CN114725294A - Quantum dot light-emitting device, preparation method thereof and display device - Google Patents
Quantum dot light-emitting device, preparation method thereof and display device Download PDFInfo
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- CN114725294A CN114725294A CN202210262011.1A CN202210262011A CN114725294A CN 114725294 A CN114725294 A CN 114725294A CN 202210262011 A CN202210262011 A CN 202210262011A CN 114725294 A CN114725294 A CN 114725294A
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/166—Electron transporting layers comprising a multilayered structure
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a quantum dot light-emitting device, a preparation method thereof and a display device. The quantum dot light emitting device includes: an anode; a quantum dot layer disposed on one side of the anode; the electron transmission layer is arranged on one side, far away from the anode, of the quantum dot layer and comprises a first sub electron transmission layer and a second sub electron transmission layer which are arranged in a stacked mode, and the first sub electron transmission layer is arranged close to the quantum dot layer; a cathode disposed on a side of the electron transport layer away from the anode, wherein the material of the first sub-electron transport layer comprises ZnTiO3And the material of the second sub electron transport layer comprises Alq 3. Thereby, the injection and transport of electrons and holes can be balanced, thereby improving the efficiency of the device.
Description
Technical Field
The invention relates to the technical field of quantum dots, in particular to a quantum dot light-emitting device, a preparation method thereof and a display device.
Background
Quantum dots have been widely used in light emitting diodes, solar cells, biological imaging, detectors, etc., and quantum dot light emitting diodes (QLEDs) are a competitive partner for next generation display technologies due to their advantages, such as high color purity, adjustable light emitting color, and good stability. However, most of the research work related to QLEDs still stays in the experimental stage, and the main reason for limiting the step of QLED industrialization is the efficiency and lifetime of QLED devices.
Because the hole mobility in the conventional QLED device is smaller than the electron mobility, the injection and transmission efficiency of electrons in the device is far higher than that of holes, so that the injection of the electrons and the injection of the holes are not balanced, and the improvement of the device efficiency is limited; in addition, a material of a commonly used electron transport layer in the QLED device is zinc oxide (ZnO), and the ZnO has relatively many surface defect states, and the ZnO electron transport layer is in direct contact with the quantum dot layer, which easily causes fluorescence quenching of the quantum dot, and single ZnO is extremely unstable in air and is easily agglomerated.
Therefore, the current quantum dot light emitting device and the preparation method thereof still need to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
In one aspect of the present invention, the present invention provides a quantum dot light emitting device including: an anode; a quantum dot layer disposed on one side of the anode; the electron transmission layer is arranged on one side, far away from the anode, of the quantum dot layer and comprises a first sub electron transmission layer and a second sub electron transmission layer which are arranged in a stacked mode, and the first sub electron transmission layer is arranged close to the quantum dot layer; a cathode disposed on a side of the electron transport layer away from the anode, wherein the material of the first sub-electron transport layer comprises ZnTiO3And the material of the second sub electron transport layer comprises Alq 3. Therefore, the first sub-electron transport layer and the second sub-electron transport layer can improve the electron injection barrier and slow down the electron injection rate, thereby effectively improving the problem that the electron injection and transport rates are far greater than the hole injection and transport rates, and balancingInjection and transport of electrons and holes, thereby improving the efficiency of the device.
According to an embodiment of the present invention, the quantum dot light emitting device further comprises: a hole injection layer disposed between the anode and the quantum dot layer; a hole transport layer disposed between the hole injection layer and the quantum dot layer.
According to the embodiment of the invention, the material of the hole injection layer comprises at least one of PEDOT PSS, PTPDES TPBAH, PFO-co-NEPBN F4-TCNQ, molybdenum oxide, tungsten oxide, NiO and CuO.
According to an embodiment of the present invention, the material of the hole transport layer includes at least one of TFB, PVK, TCTA, TPD, poly TPD, and CBP.
According to an embodiment of the present invention, the quantum dot layer includes at least one of group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, or group IV elements.
According to an embodiment of the present invention, a material of the quantum dot layer includes at least one of an inorganic perovskite type semiconductor and an organic-inorganic hybrid perovskite type semiconductor.
According to the embodiment of the invention, the structural general formula of the inorganic perovskite type semiconductor is CsMX3Wherein M is a divalent metal cation and X is a halogen anion; the structural general formula of the organic-inorganic hybrid perovskite type semiconductor is BNY3Wherein B is an organic amine cation, N is a divalent metal cation, and Y is a halogen anion; optionally, M and N each independently comprise Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+And Eu2+At least one of; optionally, X and Y each independently comprise Cl-、Br-Or I-At least one of (a).
In another aspect of the invention, the invention providesThere is provided a method of making a quantum dot light emitting device as hereinbefore described, the method comprising: forming an anode; coating a quantum dot solution on one side of the anode, and heating to obtain a quantum dot layer; forming an electron transport layer on one side of the quantum dot layer away from the anode; evaporating and forming a cathode on one side of the electron transport layer far away from the anode, wherein the forming of the electron transport layer comprises the following steps: coating ZnTiO on one side of the quantum dot layer away from the anode3Heating the ethylene glycol ethyl ether solution to obtain a first sub electron transport layer; and coating an ethanol solution of Alq3 on the surface of the first sub electron transport layer away from the anode, and performing heating treatment to obtain a second sub electron transport layer. The hole injection and transmission efficiency of the quantum dot light-emitting device prepared by the method is matched with the electron injection and transmission efficiency, a better balance state is achieved, the efficiency of the quantum dot light-emitting device can be effectively improved, and the service life of the quantum dot light-emitting device is prolonged.
