CN112397659B - Composite material, preparation method thereof and quantum dot light-emitting diode - Google Patents
Composite material, preparation method thereof and quantum dot light-emitting diode Download PDFInfo
- Publication number
- CN112397659B CN112397659B CN201910763104.0A CN201910763104A CN112397659B CN 112397659 B CN112397659 B CN 112397659B CN 201910763104 A CN201910763104 A CN 201910763104A CN 112397659 B CN112397659 B CN 112397659B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- dot light
- composite material
- metal
- metal compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
-
- 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
-
- 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
- H10K50/80—Constructional details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
Abstract
The invention belongs to the technical field of panel display, and particularly relates to a composite material, a preparation method thereof and a quantum dot light-emitting diode. The composite material of the present invention comprises: metal compound nanoparticles and thiophenol compounds; the thiophenol compound is connected with the surface of the metal compound nanoparticle through a sulfydryl, and the sulfydryl is bonded with the metal atom of the metal compound nanoparticle; the metal compound nanoparticles are metal oxides and/or metal sulfides. The preparation method of the composite material comprises the following steps: providing metal compound nanoparticles, thiophenol compounds and alcohol, mixing the metal compound nanoparticles, the thiophenol compounds and the alcohol, and carrying out heating reaction to prepare a precursor solution; and carrying out solid-liquid separation treatment on the precursor solution to obtain the composite material. The composite material is used for preparing an electron transmission layer in the quantum dot light-emitting diode, so that the electron transmission capability is improved, and the light-emitting performance of the quantum dot light-emitting diode is effectively improved on the whole.
Description
Technical Field
The invention belongs to the technical field of panel display, and particularly relates to a composite material, a preparation method thereof and a quantum dot light-emitting diode.
Background
Quantum dot electroluminescence is a novel solid-state illumination technology, has the advantages of low cost, light weight, high response speed, high color saturation and the like, has wide development prospect, and has become one of important research directions of new generation Light Emitting Diode (LED) illumination. The light emitting mechanism of the currently studied quantum dot light emitting diode (QLED) device is: electrons injected from the cathode are transmitted into the quantum dot light-emitting layer through the electron transmission layer and are subjected to composite radiation light-emitting with the holes.
In recent years, inorganic semiconductors have been studied as an electron transport layer in a relatively hot manner. In order to further improve the light emitting performance of quantum dot light emitting diodes, surface chemical modification of inorganic semiconductors with some small molecule ligands has been attempted. At present, common small molecule ligands are mainly thiol, fatty acid, amine, organic phosphoric acid and the like, and the small molecule ligands are used for surface modification of inorganic semiconductors, although the light emitting performance of the quantum dot light emitting diode can be improved to a certain extent, the effect is limited, and further improvement and development are still needed.
Disclosure of Invention
The invention mainly aims to provide a composite material, aiming at improving the light-emitting performance of a quantum dot light-emitting diode.
The invention also aims to provide a preparation method of the composite material.
It is another object of the present invention to provide a quantum dot light emitting diode.
In order to achieve the above object, the present invention provides the following technical solutions:
a composite material, comprising: metal compound nanoparticles and thiophenol compounds; the thiophenol compound is connected with the surface of the metal compound nanoparticle through a sulfydryl, and the sulfydryl is bonded with the metal atom of the metal compound nanoparticle;
the metal compound nanoparticles are metal oxides and/or metal sulfides.
The composite material provided by the invention adopts the thiophenol compound as the micromolecular ligand, and the sulfydryl of the thiophenol compound is bonded with the metal atom of the metal compound nano-particle, so that the surface modification of the metal compound nano-particle is effectively realized. The strong electron density of the aromatic ring in the thiophenol compound is used as a strong electron donor to generate an electron transfer reaction with the surface of the metal compound nano-particle, so that the conductivity of the composite material is increased, the composite material is applied to the preparation of an electron transmission layer in the quantum dot light-emitting diode, electrons and holes can be promoted to be effectively compounded in the quantum dot light-emitting layer, the electron transmission capability is improved, the influence of exciton accumulation on the performance of the device is reduced, and the light-emitting performance of the quantum dot light-emitting diode is effectively improved on the whole.
Correspondingly, the preparation method of the composite material comprises the following steps:
providing metal compound nanoparticles, thiophenol compounds and alcohol, mixing the metal compound nanoparticles, the thiophenol compounds and the alcohol, and carrying out heating reaction to prepare a precursor solution;
and carrying out solid-liquid separation treatment on the precursor solution to obtain the composite material.
According to the preparation method of the composite material, the metal compound nanoparticles and the thiophenol compounds are heated and reacted in alcohol, and then solid-liquid separation treatment is carried out, so that the metal compound nanoparticles are subjected to surface modification by using the thiophenol compounds, the thiophenol compounds and the metal compound nanoparticles are stably bonded, the method is simple and convenient to operate, expensive equipment is not needed, the reaction process is controllable, the quality is stably guaranteed, and large-scale production is facilitated.
Correspondingly, a quantum dot light emitting diode comprises a cathode and an anode which are oppositely arranged, a quantum dot light emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the quantum dot light emitting layer, wherein the electron transport layer comprises the following materials: the composite material or the composite material prepared by the preparation method.
According to the quantum dot light-emitting diode provided by the invention, the material of the electron transmission layer comprises the composite material, the recombination efficiency of electrons and holes in the quantum dot light-emitting layer is high, the quantum dot light-emitting diode has good electron transmission capability, and the light-emitting performance of the quantum dot light-emitting diode can be integrally improved.
Drawings
FIG. 1 is a flow chart of a method for preparing a composite material according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
Reference numerals: the light-emitting diode comprises a substrate 1, an anode 2, a hole transport layer 3, a quantum dot light-emitting layer 4, an electron transport layer 5 and a cathode 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the embodiments of the present invention, any ratio of the amounts of the components of the composition according to the description of the embodiments of the present invention may be enlarged or reduced within the scope of the disclosure of the description of the embodiments of the present invention. Specifically, the mass described in the description of the embodiments of the present invention may be a unit of weight known in the field of materials such as μ g, mg, g, kg, etc.
A composite material, comprising: metal compound nanoparticles and thiophenol compounds; the thiophenol compound is connected with the surface of the metal compound nanoparticle through a sulfydryl, and the sulfydryl is bonded with the metal atom of the metal compound nanoparticle;
the metal compound nanoparticles are metal oxides and/or metal sulfides.
According to the composite material provided by the embodiment of the invention, the thiophenol compound is used as a micromolecular ligand, and the sulfydryl of the thiophenol compound is bonded with the metal atom of the metal compound nanoparticle, so that the surface modification of the metal compound nanoparticle is effectively realized. The strong electron density of the aromatic ring in the thiophenol compound is used as a strong electron donor to generate an electron transfer reaction with the surface of the metal compound nano-particle, so that the conductivity of the composite material is increased, the composite material is applied to the preparation of an electron transmission layer in the quantum dot light-emitting diode, electrons and holes can be promoted to be effectively compounded in the quantum dot light-emitting layer, the electron transmission capability is improved, the influence of exciton accumulation on the performance of the device is reduced, and the light-emitting performance of the quantum dot light-emitting diode is effectively improved on the whole.
Specifically, the metal compound nanoparticles are a host material of the composite material in the embodiment of the invention, and are an n-type semiconductor material. In an embodiment of the present invention, the metal compound nanoparticles are metal oxides and/or metal sulfides, preferably water-soluble nanomaterials. In the later process, the metal oxide and/or the metal sulfide are/is easy to dissolve in aqueous solution, the film forming property is good, the structural integrity of the quantum dot light-emitting diode is ensured, and the light-emitting performance of the quantum dot light-emitting device is improved.
As an embodiment, the metal compound nanoparticles are metal oxides, preferably, the metal oxides include ZnO, tiO 2 、SnO 2 And ZrO 2 At least one of (1). The preparation method of the metal compound nanoparticles comprises the following steps: providing a metal salt, dissolving the metal salt in alcohol to prepare a salt solution; providing alkali liquor, adding the alkali liquor into the salt solution for mixing, stirring for 4-6 hours at the temperature of 60-90 ℃, cooling the reaction liquid, and then adopting a precipitator, such as ethyl acetate, to precipitate the metal compound nanoparticles prepared by the reaction. The composite material prepared by the method has good water solubility, is easy to form a film, and can improve the luminescence property of the quantum dot luminescent device. The metal salt is a precursor salt corresponding to a metal oxide which can be used as an electron transport layer, and is preferably a titanium salt, a zinc salt, a tin salt, a zirconium salt and the like; in the step of the salt solution, the concentration of the metal salt is 0.2-1mol/L, the concentration of the metal salt is lower than 0.2mol/L, and the reaction rate is slow; the concentration of the metal salt is more than 1mol/L, the reaction rate is high, and the agglomeration of nano particles can be caused. The zinc salt is soluble inorganic zinc salt or organic zinc salt, including but not limited to zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate dihydrate and the like; the titanium salts include, but are not limited to, titanium nitrate, titanium chloride, titanium sulfate, titanium bromide, and the like; the tin salt is soluble inorganic tin salt or organic tin salt, including but not limited to tin nitrate, tin chloride, tin sulfate, tin methane sulfonate, tin ethane sulfonate, tin propane sulfonate and the like; such alcohols include, but are not limited to, isopropanol, ethanol, propanol, butanol, methanol, and the like; the alkali solution includes, but is not limited to, ammonia, potassium hydroxide, sodium hydroxide, lithium hydroxide, ethanolamine, ethylene glycol, diethanolamine, triethanolamine, ethylenediamine, etc. Further, in the step of adding the alkali liquor into the salt solution for mixing, the pH value of the mixed liquor is adjusted to 12-13, the pH value is directly related to the concentration of hydroxide ions in the solution, and the generation of metal oxide nanoparticles is not facilitated when the pH value is too large or too small. Further, in the step of adding the alkali solution to the salt solution for mixing,the molar ratio of hydroxide ions of the alkali liquor to metal ions of the salt solution is (1.8-4.5): 1, so that a compact composite material can be obtained after subsequent high-temperature annealing. During the reaction, the metal salt reacts with the alkali solution to form hydroxide (M (OH) x ) Then, M (OH) x Condensation polymerization reaction is carried out, and MO is generated by dehydration x It is understood that the amount of the hydroxide ion used in the reaction system is directly related to the valence of the corresponding metal cation. When the metal ion is +2 (Zn) 2+ ) The molar ratio of hydroxide ions to metal cations is 2:1, the molar ratio of hydroxide ions to metal cations is kept between 1.8 and 2.5:1, and oxide nanoparticles can be generated; when the metal cation is +4 (Ti) 4+ 、Sn 4+ 、Zr 4+ ) The molar ratio of hydroxide ions to metal cations is 4:1, and the molar ratio of hydroxide ions to metal cations is maintained at (3.5-4.5): 1, so that oxide nanoparticles can be generated. It is readily understood that when the molar ratio of hydroxide ion to metal cation is less than 1.8<When 12, the metal salt is excessive, and the reaction is insufficient; when the molar ratio of hydroxide ion to metal cation is greater than 2.5>At 13, too high a pH results in a slow hydrolysis and polycondensation rate of the sol in the system.
As another embodiment, the metal compound nanoparticles are metal sulfides, preferably, the metal sulfides include ZnS and/or In 2 S 3 . In some embodiments, the metal compound nanoparticles are ZnS nanoparticles, and the preparation method thereof comprises: dissolving a zinc source and a sulfur source in an organic solvent, and reacting for more than 4 hours at 70-90 ℃; in the reaction system, the molar ratio of zinc to sulfur is 1 (1-1.5). The composite material prepared by the method has good water solubility, is easy to form a film, and can improve the luminescence property of the quantum dot luminescent device. Wherein the zinc source is selected from soluble inorganic zinc salt or organic zinc salt, such as zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate dihydrate, etc.; the sulfur source is selected from at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide; the organic solvent is selected from at least one of isopropanol, ethanol, propanol, butanol and methanol; the mixture isStirring at constant temperature, cooling the reaction solution, and precipitating the metal compound nanoparticles obtained by the reaction with a precipitant such as ethyl acetate.
Specifically, the thiophenol compound is used for carrying out surface modification on the metal compound nanoparticles. In the embodiment of the invention, the structural formula of the thiophenol compound is preferably Ar-SH; wherein Ar is substituted or unsubstituted aryl; in substituted aromatic groups, the substituent is an electron donating group. It is understood that the hydrocarbyl group is an alkane composed of C and H, such as: methyl, methylene, ethyl, and the like; the electron-donating group is a group capable of increasing the electron cloud density on the aromatic ring, and includes, but is not limited to, alkyl, alkoxy, hydroxyl, amino, and the like. In a preferred embodiment, ar is a substituted aromatic group, and the substituent is an electron donating group, such as methyl, ethyl, propyl, or the like, which can further increase the electron cloud density on the aromatic ring, increase the conductivity of the composite material, and improve the light emitting performance of the quantum dot light emitting diode. Further, ar is substituted or unsubstituted phenyl; in the substituted phenyl group, the substituent is selected from a hydrocarbon group or a hydrocarbon group derivative having a carbon number of 1 to 6. In some embodiments, the thiophenols are selected from at least one of thiophenol, 4-methylphenthiophenol, 3-methylphenthiophenol, 2-ethylthiophenol, 3-ethylthiophenol, 4-tert-butylthiophenol, 2,4-dimethylthiophenol, 2,5-dimethylthiophenol, 2,6-dimethylthiophenol.
In the embodiment of the invention, the thiol compound is bonded with the metal atom of the metal compound nanoparticle through a thiol group, so that the surface modification of the metal compound nanoparticle is effectively realized. In some test examples, compared with metal compound nanoparticles which are not subjected to surface modification, the metal compound nanoparticles subjected to surface modification of the thiophenol compound have the advantages that the work function is effectively reduced, the electron transfer capacity is better, and the metal compound nanoparticles can be used as a good electron transfer material and are used for improving the light emitting performance of the quantum dot light emitting diode.
In a preferred embodiment of the present invention, the molar ratio of the thiophenol compound to the metal compound nanoparticles in the composite material is (2-3): 1. Within the range of the proportion, the thiophenol compound can be well modified on the surface of the metal compound nano-particles, so that the composite material disclosed by the embodiment of the invention has good electron transport capability. In some embodiments, the molar ratio of sulfur to zinc in the composite is preferably 2:1, 2.5, 1 or 3:1.
In a preferred embodiment of the present invention, the composite material has a particle size of 5 to 10nm, and is excellent in dispersibility and can be easily formed into a uniform film.
Accordingly, referring to fig. 1, a method for preparing the composite material includes the following steps:
s01, providing metal compound nanoparticles, thiophenol compounds and alcohol, mixing the metal compound nanoparticles, the thiophenol compounds and the alcohol, and carrying out heating reaction to prepare a precursor solution;
s02, carrying out solid-liquid separation treatment on the precursor solution to obtain the composite material.
According to the preparation method of the composite material provided by the embodiment of the invention, the metal compound nanoparticles and the thiophenol compound are heated in alcohol for reaction, and then solid-liquid separation treatment is carried out, so that the metal compound nanoparticles are subjected to surface modification by using the thiophenol compound, the thiophenol compound and the metal compound nanoparticles are stably bonded, the method is simple and convenient to operate, expensive equipment is not needed, the reaction process is controllable, the quality is stably ensured, and the large-scale production is facilitated.
