116234345A CN 116234345 A CN116234345 A CN 116234345A CN 202111460542 A CN202111460542 A CN 202111460542A CN 116234345 A CN116234345 A CN 116234345A
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- electroluminescent device
- thermistor
- light
- electron transport
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/008—Thermistors
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The electroluminescent device comprises a thermistor layer arranged between a light-emitting layer and an electron transport layer, wherein the thermistor layer comprises a thermosensitive material with positive temperature coefficient resistance, so that the phenomenon that the conductivity of the electron transport layer is increased due to electrifying aging is improved, the injection of electrons and holes is balanced, and the performance of the device is improved; and the thermistor layer can realize dynamic change of resistivity along with the change of the conductivity of the electron transport layer, so that the problem of reduced resistance performance of the resistor layer caused by device aging is prevented.
Description
Technical Field
The application relates to the field of photoelectric devices, in particular to an electroluminescent device, a preparation method thereof and a display device.
Background
Electroluminescent, also known as electroluminescence, is a physical phenomenon in which electrons excited by an electric field collide with a luminescence center to cause transition, change and recombination of electrons between energy levels to cause luminescence.
The QLED (Quantum Dots Light-emission Diode) is an emerging electroluminescent device, and the basic structure of the QLED is a sandwich structure consisting of a hole transport layer, a luminescent layer and an electron transport layer. The QLED is a novel technology between liquid crystal and OLED, the QLED core technology is Quantum Dot, and the Quantum Dot is a particle with the particle diameter less than 10nm and consists of zinc, cadmium, sulfur and selenium atoms. This material has an extremely specific property: when the quantum dot is stimulated by photoelectricity, colored light is emitted, and the color is determined by the materials composing the quantum dot and the size and shape of the quantum dot. Because of this property, it is possible to change the color of the light emitted from the light source. The light-emitting wavelength range of the quantum dots is very narrow, the color is pure, and the color can be adjusted, so that the picture of the quantum dot display is clearer and brighter than that of the liquid crystal display.
However, in the process of power-on aging of the QLED device, there is often a problem of unbalanced carrier injection, which affects the performance of the device.
Content of the application
The embodiment of the application provides an electroluminescent device, a preparation method thereof and a display device, and aims to improve the performance of the device.
In a first aspect, embodiments of the present application provide an electroluminescent device, including: the cathode is arranged on the anode, the anode is arranged on the cathode, the light-emitting layer is arranged close to the anode, the electron-transporting layer is arranged close to the cathode, a thermistor layer is arranged between the light-emitting layer and the electron-transporting layer, and the thermistor layer comprises a thermosensitive material with a positive temperature coefficient.
Optionally, the material of the thermistor layer further comprises a first high molecular polymer.
Optionally, the thermosensitive material is selected from superconducting carbon black, and/or metal nanoparticles selected from at least one of silver, platinum or gold nanoparticles.
Optionally, the mass ratio of the superconducting carbon black to the first high molecular polymer is 1: (5-20); and/or the mass ratio of the metal nano-particles to the first high molecular polymer is 1: (10-20).
Optionally, the first high molecular polymer is selected from at least one of polyethylene, polycarbonate or polymethyl methacrylate, and/or,
the resistivity of the superconducting carbon black is 0.8Ω·m to 1.2Ω·m; and/or the number of the groups of groups,
The particle size of the metal nanoparticles is 5nm to 8nm.
Optionally, the material of the thermistor layer is composed of the first high molecular polymer and superconducting carbon black, or the material of the thermistor layer is composed of the first high molecular polymer and metal nano particles.
Optionally, the material of the thermistor layer further comprises a second high molecular polymer, and the second high molecular polymer is at least one selected from polyvinyl alcohol or povidone.
Optionally, the mass ratio of the second high molecular polymer to the first high molecular polymer is 1: (5-10).
Optionally, the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, and the material of the organic light-emitting layer is at least one selected from a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a blue light-emitting TBPe fluorescent material, a green light-emitting TTPA fluorescent material, an orange light-emitting TBRb fluorescent material and a red light-emitting DBP fluorescent material; the quantum dot luminescent layer is made of at least one of single-structure quantum dots and core-shell structure quantum dots, wherein the single-structure quantum dots are at least one of II-VI group compounds, III-V group compounds, IV-VI group compounds and I-III-VI group compounds, the II-VI group compounds are at least one of CdSe, cdS, cdTe, znO, znSe, znS, cdTe, znTe, hgS, hgSe, hgTe, cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe and CdZnSTe, and the III-V group compounds are at least one of InP, inAs, gaP, gaAs, gaSb, inSb, alAs, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP; at least one IV-VI compound selected from SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe, snPbSTe; the I-III-VI compound is selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of the quantum dots of the core-shell structure, the core of which is selected from the single coreAny one of the quantum dots with the structure, wherein a shell material of the quantum dot with the core-shell structure is at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; and/or the number of the groups of groups,
the material of the electron transport layer is selected from the group consisting of: znO, tiO 2 、MgO、Al 2 O 3 At least one of (a) and (b); and/or the number of the groups of groups,
the cathode material is selected from: at least one of an Ag electrode, an Al electrode, an Au electrode, a Pt electrode, or an alloy electrode; and/or the number of the groups of groups,
the anode material is selected from a metal oxide electrode or a composite electrode, the metal oxide electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, 1ZO, MZO and AMO, and the composite electrode is AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 ZnS/Ag/ZnS or ZnS/Al/ZnS.
Optionally, the thickness of the thermistor layer is 15nm to 25nm.
In a second aspect, the present application further provides a method for preparing an electroluminescent device, including the following steps:
preparing a light emitting layer on an anode;
preparing a thermistor layer on the light-emitting layer;
preparing an electron transport layer on the thermistor layer; and
Preparing a cathode on the electron transport layer to obtain the electroluminescent device;
alternatively, an electron transport layer is prepared on the cathode;
preparing a thermistor layer on the electron transport layer;
preparing a light emitting layer on the thermistor layer; and
preparing an anode on the light-emitting layer to obtain the electroluminescent device;
wherein the material of the thermistor layer comprises a thermosensitive material with positive temperature coefficient.
Optionally, the preparation method of the material of the thermistor layer comprises the following steps: and mixing and heating the first high molecular polymer and the thermosensitive material to obtain the material of the thermosensitive resistor layer.
Optionally, the thermosensitive material is selected from at least one of superconducting carbon black or metal nanoparticles.
In a third aspect, the present application also provides a display device comprising an electroluminescent device according to the first aspect, or comprising an electroluminescent device prepared by the preparation method according to the second aspect.
According to the QLED device, the thermistor layer is arranged between the light-emitting layer and the electron transport layer, the material of the thermistor layer comprises a thermosensitive material with a positive temperature coefficient, and heat is generated due to aging of the electron transport layer in the electrifying process of the QLED device, so that the resistance of the thermosensitive material is increased, the phenomenon that the conductivity of the electron transport layer is increased due to aging is improved, the injection of electrons and holes is balanced, and the performance of the device is improved; the thermistor layer can dynamically change the resistivity along with the change of the conductivity of the electron transport layer, so that the problem of resistance performance reduction of the resistor layer caused by device aging is prevented.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below.
Fig. 1 is a schematic structural diagram of a positive structure of an electroluminescent device according to an embodiment of the present application;
FIG. 2 is a schematic structural diagram of an inversion structure of an electroluminescent device according to an embodiment of the present application;
FIG. 3 is a flow chart of a method for fabricating a positive structure of an electroluminescent device according to an embodiment of the present application;
fig. 4 is a flowchart of a method for preparing an inversion structure of an electroluminescent device according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
The embodiment of the application provides an electroluminescent device, a preparation method thereof 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 addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the present application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. Whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the range referred to.
First, an embodiment of the present application provides an electroluminescent device, including: the cathode, the anode, the luminescent layer and the electron transmission layer are arranged between the cathode and the anode, the luminescent layer is close to the anode, the electron transmission layer is close to the cathode, a thermistor layer is further arranged between the luminescent layer and the electron transmission layer, and the material of the thermistor layer comprises a thermosensitive material with positive temperature coefficient, namely, when the temperature of the thermosensitive material rises, the resistivity of the thermosensitive material rises.
According to the method, the thermistor layer with the positive temperature coefficient is arranged between the light-emitting layer and the electron transport layer, so that in the electrifying process of the QLED device, the electron transport layer is aged to generate heat, the resistance of the thermosensitive material is increased, the phenomenon that the electric conductivity of the electron transport layer is increased due to ageing (caused by illumination or electrifying) is improved, the injection of electrons and holes is balanced, and the performance of the device is improved; the thermistor layer can dynamically change the resistivity along with the change of the conductivity of the electron transport layer, so that the problem of resistance performance reduction of the resistor layer caused by device aging is prevented.
In some embodiments, the material of the thermistor layer further includes a first high molecular polymer, which may improve the film forming property of the thermistor layer, and the first high molecular polymer may be a high-transparency, high-strength high molecular material, for example: polyethylene, polycarbonate, polymethyl methacrylate, and the like.
In some embodiments of the present application, the thermally sensitive material is selected from a positive temperature coefficient material, such as superconducting carbon black, and/or metal nanoparticles. The materials can effectively improve the conductivity and the processability of the high polymer materials. When the superconducting carbon black and/or the metal nano particles and the first high molecular polymer are in proper proportion, the thermosensitive material has better stability, transparency and positive temperature coefficient resistance.
For example: when the thermistor layer includes a superconductive carbon black and a first high molecular polymer, in some embodiments, the mass ratio of the superconductive carbon black to the first high molecular polymer is 1: (5-20) if the content of the superconducting carbon black is too low, the resistance variability of the thermistor layer with temperature change will decrease, and if the content of the superconducting carbon black is too high, the light transmittance of the thermistor layer will be poor. It is understood that the mass ratio of the superconductive carbon black to the first high molecular polymer may be 1: any value within the range of (5 to 20), for example: 1: 5. 1: 6. 1: 7. 1: 8. 1: 9. 1: 10. 1: 11. 1: 12. 1: 13. 1: 14. 1: 15. 1: 16. 1: 17. 1: 18. 1: 19. 1:20, etc., or 1: other values not listed in the range of (5-20).
For another example, when the thermistor layer includes metal nanoparticles and a first high molecular polymer, in some embodiments, the mass ratio of the metal nanoparticles to the first high molecular polymer is 1: (10-20) if the content of the metal nanoparticles is too low, the resistance variability of the thermistor layer with temperature change will decrease, and if the content of the metal nanoparticles is too high, the light transmittance of the thermistor layer will be poor. It is understood that the mass ratio of the metal nanoparticle to the first high molecular polymer may be 1: any value within the range of (10 to 20), for example: 1: 10. 1: 11. 1: 12. 1: 13. 1: 14. 1: 15. 1: 16. 1: 17. 1: 18. 1: 19. 1:20, etc., or 1: other values not listed in the range of (10-20).
In some embodiments, the superconducting carbon black, and/or the metal nanoparticles are uniformly dispersed in the first high molecular polymer.
In order to further enhance the film forming property and surface smoothness of the thermistor layer, in some embodiments, the material of the thermistor layer further includes a second high molecular polymer: at least one of ethylene-vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA) or povidone (PVP), unlike the first high molecular material, the second high molecular material is a substance which further improves the film forming property of the thermistor layer on the basis of the first high molecular polymer, and the material has the characteristics of good rebound force, strong tensile force, high toughness and softness, so that the film forming property of the whole thermistor layer can be improved by adding the material.
In some embodiments, the mass ratio of the EVA to the first high molecular polymer is 1: (5-10) at this ratio, the thermistor layer is excellent in film forming property and smoothness. It is understood that the mass ratio of the EVA to the first high molecular polymer may be 1: any value within the range of (5 to 10), for example: 1: 5. 1: 6. 1: 7. 1: 8. 1: 9. 1:10, etc., or 1: other values not listed in the range of (5-10).
In some embodiments, the superconductive carbon black has a resistivity of 0.8Ω·m to 1.2Ω·m, and within this resistivity range, the temperature-dependent resistance variability of the thermistor layer may be better. It is understood that the resistivity of the superconducting carbon black may be arbitrarily taken in the range of 0.8Ω·m to 1.2Ω·m, for example, 0.8Ω·m, 0.85Ω·m, 0.9Ω·m, 0.95Ω·m, 1.0Ω·m, 1.05Ω·m, 1.1Ω·m, 1.15Ω·m, 1.2Ω·m, or the like, or other unlisted values of 0.8Ω·m to 1.2Ω·m.
In some embodiments, the metal nanoparticles are selected from at least one of silver, platinum, or gold nanoparticles. The metal nanoparticles have a particle diameter of 5nm to 8nm, and in this particle diameter range, the resistance variability of the thermistor layer with temperature change is better. It will be appreciated that the particle size of the metal nanoparticles may be any value in the range of 5nm to 8nm, for example 5nm, 5.5nm, 6nm, 6.5nm, 7nm, 7.5nm, 8nm, etc., or other non-listed values of 5nm to 8 nm.
The electroluminescent device may be of either a positive or negative type. In the positive configuration the anode is disposed on the substrate. In the inversion structure the cathode is disposed on the substrate. Whether in a positive type structure or an inverse type structure, an electron functional layer such as an electron injection layer and a hole blocking layer can be arranged between the cathode and the light-emitting layer, and a hole functional layer such as a hole transport layer, a hole injection layer and an electron blocking layer can be arranged between the anode and the light-emitting layer. For example:
fig. 1 shows a schematic diagram of a positive structure of an electroluminescent device according to an embodiment of the present application, as shown in fig. 1, the positive structure quantum dot device includes a substrate 110, an anode 120 disposed on a surface of the substrate 110, a hole transport layer 130 disposed on a surface of the anode 120, a light emitting layer 140 disposed on a surface of the hole transport layer 130, a thermistor layer 150 disposed on a surface of the light emitting layer 140, an electron transport layer 160 disposed on a surface of the thermistor layer 150, and a cathode 170 disposed on a surface of the electron transport layer 160.
Fig. 2 is a schematic diagram of an inversion structure of a quantum dot device according to an embodiment of the present application, and as shown in fig. 2, the inversion structure quantum dot device includes a substrate 110, a cathode 170 disposed on a surface of the substrate 110, an electron transport layer 160 disposed on a surface of the cathode 170, a thermistor layer 150 disposed on a surface of the electron transport layer 160, a light emitting layer 140 disposed on a surface of the thermistor layer 150, a hole transport layer 130 disposed on a surface of the light emitting layer 140, and an anode 120 disposed on a surface of the hole transport layer 130.
In the embodiments of the present application, the materials of the respective functional layers are common materials in the art, for example:
the substrate may be a rigid substrate or a flexible substrate. Specific materials may include at least one of glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone.
The anode material may be: a metal oxide electrode or a composite electrode, wherein the metal oxide electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, 1ZO, MZO and AMO, and the composite electrode is AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 ZnS/Ag/ZnS or ZnS/Al/ZnS.
The hole injection layer material may be: poly (ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS), poly (9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) -diphenylamine) (TFB), polyarylamines, poly (N-vinylcarbazole), polyaniline, polypyrrole, N, N, N ', N' -tetrakis (4-methoxyphenyl) -benzidine (TPD), 4-bis [ N- (1-naphthyl) -N-phenyl-amino ] biphenyl (. Alpha. -NPD), 4 '-tris [ phenyl (m-tolyl) amino ] triphenylamine (m-MTDATA), 4',4 '-tris (N-carbazolyl) -triphenylamine (TCTA), 1-bis [ (di-4-tolylamino) phenylcyclohexane (TAPC), 4' -tris (diphenylamino) triphenylamine (TDATA) doped with tetrafluoro-tetracyano-quinone dimethane (F4-TCNQ), p-doped phthalocyanines (e.g., F4-TCNQ-doped zinc phthalocyanine (ZnPc)), F4-TCNQ doped N, N '-diphenyl-N, N' -bis (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (alpha-NPD), hexaazabenzophenanthrene-hexanitrile (HAT-CN); or a combination of any one or more of the above.
The hole transport layer may be made of: arylamines, such as 4,4' -N, N ' -dicarbazolyl-biphenyl (CBP), N ' -diphenyl-N, N ' -bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine (a-NPD), N ' -diphenyl-N, N ' -bis (3-methylphenyl) - (1, 1' -biphenyl) -4,4' -diamine (TPD), N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -spiro (spiro-TPD), N ' -bis (4- (N, N ' -diphenyl-amino) phenyl) -N, N ' -diphenyl benzidine (DNTPD), 4' -tris (N-carbazolyl) -triphenylamine (TCTA), tris (3-methylphenyl-phenylamino) -triphenylamine (m-MTDATA), poly [ (9, 9' -dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butylphenyl) diphenylamine)) ] (TFB) and poly (4-butylphenyl-diphenylamine) (poly-TPD); polyaniline; polypyrrole; poly (p) phenylenevinylenes and derivatives thereof, such as poly (phenylenevinylene) (PPV), poly [ 2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylenevinylene ] (MEH-PPV) and poly [ 2-methoxy-5- (3 ',7' -dimethyloctyloxy) -1, 4-phenylenevinylene ] (MOMO-PPV); copper phthalocyanine; aromatic tertiary amines or polynuclear aromatic tertiary amines; 4,4 '-bis (p-carbazolyl) -1,1' -biphenyl compounds; n, N' -tetraarylbenzidine; PEDOT PSS and its derivatives; poly (N-vinylcarbazole) (PVK) and derivatives thereof; polymethacrylate and derivatives thereof; poly (9, 9-octylfluorene) and derivatives thereof; poly (spirofluorene) and derivatives thereof; n, N '-bis (naphthalen-1-yl) -N, N' -diphenyl benzidine (NPB); spiro NPB; or a combination of any one or more of the above.
The light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, and the material of the organic light-emitting layer is selected from at least one of a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a blue light-emitting TBPe fluorescent material, a green light-emitting TTPA fluorescent material, an orange light-emitting TBRb fluorescent material and a red light-emitting DBP fluorescent material; the material of the quantum dot light emitting layer may be selected from, but not limited to, at least one of single structure quantum dots and core-shell structure quantum dots. The single-structure quantum dot includes a single-component quantum dot or an alloy-structure quantum dot, and the single-component quantum dot may be selected from at least one of group II-VI compounds, group III-V compounds, and group IV-VI compounds, but is not limited thereto. By way of example, the group II-VI compound may be selected from at least one of, but not limited to CdSe, cdS, cdTe, znO, znSe, znS, cdTe, znTe, hgS, hgSe, hgTe; the III-V compounds may be selected from, but are not limited to, at least one of InP, inAs, gaP, gaAs, gaSb, inSb, alAs, alN and AlP; or group IV-VI SnS, snSe, snTe, pbS, pbSe, pbTe.
The quantum dots of the alloy structure are selected from, but not limited to, at least one of group II-VI, group III-V, group IV-VI or group I-III-VI compounds, and by way of example, the quantum dots of the alloy structure may be selected from group II-VI: cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cd SeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe, hgZnSTe; or III-V: inAsP, inNP, inNSb, gaAlNP, inAlNP, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNAs, inPAs, inPSb, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNAs, inAlNSb, inAlPAs, inAlPSb; or groups IV-VI: snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe, snPbSTe; the I-III-VI compound may be selected from, but is not limited to, cuInS 2 、CuInSe 2 AgInS 2 At least one of them.
The core of the quantum dot of the core-shell structure can be selected from any one of the quantum dots of the single structure, and the shell material of the quantum dot of the core-shell structure can be selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS, but not limited to. As an example, the quantum dots of the core-shell structure may be selected from, but not limited to, at least one of CdZnSe/CdZnS/ZnS, cdZnSe/ZnS, cdSe/ZnS, cdTe/CdS, cdS/ZnS, cdTe/ZnS, inP/ZnS, cdSe/ZnSe/ZnS, znSeTe/ZnS, cdSe/CdZnSeS/ZnS, inP/ZnSe/ZnS, and InP/ZnSeS/ZnS.
The electron transport material may be composed of an inorganic material and/or an organic material. When inorganic, it may be: metal/non-metal oxides (e.g., tiO) undoped or doped with aluminum (Al), magnesium (Mg), indium (In), lithium (Li), gallium (Ga), cadmium (Cd), cesium (Cs), or copper (Cu) 2 、ZnO、ZrO、SnO 2 、WO 3 、Ta 2 O 3 、HfO 3 、Al 2 O 3 、ZrSiO 4 、BaTiO 3 And BaZrO 3 ). In the case of an organic material, the organic material may be formed of an organic material such as an oxazole compound, an isoxazole compound, a triazole compound, an isothiazole compound, an oxadiazole compound, a thiadiazole compound, a perylene compound, or an aluminum complex. In the embodiments of the present application, the electron transport material is selected from, for example, zinc oxide, dioxygenWhen the metal oxides such as titanium oxide, magnesium oxide and aluminum oxide are used, the electron mobility of the materials is obviously increased in the aging process of the device, so that compared with other materials, the thermistor layer has the effect of obviously balancing the injection of electrons and holes when the metal oxide is used as an electron transport material, and improving the performance of the device.
The cathode material may be: at least one of an Ag electrode, an Al electrode, an Au electrode, a Pt electrode, or an alloy electrode.
The thickness of the anode is 20 nm-200 nm (nanometers); the thickness of the hole injection layer is 20 nm-200 nm; the thickness of the hole transport layer is 30 nm-180 nm; the total thickness of the light-emitting layer is 30 nm-180 nm. The thickness of the electron transport layer is 10 nm-180 nm; the thickness of the thermistor layer is 15nm to 25nm; the thickness of the cathode is 40 nm-190 nm.
The application also provides a preparation method of the electroluminescent device, fig. 3 shows a preparation method of a positive structure of the electroluminescent device according to the embodiment of the application, and as shown in fig. 3, the preparation method of the electroluminescent device of the positive structure comprises the following steps:
s10, preparing a luminescent layer on an anode substrate;
s20, preparing a thermistor layer on the light-emitting layer;
s30, preparing an electron transport layer on the thermistor layer; and
s40, preparing a cathode on the electron transport layer to obtain the electroluminescent device.
Wherein the material of the thermistor layer comprises a thermosensitive material with positive temperature coefficient.
Fig. 4 shows a method for preparing an inversion structure of an electroluminescent device according to an embodiment of the present application, and as shown in fig. 4, the method for preparing an inversion structure electroluminescent device includes the following steps:
s100, preparing an electron transport layer on a cathode substrate;
s200, preparing a thermistor layer on the electron transport layer;
s300, preparing a light-emitting layer on the thermistor layer; and
s400, preparing an anode on the light-emitting layer to obtain the electroluminescent device;
wherein the material of the thermistor layer comprises a thermosensitive material with positive temperature coefficient.
In some embodiments, the method of preparing the material of the thermistor layer includes: and mixing and heating the first high molecular polymer and the thermosensitive material to obtain the material of the thermosensitive resistor layer.
In some embodiments, the thermally sensitive material is selected from at least one of a superconducting carbon black or a metal nanoparticle.
To ensure adequate mixing of the first high molecular polymer and the heat sensitive material, in some embodiments, the heated temperature is 100 ℃ to 120 ℃ and/or the mixing time is greater than 12 hours, if the mixing time is too short or the temperature is too low, the mixing is not uniform; if the temperature is too high, the stability of the heat-sensitive material or the first high molecular polymer structure will be affected, and it will be understood that the heating temperature may be any value in the range of 100 ℃ to 120 ℃, for example: 100 ℃, 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃, 120 ℃, etc., or other unlisted values in the range of 100 ℃ to 120 ℃.
Based on the same conception, the application also provides a display device, which comprises the electroluminescent device described in any one of the above, or comprises the electroluminescent device prepared by the preparation method described in any one of the above, and the structure, the implementation principle and the effect are similar, and are not repeated here. In a specific embodiment, the display device is a QLED.
Alternatively, the display device may be: the lighting lamp and the backlight source are any products or components with display functions, such as mobile phones, tablet computers, televisions, displays, notebook computers, digital photo frames, navigator and the like.
It should be noted that, the drawings relate to only the structures related to the embodiments of the present application, and other structures may refer to the general designs.
In addition, for a better understanding of the present application, the present application also provides the following specific examples.
Example 1:
the embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer is spin-coated on 80 nm-thick ITO, and the specific material is PEDOT: PSS, and the thickness is 20nm.
(2) And spin-coating a hole transport layer on the hole injection layer, wherein the specific material is TFB, and the thickness is 25nm.
(3) And spin-coating a luminescent layer on the hole transport layer, wherein the luminescent layer is made of CdZnSe and has a thickness of 25nm.
(4) A thermistor layer is spin-coated on the light-emitting layer, the thickness of the thermistor layer is 20nm, the thermistor layer is composed of polycarbonate and superconductive carbon black, and the mass ratio of the superconductive carbon black to the polycarbonate is 1:5.
the preparation process of the thermistor layer specifically comprises the following steps: the polycarbonate and the superconductive carbon black are dissolved in DMF solvent, the final composition of the thermistor material solution with the concentration of 10mg/mL is spun on the light-emitting layer by a spin coating method, and the solution is heated for 30min at 120 ℃ to enable the solution to be fully formed into a film.
(5) An electron transport layer is spin-coated on the thermistor layer, wherein the specific material is ZnO, and the thickness is 30nm.
(6) And evaporating Ag electrode with thickness of 100nm. And finally, packaging to form the electroluminescent device.
Example 2:
the embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer is spin-coated on 80nm ITO, and the specific material is PEDOT: PSS, and the thickness is 20nm.
(2) Spin-coating a hole transport layer on the hole injection layer, wherein the specific material is TFB, and the thickness is 25nm;
(3) Spin-coating a luminescent layer on the hole transport layer, wherein the specific material is CdZnSe, and the thickness is 25nm;
(4) A thermistor layer is spin-coated on the luminous layer, the thickness of the layer is 20nm, the layer is composed of polycarbonate and superconductive carbon black, and the mass ratio of the superconductive carbon black to the polycarbonate is 1:8.
the preparation process of the thermistor layer specifically comprises the following steps: the polycarbonate and the superconductive carbon black are dissolved in DMF solvent to form a thermistor material solution with the concentration of 10mg/mL, the thermistor material solution is screwed on the light-emitting layer by a spin coating mode, and the solution is heated for 30min at 120 ℃ to enable the solution to be fully formed into a film.
(5) An electron transport layer is spin-coated on the thermistor layer, wherein the specific material is ZnO, and the thickness is 30nm.
(6) And evaporating Ag electrode with thickness of 100nm. And finally, packaging to form the electroluminescent device.
Example 3:
the embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer is spin-coated on 80nm ITO, and the specific material is PEDOT: PSS, and the thickness is 20nm.
(2) And spin-coating a hole transport layer on the hole injection layer, wherein the specific material is TFB, and the thickness is 25nm.
(3) And spin-coating a luminescent layer on the hole transport layer, wherein the specific material is CdZnSe, and the thickness is 25nm.
(4) A thermistor layer is spin-coated on the luminous layer, the thickness of the layer is 20nm, the layer is composed of polycarbonate and superconductive carbon black, and the mass ratio of the superconductive carbon black to the polycarbonate is 1:20.
the preparation process of the thermistor layer specifically comprises the following steps: polycarbonate and superconducting carbon black are dissolved in DMF solvent to form a thermistor material solution with the concentration of 10mg/mL, the solution is screwed on a light-emitting layer by a spin coating mode, and the solution is heated for 30min at 120 ℃ to enable the solution to be fully formed into a film.
(5) An electron transport layer is spin-coated on the thermistor layer, wherein the specific material is ZnO, and the thickness is 30nm.
(6) Evaporating Ag electrode with thickness of 100nm, and packaging to form electroluminescent device.
Example 4:
the embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer is spin-coated on 80nm ITO, and the specific material is PEDOT: PSS, and the thickness is 20nm.
(2) And spin-coating a hole transport layer on the hole injection layer, wherein the specific material is TFB, and the thickness is 25nm.
(3) And spin-coating a luminescent layer on the hole transport layer, wherein the specific material is CdZnSe, and the thickness is 25nm.
(4) A thermistor layer is spin-coated on the luminous layer, the thickness of the layer is 20nm, the layer is composed of polycarbonate, superconductive carbon black and EVA, and the mass ratio of the superconductive carbon black to the polycarbonate is 1:8, the mass ratio of EVA to polycarbonate is 1:5.
the preparation process of the thermistor layer specifically comprises the following steps: the superconductive carbon black, the polycarbonate and the EVA are dissolved in DMF solvent to form a thermistor material solution with the concentration of 10mg/mL, the solution is spin-coated on the luminous layer by spin coating, and the solution is heated for 30min at 120 ℃ to fully form a film.
(5) An electron transport layer is spin-coated on the thermistor layer, wherein the specific material is ZnO, and the thickness is 30nm.
(6) And evaporating Ag electrode with thickness of 100nm. And finally, packaging to form the electroluminescent device.
Example 5:
The embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer is spin-coated on 80nm ITO, the material is PEDOT: PSS, and the thickness is 20nm.
(2) And spin-coating a hole transport layer on the hole injection layer, wherein the specific material is TFB, and the thickness is 25nm.
(3) And spin-coating a luminescent layer on the hole transport layer, wherein the specific material is CdZnSe, and the thickness is 25nm.
(4) A thermistor layer is spin-coated on the luminous layer, the thickness of the layer is 20nm, the layer is composed of polycarbonate, superconductive carbon black and EVA, and the mass ratio of the superconductive carbon black to the polycarbonate is 1:8, the mass ratio of EVA to polycarbonate is 3:20.
the preparation process of the thermistor layer specifically comprises the following steps: three substances, namely superconducting carbon black, polycarbonate and EVA, are dissolved in DMF solvent to finally form a thermistor material solution with the concentration of 10mg/mL, the solution is screwed on a light-emitting layer by a spin coating mode, and the solution is heated for 30min at 120 ℃ to fully form a film.
(5) An electron transport layer is spin-coated on the thermistor layer, wherein the specific material is ZnO, and the thickness is 30nm.
(6) And evaporating Ag electrode with thickness of 100nm. And finally, packaging to form the electroluminescent device.
Example 6:
the embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer is spin-coated on 80nm ITO, and the specific material is PEDOT: PSS, and the thickness is 20nm.
(2) And spin-coating a hole transport layer on the hole injection layer, wherein the specific material is TFB, and the thickness is 25nm.
(3) And spin-coating a luminescent layer on the hole transport layer, wherein the specific material is CdZnSe, and the thickness is 25nm.
(4) A thermistor layer is spin-coated on the luminous layer, the thickness of the layer is 20nm, the layer is composed of polycarbonate, superconductive carbon black and EVA, and the mass ratio of the superconductive carbon black to the polycarbonate is 1:8, the mass ratio of EVA to polycarbonate is 1:10.
the preparation process of the thermistor layer specifically comprises the following steps: three substances, namely superconducting carbon black, polycarbonate and EVA, are dissolved in DMF solvent to finally form a thermistor material solution with the concentration of 10mg/mL, the solution is screwed on a light-emitting layer by a spin coating mode, and the solution is heated for 30min at 120 ℃ to fully form a film.
(5) An electron transport layer is spin-coated on the thermistor layer, wherein the specific material is ZnO, and the thickness is 30nm.
(6) And evaporating Ag electrode with thickness of 100nm. And finally, packaging to form the electroluminescent device.
Example 7:
the embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer is spin-coated on 80nm ITO, and the specific material is PEDOT: PSS, and the thickness is 20nm.
(2) And spin-coating a hole transport layer on the hole injection layer, wherein the specific material is TFB, and the thickness is 25nm.
(3) And spin-coating a luminescent layer on the hole transport layer, wherein the specific material is CdZnSe, and the thickness is 25nm.
(4) Spin-coating a thermistor layer on the light-emitting layer, wherein the thickness of the layer is 20nm, the thermistor layer consists of polycarbonate and Ag metal nano particles, and the mass ratio of the Ag metal nano particles to the polycarbonate is 1:10.
the preparation process of the thermistor layer specifically comprises the following steps: the Ag metal nano particles and polycarbonate are dissolved in DMF solvent to form a thermistor material solution with the concentration of 10mg/mL, the solution is screwed on the light-emitting layer by a spin coating mode, and the solution is heated for 30min at 120 ℃ to enable the solution to be fully formed into a film.
(5) An electron transport layer is spin-coated on the thermistor layer, wherein the specific material is ZnO, and the thickness is 30nm.
(6) And evaporating Ag electrode with thickness of 100nm. And finally, packaging to form the electroluminescent device.
Example 8:
the embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer is spin-coated on 80nm ITO, and the specific material is PEDOT: PSS, and the thickness is 20nm.
(2) And spin-coating a hole transport layer on the hole injection layer, wherein the specific material is TFB, and the thickness is 25nm.
(3) And spin-coating a luminescent layer on the hole transport layer, wherein the specific material is CdZnSe, and the thickness is 25nm.
(4) Spin-coating a thermistor layer on the light-emitting layer, wherein the thickness of the layer is 20nm, the thermistor layer consists of polycarbonate and Ag metal nano particles, and the mass ratio of the Ag metal nano particles to the polycarbonate is 3:40, the two substances are dissolved in DMF solvent, the final composition of the thermistor material solution with the concentration of 10mg/mL is spun on the light-emitting layer by a spin coating mode, and the solution is heated for 30min at 120 ℃ to enable the solution to be fully formed into a film.
(5) An electron transport layer is spin-coated on the thermistor layer, wherein the specific material is ZnO, and the thickness is 30nm.
(6) And evaporating Ag electrode with thickness of 100nm. And finally, packaging to form the electroluminescent device.
Example 9:
the embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer is spin-coated on 80nm ITO, and the specific material is PEDOT: PSS, and the thickness is 20nm.
(2) And spin-coating a hole transport layer on the hole injection layer, wherein the specific material is TFB, and the thickness is 25nm.
(3) And spin-coating a luminescent layer on the hole transport layer, wherein the specific material is CdZnSe, and the thickness is 25nm.
(4) Spin-coating a thermistor layer on the light-emitting layer, wherein the thickness of the layer is 20nm, the thermistor layer consists of polycarbonate and Ag metal nano particles, and the mass ratio of the Ag metal nano particles to the polycarbonate is 1:20, the two substances are dissolved in DMF solvent to finally form thermistor material solution with the concentration of 10mg/mL, the solution is screwed on the light-emitting layer by a spin coating mode, and the solution is heated for 30min at 120 ℃ to enable the solution to be fully formed into a film.
(5) An electron transport layer is spin-coated on the thermistor layer, wherein the specific material is ZnO, and the thickness is 30nm.
(6) And evaporating Ag electrode with thickness of 100nm. And finally, packaging to form the electroluminescent device.
Comparative example 1:
the embodiment provides a positive bottom emission electroluminescent device, and the preparation method of the device comprises the following steps:
(1) A hole injection layer was spin coated on the ITO.
(2) And spin-coating a hole transport layer on the hole injection layer.
(3) And spin-coating a light-emitting layer on the hole transport layer.
(4) And spin-coating an electron transport layer on the light-emitting layer.
(5) Evaporating Ag electrode, and packaging to obtain electroluminescent device.
Verification example
The performance of the electroluminescent devices provided in each example and comparative example was evaluated by testing the maximum EQE, measured time of T95, lifetime of T95-1K, etc. of the devices, and the test results are shown in table 1.
TABLE 1
Note that: EQE is the external quantum efficiency; t95 represents the time taken for the brightness of the device to decay from 100% to 95%; T95-1K represents the time taken for the luminance to decay from 100% to 95% when the device is at a luminance of 1000 nit.
As can be seen from table 1: after the thermistor layer is added in the electroluminescent device, the performances of T95-1K, EQE and T95 of the device are obviously improved, and the thermistor layer generates heat along with the electron transport layer, so that the resistance is increased, and the injection of electrons and holes is balanced. In addition, as is clear from comparison of examples 4 to 6 with other examples, when the ethylene-vinyl acetate copolymer was added to the thermistor layer, the performance of balancing the injection of electrons and holes was better, and thus it was shown that better results were exhibited in terms of T95-1K, EQE and T95 performance, which were caused by the fact that the ethylene-vinyl acetate copolymer could improve the film forming property and the surface smoothness of the thermistor layer, and thus the thermistor layer had better resistance variability.
In summary, the present application provides an electroluminescent device, a method for manufacturing the same, and a display device, wherein a thermistor layer is disposed between a light emitting layer and an electron transport layer, and the thermistor layer comprises a thermosensitive material, and the thermosensitive material has a positive temperature coefficient of resistance, and the thermosensitive material has a resistance that increases with heat generated by aging of the electron transport layer during the energizing process of the QLED device, so as to improve the phenomenon that the electron transport layer has conductivity that increases due to aging, and further balance the injection of electrons and holes, and improve the performance of the device; the thermistor layer can dynamically change the resistivity along with the change of the conductivity of the electron transport layer, so that the problem of resistance performance reduction of the resistor layer caused by device aging is prevented. In addition, the method provided by the embodiment is simple to operate, low in cost and good in repeatability, and has a wide application prospect in the field of photoelectric display.
The above describes in detail an electroluminescent device, a method for manufacturing the same, and a display device provided in the embodiments of the present application, and specific examples are applied herein to illustrate principles and embodiments of the present application, where the above description of the embodiments is only for helping to understand the method and core ideas of the present application; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.
Claims (14)
1. An electroluminescent device, comprising: the cathode, the positive pole and establish luminescent layer and electron transport layer between the negative pole with the positive pole, luminescent layer is close to the positive pole sets up, electron transport layer is close to the negative pole sets up, luminescent layer with still be equipped with the thermistor layer between the electron transport layer, the material of thermistor layer includes the thermosensitive material that has positive temperature coefficient.
2. The electroluminescent device of claim 1, wherein the material of the thermistor layer further comprises a first high molecular polymer.
3. Electroluminescent device according to claim 2, characterized in that the heat sensitive material is selected from the group consisting of superconductive carbon black, and/or metal nanoparticles, wherein the metal nanoparticles are selected from at least one of silver, platinum or gold nanoparticles.
4. An electroluminescent device according to claim 3, characterized in that the mass ratio of the superconductive carbon black to the first high molecular polymer is 1: (5-20); and/or the mass ratio of the metal nano-particles to the first high molecular polymer is 1: (10-20).
5. An electroluminescent device as claimed in claim 3, characterized in that the first high-molecular polymer is selected from at least one of polyethylene, polycarbonate or polymethyl methacrylate, and/or,
The resistivity of the superconducting carbon black is 0.8Ω·m to 1.2Ω·m; and/or the number of the groups of groups,
the particle size of the metal nanoparticles is 5nm to 8nm.
6. An electroluminescent device according to claim 3, characterized in that the material of the thermistor layer consists of the first high molecular polymer and superconducting carbon black or the material of the thermistor layer consists of the first high molecular polymer and metal nanoparticles.
7. The electroluminescent device of claim 2, wherein the material of the thermistor layer further comprises a second high molecular polymer selected from at least one of ethylene-vinyl acetate copolymer, polyvinyl alcohol, or povidone.
8. The electroluminescent device of claim 7, wherein the mass ratio of the second high molecular polymer to the first high molecular polymer is 1: (5-10).
9. The electroluminescent device according to claim 1, wherein the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer, and a material of the organic light-emitting layer is at least one selected from a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a blue light-emitting TBPe fluorescent material, a green light-emitting TTPA fluorescent material, an orange light-emitting TBRb fluorescent material, and a red light-emitting DBP fluorescent material; the material of the quantum dot luminescent layer is at least one selected from single-structure quantum dots and core-shell structure quantum dots, and the single-structure quantum dots are selected from II-VI group compounds, III-V group compounds, IV-VI group compounds and I-III-VI group compounds At least one group II-VI compound selected from at least one of CdSe, cdS, cdTe, znO, znSe, znS, cdTe, znTe, hgS, hgSe, hgTe, cdZnS, cdZnSe, cdZnTe, znSeS, znSeTe, znTeS, cdSeS, cdSeTe, cdTeS, cdZnSeS, cdZnSeTe and CdZnSTe, and at least one group III-V compound selected from InP, inAs, gaP, gaAs, gaSb, inSb, alAs, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP; at least one IV-VI compound selected from SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe, snPbSTe; the I-III-VI compound is selected from CuInS 2 、CuInSe 2 AgInS 2 The core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; and/or the number of the groups of groups,
the material of the electron transport layer is selected from the group consisting of: znO, tiO 2 、MgO、Al 2 O 3 At least one of (a) and (b); and/or the number of the groups of groups,
the cathode material is selected from: at least one of an Ag electrode, an Al electrode, an Au electrode, a Pt electrode, or an alloy electrode; and/or the number of the groups of groups,
The anode material is selected from a metal oxide electrode or a composite electrode, the metal oxide electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, 1ZO, MZO and AMO, and the composite electrode is AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, tiO 2 /Ag/TiO 2 、TiO 2 /Al/TiO 2 ZnS/Ag/ZnS or ZnS/Al/ZnS.
10. An electroluminescent device as claimed in claim 1, characterized in that the thickness of the thermistor layer is 15nm to 25nm.
11. The preparation method of the electroluminescent device is characterized by comprising the following steps:
preparing a light emitting layer on an anode;
preparing a thermistor layer on the light-emitting layer;
preparing an electron transport layer on the thermistor layer; and
preparing a cathode on the electron transport layer to obtain the electroluminescent device;
alternatively, an electron transport layer is prepared on the cathode;
preparing a thermistor layer on the electron transport layer;
preparing a light emitting layer on the thermistor layer; and
preparing an anode on the light-emitting layer to obtain the electroluminescent device;
wherein the material of the thermistor layer comprises a thermosensitive material with positive temperature coefficient.
12. The method of manufacturing an electroluminescent device according to claim 11, wherein the method of manufacturing a material of the thermistor layer comprises: and mixing and heating the first high molecular polymer and the thermosensitive material to obtain the material of the thermosensitive resistor layer.
13. The method of manufacturing an electroluminescent device according to claim 11, wherein the thermosensitive material is at least one selected from superconducting carbon black and metal nanoparticles.
14. A display device comprising the electroluminescent device according to any one of claims 1 to 10 or comprising the electroluminescent device produced by the production method according to any one of claims 11 to 13.
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