According to an embodiment of the invention, the ZnTiO3The preparation method of the ethylene glycol ethyl ether solution comprises the following steps: with ZnCl2And TiCl4Taking ammonia water as a mineralizer as a raw material, taking deionized water as a medium in a reaction kettle, and enabling ZnCl to be in the reaction kettle2、TiCl4Reacting with ammonia water at the temperature of 270-290 ℃ for 8-10 h; then carrying out high-temperature annealing treatment on the reaction product in the reaction kettle to obtain ZnTiO3(ii) a Finally preparing ZnTiO3The temperature of the ethylene glycol ethyl ether solution is 800-900 ℃ optionally.
According to an embodiment of the invention, the method further comprises: coating a hole injection layer coating solution on the surface of the anode, and heating to obtain the hole injection layer; and coating a hole transport layer coating solution on the surface of the hole injection layer far away from the anode, and heating to obtain the hole transport layer.
In yet another aspect of the present invention, the present invention provides a display apparatus comprising the quantum dot light emitting device described above. Thus, the display device has all the features and advantages of the quantum dot light emitting device described above, and will not be described herein again. In general, the display device has good display effect and long service life.
Drawings
Fig. 1 shows a schematic structural view of a quantum dot light emitting device according to an embodiment of the present invention;
fig. 2 shows a schematic structural view of a quantum dot light emitting device according to another embodiment of the present invention;
fig. 3 is a graph showing the film formation effect of the quantum dot light-emitting device of example 1;
fig. 4 is a graph showing the film formation effect of the quantum dot light-emitting device of comparative example 1;
FIG. 5 is a diagram showing the film formation effect of the quantum dot light-emitting device of example 2;
fig. 6 is a graph showing the film forming effect of the quantum dot light emitting device of comparative example 2.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In one aspect of the present invention, the present invention proposes a quantum dot light emitting device, which includes an anode 100, a quantum dot layer 200, an electron transport layer 300, and a cathode 400, with reference to fig. 1. Specifically, referring to fig. 1, a quantum dot layer 200 is disposed on one side of an anode 100, an electron transport layer 300 is disposed on one side of the quantum dot layer 200 away from the anode, and the electron transport layer 300 includes a first sub electron transport layer 310 and a second sub electron transport layer 320 which are stacked, the first sub electron transport layer 310 being disposed adjacent to the quantum dot layer 200, and a cathode 400 being disposed on one side of the electron transport layer 300 away from the anode, wherein a material of the first sub electron transport layer 310 includes ZnTiO3And the material of the second sub electron transport layer includes Alq 3. Thus, the first and second sub electron transport layers can improve electron injectionThe potential barrier is used for slowing down the electron injection rate, so that the problem that the electron injection and transmission rate is far greater than the hole injection and transmission rate is effectively solved, the injection and transmission of electrons and holes can be balanced, and the efficiency (including external quantum efficiency) of the quantum dot light-emitting device is improved; in addition, the fluorescence quenching of the quantum dots can be reduced, and the overall performance of the quantum dot light-emitting device is improved; and the service life of the quantum dot light-emitting device can be prolonged.
The following explains the principle that the technical solution of the present invention can achieve the above-mentioned effects: the commonly used electron transport layer material is ZnO, the ZnO surface has more defect states, the direct contact with a quantum dot layer can cause the fluorescence quenching of the quantum dot, specifically, the surface of the quantum dot has a large amount of ligands, such as carboxyl, hydroxyl, amino and the like, when the groups are combined with metal ion surface groups, a compound can be formed and adsorbed on the surface of the quantum dot, the quantum dot agglomeration is caused, the particle size is enlarged, and the fluorescence quenching is caused; in addition, single ZnO is extremely unstable in air and is easy to agglomerate, so that the quality problems of uneven formed film layers, black spots and the like are caused. The inventors have found that TiO2Has better stability in air and slower electron mobility compared with ZnO, and ZnTiO3Electron mobility in TiO2And between ZnO, ZnTiO3Moderate electron mobility and is comparable to ZnO, ZnTiO3The stability is good, and the material is an ideal electron transport layer material; aluminum can be used as a cathode in the quantum dot light-emitting device, and the barrier difference of tris (8-hydroxyquinoline) aluminum (Alq3) and an aluminum electrode (the barrier difference of Alq3 and aluminum is 1.2eV) is compared with ZnTiO3(the barrier difference between Alq3 and aluminum is 0.4eV), ZnTiO compound is produced3The electron transport layer is laminated with Alq3 to improve the electron injection barrier, slow down the electron injection rate, balance the injection and transport of electron-hole, and simultaneously, ZnTiO3The fluorescence quenching of the quantum dots can be improved, so that the device has better performance, and the service life of the device can be effectively prolonged.
According to an embodiment of the present invention, the anode 100 may include ITO (indium tin oxide), IZO (indium zinc oxide), and the like. Therefore, the material has better conductivity, and is beneficial to improving the overall performance of the quantum dot light-emitting device.
According to some embodiments of the present invention, the material of quantum dot layer 200 may include at least one of group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, or group IV elements. Thus, the quantum dot layer can emit light by excitation of holes and electrons. According to some embodiments of the invention, the material of the quantum dot layer 200 may include, but is not limited to, one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgTe, PbS, PbSe, PbTe, GaP, GaAs, InP, InAs, and other binary, ternary, and quaternary compounds.
According to other embodiments of the present invention, the material of the quantum dot layer 200 may include at least one of an inorganic perovskite type semiconductor, an organic-inorganic hybrid perovskite type semiconductor. Thus, the quantum dot layer formed of the above material can emit light by excitation of holes and electrons.
According to some embodiments of the invention, the inorganic perovskite semiconductor has the general structural formula CsMX3Wherein M is a divalent metal cation and X is a halogen anion. According to some embodiments of the invention, M may comprise Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+And Eu2+X may comprise Cl-、Br-Or I-At least one of (a).
According to some embodiments of the present invention, the organic-inorganic hybrid perovskite semiconductor has a general structural formula of BNY3Wherein B is an organic amine cation, N is a divalent metal cation, and Y is a halogen anion. According to some embodiments of the invention, N may include Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+And Eu2+At least one of (1), Y may be a bagIncluding Cl-、Br-Or I-At least one of (a). According to other embodiments of the present invention, the organic amine cation may be selected from, but is not limited to, CH3(CH2)n-2NH3 +(n.gtoreq.2) or NH3(CH2)nNH3 2+(n is more than or equal to 2); when n is 2, the inorganic metal halide is octahedral MX6 4-The metal cations M are positioned in the center of a halogen octahedron through connection in a roof-sharing mode, and the organic amine cations B are filled in gaps among the octahedrons to form an infinitely extending three-dimensional structure; when n > 2, inorganic metal halide octahedron MX connected in a common vertex mode6 4-The organic amine cation double molecular layer (protonated monoamine) or the organic amine cation single molecular layer (protonated diamine) is inserted between the layers, and the organic layer and the inorganic layer are mutually overlapped to form a stable two-dimensional layered structure.
According to the embodiment of the invention, the cathode 400 is made of aluminum, so that the cathode has good conductivity, which is beneficial to improving the performance of the quantum dot light-emitting device.
According to some embodiments of the present invention, referring to fig. 2, the quantum dot light emitting device may further include: a hole injection layer 500 and a hole transport layer 600, wherein the hole injection layer 500 is disposed between the anode 100 and the quantum dot layer 200, and the hole transport layer 600 is disposed between the hole injection layer 500 and the quantum dot layer 200. Thereby, the overall performance of the quantum dot light emitting device can be further improved.
According to some embodiments of the present invention, the material of the hole injection layer 500 may include at least one of PEDOT: PSS, PTPDES: TPBAH, PFO-co-NEPBN: F4-TCNQ, molybdenum oxide, tungsten oxide, NiO, and CuO. The hole injection layer 500 is made of the above materials, has a proper hole injection rate, and can further improve the overall performance of the quantum dot light-emitting device.
Wherein PEDOT is PSS (poly (3, 4-ethylenedioxythiophene: polystyrolsulfon acid salt)), PTPDES (tetraphenyldiamine-containing polyarylethersulfone polymer), TPBAH (PTPDES: TPBAH is P-doped composition of PTPDES, TPBAH (tris (4-bromophenyl) aminium hexachloroantimonate, 3 (4-bromophenyl) ammonium hexachloroantimonate, which is an electron acceptor of bromophenyl salt and can be P-doped)), PFO-co-NEPBN (poly (9, 9-dioctylfluorone-co-bis-N, N- (4-ethoxycarbonylphenyl) -bis-N, N-octylphenylbenzidine, poly (9, 9-dioctylphenyldiamine-co-N, N- (4-ethoxycarbonylbis-PBN, PFO-PBQ-PBN) is P-doped composition of PFoP-PBQ-N, PFO-4-bis-octylphenylfluorene-N-PFO-N-PBO-PFO-PBO-N, F4-TCNQ (2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane, a small molecule P-type dopant that can be P-doped)).
According to an embodiment of the present invention, the material of the hole transport layer 600 may include at least one of TFB, PVK, TCTA, TPD, poly TPD, and CBP. Therefore, the hole transport layer has a proper hole transport rate, and the overall performance of the quantum dot light-emitting device is further improved. Wherein, TFB refers to 1,2,4, 5-tetra (trifluoromethyl) benzene, PVK refers to polyvinylcarbazole, TCTA refers to 4,4,4, -tri (carbazol-9-yl) triphenylamine, TPD refers to N, N ' -diphenyl-N, N ' -di (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine, Poly TPD (Poly: TPD) refers to a polymer of TPD, and CBP refers to 4,4' -di (9-carbazol) biphenyl.
In addition, according to other embodiments of the present invention, referring to fig. 2, the quantum dot light emitting device may further include a substrate 700, wherein the substrate 700 is disposed at a side of the anode 100 away from the quantum dot layer 200. The substrate 700 may be made of glass, so that the substrate can provide a good supporting function for the anode, the quantum dot layer, the electron transport layer, the cathode, and the like, thereby improving the stability of the quantum dot light emitting device.
In general, the quantum dot light-emitting device provided by the invention adopts ZnTiO layers arranged in a laminating way3The first sub-electron transport layer and the Alq3 second sub-electron transport layer can improve an electron injection barrier, slow down the injection and transport rate of electrons, further balance the injection and transport of electrons and holes, and improve the fluorescence quenching of quantum dots, further effectively improve the efficiency of the quantum dot light-emitting device, and prolong the service life of the quantum dot light-emitting device.
In another aspect of the present invention, the present invention provides a method of preparing the aforementioned quantum dot light emitting device, the method comprising:
s100: an anode 100 is formed.
First, the anode 100 is formed. According to some embodiments of the present invention, the anode 100 may be formed on one surface of the substrate 700. The substrate 700 can be made of glass, the substrate 700 made of glass can provide a good supporting effect for the quantum dot light-emitting device, and the glass surface is smooth, so that the evaporation or coating of a subsequent functional film layer is facilitated.
According to other embodiments of the present invention, the substrate 700 may be cleaned prior to forming the anode 100 to facilitate subsequent formation of an anode on the substrate surface.
According to some embodiments of the present invention, the anode 100 may be patterned, that is, the anode 100 may include a plurality of sub-anodes, and a plurality of sub-light emitting structures may be formed, each of which may be individually controlled by a respective sub-anode.
In addition, a specific method of forming the anode in the present invention is not particularly limited as long as a flat anode structure can be formed on the surface of the substrate. The specific materials for the anode have been described above and will not be described in detail.
S200: one side of the anode is coated with quantum dot solution and heated to obtain the quantum dot layer 200.
After the anode 100 is formed, a quantum dot solution is applied to one side of the anode 100, and then a heating process is performed, resulting in the quantum dot layer 200. The material of the quantum dot layer 200 has been described in detail above, and is not described herein again.
According to some embodiments of the present invention, the quantum dot solution may be filtered by using a filter (e.g., a filter with a pore size of 0.25 μm) to obtain a quantum dot with a particle size of not more than 0.25 μm, coated on one side of the anode 100, and then heated to obtain the quantum dot layer 200. According to some embodiments of the present invention, the quantum dot solution may be applied by spin coating, the spin coating rate may be 2000rpm to 5000rpm, for example, 2000rpm, 2500rpm, 3000rpm, 3500rpm, 4000rpm, 4500rpm, 5000rpm, and the like, and the spin coating time may be 20s to 40s, for example, 20s, 25s, 30s, 35s, 40s, and the like, so that a uniform and flat quantum dot coating layer may be formed; then, the quantum dot coating layer is subjected to a heating treatment (e.g., annealing treatment) at a temperature of 55 ℃ to 65 ℃, for example, 55 ℃, 58 ℃, 60 ℃, 63 ℃, 65 ℃ or the like, for a time of 4min to 6min, for example, 4min, 5min, 6min or the like, whereby the solvent or volatile substances in the quantum dot coating layer can be removed to obtain a flat and uniform quantum dot layer.
In addition, according to other embodiments of the present invention, before forming the quantum dot layer 200, a hole injection layer 500 may also be formed on the surface of the anode 100 away from the substrate 700. According to some embodiments of the invention, the step of forming the hole injection layer comprises: a hole injection layer coating liquid is coated on the surface of the anode 100 (the surface remote from the substrate 700) and heat treatment is performed, resulting in the hole injection layer 500. The material of the hole injection layer 500 has been described in detail above, and is not described herein again.
According to some embodiments of the present invention, the hole injection layer coating solution is obtained by filtering the hole injection layer aqueous solution using a filter head (e.g., a filter head having a pore size of 0.45 um), wherein the filtering may remove larger particles of the hole injection layer particles, and then coating the hole injection layer coating solution on the surface of the anode 100, followed by a heating process, to obtain the hole injection layer 500. According to some embodiments of the present invention, when the hole injection layer coating solution is applied, spin coating may be performed at a spin coating rate of 2500rpm to 3500rpm, for example, 2500rpm, 2800rpm, 3000rpm, 3200rpm, 3500rpm, etc., and a spin coating time may be 20s to 40s, for example, 20s, 25s, 30s, 35s, 40s, etc., so that a uniform and flat hole injection layer coating layer may be formed in a short time using a suitable rotation speed; after the hole injection layer coating layer is formed, the coating layer is heated (e.g., annealed), according to other embodiments of the present invention, the heating temperature may be 130 ℃ to 150 ℃, for example, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, and the like, and the heating time may be 20min to 40min, for example, 20min, 25min, 30min, 35min, 40min, and the like, so that the solvent or the volatile substance in the hole injection layer coating layer may be removed to obtain the hole injection layer.
According to some embodiments of the present invention, before forming the hole injection layer 500, the substrate 700 with the anode 100 formed thereon may be further cleaned, and the cleaning step includes:
and (3) carrying out ultrasonic cleaning on the substrate with the anode sequentially by using a glass cleaning agent, deionized water, acetone and isopropanol, drying, and carrying out ultraviolet ozone treatment. Wherein, the drying method can be drying by a nitrogen gun, and the method does not need heating and does not cause adverse effect on the substrate or the anode. The substrate with the anode is sequentially cleaned by different cleaning materials in an ultrasonic mode, impurities (including organic matters and the like) on the surface of the substrate or the anode can be removed, and residual impurities can be further removed through ultraviolet ozone treatment.
Further, before the quantum dot layer 200 is formed, a hole transport layer 600 may be formed on the surface of the hole injection layer 500. According to some embodiments of the present invention, a hole transport layer coating solution may be coated on a surface of the hole injection layer 500 away from the anode 100, and heat treated to obtain the hole transport layer 600. The material of the hole transport layer 600 has been described in detail above, and is not described herein again.
According to some embodiments of the present invention, after the hole injection layer 500 is formed, the sample is transferred to a glove box, and the formulated hole transport layer coating liquid is coated on the surface of the hole injection layer 500 away from the anode 100, followed by a heat treatment, to obtain the hole transport layer 600. According to some embodiments of the present invention, the hole transport layer coating solution may be applied by spin coating, in which the spin coating rate may be 1500rpm to 2500rpm, specifically, 1500rpm, 1800rpm, 2000rpm, 2300rpm, 2500rpm, and the like, and the spin coating time may be 35s to 55s, for example, 35s, 38s, 40s, 45s, 50s, 55s, and the like, and thus, the hole transport layer coating layer may be formed at a suitable rotation speed for a short time; after the hole transport layer coating layer is formed, the coating layer is subjected to a heating treatment (e.g., annealing treatment) at a temperature of 100 to 120 ℃, e.g., 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, etc., for a heating time of 20 to 40min, e.g., 20min, 23min, 25min, 28min, 30min, 32min, 35min, 38min, 40min, etc., whereby the solvent or volatile substance in the hole transport layer coating layer can be removed to obtain the flat hole transport layer 600.
As will be appreciated by those skilled in the art, when a hole injection layer is provided, the quantum dot layer is disposed on the side of the hole injection layer remote from the anode; when the hole transport layer is provided, the quantum dot layer is provided on the side of the hole transport layer away from the anode.
S300: an electron transport layer 300 is formed on the side of the quantum dot layer away from the anode.
In this step, the electron transport layer 300 is formed on the side of the quantum dot layer 200 away from the anode 100. According to some embodiments of the present invention, the step of forming the electron transport layer 300 further includes forming a first sub electron transport layer 310 and forming a second sub electron transport layer 320.
According to some embodiments of the present invention, the step of forming the first sub electron transport layer 310 includes: coating ZnTiO on the side of quantum dot layer 200 away from anode 1003And heating the ethylene glycol ethyl ether solution to obtain the first sub electron transport layer 310. In this step, ZnTiO can be coated by spin coating3The ethylene glycol ether solution of (1) may have a spin rate of 1500rpm to 3500rpm, specifically, 1500rpm, 1800rpm, 2000rpm, 2300rpm, 2500rpm, 2700rpm, 3000rpm, 3200rpm, 3500rpm and the like, and a spin time of 25s to 35s, for example, 25s, 28s, 30s, 32s, 35s and the like, whereby ZnTiO can be formed3The ethylene glycol ethyl ether solution is uniformly coated on the surface of the quantum dot layer far away from the substrate to form a first sub-electron transport layer coating layer; heating the first electron transport layer coating layer at 55-65 deg.C (such as 55 deg.C, 58 deg.C, 60 deg.C, 63 deg.C, 65 deg.C) for 10min-20 minmin may be, for example, 10min, 12min, 15min, 18min, 20min, or the like, whereby the solvent in the first sub electron transport layer coating layer may be removed to obtain a uniform and flat first sub electron transport layer.
According to some embodiments of the invention, the ZnTiO compound is a compound of formula (I)3The preparation method of the ethylene glycol ethyl ether solution comprises the following steps: with ZnCl2And TiCl4Taking ammonia water as a mineralizer as a raw material, taking deionized water as a medium in a reaction kettle, and enabling ZnCl to be contained in the reaction kettle2、TiCl4Reacting with ammonia water at the temperature of 270-290 ℃ for 8-10 h; then carrying out high-temperature annealing treatment on the reaction product in the reaction kettle to obtain ZnTiO3(ii) a Finally preparing ZnTiO3Ethylene glycol ethyl ether solution. ZnTiO thus formed3Has good performance, can improve electron injection barrier, and ZnTiO prepared by using the electron injection barrier3The ethylene glycol ethyl ether solution can be well coated on the surface of the quantum dot layer, and the first sub electron transport layer with excellent performance can be obtained through heating treatment. According to some embodiments of the invention, the temperature for performing the high-temperature annealing treatment on the reaction product in the reaction kettle can be 800-900 ℃, thereby being beneficial to further improving the performance of the first electron transport layer and further being beneficial to improving the performance of the quantum dot device.
According to some embodiments of the present invention, the step of forming the second sub electron transport layer 320 includes: an ethanol solution of Alq3 was coated on the surface of the first sub electron transport layer 310 away from the anode 100, and heat treatment was performed to obtain a second sub electron transport layer 320. According to some embodiments of the present invention, a spin coating may be performed to coat the surface of the first sub electron transport layer 310 away from the anode 100 with an ethanol solution of Alq3, where the spin coating rate may be 1500rpm to 3500rpm, specifically, 1500rpm, 1800rpm, 2000rpm, 2300rpm, 2500rpm, 2700rpm, 3000rpm, 3200rpm, 3500rpm, and the like, and the spin coating time may be 25s to 35s, for example, 25s, 28s, 30s, 3 s, 35s, and the like, so that the ethanol solution of Alq 8932 may be uniformly coated on the surface of the first sub electron transport layer away from the anode to form a second sub electron transport layer coating layer; the second electron transport layer coating layer is subjected to a heating treatment (e.g., annealing treatment) at a temperature of 75 to 85 ℃, for example, 75 ℃, 77 ℃, 80 ℃, 82 ℃, 85 ℃ or the like, for a time of 25 to 35min, for example, 25min, 27min, 30min, 32min, 35min or the like, thereby removing the solvent from the second electron transport layer coating layer to obtain the second electron transport layer.
S400: the cathode 400 is formed on the side of the electron transport layer 300 away from the anode 100 by evaporation.
In this step, the cathode 400 is vapor-deposited on the side of the electron transport layer 300 remote from the anode 100. According to some embodiments of the present invention, aluminum may be evaporated on the side of the electron transport layer 300 away from the anode 100, resulting in the cathode 400. Therefore, the cathode can be formed by utilizing a mature process, and the yield of products is favorably improved.
In general, the quantum dot light-emitting device prepared by the method can form uniform and flat film layer structures, and the electron transmission layer is made of ZnTiO3The first sub-electron transport layer and the Alq3 second sub-electron transport layer are formed in a stacked mode, an electron injection barrier can be improved, the electron injection rate can be effectively reduced, the problem that the electron injection rate and the electron transport rate are far larger than the hole injection rate and the hole transport rate is solved, the injection and the transport of electrons and holes are balanced, the efficiency of the device is improved, and the service life of the device is prolonged.
In yet another aspect of the present invention, the present invention provides a display apparatus comprising the quantum dot light emitting device described above. Thus, the display device has all the features and advantages of the quantum dot light emitting device described above, and thus, the description thereof is omitted. In general, the display device has good display effect and long service life.
According to the embodiment of the present invention, the specific type of the display device has no special requirement, and those skilled in the art can flexibly select the display device according to actual requirements, for example, the display device can be a mobile phone, an iPad, a notebook, or the like.
It can be understood by those skilled in the art that the display device has the necessary structure and components of a conventional display device besides the aforementioned quantum dot light emitting device, and taking a mobile phone as an example, the display device further includes necessary structures and components of a battery rear cover, a middle frame, a touch panel, an audio module, a main board and the like besides the aforementioned quantum dot light emitting device.
The present invention is illustrated below by specific examples, and it will be understood by those skilled in the art that the following specific examples are for illustrative purposes only and do not limit the scope of the present invention in any way. The examples do not specify particular techniques or conditions, and are performed according to techniques or conditions described in literature in the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Step 1: forming an ITO anode on the surface of a glass substrate, and cleaning the glass substrate with the ITO anode: and (3) placing the glass substrate with the ITO anode in a glass cleaning agent, deionized water, acetone and isopropanol in sequence for ultrasonic cleaning, then blowing the surface by using a nitrogen gun, and then carrying out ultraviolet ozone treatment for 5 min.
Step 2: preparation of hole injection layer: the hole injection layer coating solution was obtained by filtering an aqueous solution of the hole injection layer (i.e., an aqueous solution of PEDOT: PSS (4083)) with a filter head having a pore diameter of 0.45um, and then the hole injection layer coating solution was spin-coated on the surface of the ITO anode remote from the glass substrate at a spin-coating rate of 3000rpm for 30s, followed by heating at 140 ℃ for 30min to form the hole injection layer. Wherein the material of the hole injection layer is PEDOT: PSS.
And step 3: preparation of hole transport layer: after the hole injection layer was formed, the sample was transferred to a glove box, and the prepared chlorobenzene solution for the hole transport layer (chlorobenzene solution of TFB) was spin-coated on the surface of the hole injection layer away from the substrate at a spin-coating rate of 2000rpm for 45s, followed by heating at 120 ℃ for 20min to form the hole transport layer. The material of the hole transport layer is TFB.
And 4, step 4: preparation of quantum dot layer:
1.2mmol of indium acetate (in (Ac))3) 0.6mmol of zinc acetate (Zn (Ac))2) And 3.6mmol Palmitic Acid (PA) were placed in a three-necked flask, heated to 150 ℃ and 0.8mmol tris (trimethylsilyl) phosphine ((TMS)3P) was dissolved in 1ml tri-n-octylphosphine (TOP) and poured into the above solution, and the temperature was rapidly raised to 290 ℃ to react for 5min to obtain InP nuclei.
The obtained InP was driven into 5M Zn (OA)2Heating the solution to 280 ℃, dropping 1M Se-TOP solution, reacting for 30min to obtain InP/ZnSe (core-shell structure, with InP as core and ZnSe as shell).
Preparing InP/ZnSe quantum dot solution with the concentration of 20mg/ml by using OCT (n-octane), spin-coating the quantum dot solution on the surface of the hole transport layer far from the substrate at the spin-coating speed of 2000rpm for 30s, and then heating at the temperature of 60 ℃ for 5min to form the quantum dot layer.
And 5: preparation of an electron transport layer:
preparing a first sub electron transport layer: synthesis of ZnTiO by hydrothermal method3Specifically, in the reaction kettle, ZnCl is used2And TiCl4Taking ammonia water as a mineralizer as a raw material, taking deionized water as a medium, reacting for 8 hours at 270 ℃, and annealing at 800 ℃ to obtain ZnTiO3ZnTiO to be prepared3Is prepared into ZnTiO3Ethylene glycol ethyl ether solution. After forming the quantum dot layer, ZnTiO3The ethylene glycol ether solution is spin-coated on the surface of the quantum dot layer far away from the substrate, the spin-coating speed is 1500rpm, the spin-coating time is 30s, and then the quantum dot layer is heated at the temperature of 60 ℃ for 15min to obtain the first sub electron transport layer. Wherein, the material of the first sub-electron transport layer is ZnTiO3。
Preparing a second sub electron transport layer: an ethanol solution of Alq3 was spin-coated on the surface of the first sub electron transport layer away from the substrate at a spin rate of 1500rpm for 30s, followed by heating at a temperature of 80 ℃ for 30min to form a second sub electron transport layer. The material of the second sub electron transport layer is Alq 3.
Step 6: preparing a cathode: after the second electron transport layer was formed, the sample was transferred to an evaporation coater where the surface of the second electron transport layer remote from the substrateAt a pressure of less than 5X 10-5And (3) evaporating and forming an Al electrode (cathode) under a high vacuum condition of Pa, thereby preparing the device A.
Comparative example 1
Different from the embodiment 1, after the quantum dot layer is formed, an ethanol solution of ZnO is spin-coated on the surface of the quantum dot layer away from the substrate at a spin-coating speed of 1500rpm for 30s, and then the quantum dot layer is heated at a temperature of 60 ℃ for 15min to obtain the electron transport layer, wherein the material of the electron transport layer is ZnO. After the electron transport layer was formed, the sample was transferred to an evaporation coater at a pressure of less than 5X 10 on the surface of the electron transport layer remote from the substrate-5And (3) evaporating and forming an Al electrode (cathode) under a high vacuum condition of Pa, thereby preparing a device B.
Comparative example 2
Unlike example 1, after the quantum dot layer was formed, an ethanol solution of Alq3 was spin-coated on the surface of the quantum dot layer away from the substrate at a spin-coating rate of 1500rpm for 30s, followed by heating at a temperature of 80 ℃ for 30min to form a first sub electron transport layer. The material of the first sub-electron transport layer is Alq 3. An ethanol solution of zinc oxide was spin-coated on the surface of the first sub electron transport layer away from the substrate at a spin-coating rate of 1500rpm for 30s, followed by heating at 80 ℃ for 30min to form a second sub electron transport layer. The second sub electron transport layer is made of ZnO. After the electron transport layer was formed, the sample was transferred to an evaporation coater at a pressure of less than 5X 10 on the surface of the electron transport layer remote from the substrate-5And (3) evaporating and forming an Al electrode (cathode) under a high vacuum condition of Pa, thereby preparing a device B.
Example 2
Step 1: forming an ITO anode on the surface of a glass substrate, and cleaning the glass substrate with the ITO anode: and (3) placing the glass substrate with the ITO anode in a glass cleaning agent, deionized water, acetone and isopropanol in sequence for ultrasonic cleaning, then blowing the surface by using a nitrogen gun, and then carrying out ultraviolet ozone treatment for 5 min.
Step 2: preparation of hole injection layer: the hole injection layer coating solution was obtained by filtering an aqueous solution of the hole injection layer (i.e., an aqueous solution of PEDOT: PSS (4083)) with a filter head having a pore diameter of 0.45um, and then the hole injection layer coating solution was spin-coated on the surface of the ITO anode remote from the glass substrate at a spin-coating rate of 3000rpm for 30s, followed by heating at 140 ℃ for 30min to form the hole injection layer. Wherein the material of the hole injection layer is PEDOT: PSS.
And 3, step 3: preparation of hole transport layer: after the hole injection layer was formed, the sample was transferred to a glove box, and the prepared hole transport layer chlorobenzene solution (chlorobenzene solution of TFB) was spin-coated on the surface of the hole injection layer remote from the substrate at a spin-coating rate of 2000rpm for 45s, followed by heating at 120 ℃ for 20min to form the hole transport layer. The material of the hole transport layer is TFB.
And 4, step 4: preparation of quantum dot layer:
preparation of CdSe core:
placing 8mmol of cadmium oxide, 8mL of OA (Oleic Acid) and 72mL of ODE (octadecene) in a three-neck flask, vacuumizing by using a vacuum pump, flushing argon, repeating for many times, filling the three-neck flask with argon, and slowly heating to 240 ℃ to fully react to generate cadmium oleate. And continuously heating, quickly injecting the precursor Se-TOP into a reaction system (cadmium oleate) at 280 ℃, then continuously heating to 320 ℃, and reacting for 5min to obtain the CdSe core.
The obtained CdSe core was driven into 5M Zn (OA)2And (3) heating the solution to 315 ℃, dropping 1M S-TOP solution, and reacting for 30min to obtain the CdSe/ZnS quantum dot (with a core-shell structure, CdSe as a core and ZnS as a shell).
Preparing CdSe/ZnS quantum dot solution with OCT (n-octane) with concentration of 20mg/ml, spin-coating the quantum dot solution on the surface of the hole transport layer far from the substrate at 2000rpm for 30s, and heating at 60 deg.C for 5min to form quantum dot layer.
And 5: preparation of an electron transport layer:
preparing a first sub electron transport layer: synthesis of ZnTiO by hydrothermal method3In a reaction kettle, ZnCl is added2And TiCl4Taking ammonia water as a mineralizer as a raw material, taking deionized water as a medium, reacting for 8 hours at 270 ℃, and annealing at 800 ℃ to obtain ZnTiO3ZnTiO to be prepared3Is prepared into ZnTiO3Ethylene glycol ethyl ether solution. After forming the quantum dot layer, ZnTiO is added3The ethylene glycol ethyl ether solution is coated on the surface of the quantum dot layer far away from the substrate in a spin mode, the spin coating speed is 1500rpm, the spin coating time is 30s, and then the quantum dot layer is heated for 15min at the temperature of 60 ℃ to obtain a first sub electron transport layer. Wherein, the material of the first sub-electron transport layer is ZnTiO3。
Preparing a second sub electron transport layer: an ethanol solution of Alq3 was spin-coated on the surface of the first sub electron transport layer away from the substrate at a spin rate of 1500rpm for 30s, followed by heating at a temperature of 80 ℃ for 30min to form a second sub electron transport layer. The material of the second sub-electron transport layer is Alq 3.
Step 6: preparing a cathode: after the formation of the second electron transport layer, the sample was transferred to an evaporation coater at a pressure of less than 5X 10 on the surface of the second electron transport layer remote from the substrate-5And (3) evaporating and forming an Al electrode (cathode) under a high vacuum condition of Pa, thereby preparing the device C.
Comparative example 3
Different from the embodiment 2, after the quantum dot layer is formed, an ethanol solution of ZnO is spin-coated on the surface of the quantum dot layer away from the substrate at a spin-coating speed of 1500rpm for 30s, and then the quantum dot layer is heated at a temperature of 60 ℃ for 15min to obtain the electron transport layer, wherein the material of the electron transport layer is ZnO. After the electron transport layer was formed, the sample was transferred to an evaporation coater at a pressure of less than 5X 10 on the surface of the electron transport layer remote from the substrate-5And (3) evaporating and coating the Al electrode under the high vacuum condition of Pa to prepare the device D.
The devices in each of the examples and comparative examples were tested to obtain the film formation quality, lifetime, and efficiency (external quantum efficiency) of each device.
The film forming quality test procedure was as follows: the film quality was observed under an Atomic Force Microscope (AFM).
The life test method is as follows: the service life is tested in the ocean optical EQE test system, and the time used when the maximum brightness of the film layer is reduced to 95% along with the change of time is taken, and the value obtained by multiplying the time by a proportionality coefficient is recorded as the service life of the device T95 (namely the service life of the device in the table 1).
External Quantum Efficiency (EQE): external quantum efficiency, i.e., the luminous efficiency of the device, is the ratio of the number of photons emitted and the number of electrons injected by a quantum dot light emitting diode device in a certain direction.
The results of the sample efficiency and life test for each example and comparative example are reported in table 1.
TABLE 1 sample efficiency and Life test results for each of the examples and comparative examples
| Device numbering | Device efficiency (EQE, external quantum efficiency) | Device lifetime |
| Device A | 5％-8％ | 200h-300h |
| Device B | 1％-3％ | 50h-100h |
| Device B | 2％-4％ | 100h-150h |
| Device C | 12％-16％ | 150-200h |
| Device D | 5％-8％ | 50-80h |
It is to be noted that for each sample, device efficiency and device lifetime were tested on 10 samples, and therefore all values were measured as ranges. As is clear from Table 1, ZnTiO was formed in both example 1 and example 23The first sub electron transport layer and the Alq3 second sub electron transport layer are adopted, so that the external quantum efficiency of the device A and the device C is high, and the service life is long; compared with the device A, the device B only takes ZnO as an electron transport layer, so that the external quantum efficiency of the device B is obviously lower than that of the device A, and the service life of the device B is shorter; compared with the device B, the device B takes Alq3 and ZnO as the composite electron transport layer, the external quantum efficiency and the service life of the device B are better than those of the device B with a single electron transport layer, and compared with the device A, ZnTiO is not formed in the device B3The electron transport layer structure laminated with Alq3 has an improvement effect on quantum dot injection barrier and an improvement effect on fluorescence quenching of quantum dots, so that the external quantum efficiency and the service life of the device B are lower than those of the device A; compared with the device C, the device D only takes ZnO as an electron transport layer, the external quantum efficiency is obviously lower than that of the device C, and the service life of the device is relatively short.
Fig. 3 to 6 are graphs showing the results of the film formation quality tests of the device a, the device B, the device C, and the device D, respectively, and it can be seen from fig. 3 and 5 that the film formation quality of the devices in examples 1 and 2 is good, and the film formation is uniform and flat; as can be seen from fig. 4 and 6, the devices of comparative example 1 and comparative example 2 have poor film formation quality, non-uniform film formation, and relatively obvious wrinkles and spots (caused by zinc oxide agglomeration).
The above experimental results show that ZnTiO3The first sub electron transport layer and the Alq3 second sub electron transport layer can significantly improve the film formation quality of the device,and the efficiency of the device can be obviously improved, and the service life of the device can be prolonged.
The terms "first" and "second" are used herein for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description herein, reference to the term "one embodiment," "another embodiment," "some embodiments," "some specific embodiments," or "other specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A quantum dot light emitting device, comprising:
an anode;
a quantum dot layer disposed on one side of the anode;
the electron transmission layer is arranged on one side, far away from the anode, of the quantum dot layer and comprises a first sub electron transmission layer and a second sub electron transmission layer which are arranged in a stacked mode, and the first sub electron transmission layer is arranged close to the quantum dot layer;
a cathode disposed on a side of the electron transport layer away from the anode,
wherein the material of the first sub-electron transport layer comprises ZnTiO3And the material of the second sub electron transport layer comprises Alq 3.
2. The quantum dot light-emitting device according to claim 1, further comprising:
a hole injection layer disposed between the anode and the quantum dot layer;
a hole transport layer disposed between the hole injection layer and the quantum dot layer.
3. The QDS device according to claim 2, wherein the hole injection layer is made of at least one of PEDOT PSS, PTPDES TPBAH, PFO-co-NEPBN F4-TCNQ, molybdenum oxide, tungsten oxide, NiO and CuO, and the hole transport layer is made of at least one of TFB, PVK, TCTA, TPD, poly TPD and CBP.
4. The quantum dot light-emitting device according to claim 1, wherein the material of the quantum dot layer comprises at least one of group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, or group IV simple substance.
5. The quantum dot light-emitting device according to claim 1, wherein a material of the quantum dot layer includes at least one of an inorganic perovskite type semiconductor, an organic-inorganic hybrid perovskite type semiconductor.
6. The quantum of claim 5The point light emitting device is characterized in that the structural general formula of the inorganic perovskite type semiconductor is CsMX3Wherein M is a divalent metal cation and X is a halide anion;
the structural general formula of the organic-inorganic hybrid perovskite type semiconductor is BNY3Wherein B is an organic amine cation, N is a divalent metal cation, and Y is a halogen anion;
optionally, M and N each independently comprise Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+And Eu2+At least one of;
optionally, X and Y each independently comprise Cl-、Br-Or I-At least one of (a).
7. A method of making the quantum dot light-emitting device of any one of claims 1-6, comprising:
forming an anode;
coating a quantum dot solution on one side of the anode, and heating to obtain a quantum dot layer;
forming an electron transport layer on one side of the quantum dot layer away from the anode;
evaporating to form a cathode on the side of the electron transport layer far away from the anode,
wherein forming the electron transport layer comprises:
coating ZnTiO on one side of the quantum dot layer away from the anode3Heating the ethylene glycol ethyl ether solution to obtain a first sub electron transport layer;
and coating an ethanol solution of Alq3 on the surface of the first sub electron transport layer away from the anode, and performing heating treatment to obtain a second sub electron transport layer.
8. The method of claim 7, wherein the ZnTiO is in a form selected from the group consisting of3The preparation method of the ethylene glycol ethyl ether solution comprises the following steps:
with ZnCl2And TiCl4Taking ammonia water as a mineralizer as a raw material, taking deionized water as a medium in a reaction kettle, and enabling ZnCl to be in the reaction kettle2、TiCl4Reacting with ammonia water at the temperature of 270-290 ℃ for 8-10 h;
then carrying out high-temperature annealing treatment on the reaction product in the reaction kettle to obtain ZnTiO3；
Finally preparing ZnTiO3The ethylene glycol-ethyl ether solution is prepared by dissolving ethylene glycol-ethyl ether,
optionally, the temperature of the high-temperature annealing treatment is 800-900 ℃.
9. The method of claim 7 or 8, further comprising:
coating a hole injection layer coating solution on the surface of the anode, and heating to obtain the hole injection layer;
and coating a hole transport layer coating solution on the surface of the hole injection layer far away from the anode, and heating to obtain the hole transport layer.
10. A display device comprising a QD light emitting device according to any of claims 1 to 6.
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| CN109148704A (en) * | 2018-08-20 | 2019-01-04 | 纳晶科技股份有限公司 | Quanta point electroluminescent device and preparation method thereof |
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