CN112320838A - Nano material and preparation method and application thereof - Google Patents

Nano material and preparation method and application thereof Download PDF

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CN112320838A
CN112320838A CN201910718186.7A CN201910718186A CN112320838A CN 112320838 A CN112320838 A CN 112320838A CN 201910718186 A CN201910718186 A CN 201910718186A CN 112320838 A CN112320838 A CN 112320838A
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quantum dot
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CN112320838B (en
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何斯纳
吴龙佳
吴劲衡
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TCL Research America Inc
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Abstract

The invention provides a nano material, which comprises In2S3Nano material and doped In2S3W in the nanomaterial. The nano material provided by the invention is prepared by adding In2S3Doping high valence state difference metal W In nano material to raise In2S3Carrier mobility of the nanomaterial.

Description

Nano material and preparation method and application thereof
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.
In2S3Is an n-type semiconductor material with the conductive forbidden band width of 2.0-2.3eV, has higher electron mobility, and determines In2S3Can be used as a suitable electron transport layer material. At the same time, In2S3Is a III-VI semiconductor material with three crystal structures of-In2S3(cubic system), -In2S3(tetragonal system) and-In2S3The 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, In2S3The 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, aiming at solving the problem of In2S3When 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 In2S3Nano material and doped In2S3W 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 In2S3Nano material and doped In2S3W 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 In2S3Doping high valence state difference metal W In nano material to raise In2S3Carrier mobility of the nanomaterial. When In2S3When W is doped into the nano material, the majority of W atoms are W6+W is solid-dissolved6+Occupy In the crystal lattice3+A few by W5+And W4+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 atoms to form 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 form free electrons, and the free electrons are oriented under the action of an external electric fieldMove and 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 photons6+、W5+And W4+Can be switched between by absorbing or releasing energy) and then drifted between different oxidation states, and thus, W5+And W6+And W4+And W5+A valence-state hopping conduction mechanism exists between the two. This valence-hopping conduction mechanism helps to increase In2S3The 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 In2S3The 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 quantum dot light-emitting diode provided by the invention is doped with In by the W2S3The nano material is used as an electron transport layer material. In can be increased due to the doping of W2S3The 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 In2S3Nano materialTherefore, the quantum dot light-emitting diode prepared by the invention 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 the 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 is simple to operate and mature and reliable in 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 are not intended to 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 implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In a first aspect, embodiments of the present invention provide a nanomaterial comprising In2S3Nano material and doped In2S3W in the nanomaterial.
The nano material provided by the embodiment of the invention is prepared by adding In2S3Doping high valence state difference metal W In nano material to raise In2S3Carrier mobility of the nanomaterial. When In2S3When the nano material is doped with W, the dopingW is mostly W6+W is solid-dissolved6+Occupy In the crystal lattice3+A few by W5+And W4+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 atoms to form 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 photons6+、W5+And W4+Can be switched between by absorbing or releasing energy) and then drifted between different oxidation states, and thus, W5+And W6+And W4+And W5+A valence-state hopping conduction mechanism exists between the two. This valence-hopping conduction mechanism helps to increase In2S3The 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 In2S3Amount of doping In the nanomaterial, and the obtained doped In2S3The performance of the nano-material is greatly influenced, especially when the doped In is used2S3When 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 In2S3The 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 In2S3The 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 In2S3The solid solubility in the nanomaterial reaches saturation. The doping amount continues to increaseWhen W is excessively added, excess W is accumulated In2S3The surface of the crystal grain forms a new phase, and the nanometer In is reduced2S3Effective specific surface area of (a); meanwhile, excessive doping of W causes In2S3Mutation of the lattice to form a new lattice, accompanied by WO3Eventually leading to changes in the properties of the nanomaterial.
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 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 In2S3The 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 provided2S3Indium 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 in the organic solvent environment, indium ions in the indium salt and tungsten ions in the tungsten salt can react with sulfur in the sulfur source to grow into nano-crystalline grains. It is composed ofThe 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, ethanol, propanol, butanol, pentanol, hexanol, 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 0.2-1.0 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 added2S3A crystal; the molar ratio of indium salt to tungsten salt can ensure doped In2S3W In the nanomaterial is suitable to overcome In2S3The 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 In2S3Nanomaterial with tungsten doped to In2S3In of nanomaterial3+Site to obtain tungsten doped In2S3And (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 In2S3Nanomaterial with tungsten doped to In2S3In of nanomaterial3+Site to obtain tungsten doped In2S3And (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 obtained2S3A nanomaterial; in particular, when W is doped with In2S3When 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 subsequently2S3The 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: when 1, the sulfur salt is excessive,excess sulphur salt is not easily removed in subsequent steps.
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 a temperature of 60-80 ℃ and the reaction time is 2-4 h. Under the temperature condition, the doping of W atoms In is facilitated2S3And is mainly W6+Form of (2) occupies In the crystal lattice3+To obtain W-doped In2S3。
In the step S02, the precursor solution is cooled to room temperature, where the room temperature is 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 solution2S3And (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 the 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 In2S3Nanomaterial comprising In2S3Nano material and doped In2S3W In a nanomaterial, and the doped In2S3In 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 W2S3The nano material is used as an electron transport layer material. In can be increased due to the doping of W2S3The 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 In2S3The 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 the positive-type structure device, 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 a surface of the substrate, an electron transport layer disposed on a surface of the cathode, a quantum dot light emitting layer disposed on a surface of the electron transport layer, a hole transport layer disposed on a surface of the quantum dot light emitting layer, an electron injection layer disposed on a surface of the hole transport layer, and an anode disposed on a 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, 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 the 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 material of the electron transport layer is W doped with In2S3Nano-materials, and thus, the present inventionThe prepared quantum dot light-emitting diode 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, and improve the device and the 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 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 the anode substrate or the cathode substrate 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 In2S3The 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 common machine packaging or 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 the metal salt.
According to S2-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 In2S3A 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 the metal salt.
According to S2-With indium tungsten metalThe molar ratio of 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 In2S3And (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 S2-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 In2S3A 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 In2S3Nanomaterial (W-In)2S3) 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 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 In2S3Nanomaterial (W-In)2S3) 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 In2S3Nanomaterial (W-In)2S3) 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 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 In2S3Nanomaterial (W-In)2S3) And 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;
an anode is prepared 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 transmission layer arranged between the cathode and the quantum dot light-emitting layer, and a quantum dot light-emitting layer arranged between the anode and the cathodeAnd 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 In2S3Nanomaterial (W-In)2S3) 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 In2S3Nanomaterial (W-In)2S3) 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;
an anode is prepared on the hole transport layer.
Comparative example 1
Quantum dotThe 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 transmission layer arranged between the cathode and the quantum dot light-emitting layer, and a hole transmission 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 In2S3Nanomaterial (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) region in the relation diagram, and then calculating the electron mobility according to a well-known Child's law formula:
J＝(9/8)εrε0μeV2/d3
wherein J represents current density in mAcm-2；εrDenotes the relative dielectric constant,. epsilon0Represents the vacuum dielectric constant; mu.seDenotes the electron mobility in cm2V-1s-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: 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
Figure BDA0002156193720000171
Figure BDA0002156193720000181
As can be seen from Table 1 above, examples 1 to 3 of the present invention provide materials In which W is doped2S3Nanomaterial (W-In)2S3) The electron transport film of (1) has a resistivity electron mobility significantly higher than that of In comparative example 12S3The resistivity of the electron transport film made of the nanomaterial was significantly higher than that of In comparative example 12S3Electron 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)2S3Nano material) has an external quantum efficiency significantly higher than that of the electron transport layer material In comparative example 12S3The 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 CdXZn1-XS/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 (12)

1. A nanomaterial, characterized In that the nanomaterial comprises In2S3Nano material and doped In2S3W in the nanomaterial.
2. The nanomaterial according to claim 1, wherein a molar ratio of In to W In the nanomaterial is 1:0.05 to 0.1.
3. 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;
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.
4. The method for preparing nanomaterial according to claim 3, 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.
5. The method for preparing a nanomaterial according to claim 3, 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.
6. The method for preparing a nanomaterial according to claim 5, wherein 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.
7. The method for preparing nanomaterial according to any of claims 3 to 6, wherein the indium salt is at least one selected from 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.
8. 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 In2S3Nano material and doped In2S3W in the nanomaterial.
9. The qd-led of claim 7, wherein the molar ratio of In to W In the electron transport layer is 1: 0.05-0.1.
10. The qd-led of claim 8 or claim 9, wherein the electron transport layer has a thickness of 20nm to 60 nm.
11. 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;
and after the precursor solution is deposited on the surface of the substrate, annealing treatment is carried out to obtain the electron transport layer.
12. The method of claim 11, wherein the annealing step is performed at a temperature of 200 ℃ to 300 ℃.
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