CN112320838B - Nano material and preparation method and application thereof - Google Patents
Nano material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112320838B CN112320838B CN201910718186.7A CN201910718186A CN112320838B CN 112320838 B CN112320838 B CN 112320838B CN 201910718186 A CN201910718186 A CN 201910718186A CN 112320838 B CN112320838 B CN 112320838B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- dot light
- salt
- transport layer
- indium
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a nano material, which comprises In 2 S 3 Nano material and doped In 2 S 3 W in the nanomaterial. The nano material provided by the invention is prepared by adding In 2 S 3 Doping high valence state difference metal W In nano material to raise In 2 S 3 Carrier mobility of the nanomaterial.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a nano material and a preparation method thereof, and a quantum dot light-emitting diode and a preparation method thereof.
Background
The semiconductor quantum dots have quantum size effect, and people can realize the required light emission with specific wavelength by regulating and controlling the size of the quantum dots, wherein the light emission wavelength tuning range of the CdSe QDs can be from blue light to red light. In the conventional inorganic electroluminescent device, electrons and holes are injected from a cathode and an anode, respectively, and then recombined in a light emitting layer to form excitons for light emission. Conduction band electrons in wide bandgap semiconductors can be accelerated under high electric fields to obtain high enough energy to strike QDs to cause it to emit light. The metal sulfide is a compound formed by combining metal ions and sulfur ions, and the excellent performance of the compound cannot be ignored, and particularly, the sulfide of the transition metal is more important modern inorganic material. Chalcogenide semiconductor materials have been widely used in the fields of solar cells, catalysts, conductive coatings, electrodes, sensors, thermoelectric refrigeration materials, and the like.
In 2 S 3 Is an n-type semiconductor material with the conductive forbidden band width of 2.0-2.3eV, has higher electron mobility, and determines In 2 S 3 Can be used as a suitable electron transport layer material. At the same time, In 2 S 3 Is a III-VI semiconductor material with three crystal structures of-In 2 S 3 (cubic system), -In 2 S 3 (tetragonal system) and-In 2 S 3 the indium sulfide has the advantages of stable chemical property, abundant resources and low price (trigonal system), and the indium sulfide can have better electron transport property by doping. However, In 2 S 3 The forbidden band width is narrower, the conduction band is high, and the single use of the material as an electron transport layer can cause the difficulty of electron injection and the insufficient electron transport capability.
Disclosure of Invention
The invention aims to provide a nano material and a preparation method thereof, and aims to solve the problem of In 2 S 3 When the material is singly used as an electron transport layer material, electrons are difficult to inject, and the electron transport capability is insufficient.
The invention also aims to provide a quantum dot light-emitting diode using the nano material as an electron transport layer material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a nanomaterial comprising In 2 S 3 Nano material and doped In 2 S 3 W in the nanomaterial.
The second aspect of the present invention provides a method for preparing a nanomaterial, comprising the steps of:
dissolving indium salt and tungsten salt in an organic solvent to prepare a mixed solution of the indium salt and the tungsten salt; adding a sulfur source into the mixed solution, and mixing and reacting at the temperature not higher than the boiling point of the organic solvent to prepare a precursor solution;
and after the precursor solution is cooled to room temperature, carrying out solid-liquid separation treatment on the precursor solution to collect solid matters, and drying after cleaning to obtain the nano material.
A third aspect of the present invention provides a quantum dot light emitting diode comprising a laminated structure of a cathode and an anode which are oppositely disposed, a quantum dot light emitting layer disposed between the cathode and the anode, and an electron transporting layer disposed between the cathode and the quantum dot light emitting layer, a material of the electron transporting layer including In 2 S 3 Nano material and doped In 2 S 3 W in the nanomaterial.
The fourth aspect of the present invention provides a method for manufacturing a quantum dot light emitting diode, comprising the steps of:
dissolving indium salt and tungsten salt in an organic solvent to prepare a mixed solution of the indium salt and the tungsten salt; adding a sulfur source into the mixed solution, and mixing and reacting at the temperature not higher than the boiling point of the organic solvent to prepare a precursor solution;
and after the precursor solution is deposited on the surface of the substrate, annealing treatment is carried out to obtain the electron transport layer.
The nano material provided by the invention is prepared by adding In 2 S 3 Doping high valence state difference metal W In nano material to raise In 2 S 3 Carrier mobility of the nanomaterial. When In 2 S 3 When W is doped into the nano material, the majority of W atoms are W 6+ W is solid-dissolved 6+ Occupy In the crystal lattice 3+ A few by W 5+ And W 4+ And (4) doping. Two of the 6 valence electrons of W combine with sulfur and form saturated bonds, and the remaining 4 electrons are separated from the impurity atom, forming 4 excess valence electrons. The energy level of the redundant valence electrons is positioned at a position slightly lower than the bottom of the conduction band in the energy gap, so that enough energy can be obtained at normal temperature to jump to the conduction band to become free electrons, and the free electrons directionally move under the action of an external electric field to conduct electricity. At the same time, due to ionization of the localized electrons, polarized ions are formed and absorb the energy (W) of the incident photons 6+ 、W 5+ And W 4+ Can be switched between by absorbing or releasing energy) and then drifted between different oxidation states, and thus, W 5+ And W 6+ And W 4+ And W 5+ A valence-state hopping conduction mechanism exists between the two. This valence-hopping conduction mechanism helps to increase In 2 S 3 The carrier mobility of the nano material improves the conductivity of the material, promotes the effective recombination of electrons and holes in quantum dots, reduces the influence of exciton accumulation on the performance of the quantum dot light-emitting diode device, and improves the performance of the quantum dot light-emitting diode device and the display performance.
The preparation method of the nano material provided by the invention only needs to dissolve indium salt and tungsten salt in an organic solvent, then adds a sulfur source for reaction, and obtains the nano material through solid-liquid separation treatment. The method is simple to operate and easy to realize large-scale preparation. More importantly, the nano material prepared by the method provided by the invention can improve In 2 S 3 The carrier mobility of the nano material improves the material conductivity, promotes the effective recombination of electrons and holes in quantum dots, reduces the influence of exciton accumulation on the performance of the quantum dot light-emitting diode device, and improves the performance of the quantum dot light-emitting diode device and the display performance.
The quantum dot light-emitting diode provided by the invention is doped with In by the W 2 S 3 The nano material is used as an electron transport layer material. In can be increased due to the doping of W 2 S 3 The carrier mobility of the nano material improves the conductivity of the film layer, promotes the effective recombination of electrons and holes in the quantum dots, reduces the influence of exciton accumulation on the performance of the quantum dot light-emitting diode device, and improves the performance of the quantum dot light-emitting diode device and the display performance.
According to the preparation method of the quantum dot light-emitting diode, a precursor solution formed by the reaction of indium salt, tungsten salt and a sulfur source is deposited on the surface of a substrate and then is subjected to annealing treatment, so that an electron transport layer is prepared. The obtained material of the electron transport layer is W doped with In 2 S 3 The quantum dot light-emitting diode prepared by the method can improve the electron transmission capability, promote the effective recombination of electron-hole in the quantum dot, reduce the influence of exciton accumulation on the performance of the quantum dot light-emitting diode device, and improve the device and display performance of the quantum dot light-emitting diode. In addition, the method only needs to change the material of the electron transport layer on the basis of the conventional preparation method of the quantum dot light-emitting diode, and has simple operation and mature and reliable process.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a nanomaterial provided by an embodiment of the present invention;
fig. 2 is a schematic diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to imply that the number of technical features indicated are in fact significant. 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 a first aspect, embodiments of the present invention provide a nanomaterial comprising In 2 S 3 Nano material and In doped In 2 S 3 W in the nanomaterial.
The nano material provided by the embodiment of the invention is prepared by adding In 2 S 3 Doping high valence state difference metal W In nano material to raise In 2 S 3 Carrier mobility of the nanomaterial. When In 2 S 3 When W is doped into the nano material, the majority of W atoms are W 6+ Form solid solution of W 6+ Occupy In the crystal lattice 3+ A few by W 5+ And W 4+ And (6) doping. Two of the 6 valence electrons of W combine with sulfur and form saturated bonds, and the remaining 4 electrons are separated from the impurity atom, forming 4 excess valence electrons. The energy level of the redundant valence electrons is positioned at a position slightly lower than the bottom of the conduction band in the energy gap, so that enough energy can be obtained at normal temperature to jump to the conduction band to become free electrons, and the free electrons directionally move under the action of an external electric field to conduct electricity. At the same time, due to ionization of the localized electrons, polarized ions are formed and absorb the energy (W) of the incident photons 6+ 、W 5+ And W 4+ Can be generated by absorbing or releasing energySwitching) and then drift between different oxidation states, hence, at W 5+ And W 6+ And W 4+ And W 5+ A valence-state hopping conduction mechanism exists between the two. This valence-hopping conduction mechanism helps to increase In 2 S 3 The carrier mobility of the nano material improves the conductivity of the material, promotes the effective recombination of electrons and holes in quantum dots, reduces the influence of exciton accumulation on the performance of the quantum dot light-emitting diode device, and improves the performance of the quantum dot light-emitting diode device and the display performance.
In the embodiment of the invention, W is In 2 S 3 Amount of doping In the nanomaterial, and the obtained doped In 2 S 3 The performance of the nano-material is greatly influenced, especially when the doped In is used 2 S 3 When the nano material is used as an electron transport layer material of a quantum dot light-emitting diode, the performance of the electron transport layer can be directly influenced. In particular, doping to In 2 S 3 The W content in the nano material meets the following requirements: the molar ratio of In to W is 1: 0.05-0.1, so that In 2 S 3 The nano material has better electron transport efficiency and can be used as an electron transport layer material. When the doping amount of W is too low, effective doping cannot be achieved because W tungsten is lost during the reaction. When the molar ratio of In to W is more than 1: after 0.1, W is In 2 S 3 The solid solubility in the nanomaterial reaches saturation. As the doping amount continues to increase, excess W accumulates In 2 S 3 New phase is formed on the surface of crystal grain, and nanometer In is reduced 2 S 3 Effective specific surface area of (a); meanwhile, excessive doping of W causes In 2 S 3 Mutation of the lattice to form a new lattice, accompanied by WO 3 Finally, the properties of the nano material are changed.
The nano material provided by the embodiment of the invention can be prepared by the following method.