Specifically, in step S01, the metal compound nanoparticles, the thiophenol compound, and the alcohol are mixed and subjected to a heating reaction. In the embodiment of the invention, the molar ratio of the thiophenol compound to the metal compound nano-particles is (2-3): 1. Within the range of the proportion, the thiophenol compound can be well modified on the surface of the metal compound nano-particles, so that the composite material disclosed by the embodiment of the invention has good electron transport capability. When the molar ratio of the thiophenol compound to the metal compound nanoparticles is less than 2:1, the concentration of the thiophenol compound is smaller and smaller along with the progress of raw material reaction, the reaction strain is slow, and even the thiophenol compound cannot be completely adsorbed on the surface of the metal compound nanoparticles; when the molar ratio of the thiophenols to the metal compound nanoparticles is greater than 6:1, the reaction proceeds too quickly and the performance of the material is affected in the subsequent high temperature annealing step due to the removal of excess thiophenols. In some embodiments, the molar ratio of the thiophenols and the metal compound nanoparticles is preferably 4:1, 5:1, or 6:1.
Preferably, in the step of performing the heating reaction, the reaction temperature is 60 to 80 ℃ and the reaction time is 2 to 4 hours. In some embodiments, the temperature of the reaction is 60, 62, 65, 66, 68, 70, 71, 73, 75, 77, 79, 80 ℃; in other embodiments, the reaction time is 2, 2.5, 2.7, 3, 3.1, 3.3, 3.5, 3.7, 4 hours; in still other embodiments, the heating reaction is accompanied by constant temperature stirring.
Specifically, in step S02, the precursor solution is subjected to solid-liquid separation treatment to separate and obtain the composite material. In one embodiment, the composite material in the precursor solution is separated out through sedimentation treatment, and sediments are collected, cleaned and dried to obtain the composite material; wherein the sedimentation treatment can be achieved by adding a precipitant. In another embodiment, the precursor solution can be further prepared into a film to obtain a thin film. Specifically, after the precursor solution is deposited on a substrate, a thin film is prepared through annealing treatment. Further, in the step of performing high-temperature annealing on the precursor solution, the temperature of the high-temperature annealing is 200-350 ℃. In some embodiments, the high temperature anneal is at a temperature of 200, 220, 240, 250, 260, 290, 300, 320, 350 ℃.
Under the comprehensive action of the optimized condition parameters such as the molar ratio, the concentration, the temperature, the time and the like of the raw materials, the comprehensive performance of the composite material obtained by the preparation method provided by the embodiment of the invention can be optimized.
Correspondingly, a quantum dot light emitting diode comprises a cathode and an anode which are oppositely arranged, a quantum dot light emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the quantum dot light emitting layer, wherein the electron transport layer comprises the following materials: the composite material is described above.
According to the quantum dot light-emitting diode provided by the embodiment of the invention, the material of the electron transport layer comprises the composite material, the electron and hole have high composite efficiency in the quantum dot light-emitting layer, and the quantum dot light-emitting diode has good electron transport capability, and can improve the light-emitting performance of the quantum dot light-emitting diode on the whole.
In some embodiments, the electron transport layer has a thickness of 20-60nm.
In the embodiment of the present invention, each quantum dot light emitting diode includes an anode, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a cathode, which are sequentially stacked, and it can be understood that, in addition to the hole transport layer, the quantum dot light emitting layer, and the electron transport layer, the quantum dot light emitting diode further includes other film layer structures, for example: a substrate, a hole injection layer, an electron injection layer, etc. In the embodiment of the present invention, the qd-led may have a positive structure or an inverse structure, wherein the positive structure and the inverse structure are different mainly in that: an anode of a positive structure is connected with the substrate and is arranged on the surface of the substrate in a laminated mode by taking the anode as a bottom electrode; the cathode of the inversion structure is connected with the substrate, and is used as a bottom electrode to be stacked on the surface of the substrate.
As shown in fig. 2, the quantum dot light emitting diode is a positive type structure, and includes a substrate 1, an anode 2, a hole transport layer 3, a quantum dot light emitting layer 4, an electron transport layer 5, and a cathode 6, which are stacked in this order.
In embodiments of the present invention, hole transport materials conventional in the art may be used, including but not limited to TFB, PVK, poly-TPD, TCTA, PEDOT: PSS, CBP, etc., or any combination thereof, as well as other high performance hole transport materials. In the embodiment of the present invention, the thickness of the hole transport layer is preferably 20 to 60nm, and more preferably 50nm.
In the embodiment of the invention, the quantum dot light-emitting layerThe method has the characteristics of wide excitation spectrum, continuous distribution, high stability of emission spectrum and the like, and is selected as oil-soluble quantum dots, and comprises the following steps: binary phase, ternary phase and quaternary phase quantum dots. Wherein the binary phase quantum dots include but are not limited to CdS, cdSe, cdTe, inP, agS, pbS, pbSe, hgS, and the ternary phase quantum dots include but are not limited to Zn X Cd 1-X S、Cu X In 1-X S、Zn X Cd 1-X Se、Zn X Se 1-X S、Zn X Cd 1-X Te、PbSe X S 1-X The quaternary phase quantum dots include but are not limited to Zn X Cd 1-X S/ZnSe、Cu X In 1-X S/ZnS、Zn X Cd 1-X Se/ZnS、CuInSeS、Zn X Cd 1-X Te/ZnS、PbSe X S 1-X and/ZnS. In the embodiment of the invention, the quantum dot light-emitting layer can be any one of red, green and blue quantum dots, or yellow quantum dots. In the embodiment of the present invention, the thickness of the quantum dot light emitting layer is preferably 20 to 60nm.
In the embodiment of the present invention, the electron transport layer is a thin film layer made of the composite material provided in the embodiment of the present invention, and the preparation method is a spin coating process, including but not limited to, a drop coating, a spin coating, a dipping, a coating, a printing, an evaporation coating, and the like. In some embodiments, a substrate on which a quantum dot light emitting layer is spin-coated is placed on a spin coater, a precursor solution with a certain concentration is prepared to spin-coat a film, the thickness of the light emitting layer is controlled to be about 20-60nm by adjusting the concentration of the solution, the spin-coating speed (preferably, the rotation speed is between 2000-6000 rpm) and the spin-coating time, and then a high-temperature annealing process is performed to form the film. The step can be annealing in air or in nitrogen atmosphere, and the annealing atmosphere is selected according to actual needs.
In the embodiment of the invention, the cathode is selected from metallic silver or metallic aluminum. In some embodiments, the cathode is a layered metallic silver or metallic aluminum with a thickness of 15-30 nm; in other embodiments, the cathode is a nano Ag wire or a Cu wire.
Correspondingly, the embodiment of the invention also provides a preparation method of the quantum dot light-emitting diode with the structure shown in fig. 2, which comprises the following steps:
1) Providing a substrate, and depositing an anode, a hole transport layer and a quantum dot light emitting layer on the substrate in sequence;
2) Preparing the precursor solution, continuously coating the precursor solution on the quantum dot light-emitting layer, and carrying out high-temperature annealing at 200-350 ℃ to prepare an electron transport layer;
3) Continuously vacuum evaporating an electron cathode on the electron transport layer;
4) And packaging the obtained QLED.
In some embodiments, the vacuum evaporation speed of step 3) is about 0.01-0.5nm/s.
In other embodiments, the anode is selected to be an ITO film layer.
In the embodiment of the present invention, the encapsulation process in step 4) may be implemented by a conventional machine, or may be implemented by manual encapsulation. In some embodiments, to ensure device stability, the packaging process environment has an oxygen content and a water content of less than 0.1ppm.
Further, in order to obtain high-quality metal oxide nanoparticles with the surface modified by the thiophenol compounds, the ITO film layer needs to be subjected to a pretreatment process, and the basic specific treatment steps include: cleaning the whole ITO conductive glass by using a cleaning agent, preliminarily removing stains on the surface, then sequentially carrying out ultrasonic cleaning in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min respectively to remove impurities on the surface, and finally blowing the ITO conductive glass by using high-purity nitrogen to dry the ITO conductive glass.
In order to make the above details and operation of the present invention clearly understandable to those skilled in the art, and to make the advanced performance of the composite material, the preparation method thereof and the quantum dot light emitting diode according to the embodiments of the present invention obvious, the embodiments of the present invention are illustrated below by way of examples.
Example 1
The composite material prepared by the embodiment is ZnS nanoparticles with thiophenol surface modification, and the specific process flow is as follows:
1. weighing zinc chloride, adding into 50mL ethanol,stirring and dissolving at 80 ℃ to form a salt solution with the total concentration of 0.5M; weighing sodium sulfide, and dissolving the sodium sulfide in 10mL of ethanol to prepare a sodium sulfide solution; then, according to S 2- And Zn 2+ The molar ratio of (1.2) to (1), adding a sodium sulfide solution to a salt solution to form a mixed solution with a pH of 12, and then stirring at 80 ℃ for 4 hours to obtain a uniform and transparent reaction solution; then, after the reaction liquid is cooled, ethyl acetate is used for separation, a small amount of ethanol is used for dissolution after centrifugation, the separation and dissolution steps are repeated for 3 times, and the ZnS nano particles are prepared through drying;
2. adding ZnS nano particles into 30mL of ethanol to form a solution with the total concentration of 1M; then adding thiophenol, and continuing stirring at 70 ℃ for 2 hours to obtain a uniform and transparent precursor solution; wherein the molar ratio of ZnS to thiophenol is 1:2;
3. and after the precursor solution is cooled, spin-coating the precursor solution on the treated ITO by using a spin coater, and annealing at 300 ℃.
Example 2
The embodiment prepares a composite material, which is ZnO nanoparticles with 4-methylthiophenol surface modification, and the specific process flow is as follows:
1. weighing zinc nitrate, adding the zinc nitrate into 50mL of methanol, and stirring and dissolving at 60 ℃ to form a salt solution with the total concentration of 0.5M; weighing ethanolamine, and dissolving the ethanolamine in 10mL of methanol to prepare alkali liquor; then according to ethanolamine and Zn 2+ The molar ratio of 2:1, adding alkali liquor into the salt solution to form a mixed solution with the pH of 12, and then stirring for 4 hours at 60 ℃ to obtain a uniform and transparent reaction solution; then, after the reaction liquid is cooled, using heptane to separate out, centrifuging, using a small amount of ethanol to dissolve, repeating the steps of separating out and dissolving for 3 times, drying, and preparing ZnO nano-particles;
2. adding ZnO nanoparticles into 30mL of methanol to form a solution with the total concentration of 1M; then adding 4-methyl thiophenol, and continuing stirring for 2 hours at 60 ℃ to obtain a uniform and transparent precursor solution; wherein, the molar ratio of ZnO to 4-methyl thiophenol is 1;
3. and after the precursor solution is cooled, spin-coating the precursor solution on the treated ITO by using a spin coater, and annealing at 300 ℃.
Example 3
This example prepared a composite material, 2-ethylthiophenol surface-modified TiO 2 The specific process flow of the nano particles is as follows:
1. weighing titanium sulfate, adding the titanium sulfate into 50mL of propanol, and stirring and dissolving at 80 ℃ to form a salt solution with the total concentration of 0.5M; weighing potassium hydroxide, and dissolving the potassium hydroxide in 10mL of propanol to prepare alkali liquor; then, according to OH - And Ti 4+ The molar ratio of (1) is 4.5, adding alkali liquor into a salt solution to form a mixed solution with the pH of 12, and then stirring for 4 hours at 80 ℃ to obtain a uniform and transparent reaction solution; then, after the reaction liquid is cooled, octane is used for precipitation, after centrifugation, a small amount of ethanol is used for dissolution, the precipitation and dissolution steps are repeated for 3 times, and drying is carried out to prepare TiO 2 A nanoparticle;
2. adding TiO into the mixture 2 Adding the nanoparticles into 30mL of propanol to form a solution with a total concentration of 1M; then adding 2-ethyl thiophenol, and continuing stirring for 2h at 80 ℃ to obtain a uniform and transparent precursor solution; wherein, tiO 2 The molar ratio of 2-ethylthiophenol to 2-ethylthiophenol is 1:3;
3. and after the precursor solution is cooled, spin-coating the precursor solution on the treated ITO by using a spin coater, and annealing at 300 ℃.
Example 4
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the anode is arranged on a substrate. The substrate is made of a glass sheet, the anode is made of an ITO (indium tin oxide) substrate, the hole transport layer is made of a TFB (tunneling glass) material, the electron transport layer is made of a ZnS nano material with a thiophenol surface modified, and the cathode is made of Al.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
providing an ITO substrate, and preparing a hole transport layer on the ITO substrate;
depositing a quantum dot light emitting layer on the hole transport layer;
depositing the precursor solution obtained in the method of the embodiment 1 on the quantum dot light-emitting layer, and annealing at 250 ℃ to prepare an electron transport layer;
a cathode on the electron transport layer.
Example 5
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the anode is arranged on a substrate. The substrate is made of a glass sheet, the anode is made of an ITO (indium tin oxide) substrate, the hole transport layer is made of a TFB (polycrystalline silicon nitride), the electron transport layer is made of a ZnO nano material modified by a 4-methylthiophenol surface, and the cathode is made of Al.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
providing an ITO substrate, and preparing a hole transport layer on the ITO substrate;
depositing a quantum dot emissive layer on the hole transport layer;
preparing a precursor solution obtained by depositing the method in the embodiment 2 on the quantum dot light-emitting layer, and annealing at 250 ℃ to prepare an electron transport layer;
preparing a cathode on the electron transport layer.
Example 6
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the anode is arranged on a substrate. Wherein the substrate is made of glass sheet, the anode is made of ITO substrate, the hole transport layer is made of TFB, and the electron transport layer is made of 2-ethylthiophenolSurface-modified TiO 2 The cathode is made of Al.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
providing an ITO substrate, and preparing a hole transport layer on the ITO substrate;
depositing a quantum dot light emitting layer on the hole transport layer;
preparing a precursor solution obtained by depositing the method in the embodiment 3 on the quantum dot light-emitting layer, and annealing at 250 ℃ to prepare an electron transport layer;
preparing a cathode on the electron transport layer.
Example 7
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the cathode is arranged on a substrate. The material of the substrate is a glass sheet, the material of the cathode is an ITO substrate, the material of the hole transport layer is TFB, the material of the electron transport layer is ZnS nano material modified by thiophenol, and the material of the anode is Al.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
providing a cathode substrate, depositing the precursor solution obtained in the method of the embodiment 1 on the cathode substrate, and annealing at 250 ℃ to prepare an electron transport layer;
preparing a quantum dot light-emitting layer on the electron transport layer, and preparing a hole transport layer on the quantum dot light-emitting layer;
and preparing an anode on the hole transport layer.
Example 8
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the cathode is arranged on a substrate. The substrate is made of a glass sheet, the cathode is made of an ITO (indium tin oxide) substrate, the hole transport layer is made of TFB (polycrystalline silicon nitride), the electron transport layer is made of a ZnO nano material modified by a 4-methylthiophenol surface, and the anode is made of Al.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
providing a cathode substrate, depositing the precursor solution obtained in the method of the embodiment 2 on the cathode substrate, and annealing at 250 ℃ to prepare an electron transport layer;
preparing a quantum dot light-emitting layer on the electron transport layer, and preparing a hole transport layer on the quantum dot light-emitting layer;
an anode is prepared on the hole transport layer.
Example 9
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the cathode is arranged on a substrate. Wherein the substrate is made of glass sheet, the cathode is made of ITO substrate, the hole transport layer is made of TFB, and the electron transport layer is made of 2-ethylthiophenol surface-modified TiO 2 The nano material and the anode are made of Al.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
providing a cathode substrate, depositing the precursor solution obtained in the method of the embodiment 3 on the cathode substrate, and annealing at 250 ℃ to prepare an electron transport layer;
preparing a quantum dot light-emitting layer on the electron transport layer, and preparing a hole transport layer on the quantum dot light-emitting layer;
an anode is prepared on the hole transport layer.
Comparative example 1
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the anode is arranged on a substrate. The substrate is made of a glass sheet, the anode is made of an ITO (indium tin oxide) substrate, the hole transport layer is made of TFB (polycrystalline silicon), the electron transport layer is made of commercial ZnS (zinc sulfide) (purchased from sigma company), and the cathode is made of Al.
Comparative example 2
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the anode is arranged on a substrate. The substrate is made of a glass sheet, the anode is made of an ITO substrate, the hole transport layer is made of a TFB material, the electron transport layer is made of a commercial ZnO material (purchased from sigma company), and the cathode is made of Al.
Comparative example 3
A quantum dot light-emitting diode comprises a laminated structure of an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transport layer arranged between the anode and the quantum dot light-emitting layer, wherein the anode is arranged on a substrate. Wherein the substrate is made of glass sheet, the anode is made of ITO substrate, the hole transport layer is made of TFB, and the electron transport layer is made of commercial TiO 2 The material (available from sigma) of the cathode was Al.
The electron transport films prepared in examples 1 to 3, the electron transport films prepared in comparative examples 1 to 3, the quantum dot light emitting diodes prepared in examples 4 to 9 and comparative examples 1 to 3 were subjected to performance tests, and the test indexes and the test methods were as follows:
(1) Electron mobility: testing the current density (J) -voltage (V) of the quantum dot light emitting diode, drawing a curve relation graph, fitting a Space Charge Limited Current (SCLC) region in the relation graph, and then calculating the electron mobility according to a well-known Child, s law formula:
J＝(9/8)ε r ε 0 μ e V 2 /d 3
wherein J represents current density in mAcm -2 ；ε r Denotes the relative dielectric constant,. Epsilon 0 Represents the vacuum dielectric constant; mu.s e Denotes the electron mobility in cm 2 V -1 s -1 (ii) a V represents the drive voltage, in units of V; d represents the film thickness in m.
(2) Resistivity: the resistivity of the electron transport film is measured by the same resistivity measuring instrument.
(3) External Quantum Efficiency (EQE): measured using an EQE optical test instrument.
Note: the electron mobility and resistivity were tested as single layer thin film structure devices, namely: cathode/electron transport film/anode. The external quantum efficiency test is the QLED device, namely: anode/hole transport film/quantum dot/electron transport film/cathode, or cathode/electron transport film/quantum dot/hole transport film/anode.
The test results are shown in table 1 below:
TABLE 1
As can be seen from table 1 above, the materials provided in examples 1 to 3 of the present invention are electron transport films of metal compound nanoparticles and thiophenol compounds, and the resistivity is significantly lower than that of the electron transport films made of the metal compound nanomaterials in comparative examples 1 to 3, and the electron mobility is significantly higher than that of the electron transport films made of the metal compound nanomaterials in comparative examples 1 to 3.
The external quantum efficiency of the quantum dot light-emitting diodes (the electron transport layer materials are metal compound nanoparticles and thiophenol compounds) provided in the embodiments 4 to 9 of the present invention is significantly higher than that of the quantum dot light-emitting diodes made of metal compound nanoparticles in the comparative examples 1 to 3, which indicates that the quantum dot light-emitting diodes obtained in the embodiments have better light-emitting efficiency.
It is noted that the embodiments provided by the present invention all use blue light quantum dots Cd X Zn 1-X S/ZnS is used as a material of a luminescent layer, is based on that a blue light luminescent system uses more systems (the blue light quantum dot luminescent diode has more reference value because high efficiency is difficult to achieve), and does not represent that the invention is only used for the blue light luminescent system.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A composite material applied to an electron transport layer of a quantum dot Light Emitting Diode (LED), comprising: metal compound nanoparticles and thiophenol compounds; the thiophenol compound is connected with the surface of the metal compound nanoparticle through a sulfydryl, and the sulfydryl is bonded with the metal atom of the metal compound nanoparticle;
the metal compound nanoparticles are metal oxides and/or metal sulfides;
the structural formula of the thiophenol compound is Ar-SH;
wherein Ar is substituted aryl;
in the substituted aromatic group, the substituent is an electron donating group, specifically: methyl, ethyl or propyl;
the metal oxide comprises ZnO and TiO 2 、SnO 2 And ZrO 2 At least one of (1).
2. The composite material of claim 1, wherein the metal compound nanoparticles are water-soluble nanomaterials.
3. The composite material according to claim 1 or 2, wherein the molar ratio of the thiophenol compound to the metal compound nanoparticles in the composite material is (2-3): 1.
4. Composite material according to claim 1 or 2, characterized in that the metal sulphide comprises zinc sulphide and/or indium sulphide.
5. A process for the preparation of a composite material according to any one of claims 1 to 4, characterized in that it comprises the following steps:
providing metal compound nanoparticles, thiophenol compounds and alcohol, mixing the metal compound nanoparticles, the thiophenol compounds and the alcohol, and carrying out heating reaction to prepare a precursor solution;
carrying out solid-liquid separation treatment on the precursor solution to obtain the composite material;
the metal compound nanoparticles are metal oxides and/or metal sulfides;
the structural formula of the thiophenol compound is Ar-SH;
wherein Ar is substituted aryl;
in the substituted aromatic group, the substituent is an electron donating group, specifically: methyl, ethyl or propyl;
the metal oxide comprises ZnO and TiO 2 、SnO 2 And ZrO 2 At least one of (a).
6. The production method according to claim 5, characterized in that, in the step of preparing the precursor solution, the molar ratio of the thiophenol compound to the metal compound nanoparticles is (2-3): 1; and/or
The metal compound nanoparticles are water-soluble nanomaterials.
7. The method according to claim 5, wherein the heating reaction is carried out at a reaction temperature of 60 to 80 ℃ for 2 to 4 hours.
8. The production method according to any one of claims 5 to 7, wherein the metal sulfide includes zinc sulfide and/or indium sulfide.
9. A quantum dot light emitting diode comprising a cathode and an anode disposed opposite to each other, a quantum dot light emitting layer disposed between the cathode and the anode, and an electron transport layer disposed between the cathode and the quantum dot light emitting layer, wherein the electron transport layer is made of a material comprising: the composite material according to any one of claims 1 to 4, or the composite material produced by the production method according to any one of claims 5 to 8.
10. The quantum dot light-emitting diode of claim 9, wherein the electron transport layer has a thickness of 20-60nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910763104.0A CN112397659B (en) | 2019-08-19 | 2019-08-19 | Composite material, preparation method thereof and quantum dot light-emitting diode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910763104.0A CN112397659B (en) | 2019-08-19 | 2019-08-19 | Composite material, preparation method thereof and quantum dot light-emitting diode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112397659A CN112397659A (en) | 2021-02-23 |
| CN112397659B true CN112397659B (en) | 2023-02-07 |
Family
ID=74603347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910763104.0A Active CN112397659B (en) | 2019-08-19 | 2019-08-19 | Composite material, preparation method thereof and quantum dot light-emitting diode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112397659B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122241A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Quantum dot material and preparation method thereof, quantum dot light-emitting diode and light-emitting device |
| CN113717715B (en) * | 2021-08-31 | 2023-12-12 | 北京京东方技术开发有限公司 | Material of electron transport layer, preparation method of material and quantum dot light emitting diode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394900A (en) * | 2002-08-08 | 2003-02-05 | 吉林大学 | Preparation method of nano particles with high refractive index and polymer nano composite film material |
| JP2003089522A (en) * | 2001-09-12 | 2003-03-28 | Mitsui Chemicals Inc | Ultrafine particle of composite modified metal chalcogenide |
| CN1687225A (en) * | 2005-03-26 | 2005-10-26 | 吉林大学 | Method for preparing transparent optical material of polymer in high nano phase |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130074815A (en) * | 2011-12-20 | 2013-07-05 | 한국과학기술원 | All solution processible light-emitting device |
| CA2948486A1 (en) * | 2014-05-09 | 2015-11-12 | Massachusetts Institute Of Technology | Energy level modification of nanocrystals through ligand exchange |
| CN106784191B (en) * | 2016-12-27 | 2019-12-13 | Tcl集团股份有限公司 | QLED device and preparation method thereof |
| CN109935708A (en) * | 2017-12-15 | 2019-06-25 | Tcl集团股份有限公司 | LED device and preparation method thereof |
| CN109962179B (en) * | 2017-12-26 | 2021-02-19 | Tcl科技集团股份有限公司 | Thin film, preparation method thereof and QLED device |
-
2019
- 2019-08-19 CN CN201910763104.0A patent/CN112397659B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003089522A (en) * | 2001-09-12 | 2003-03-28 | Mitsui Chemicals Inc | Ultrafine particle of composite modified metal chalcogenide |
| CN1394900A (en) * | 2002-08-08 | 2003-02-05 | 吉林大学 | Preparation method of nano particles with high refractive index and polymer nano composite film material |
| CN1687225A (en) * | 2005-03-26 | 2005-10-26 | 吉林大学 | Method for preparing transparent optical material of polymer in high nano phase |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112397659A (en) | 2021-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112538163B (en) | Composite material, preparation method thereof and quantum dot light emitting diode | |
| CN112397659B (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN109935662B (en) | Electron transport material, preparation method thereof and light emitting diode | |
| CN112349850A (en) | Inorganic semiconductor material and preparation method thereof | |
| CN113120947A (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN111384244B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN112625674B (en) | Composite material, quantum dot light-emitting diode and preparation method thereof | |
| CN113121382B (en) | Metal compound material and preparation method thereof, quantum dot light emitting diode and light emitting device | |
| CN110838560A (en) | Core-shell nano material, preparation method thereof and quantum dot light-emitting diode | |
| CN111384245B (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN112397670B (en) | Composite material and preparation method thereof and quantum dot light-emitting diode | |
| CN112397656B (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN112397661B (en) | Nano material, preparation method thereof and quantum dot light-emitting diode | |
| CN112542554B (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN112397655B (en) | Composite material and preparation method thereof and quantum dot light-emitting diode | |
| CN113045211B (en) | Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof | |
| CN113054062B (en) | Nano material and preparation method thereof, quantum dot light-emitting diode and light-emitting device | |
| CN112625671B (en) | Core-shell nano material, preparation method and application thereof, and quantum dot light-emitting diode | |
| CN114276551B (en) | Composite nano material, preparation method thereof and quantum dot light emitting diode | |
| CN112349870B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN112397617B (en) | Doped tungsten oxide nano material, preparation method thereof and inorganic hole transport material | |
| CN113054118B (en) | Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof | |
| CN113130772B (en) | Nanocomposite material, preparation method thereof, solution composition and light emitting diode | |
| CN112397620A (en) | Nano composite particle and preparation method and application thereof | |
| CN114520297A (en) | Nano material and preparation method thereof and quantum dot light-emitting diode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 516006 TCL science and technology building, No. 17, Huifeng Third Road, Zhongkai high tech Zone, Huizhou City, Guangdong Province Applicant after: TCL Technology Group Co.,Ltd. Address before: 516006 Guangdong province Huizhou Zhongkai hi tech Development Zone No. nineteen District Applicant before: TCL Corp. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |