Patent Description:
The present disclosure generally relates to the quantum dot technology field and, more particularly, to a nanomaterial, a light-emitting diode device, and a preparation method of the light-emitting diode device.

ZnO is a direct bandgap n-type semiconductor material with a wide band gap of <NUM>. 37eV and a low work function of <NUM>. 7eV and has advantages of good stability, high transparency, safety, and non-toxicity, which makes ZnO a suitable electron transport layer material. ZnO has many potential advantages. First, exciton binding energy of ZnO achieves as high as 60meV, which is much higher than other wide-bandgap semiconductor materials (25meV for GaN) and <NUM> times higher than room temperature thermal energy (26meV). Thus, excitons of ZnO are stable at room temperature. Second, ZnO has a hexagonal wurtzite structure and exhibits strong spontaneous polarization. In a ZnO-based heterostructure, the strain of the material can lead to extremely strong piezoelectric polarization, which in turn leads to the generation of polarization effect in the ZnO-based heterostructure. In a polarization electric field generated by the polarization, interfacial polarization charges with high concentration are induced on a ZnO heterojunction surface, thereby regulating the energy band of the material to further affect the related structure and device performance.

However, when ZnO nanoparticles are used as the electron transport layer, a surface defect of ZnO such as hydroxyl and oxygen vacancies inevitably leads to degradation of the device performance.

Therefore, the existing technology still needs to be improved and developed.

<NPL>, discloses the synthesis of core-shell ZnO/In203 nano particles.

In view of the above-mentioned deficiencies of the prior art, the purpose of the present disclosure is to provide a nanomaterial, a light-emitting diode device, and a preparation method thereof to solve the problem that the performance of the light-emitting diode device is reduced by using the ZnO nanoparticle as the electron transport layer due to the existence of many defects on the surface of the existing ZnO nanoparticle.

The technical solutions of the present disclosure are as follows.

A nanomaterial preparation method in accordance to claim <NUM> and a light emitting diode device in accordance with claim <NUM>.

A preparation method of a nanomaterial includes:.

A preparation method of a light-emitting diode includes:.

A light-emitting diode device includes a cathode, an anode, a light-emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the light-emitting layer, a material of the electron transport layer being the nanomaterial prepared by the preparation method of embodiments of the present disclosure.

Beneficial effects include that in the present disclosure, a ZnO@ In<NUM>O<NUM> core-shell structure is formed by coating the surface of the ZnO nanoparticle with the In<NUM>O<NUM> shell layer. That is, the nanomaterial is prepared. In the present disclosure, In<NUM>O<NUM> having a wide bandgap is used as the shell layer to cover the semiconductor ZnO nanoparticle that has the relatively narrow bandgap, which can effectively passivate the surface of the ZnO nanoparticle, reduce the surface defects, and alleviate the lattice mismatch. Meanwhile, the holes may be effectively blocked from being transferred from the light-emitting layer to the cathode to improve the recombination efficiency of the electrons and holes in the light-emitting layer and improve the light-emitting performance of the light-emitting device.

The present disclosure provides a nanomaterial, a light-emitting diode device, and a preparation method thereof. In order to make the purposes, technical solutions, and effects of the present disclosure clearer and more specific, the present disclosure is further described in detail below. It should be understood that specific embodiments described here are only used to explain the present disclosure, but not to limit the present disclosure.

It should be noted that expressions such as "one or more" and "at least one" involved in the present disclosure may indicate one or more of the listed items, and "a plurality of" may indicate two or more than two of these items, including any combination of a single item (type) or a plurality of items (types). For example, "at least one of methanol, ethanol, and ethylene glycol" may refer to methanol, ethanol, ethylene glycol, methanol+ethanol, methanol+ethylene glycol, ethanol+ethylene glycol, or methanol+ethanol+ethylene glycol.

ZnO is a direct bandgap n-type semiconductor material with a wide band gap of <NUM>. 37eV and a low work function of <NUM>. 7eV and has advantages of good stability, high transparency, safety, and non-toxicity, which makes ZnO a suitable electron transport layer material. However, when ZnO nanoparticles are used as the electron transport layer, surface defects of ZnO such as hydroxyl and oxygen vacancies may inevitably lead to the degradation of the device performance.

Based on this, embodiments of the present disclosure provide a nanomaterial, including a ZnO nanoparticle and an In<NUM>O<NUM> shell layer coated on a surface of the ZnO nanoparticle.

Similar to ZnO, In<NUM>O<NUM> is a semiconductor with a wider band gap than ZnO (<NUM>-<NUM> eV). In the embodiments of the present invention, the ZnO nanoparticle are used as the core, and In<NUM>O<NUM> is coated over the surface of the ZnO nanoparticle as a shell layer. The In<NUM>O<NUM> shell layer can be effectively configured to passivate the surface of the ZnO nanoparticle, reduce the surface defects, and alleviate lattice mismatch, and also effectively block a hole from being transferred from the light-emitting layer to a cathode, which improves recombination efficiency of electrons and holes in the light-emitting layer, thereby improving the light-emitting performance of the light-emitting device.

In the embodiments of the present invention, the nanomaterial further includes Au atoms or Au microclusters carried by the In<NUM>O<NUM> shell layer. In some embodiments, due to an electronegativity difference between the In<NUM>O<NUM> shell layer and the Au atoms or Au microclusters, the In<NUM>O<NUM> shell layer may be adsorbed with the Au atoms or Au microclusters together through electrostatic interaction. In some embodiments, an Au microcluster may refer to an aggregate formed by several Au atoms or Au molecules. Properties may be close to a single Au atom. An atomic-level dispersion may greatly improve the utilization of Au atoms and reduce use of a precious metal. Au atoms or Au microclusters may form a contact interface on the In<NUM>O<NUM> material, which may form an Auδ+-In<NUM>O<NUM>-x interface after activation. Auδ+ may be an Au atom with positive charges (or partially delocalized Au ions). The Au atom may have a large specific surface area and interact with the In atom of neighboring coordinated In atoms, which causes charge redistribution around the In atom, thereby causing charge redistribution to build a new electron transport path to improve electron transport properties.

In some embodiments, a preparation method of the nanomaterial is also provided. As shown in <FIG>, the method includes:.

In some embodiments, the ZnO nanoparticle can be prepared in a solution method. The preparation method may be relatively simple, have strong versatility, and be suitable for large-scale preparation. The In<NUM>O<NUM> shell layer may be deposited on the surface of the ZnO nanoparticle in a chemical co-deposition method, which has a simple preparation process, low cost, and controllable condition. In the embodiment, the In<NUM>O<NUM> shell lay may be prepared on the surface of the ZnO nanoparticle, and the In<NUM>O<NUM> shell layer may effectively passivate the surface of the ZnO nanoparticle, reduce the surface defects, alleviate the lattice mismatch, and at the same time also effectively block the hole from being transported from the light-emitting layer to the cathode, which improves the recombination efficiency of the electrons and holes in the light-emitting layer to improve the light-emitting performance of the light-emitting device.

In some embodiments, the preparation of the ZnO nanoparticles includes dissolving a zinc salt in an organic solvent to obtain a zinc salt solution, adding alkali solution to the zinc salt solution and stirring to obtain a ZnO nanoparticle solution, performing precipitation and drying on the ZnO nanoparticle solution to prepare the ZnO nanoparticle.

In some embodiments, the preparation method of the ZnO nanoparticle is the solution method. The preparation method is relatively simple, has strong versatility, and is suitable for large-scale preparation. The zinc salt may be one or more of zinc chloride, zinc nitrate, or zinc acetate, which is not limited to this. The organic solvent may be one or both of dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO), which is not limited to this. The alkali solution may be one or more of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, or ammonia water, which is not limited to this.

In some embodiments, the concentration of the zinc salt solution may range from <NUM> to <NUM>. The concentration of the alkali solution may range from <NUM> to <NUM>. A molar ratio of the hydroxide ions of the alkali solution and the molar ratio of the zinc ions may be (<NUM> to <NUM>): <NUM>. When the molar ratio of hydroxide ions and zinc ions is less than <NUM>:<NUM>, the metal salt is excessive. When the molar ratio of hydroxide ions and zinc ions is greater than <NUM>:<NUM>, a pH value may be too high, which will slow down the reaction speed of the system. Optimally, when the molar ratio of the hydroxide ions and the zinc ions is maintained at (<NUM>-<NUM>):<NUM>, a pH of <NUM> to <NUM> can be achieved, and eventually causes the particles to be evenly distributed at the subsequently obtained film.

In some embodiments, depositing the In<NUM>O<NUM> shell layer on the surface of the ZnO nanoparticle may include dissolving an indium salt in an organic solvent to obtain an indium salt solution, dissolving the ZnO nanoparticles in organic alcohol to obtain the ZnO nanoparticle alcohol solution, adding the ZnO nanoparticle alcohol solution to the indium salt solution, then adding the alkali solution and stirring, reacting to obtain a ZnO nanoparticle solution covered by the In<NUM>O<NUM> shell layer, and performing precipitation and drying on the ZnO nanoparticle solution covered with the In<NUM>O<NUM> shell layer to obtain the ZnO nanoparticles coated by the In<NUM>O<NUM> shell layer.

In some embodiments, the In<NUM>O<NUM> shell layer on the surface of the ZnO nanoparticle may be deposited in a chemical co-deposition method. The preparation process may be simple and have a low cost and controllable condition. The indium salt may be one or more of indium nitrate, indium chloride, and indium acetate, which is not limited to this. The organic solvent may be one or more of methanol, ethanol, and isopropanol, which is not limited to this. The organic alcohol may include but is not limited to at least one of methanol, ethanol, and ethylene glycol. The alkali solution may be one or more of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and ammonia water species, but is not limited to this. In this embodiment, the concentration of the indium salt solution may range from <NUM> to <NUM>.

During the reaction, the pH value of the solution being too high or too low may have a significant influence on the purity and yield of the product. As an example, the reaction conditions may be maintained at pH <NUM> to10.

In some embodiments, a preparation method of the nanomaterial may be also provided. As shown in <FIG>, which includes:.

The ZnO nanoparticle covered by the In<NUM>O<NUM> shell layer may be dissolved in the organic alcohol to obtain an In<NUM>O<NUM> shell layer covered ZnO nanoparticle alcohol solution. Gold salt and the In<NUM>O<NUM> shell layer covered ZnO nanoparticle alcohol solution may be added to a mixed solution composed of oleylamine and octadecene and stirred at <NUM> to <NUM>. Au atoms and/or Au microclusters may be loaded on the In<NUM>O<NUM> shell layer to prepare the nanomaterial.

In some embodiments, the octadecene can be used as a reducing agent to reduce the gold salt to Au atoms to be loaded on the In<NUM>O<NUM> shell layer. The oleylamine can be used as a dispersant to inhibit excessive aggregation of Au atoms. In some embodiments, Au atoms and/or Au microclusters may be introduced on the In<NUM>O<NUM> shell layer. The Au microclusters may refer to aggregates formed by several Au atoms or Au molecules and have properties close to a single Au atom. With atomic-level dispersion, a utilization rate of Au atoms may be greatly improved, which reduces use of a noble metal. Au atoms or Au microclusters may form a contact interface on the In<NUM>O<NUM> material, and Auδ+-In<NUM>O<NUM>-x interface may be formed after activation. Auδ+ may represent activated Au atoms with positive charges (or partially delocalized Au ions) on the interface. Au atoms may have a large specific surface area, which interacts with neighboring coordinated In atoms to cause a redistribution of charges around the In atoms to cause charge redistribution. Thus, a new electron transport path may be formed, and the electron transport performance may be improved.

In some embodiments, the gold salt may include but is not limited to one or more of chloroauric acid, ammonium tetrachloroaurate hydrate, or (triphenylphosphine) gold chloride. The organic alcohol may include but is not limited to at least one of methanol, ethanol, or ethylene glycol.

In a preparation method of the nanomaterial of embodiments of the present disclosure, ZnO nanoparticles may be synthesized in the solution method. Then, the In<NUM>O<NUM> shell layer may be deposited on the surface of the ZnO nanoparticle in a chemical co-deposition method. Then, Au atoms or Au microclusters may be loaded on the In<NUM>O<NUM> in a dipping method to prepare the nanomaterial. The preparation method of the present disclosure may be relatively simple and has strong versatility. Thus, the use of the precious metals may be reduced, and the method is suitable for large-scale preparation.

In an embodiment in accordance to the present invention, a light-emitting diode device is also provided, which includes an electron transport layer. An electron transport layer material may be the nanomaterial described in the present disclosure or the nanomaterial prepared by the preparation method described in the present disclosure. As an example, the light-emitting diode device may be a QLED device or an OLED device.

A nanomaterial, a preparation method thereof, and a light-emitting diode of the present disclosure are further described in the following embodiments.

In embodiment <NUM> of the present disclosure, zinc chloride, sodium hydroxide, indium nitrate, and chloroauric acid are used as examples for a detailed introduction.

In embodiment <NUM> of the present disclosure, zinc nitrate hexahydrate, potassium hydroxide, indium nitrate, and chloroauric acid were used as examples for a detailed introduction.

In embodiment <NUM> of the present disclosure, zinc acetate dihydrate, tetramethylammonium hydroxide, indium nitrate, and chloroauric acid were taken as examples for a detailed introduction.

Embodiments of the present disclosure also provide a light-emitting diode device, which includes an electron transport layer. The material of the electron transport layer may be the nanomaterial or the nanomaterial prepared by the above preparation method. The light-emitting diode device may be a QLED device or an OLED device.

In some embodiments, the light-emitting diode device may be a QLED device as shown in <FIG>, which includes a substrate <NUM>, an anode <NUM>, a hole transport layer <NUM>, a quantum dot light-emitting layer <NUM>, an electron transport layer <NUM>, and a cathode <NUM>. The material of the electron transport layer <NUM> is the nanomaterial provided by the present disclosure.

In some embodiments, a preparation method of a QLED device includes the following steps.

In some embodiments, in order to obtain a high-quality nanomaterial layer, the ITO substrate may need to undergo a preprocessing process. The processing steps may include cleaning an ITO conductive glass with detergent to preliminarily remove stains on the surface, ultrasonically cleaning for <NUM> minutes in each of deionized water, isopropanol, acetone, and deionized water to remove impurities on the surface, and finally blowing dry with high-purity nitrogen to obtain the ITO anode.

In some embodiments, the preparation steps of the hole transport layer may include placing the ITO substrate on a spinner, spin coating to form a film using the prepared hole transport material solution, controlling the thickness of the film by adjusting the concentration of the solution, a spin coating speed, and spin coating time, and then performing thermal annealing at an appropriate temperature.

The hole transport layer described in the present disclosure can be made of a conventional hole transport material, including but not limited to Poly(<NUM>,<NUM>-dioctylfluorene-CON-(<NUM>-butylphenyl)diphenylamine) (TFB), polyvinylcarbazole (PVK), Poly(N,N'bis(<NUM>-butylphenyl)-N,N'-bis(phenyl)benzidine) (Poly-TPD), <NUM>,<NUM>',<NUM>''-Tris(carbazol-<NUM>-yl)triphenylamine (TCTA), Poly(<NUM>,<NUM>-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS), <NUM>,<NUM>'-bis(<NUM>-carbazole)biphenyl (CBP), or a mixture of any combination thereof, and can be another high performance hole transport material.

The concentration of the hole transport material solution may be <NUM>/mL, the spin coating speed may be <NUM> rpm/min, and the spin coating time may be <NUM>.

In some embodiments, the preparation steps of the quantum dot light-emitting layer may include placing the substrate on which the hole transport layer has been spin-coated on the spinner, spin coating to form the film using the prepared light-emitting material solution with a certain concentration, controlling the thickness of the light-emitting layer by adjusting the solution concentration, spin coating speed, and spin coating time, and drying at an appropriate temperature.

A quantum dot of the quantum dot light-emitting layer may include any one of red, green, and blue quantum dots. The quantum dot may include but is not limited to at least one of CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe, or various core-shell structure quantum dots.

The thickness of the quantum dot light-emitting layer may range from <NUM> to <NUM>.

The concentration of the light-emitting material solution may be <NUM>/mL, the spin coating speed may be <NUM> rpm/min, and the spin coating time may be <NUM>.

In some embodiments, the preparation step of the electron transport layer may include placing the substrate on which the quantum dot light-emitting layer has been spin-coated on the spinner, spin-coating to form a film using the prepared nanomaterial solution with a certain concentration, controlling the thickness of the electron transport layer by adjusting the concentration of the solution, spin coating speed, and spin coating time, and then performing annealing to form the film.

The thickness of the electron transport layer may range from <NUM> to <NUM>.

The concentration of the electron transport layer material solution may be <NUM>/mL, the spin coating speed may be <NUM> rpm/min, and the spin coating time may be <NUM>.

In some embodiments, the preparation step of the cathode may include placing the substrate on which the functional layers have been deposited into an evaporation chamber, and thermally vapor-depositing a layer of <NUM> to <NUM> metal silver or aluminum as a cathode through a mask.

In some embodiments, packaging processing may be performed on the obtained QLED device. The packaging processing may be performed by a common machine or manually.

In a packaging processing environment, oxygen content and water content may be both lower than <NUM> ppm to ensure the stability of the device.

A QLED device of the present disclosure is further explained in the following embodiments.

In embodiment <NUM> of the present disclosure, the material of the substrate <NUM> was a glass sheet, the material of the anode <NUM> was the ITO substrate, the material of the hole transport layer <NUM> was TFB, the material of the electron transport layer <NUM> was the nanomaterial prepared in embodiment <NUM>, and the material of the cathode <NUM> was Al.

In embodiment <NUM> of the present disclosure, the material of the substrate <NUM> was the glass sheet, the material of the anode <NUM> was the ITO substrate, the material of the hole transport layer <NUM> was TFB, the material of the electron transport layer <NUM> was the nanomaterial prepared in embodiment <NUM>, and the material of the cathode <NUM> was Al.

The present disclosure also provided a comparison embodiment, wherein the material of the substrate <NUM> was the glass sheet, the material of the anode <NUM> was the ITO substrate, the material of the hole transport layer <NUM> was TFB, the material of the electron transport layer <NUM> was the ZnO nanoparticle, and the material of the cathode <NUM> was Al.

The QLEDs prepared in embodiment <NUM>, embodiment <NUM>, embodiment <NUM>, and comparison embodiment were tested for performance, and light-emitting efficiency and stability were measured as follows.

Compared with the comparison embodiment, the light-emitting efficiencies of embodiment <NUM>, embodiment <NUM>, and embodiment <NUM> were significantly improved, and meanwhile, the stabilities of the diodes were improved to a certain degree.

In summary, with the nanomaterial of the present disclosure, by coating the In<NUM>O<NUM> layer on the surface of ZnO and using In<NUM>O<NUM> as a shell layer to cover the semiconductor ZnO nanoparticle with a relatively narrow bandgap, the holes may be effectively blocked from being transferred from the light-emitting layer to the electron transport layer, the surface defects of ZnO may be passivated, capturing of the electrons by the defects may be reduced, and the electron-hole recombination efficiency may be improved. Meanwhile, the conductive component of Au atoms or Au microclusters may be introduced and loaded on the surface of the In<NUM>O<NUM> shell layer to form isolated Au single atoms and Au microclusters.

The Au atom with the atomic-level dispersion may have a large specific surface area and interact with the neighboring coordinated In atom, which causes the redistribution of the charges around the In atom to build the new electron transport path to accelerate the electron transport and improve the electron transport properties of the device to cooperatively improve the electron transport properties and stability of the device.

Claim 1:
A preparation method of a light-emitting diode comprising:
preparing a nanomaterial as an electron transport layer by:
providing a ZnO nanoparticle (S10);
depositing an In<NUM>O<NUM> shell layer on a surface of the ZnO nanoparticle (S20); and
loading Au atoms and/or Au microclusters on the In<NUM>O<NUM> shell layer (S30).