Accordingly, with reference to fig. 1, a second aspect of the embodiments of the present invention provides a method for preparing a nanomaterial, including the following steps:
s01, dissolving indium salt and tungsten salt in an organic solvent to prepare a mixed solution of the indium salt and the tungsten salt; adding a sulfur source into the mixed solution, and mixing and reacting at the temperature not higher than the boiling point of the organic solvent to prepare a precursor solution;
s02, after the precursor solution is cooled to the room temperature, performing solid-liquid separation treatment on the precursor solution to collect solid substances, and drying after cleaning to obtain the nano material.
The preparation method of the nano material provided by the embodiment of the invention only needs to dissolve indium salt and tungsten salt in an organic solvent, then adds a sulfur source for reaction, and carries out solid-liquid separation treatment to obtain the nano material. The method is simple to operate and easy to realize large-scale preparation. More importantly, the nano material prepared by the method provided by the invention can improve In 2 S 3 The carrier mobility of the nano material improves the conductivity of the material, promotes the effective recombination of electrons and holes in quantum dots, reduces the influence of exciton accumulation on the performance of the quantum dot light-emitting diode device, and improves the performance of the quantum dot light-emitting diode device and the display performance.
Specifically, In the step S01, the method for preparing doped In is provided 2 S 3 Indium salts, tungsten salts and sulfur sources of the nanomaterial. The indium salt and the tungsten salt are selected from metal salts which can be dissolved in an organic solvent, and indium ions in the indium salt and tungsten ions in the tungsten salt can react with sulfur in the sulfur source in the organic solvent environment to grow into nano crystal grains. Wherein, the indium salt is preferably at least one of indium acetate, indium nitrate, indium chloride and indium sulfate, but is not limited thereto; the tungsten salt is preferably at least one of tungsten nitrate, tungsten chloride, tungsten sulfate, tungsten methane sulfonate, tungsten ethane sulfonate, and tungsten propane sulfonate, but is not limited thereto; the sulfur source is preferably at least one of sodium sulfide, potassium sulfide, thiourea, and amine sulfide, but is not limited thereto.
Dissolving the indium salt and the tungsten salt in an organic solvent to prepare a mixed solution of the indium salt and the tungsten salt, wherein the indium salt and the tungsten salt can be dissolved in the organic solvent to form a mixed solution of the indium salt and the tungsten salt; or dissolving one of the indium salt and the tungsten salt in an organic solvent, adding the other metal salt, mixing and dissolving to obtain a mixed solution of the indium salt and the tungsten salt. Wherein, the organic solvent is preferably an organic alcohol solvent. The organic alcohol solvent has a relatively large polarity and has a relatively good solubility for the indium salt and the tungsten salt listed above. Moreover, the organic alcohol solvent is milder as a reaction medium, and provides a good reaction environment for the reaction of metal salt ions and sulfur to grow nano-crystalline grains. Preferably, the organic solvent is selected from at least one of isopropyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, but is not limited thereto.
Specifically, the indium salt and the tungsten salt are dissolved in an organic solvent, and the dissolution of the metal salt can be promoted by stirring at a constant temperature to prepare a mixed solution of the indium salt and the tungsten salt. Preferably, the constant-temperature stirring is carried out at a temperature of 60 ℃ to 80 ℃. This temperature generally prevents volatilization of the organic solvent in which the metal salt is dissolved, and also promotes rapid dissolution of the indium and tungsten salts.
In the embodiment of the invention, in the step of preparing the mixed solution of the indium salt and the tungsten salt, the total concentration of the indium salt and the tungsten salt in the mixed solution is 0.2 mol/L-1.0 mol/L, and the molar ratio of the indium salt to the tungsten salt is 1: 0.05-0.1. At the moment, the concentration of the metal ions In the mixed solution is proper, so that the metal ions and sulfur can quickly react to generate W-doped In after a sulfur source is added 2 S 3 A crystal; the molar ratio of the indium salt to the tungsten salt can ensure doped In 2 S 3 W In the nanomaterial is suitable to overcome In 2 S 3 The nanometer material has electron injection defect and good electron transmission effect.
Further, a sulfur source is added to the mixed solution, and In one embodiment, the sulfur source may be directly added to the mixed solution, and reacts with indium In the mixed solution to generate In 2 S 3 Nanomaterial with tungsten doped to In 2 S 3 In of nano material 3+ Site, resulting In tungsten doped In 2 S 3 And (3) nano materials. In another embodiment, it is preferable that the sulfur source is dissolved In an organic solvent, and then added to the mixed solution, and the sulfur source reacts with indium In the mixed solution to form In 2 S 3 Nano-materials of at the same timeDoping of tungsten into In 2 S 3 In of nanomaterial 3+ Site to obtain tungsten doped In 2 S 3 And (3) nano materials. In this embodiment, the organic solvent is selected to be an organic solvent capable of dissolving the sulfur source, and at the same time, there is not much polarity difference with the organic solvent dissolving the metal ions, so as to prevent the sulfur source solution from being mixed with the mixed solution and then from generating a delamination phenomenon, which affects the reaction. Most preferably, the same organic solvent used to dissolve the sulfur source is selected as the organic solvent used to dissolve the indium salt and the tungsten salt. Specifically, the organic solvent is selected from at least one of isopropyl alcohol, ethanol, propanol, butanol, pentanol, hexanol, but is not limited thereto.
In the step, preferably, a sulfur source is added into the mixed solution according to the molar ratio of S to metal ions of 0.8-1.2: 1, so that W-doped In with a good doping effect can be obtained 2 S 3 A nanomaterial; in particular, when W is doped with In 2 S 3 When the nano material is prepared into a film, the molar ratio of S to metal ions is controlled to be 0.8-1.2: 1, so that compact and compact W-In can be conveniently obtained In the subsequent process 2 S 3 The particles on the surface of the film are uniformly distributed. When the ratio of the molar amount of S to the sum of the molar amounts of indium ions and tungsten ions is less than 0.8: 1, the metal salt is excessive, and the added tungsten cannot be completely doped. When the ratio of the molar amount of S to the sum of the molar amounts of indium ions and tungsten ions is greater than 1.2:1, the amount of the sulfur salt is excessive, and the excess sulfur salt is not easily removed in the subsequent step.
In the embodiment of the invention, the mixed solution added with the sulfur source is mixed and reacted at the temperature not higher than the boiling point temperature of the organic solvent to prepare the precursor solution. The mixing reaction is preferably carried out by stirring at constant temperature. Particularly preferably, the mixing reaction is carried out at the temperature of 60-80 ℃, and the reaction time is 2-4 h. Under the temperature condition, the doping of W atoms In is facilitated 2 S 3 And is mainly W 6+ Form of (2) occupies In the crystal lattice 3+ To obtain W-doped In 2 S 3 。
In the step S02, the invention is implemented when the precursor solution is cooled to room temperatureThe room temperature is a room temperature of 10 to 35 ℃. And then carrying out solid-liquid separation treatment to collect solid matters, and drying after cleaning to obtain the nano material. In a preferred embodiment, the solid-liquid separation is preferably performed by precipitation treatment to precipitate W-doped In the precursor solution 2 S 3 And (4) crystallizing, collecting sediments, cleaning and drying to obtain the nano material. The solid-liquid separation treatment may be achieved by adding a precipitant. The precipitant is a weakly polar and non-polar solvent such as ethyl acetate, heptane, octane, etc., but is not limited thereto.
In another embodiment, the precursor solution may be further prepared into a film to obtain an electron transport thin film. Specifically, after the precursor solution is deposited on a substrate, an electron transport film is prepared through annealing treatment. The specific process can refer to the preparation of an electron transport layer in the preparation method of the quantum dot light-emitting diode.
A third aspect of embodiments of the present invention provides a quantum dot light emitting diode, including a stacked structure of a cathode and an anode that are oppositely disposed, 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, where a material of the electron transport layer is doped In 2 S 3 Nanomaterial comprising In 2 S 3 Nano material and doped In 2 S 3 W In a nanomaterial, and the doped In 2 S 3 In the nano material, the molar ratio of In to W is 1: 0.05-0.1.
In the quantum dot light-emitting diode provided by the embodiment of the invention, In is doped with W 2 S 3 The nano material is used as an electron transport layer material. In can be increased due to the doping of W 2 S 3 The carrier mobility of the nano material improves the conductivity of the film layer, promotes the effective recombination of electrons and holes in the quantum dots, reduces the influence of exciton accumulation on the performance of the quantum dot light-emitting diode device, and improves the performance of the quantum dot light-emitting diode device and the display performance.
In the embodiment of the present invention, the material of the electron transport layer is the above-mentioned nanomaterial, and the specific principle of improving the electron transport performance of the device by using the material of the electron transport layer and the preferred molar ratio of In to W are as described above, and therefore, for the sake of brevity, details are not repeated here.
In some preferred embodiments, the thickness of the electron transport layer is 20nm to 60 nm. Since W is doped with In 2 S 3 The nano material contains a certain amount of doping state W, so that when the thickness of the electron transport layer is in the range, the electron transport performance of the device can be effectively improved. When the thickness of the electron transport layer is too thick, the resistance is easily increased, and the transport performance of the electron transport layer is adversely affected.
Specifically, the quantum dot light emitting diode according to the embodiment of the present invention has a positive structure and an inversion structure.
In one embodiment, a positive-type structure quantum dot light emitting diode includes a stacked structure including an anode and a cathode disposed opposite to each other, a quantum dot light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the quantum dot light emitting layer, and the anode is disposed on a substrate. Furthermore, an electron injection layer can be arranged between the cathode and the electron transport layer, and an electron functional layer such as a hole blocking layer can be arranged between the cathode and the quantum dot light-emitting layer; and a hole functional layer such as a hole transport layer, a hole injection layer and an electron blocking layer can be arranged between the anode and the quantum dot light-emitting layer. In some embodiments of positive type structure devices, the quantum dot light emitting diode includes a substrate, an anode disposed on a surface of the substrate, the hole injection layer disposed on a surface of the anode, a hole transport layer disposed on a surface of the hole injection layer, a quantum dot light emitting layer disposed on a surface of the hole transport layer, an electron transport layer disposed on a surface of the quantum dot light emitting layer, and a cathode disposed on a surface of the electron transport layer.
In one embodiment, an inverted structure quantum dot light emitting diode includes a stacked structure including an anode and a cathode disposed opposite each other, a quantum dot light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the quantum dot light emitting layer, and the cathode disposed on a substrate. Furthermore, an electron injection layer can be arranged between the cathode and the electron transport layer, and an electron functional layer such as a hole blocking layer can be arranged between the cathode and the quantum dot light-emitting layer; and a hole functional layer such as a hole transport layer, a hole injection layer and an electron blocking layer can be arranged between the anode and the quantum dot light-emitting layer. In some embodiments of the device with the inverted structure, the quantum dot light emitting diode includes a substrate, a cathode disposed on the surface of the substrate, an electron transport layer disposed on the surface of the cathode, a quantum dot light emitting layer disposed on the surface of the electron transport layer, a hole transport layer disposed on the surface of the quantum dot light emitting layer, an electron injection layer disposed on the surface of the hole transport layer, and an anode disposed on the surface of the electron injection layer.
Specifically, the selection of the anode is not limited strictly, and ITO may be selected, but is not limited thereto.
The material of the quantum dot light-emitting layer can be conventional quantum dot material according to conventional quantum dot type. The quantum dots of the quantum dot light-emitting layer can be one of red quantum dots, green quantum dots, blue quantum dots and yellow quantum dots. The quantum dot material may or may not contain cadmium. Specifically, the quantum dot material may be at least one of semiconductor nanocrystals of CdS, CdSe, CdTe, InSe, InTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, and CuInSe, and core-shell structure quantum dots or alloy structure quantum dots formed by the above materials. The quantum dot light-emitting layer formed by the quantum dot material has the characteristics of wide excitation spectrum, continuous distribution, high emission spectrum stability and the like. The thickness of the quantum dot light-emitting layer is 20-60 nm.
The cathode can be made of conventional cathode materials, such as metal silver or metal aluminum, or a nano Ag wire or a nano Cu wire, and the materials have low resistance so that carriers can be injected smoothly.
The material of the hole transport layer can be made of a hole transport material which is conventional in the field, and can be TFB, PVK, Poly-TPD, TCTA, PEDOT: PSS and CBP, but not limited thereto.
In some embodiments, the qd-led may further comprise an encapsulation layer. The packaging layer can be arranged on the surface of a top electrode (an electrode far away from a substrate) and can also be arranged on the surface of the whole quantum dot light-emitting diode.
The quantum dot light-emitting diode provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, with reference to fig. 2, a fourth aspect of the present invention provides a method for manufacturing a quantum dot light emitting diode, including the following steps:
E01. dissolving indium salt and tungsten salt in an organic solvent to prepare a mixed solution of the indium salt and the tungsten salt; adding a sulfur source into the mixed solution, and mixing and reacting at the temperature not higher than the boiling point of the organic solvent to prepare a precursor solution;
E02. and after the precursor solution is deposited on the surface of the substrate, annealing treatment is carried out to obtain the electron transport layer.
According to the preparation method of the quantum dot light-emitting diode provided by the embodiment of the invention, a precursor solution formed by the reaction of indium salt, tungsten salt and a sulfur source is deposited on the surface of a substrate and then is subjected to annealing treatment, so that an electron transport layer is prepared. The obtained electron transport layer is made of W-doped In 2 S 3 Therefore, the quantum dot light-emitting diode prepared by the method can improve the electron transmission capability, promote the effective recombination of electrons and holes in quantum dots, reduce the influence of exciton accumulation on the performance of the quantum dot light-emitting diode device, and improve the performance of the quantum dot light-emitting diode device and display performance. In addition, the method only needs to change the material of the electron transport layer on the basis of the conventional preparation method of the quantum dot light-emitting diode, and is simple to operate and mature and reliable in process.
In the step E01, the precursor solution is the same as the precursor solution in the nanomaterial preparation method, and the preparation method of the precursor solution is also the same as the preparation method of the precursor solution in the nanomaterial preparation method, which is specifically described above. Preferably, the total concentration of the indium salt and the tungsten salt in the mixed solution is 0.2 mol/L-1.0 mol/L, and the molar ratio of the indium salt to the tungsten salt is 1: 0.05-0.1. Preferably, in the step of preparing the precursor solution, a sulfur source is added to the mixed solution according to the molar ratio of S to metal ions of 0.8-1.2: 1. Preferably, in the step of preparing the precursor solution, the organic solvent is organic alcohol, the mixing reaction is performed at a temperature of 60 ℃ to 80 ℃, and the reaction time is 2h to 4 h.
In the step E02, in the positive type structure quantum dot light emitting diode, the bottom electrode provided on the substrate is an anode, that is, the substrate at least includes an anode substrate. In some embodiments of the invention, the substrate is an anode substrate with an anode disposed on a substrate. In some embodiments of the present invention, the substrate may be a laminated substrate in which an anode is disposed on a substrate and a hole injection layer is disposed on a surface of the anode. It should be understood that the present invention is not limited to the structures of the above-described embodiments.
In step E02, in the case of the inverse quantum dot light emitting diode, the bottom electrode provided on the substrate is a cathode, that is, the substrate at least includes a cathode substrate. In some embodiments of the invention, the substrate is a cathode substrate with a cathode disposed on a substrate. In still other embodiments of the present invention, the substrate may be a laminated substrate in which a cathode is provided on a substrate and an electron injection layer is provided on a surface of the cathode. It should be understood that the present invention is not limited to the structures of the above-described embodiments.
In the case of a positive type structure quantum dot light emitting diode, the bottom electrode provided on the substrate is an anode, that is, the substrate at least includes an anode substrate. In some embodiments of the present invention, the substrate is a laminated substrate in which an anode is disposed on a substrate and a quantum dot light emitting layer is disposed on a surface of the anode. In still other embodiments of the present invention, the substrate is a laminated substrate in which an anode is provided on a substrate, a hole transport layer is provided on a surface of the anode, and a quantum dot light emitting layer is provided on a surface of the hole injection layer. Of course, other hole-functional layers, such as a hole-injection layer, may also be disposed between the anode and the hole-transport layer. It should be understood that the present invention is not limited to the structures of the above-described embodiments.
In the preparation method of the quantum dot light-emitting diode provided by the embodiment of the invention, before the functional layer is prepared on the surface of the anode substrate or the cathode substrate, the anode substrate or the cathode substrate is preferably subjected to pretreatment. In a preferred embodiment, the step of pre-treating comprises: cleaning the anode substrate or the cathode substrate with a cleaning agent to primarily remove stains on the surface, and then sequentially performing ultrasonic cleaning in deionized water, acetone, absolute ethyl alcohol and deionized water for 10-30 min, preferably 20min, to remove impurities on the surface; and finally, drying by using high-purity nitrogen to obtain the surface of the anode substrate or the cathode substrate.
The deposition of the precursor solution on the substrate surface can be achieved by using conventional solution processing methods, including but not limited to spin coating, inkjet printing, and the like. The embodiment of the invention can control the film thickness by adjusting the concentration of the solution, the printing or spin coating speed and the deposition time.
After the precursor solution is deposited on the surface of the substrate, annealing treatment is carried out to remove the solvent In the precursor solution and improve W-doped In 2 S 3 The crystalline properties of the particles. Preferably, the annealing step is performed at a temperature of 200 to 300 ℃.
The functional layers (including but not limited to hole injection layer, electron transport layer, hole blocking layer, electron blocking layer) except the anode and cathode of the embodiments of the present invention can be prepared by conventional solution processing methods including but not limited to inkjet printing, spin coating. Similarly, the film thickness of each layer can be controlled by adjusting the concentration of the solution, the printing or spin coating speed and the deposition time; and thermal annealing treatment is carried out after the solution is deposited.
In some embodiments, the packaging process of the obtained QLED device is further included. The packaging process can adopt a common machine for packaging and can also adopt manual packaging. Preferably, the oxygen content and the water content in the packaging treatment environment are both lower than 0.1ppm so as to ensure the stability of the device.
The following description will be given with reference to specific examples and comparative examples.
Example 1
A preparation method of an electron transport film comprises the following steps:
appropriate amounts of indium chloride and sodium tungstate were added to 50ml of ethanol to form a solution with a total concentration of 0.5M, wherein the ratio of indium: the molar ratio of tungsten is 1:0.05, stirring and dissolving at the temperature of 70 ℃ to obtain a mixed solution of metal salts.
According to S 2- The molar ratio of the indium to tungsten metal ions is 1: 1, adding 10ml of ethanol solution of sodium sulfide into the mixed solution of the metal salt, and stirring for 4 hours at the temperature of 70 ℃ to obtain a uniform precursor solution.
Cooling the precursor solution, depositing on a substrate such as ITO, and annealing at 250 deg.C to obtain W-doped In 2 S 3 A film.
Example 2
A preparation method of a nano material comprises the following steps:
appropriate amounts of indium nitrate and potassium tungstate were added to 50ml of propanol to form a solution with a total concentration of 1M, wherein the ratio of indium: the molar ratio of tungsten is 1: 0.1, stirring and dissolving at the temperature of 80 ℃ to obtain a mixed solution of metal salts.
According to S 2- The molar ratio of the indium to tungsten metal ions is 1.1: 1, adding 10ml of propanol solution of sodium sulfide into the mixed solution of the metal salt, and stirring for 3 hours at the temperature of 80 ℃ to obtain a uniform precursor solution.
Adding a precipitator into the precursor solution, and collecting the settled W-doped In 2 S 3 And (3) nano materials.
Example 3
A preparation method of an electron transport film comprises the following steps:
appropriate amounts of indium sulfate and potassium tungstate were added to 50ml of methanol to form a solution with a total concentration of 0.8M, wherein the ratio of indium: the molar ratio of tungsten is 1: 0.08, stirring and dissolving at the temperature of 60 ℃ to obtain a mixed solution of the metal salt.
According to S 2- The molar ratio of the indium to tungsten metal ions is 1.2:1, adding 10ml of thiourea methanol solution into the mixed solution of the metal salt, and stirring for 4 hours at the temperature of 60 ℃ to obtain a uniform precursor solution.
Cooling the precursor solution, depositing on a substrate such as ITO, and annealing at 250 deg.C to obtain W-doped In 2 S 3 A film.
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. 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 W-doped In 2 S 3 Nanomaterial (W-In) 2 S 3 ) 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, 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 example 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. Wherein the substrate is made of glass sheetThe electrode material is ITO substrate, the material TFB of hole transport layer, and the material W of electron transport layer is doped with In 2 S 3 Nanomaterial (W-In) 2 S 3 ) 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, 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 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 W-doped In 2 S 3 Nanomaterial (W-In) 2 S 3 ) 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, 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 oppositely arranged anodesThe cathode is arranged on the substrate, the anode is arranged on the anode, the quantum dot light-emitting layer is arranged between the anode and the cathode, the electron transport layer is arranged between the cathode and the quantum dot light-emitting layer, the hole transport layer is arranged between the anode and the quantum dot light-emitting layer, and the cathode is arranged on the 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 W-doped In 2 S 3 Nanomaterial (W-In) 2 S 3 ) The cathode 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 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. 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 W-doped In 2 S 3 Nanomaterial (W-In) 2 S 3 ) 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 W-doped In 2 S 3 Nanomaterial (W-In) 2 S 3 ) 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 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;
and preparing an anode 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 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 commercial In 2 S 3 Nanomaterial (available from sigma corporation) and the material of the anode is Al.
The performance of the electron transport films prepared in examples 1 to 3, the electron transport layer in comparative example 1, the quantum dot light emitting diodes prepared in examples 4 to 9 and comparative example 1 was tested, and the test indexes and the test method were as follows:
(1) electron mobility: testing the current density (J) -voltage (V) of the quantum dot light-emitting diode, drawing a curve relation diagram, fitting a Space Charge Limited Current (SCLC) area in the relation diagram, 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 by an EQE optical measuring 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: an anode/a hole transport film/a quantum dot/an electron transport film/a cathode, or a cathode/an electron transport film/a quantum dot/a hole transport film/an anode.
The test results are shown in table 1 below:
TABLE 1
As can be seen from Table 1 above, examples 1 to 3 of the present invention provide materials In which W is doped 2 S 3 Nanomaterial (W-In) 2 S 3 ) Electron transport film of (2), resistivity electron transportThe ratio is obviously higher than that of In comparative example 1 2 S 3 The resistivity of the electron transport film made of the nanomaterial was significantly higher than that of In comparative example 1 2 S 3 An electron transport film made of nano material.
The quantum dot light-emitting diodes provided In embodiments 4 to 9 of the present invention (electron transport layer material is W-doped In) 2 S 3 Nano material) has an external quantum efficiency significantly higher than that of the electron transport layer material In comparative example 1 2 S 3 The external quantum efficiency of the quantum dot light-emitting diode made of the nano material shows that the quantum dot light-emitting diode obtained by the embodiment has better luminous 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 light emitting layer, and is based on that a blue light emitting system is a system which is used more (in addition, it is difficult for a light emitting diode based on blue quantum dots to achieve high light emitting efficiency, and therefore, the light emitting diode has a higher reference value), and does not represent that the invention is only used for the blue light emitting 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. The preparation method of the nano material is characterized by comprising the following steps of:
dissolving indium salt and tungsten salt in an organic solvent to prepare a mixed solution of the indium salt and the tungsten salt; adding a sulfur source into the mixed solution, and mixing and reacting at the temperature not higher than the boiling point of the organic solvent to prepare a precursor solution; wherein the mixing reaction is carried out at a temperature of 60-80 ℃;
and after the precursor solution is cooled to room temperature, carrying out solid-liquid separation treatment on the precursor solution to collect solid matters, and drying after cleaning to obtain the nano material.
2. The method for preparing nanomaterial according to claim 1, wherein in the step of preparing the mixed solution of indium salt and tungsten salt, the total concentration of indium salt and tungsten salt in the mixed solution is 0.2mol/L to 1.0mol/L, and the molar ratio of indium salt to tungsten salt is 1:0.05 to 0.1.
3. The method for preparing a nanomaterial according to claim 1, wherein in the step of preparing the precursor solution, a sulfur source is added to the mixed solution in a molar ratio of S to metal ions of 0.8 to 1.2: 1.
4. The method for preparing a nanomaterial according to claim 3, wherein in the step of preparing the precursor solution, the organic solvent is organic alcohol, and the reaction time of the mixing reaction is 2 to 4 hours.
5. The method for producing nanomaterials of any one of claims 1 to 4, wherein the indium salt is at least one selected from the group consisting of indium acetate, indium nitrate, indium chloride, and indium sulfate; and/or
The tungsten salt is selected from at least one of sodium tungstate, ammonium tungstate, potassium tungstate and magnesium tungstate; and/or
The organic solvent is selected from at least one of isopropanol, ethanol, propanol, butanol, pentanol and hexanol; and/or
The sulfur source is at least one selected from sodium sulfide, potassium sulfide, thiourea and amine sulfide.
6. A quantum dot light-emitting diode comprising a laminated structure of a cathode and an anode which are arranged to face each other, a quantum dot light-emitting layer provided between the cathode and the anode, and an electron transport layer provided between the cathode and the quantum dot light-emitting layer, the electron transport layer being made of a material including In 2 S 3 Nano material and In doped In 2 S 3 W in the nanomaterial.
7. The quantum dot light-emitting diode of claim 6, wherein the molar ratio of In to W In the electron transport layer is 1: 0.05-0.1.
8. The qd-led of claim 6 or claim 7, wherein the electron transport layer has a thickness of 20nm to 60 nm.
9. A preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
dissolving indium salt and tungsten salt in an organic solvent to prepare a mixed solution of the indium salt and the tungsten salt; adding a sulfur source into the mixed solution, and mixing and reacting at the temperature not higher than the boiling point of the organic solvent to prepare a precursor solution; wherein the mixing reaction is carried out at a temperature of 60-80 ℃;
and after the precursor solution is deposited on the surface of the substrate, annealing treatment is carried out to obtain the electron transport layer.
10. The method of claim 9, wherein the annealing step is performed at a temperature of 200 ℃ to 300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910718186.7A CN112320838B (en) | 2019-08-05 | 2019-08-05 | Nano material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910718186.7A CN112320838B (en) | 2019-08-05 | 2019-08-05 | Nano material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112320838A CN112320838A (en) | 2021-02-05 |
| CN112320838B true CN112320838B (en) | 2022-09-06 |
Family
ID=74319380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910718186.7A Active CN112320838B (en) | 2019-08-05 | 2019-08-05 | Nano material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112320838B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102017203A (en) * | 2008-05-02 | 2011-04-13 | Lg伊诺特有限公司 | Light-emitting element and a production method therefor |
| JP2011181695A (en) * | 2010-03-01 | 2011-09-15 | Daiwa Sangyo:Kk | Photoelectric conversion element and method of manufacturing the same |
| CN106732669A (en) * | 2016-12-21 | 2017-05-31 | 北京化工大学 | A kind of MoS as photoelectrocatalysis liberation of hydrogen material2/In2S3Composite catalyst and preparation method thereof |
| CN106848079A (en) * | 2017-02-20 | 2017-06-13 | 纳晶科技股份有限公司 | Luminous electric charge transmission compound, the ink containing it, its preparation method and QLED devices |
| CN106935717A (en) * | 2015-12-29 | 2017-07-07 | 三星显示有限公司 | Luminaire including quantum dot |
| CN109261166A (en) * | 2018-08-16 | 2019-01-25 | 华南理工大学 | A kind of preparation of the flower-like nanometer material of tin dope indium sulfide and its application in photo catalytic reduction |
| CN109967092A (en) * | 2019-05-05 | 2019-07-05 | 中国科学技术大学 | A kind of metal-doped indium sulfide nanometer sheet, preparation method and application |
-
2019
- 2019-08-05 CN CN201910718186.7A patent/CN112320838B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102017203A (en) * | 2008-05-02 | 2011-04-13 | Lg伊诺特有限公司 | Light-emitting element and a production method therefor |
| JP2011181695A (en) * | 2010-03-01 | 2011-09-15 | Daiwa Sangyo:Kk | Photoelectric conversion element and method of manufacturing the same |
| CN106935717A (en) * | 2015-12-29 | 2017-07-07 | 三星显示有限公司 | Luminaire including quantum dot |
| CN106732669A (en) * | 2016-12-21 | 2017-05-31 | 北京化工大学 | A kind of MoS as photoelectrocatalysis liberation of hydrogen material2/In2S3Composite catalyst and preparation method thereof |
| CN106848079A (en) * | 2017-02-20 | 2017-06-13 | 纳晶科技股份有限公司 | Luminous electric charge transmission compound, the ink containing it, its preparation method and QLED devices |
| CN109261166A (en) * | 2018-08-16 | 2019-01-25 | 华南理工大学 | A kind of preparation of the flower-like nanometer material of tin dope indium sulfide and its application in photo catalytic reduction |
| CN109967092A (en) * | 2019-05-05 | 2019-07-05 | 中国科学技术大学 | A kind of metal-doped indium sulfide nanometer sheet, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Effect of Tungsten Doping on the Properties of In2O3 Films;R. RESHMI KRISHNAN等;《The Minerals, Metals & Materials Society》;20190319;第1885-1896页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112320838A (en) | 2021-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102306134B1 (en) | Perovskite optoelectronic device, preparation method therefor and perovskite material | |
| Wang et al. | The improvement of near-ultraviolet electroluminescence of ZnO nanorods/MEH-PPV heterostructure by using a ZnS buffer layer | |
| CN112538163B (en) | Composite material, preparation method thereof and quantum dot light emitting diode | |
| CN110600621A (en) | Electron transport material, preparation method thereof and quantum dot light-emitting diode | |
| CN109935733B (en) | N-type ZnO film, preparation method thereof and QLED device | |
| WO2021136044A1 (en) | Quantum dot light-emitting diode and manufacturing method therefor | |
| WO2022011988A1 (en) | Nano material and preparation method therefor, and quantum dot light-emitting diode | |
| CN111384244B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN112320838B (en) | Nano material and preparation method and application thereof | |
| CN112397660B (en) | Nano material and preparation method and application thereof | |
| CN113707777B (en) | Composite material, preparation method thereof and light-emitting device | |
| CN113046077B (en) | Composite material, quantum dot light-emitting diode and preparation method thereof | |
| CN109970356B (en) | Zinc oxide nano material, preparation method thereof and luminescent device | |
| CN110752301B (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN112397620B (en) | Nano composite particle and preparation method and application thereof | |
| CN112397673B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN113130790A (en) | Nano material, preparation method thereof and quantum dot light-emitting diode | |
| CN112349870B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN113044882B (en) | Nano material and preparation method thereof, and quantum dot light-emitting diode | |
| CN110963535A (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN113054118B (en) | Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof | |
| CN113054145B (en) | Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof | |
| CN110943171A (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN112542554B (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN113054119B (en) | Composite material, preparation method and application thereof, light-emitting diode and preparation method thereof |
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 | ||
| 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. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |