CN111490170B - Quantum dot light-emitting diode and preparation method thereof - Google Patents

Quantum dot light-emitting diode and preparation method thereof Download PDF

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CN111490170B
CN111490170B CN201910075544.7A CN201910075544A CN111490170B CN 111490170 B CN111490170 B CN 111490170B CN 201910075544 A CN201910075544 A CN 201910075544A CN 111490170 B CN111490170 B CN 111490170B
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arsenic
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doped carbon
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CN111490170A (en
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何斯纳
吴龙佳
吴劲衡
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TCL Technology Group Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/166—Electron transporting layers comprising a multilayered structure
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • 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
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer

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Abstract

The invention provides a quantum dot light-emitting diode and a preparation method thereof, wherein the quantum dot light-emitting diode comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, and further comprises a first layer arranged between the cathode and the quantum dot light-emitting layer, and the material of the first layer comprises arsenic-doped carbon quantum dots. The arsenic-doped carbon quantum dots have high electron mobility, and the electron transfer performance of the device is improved.

Description

Quantum dot light-emitting diode and preparation method thereof
Technical Field
The invention relates to the field of light emitting diodes, in particular to a quantum dot light emitting diode and a preparation method thereof.
Background
There are many kinds of semiconductor materials, which can be classified into an intrinsic semiconductor, a P-type semiconductor, and an N-type semiconductor according to the characteristics of carriers; they can be subdivided into elemental semiconductors, compound semiconductors, and organic semiconductors according to their chemical composition. Among many semiconductor materials, the transition metal oxide semiconductor material not only has the physicochemical basic properties peculiar to the transition metal oxide, but also exhibits unique acoustic, optical, thermal, electrical, and other properties by taking advantage of the characteristics of the semiconductor material. It is therefore an especially important component in functional materials. At present, ZnO, NiO, TiO2、MoO3Semiconductor materials and their applications have been the focus of research on functional materials, and such semiconductor materials are widely used in applications of semiconductor optoelectronic devices (such as solar cells and light emitting diodes). Meanwhile, in order to better highlight the effect of the oxide in the application of the semiconductor optoelectronic device, the device structure work of the oxide is also concerned by extensive scientific researchers.
Disclosure of Invention
The invention provides a quantum dot light-emitting diode and a preparation method thereof, aiming at the electron transmission performance of the quantum dot light-emitting diode.
A quantum dot light-emitting diode comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, and further comprises a first layer arranged between the cathode and the quantum dot light-emitting layer, wherein the material of the first layer comprises arsenic-doped carbon quantum dots.
Carbon quantum dot itself has good electrical properties, arsenic enters carbon quantum dot by doping, arsenic atom has a 5-valent electronic structure, arsenic atom has one more p electron than carbon atom, this makes arsenic atom and carbon atom realize strong covalent bond with very easily and combine, the carbon atom of a certain position on carbon quantum dot is replaced to arsenic atom, doping makes the electron figure of system increase as the donor, change electron cloud density and the local curvature of carbon quantum dot around the arsenic atom, make it have good electron mobility, and then improved quantum dot light emitting diode's electron transmission performance.
A preparation method of a quantum dot light-emitting diode comprises the following steps:
providing an anode substrate, wherein a quantum dot light-emitting layer is arranged on the surface of the anode substrate;
providing a solution containing arsenic-doped carbon quantum dots, depositing the solution containing arsenic-doped carbon quantum dots on the surface of the quantum dot light-emitting layer, and annealing to form a first layer;
depositing a metal oxide precursor salt solution on the surface of the first layer, and annealing to form a second layer; alternatively, the first and second electrodes may be,
providing a cathode substrate;
depositing a metal oxide precursor salt solution on the surface of the cathode substrate, and annealing to form a second layer;
providing a solution containing arsenic-doped carbon quantum dots, depositing the solution containing arsenic-doped carbon quantum dots on the surface of the second layer, and annealing to form the first layer.
Carbon quantum dot itself has good electrical properties, arsenic enters carbon quantum dot by doping, arsenic atom has a 5-valent electronic structure, arsenic atom has one more p electron than carbon atom, this makes arsenic atom and carbon atom realize strong covalent bond with very easily and combine, the carbon atom of a certain position on carbon quantum dot is replaced to arsenic atom, doping makes the electron figure of system increase as the donor, change electron cloud density and the local curvature of carbon quantum dot around the arsenic atom, make it have good electron mobility, and then improved quantum dot light emitting diode's electron transmission performance. The carbon quantum dots neutralize carbon atoms and arsenic atoms to form a hybrid pz orbit, so that the LUMO energy level of the carbon quantum dots is effectively reduced, and the arsenic-doped carbon quantum dots have lower LUMO energy levels and are adaptive to a conduction band of an oxide, thereby being beneficial to injection and transmission of electrons. The invention adopts a solution method to prepare the laminated structure, and has good film forming property and simple process.
Description of the drawings:
FIG. 1 is a schematic structural diagram of a device with a positive structure according to an embodiment of the present invention
Detailed Description
The invention provides a quantum dot light-emitting diode and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Some embodiments of the present invention provide a quantum dot light emitting diode comprising a cathode, an anode, and a quantum dot light emitting layer disposed between the cathode and the anode, further comprising a first layer disposed between the cathode and the quantum dot light emitting layer, the material of the first layer comprising arsenic doped carbon quantum dots.
Carbon quantum dot itself has good electrical properties, arsenic enters carbon quantum dot by doping, arsenic atom has a 5-valent electronic structure, arsenic atom has one more p electron than carbon atom, this makes arsenic atom and carbon atom realize strong covalent bond with very easily and combine, the carbon atom of a certain position on carbon quantum dot is replaced to arsenic atom, doping makes the electron figure of system increase as the donor, change electron cloud density and the local curvature of carbon quantum dot around the arsenic atom, make it have good electron mobility, and then improved quantum dot light emitting diode's electron transmission performance.
In some embodiments, the material of the first layer consists of arsenic-doped carbon quantum dots and metal oxide nanoparticles. Carbon quantum dot itself has good electrical properties, arsenic enters carbon quantum dot by doping, arsenic atom has a 5-valent electronic structure, arsenic atom has one more p electron than carbon atom, this makes arsenic atom and carbon atom realize strong covalent bond with very easily and combine, the carbon atom of a certain position on carbon quantum dot is replaced to arsenic atom, doping makes the electron figure of system increase as the donor, change electron cloud density and the local curvature of carbon quantum dot around the arsenic atom, make it have good electron mobility, and then improved quantum dot light emitting diode's electron transmission performance. The carbon quantum dots neutralize carbon atoms and arsenic atoms to form a hybrid pz orbit, so that the LUMO energy level of the carbon quantum dots is effectively reduced, and the arsenic-doped carbon quantum dots have lower LUMO energy levels and are adaptive to a conduction band of an oxide, thereby being beneficial to injection and transmission of electrons.
In some embodiments, the qd-led further comprises a stack disposed between the cathode and the qd-light emitting layer, the stack being formed by stacking a first layer and a second layer, the first layer comprising arsenic-doped carbon quantum dots, the second layer comprising metal oxide nanoparticles, the first layer being disposed adjacent to the qd-light emitting layer, and the second layer being disposed adjacent to the cathode. By adopting the laminated structure of the first layer and the second layer, the energy level matching between the metal oxide nano-particle/arsenic doped carbon quantum dot laminated structure is good, the electron transmission path and the electron transmission direction are stable, the electron transmission to the quantum dot luminous layer is facilitated, the luminous efficiency of the device is improved, and the QLED performance is improved.
In some embodiments, the material of the first layer is metal oxide nanoparticles and the material of the second layer is arsenic doped carbon quantum dots. In some specific embodiments, in order to better adjust the LUMO energy level of the material, the molar ratio of arsenic element to carbon element in the arsenic-doped carbon quantum dot is (0.01-0.1): 1. when the doping amount of arsenic reaches a certain value (more than 0.1), the solid solubility of arsenic in the carbon quantum dots reaches saturation, and when the doping amount continues to increase, arsenic is collected on the surfaces of the carbon quantum dot crystal grains to form a new phase, so that the effective specific surface area of the nano carbon quantum dots is reduced; the increase of the doping amount causes the lattice to be mutated, and a new lattice is formed. When the doping amount of arsenic is too low, arsenic is lost during the reaction process, and thus effective doping cannot be achieved. In some specific embodiments, the first layer has a thickness of 5 to 20 nm; in some specific embodiments, the second layer has a thickness of 15 to 40 nm.
Specifically, the quantum dot light emitting diode is divided into an upright structure and an inverted structure. The positive structure comprises an anode, a cathode and a quantum dot light emitting layer, wherein the anode, the cathode and the quantum dot light emitting layer are arranged in a stacked mode, the anode of the positive structure is arranged on the substrate, hole function layers such as a hole transmission layer, a hole injection layer and an electron blocking layer can be further arranged between the anode and the quantum dot light emitting layer, and electronic function layers such as an electron transmission layer, an electron injection layer and a hole blocking layer can be further arranged between the cathode and the quantum dot light emitting layer. In some embodiments of the present invention, the electron transport layer of the quantum dot light emitting diode employs the first layer. In still other embodiments of the present invention, the electron transport layer of the quantum dot light emitting diode has a stacked structure of the first layer and the second layer.
The inverted structure comprises an anode, a cathode and a quantum dot light-emitting layer, wherein the anode and the cathode are arranged in a stacked mode, the quantum dot light-emitting layer is arranged between the anode and the cathode, the cathode of the inverted structure is arranged on the substrate, hole function layers such as a hole transmission layer, a hole injection layer and an electron blocking layer can be further arranged between the anode and the quantum dot light-emitting layer, and electronic function layers such as an electron transmission layer, an electron injection layer and a hole blocking layer can be further arranged between the cathode and the quantum dot light-emitting layer. In some embodiments of the present invention, the electron transport layer of the quantum dot light emitting diode employs the first layer. In still other embodiments of the present invention, the electron transport layer of the quantum dot light emitting diode has a stacked structure of the first layer and the second layer.
In various embodiments of the present invention, the functional layer material is a material commonly used in the art, such as:
in some embodiments, the quantum dots of the quantum dot light emitting layer are one of red, green, and blue. Can be at least one of CdS, CdSe, CdTe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe and various core-shell structure quantum dots or alloy structure quantum dots.
In some embodiments, the material of the hole transport layer is one or more of TFB, PVK, Poly-TPD, TCTA, and CBP.
In some embodiments, the metal oxide nanoparticles in the second layer are selected from one or more of ZnO, TiO2, ZrO2, and SnO 2.
And carrying out packaging treatment on the obtained QLED, wherein the packaging treatment 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.
As shown in fig. 1, a specific quantum dot light emitting diode with an inversion structure is provided, and as shown in fig. 1, a QLED device with an inversion structure sequentially includes a substrate 1, a cathode 2, an electron transport layer 3, a quantum dot light emitting layer 4, a hole transport layer 5, and an anode 6 from bottom to top. The substrate 1 is made of a glass sheet, the cathode 2 is made of an ITO substrate, the electron transport layer 3 is made of a laminated structure of a first layer 31 and a second layer 32, the first layer 31 is made of arsenic-doped carbon quantum dots, the second layer 32 is made of ZnO nanoparticles, the first layer 31 is arranged close to the quantum dot light emitting layer 4, the second layer 32 is arranged close to the cathode 2, the hole transport layer 5 is made of NiO, and the anode 6 is made of Al.
Some embodiments of the present invention provide a method for preparing a quantum dot light emitting diode with an inverted structure, wherein the method comprises the following steps:
s01, providing an anode substrate, wherein a quantum dot light-emitting layer is arranged on the surface of the anode substrate;
s02, providing a solution containing arsenic-doped carbon quantum dots, and depositing the solution containing arsenic-doped carbon quantum dots on the surface of the quantum dot light-emitting layer to form a first layer;
s03, depositing a metal oxide precursor salt solution on the surface of the first layer to form a second layer;
alternatively, the first and second electrodes may be,
some embodiments of the present invention provide a method for preparing an inverted quantum dot light emitting diode, wherein the method comprises the following steps:
s11 providing a cathode substrate;
s12, depositing a metal oxide precursor salt solution on the surface of the cathode substrate to form a second layer;
s13 providing a solution containing arsenic-doped carbon quantum dots, and depositing the solution containing arsenic-doped carbon quantum dots on a surface of the second layer to form the first layer.
Carbon quantum dot itself has good electrical properties, arsenic enters carbon quantum dot by doping, arsenic atom has a 5-valent electronic structure, arsenic atom has one more p electron than carbon atom, this makes arsenic atom and carbon atom realize strong covalent bond with very easily and combine, the carbon atom of a certain position on carbon quantum dot is replaced to arsenic atom, doping makes the electron figure of system increase as the donor, change electron cloud density and the local curvature of carbon quantum dot around the arsenic atom, make it have good electron mobility, and then improved quantum dot light emitting diode's electron transmission performance. The carbon quantum dots neutralize carbon atoms and arsenic atoms to form a hybrid pz orbit, so that the LUMO energy level of the carbon quantum dots is effectively reduced, and the arsenic-doped carbon quantum dots have lower LUMO energy levels and are adaptive to a conduction band of an oxide, thereby being beneficial to injection and transmission of electrons. The invention adopts a solution method to prepare the laminated structure, and has good film forming property and simple process. By adopting the laminated structure of the first layer and the second layer, the energy level matching between the metal oxide nano-particle/arsenic doped carbon quantum dot laminated structure is good, the electron transmission path and the electron transmission direction are stable, the electron transmission to the quantum dot luminous layer is facilitated, the luminous efficiency of the device is improved, and the QLED performance is improved.
In the above step S01, for the front-facing structure, the bottom electrode disposed on the substrate is an anode, and in some embodiments of the present invention, the anode substrate may be a substrate on which the bottom electrode and the quantum dot light emitting layer disposed on the surface of the bottom electrode are disposed; in still other embodiments of the present invention, the anode substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, a hole transport layer stacked on the surface of the substrate, and a quantum dot light emitting layer disposed on a surface of the hole transport layer; in still other embodiments of the present invention, the anode substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, a hole injection layer stacked on a surface of the substrate, a hole transport layer stacked on a surface of the hole injection layer, and a quantum dot light emitting layer disposed on a surface of the hole transport layer; in still other embodiments of the present invention, the anode substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, a hole injection layer stacked on a surface of the substrate, a hole transport layer stacked on a surface of the hole injection layer, an electron blocking layer stacked on a surface of the hole transport layer, and a quantum dot light emitting layer disposed on a surface of the electron blocking layer.
In the step S11, for the inverted structure, the bottom electrode disposed on the substrate is a cathode, and in some embodiments of the present invention, the substrate may be a substrate on which the bottom electrode is disposed; in still other embodiments of the present invention, the substrate may include a substrate, a bottom electrode stacked on a surface of the substrate; in still other embodiments of the present invention, the substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, and an electron injection layer stacked on the surface of the substrate.
In some embodiments, in step S03 or step S12, the metal salts are dissolved in an organic solvent and mixed under basic conditions to form a metal oxide precursor solution.
In some embodiments, the metal salt is one or more of a titanium salt, a zinc salt, a tin salt, and a zirconium salt, but is not limited thereto.
In some embodiments, the titanium salt is selected from a soluble inorganic titanium salt or an organic titanium salt, such as one or more of titanium acetate, titanium nitrate, titanium chloride, titanium sulfate, and titanium bromide, but not limited thereto. In some embodiments, the zinc salt is selected from soluble inorganic or organic zinc salts, such as, but not limited to, one or more of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate dihydrate. In some embodiments, the tin salt is selected from soluble inorganic or organic tin salts, such as, but not limited to, one or more of tin nitrate, tin chloride, tin sulfate, tin methane sulfonate, tin ethane sulfonate, and tin propane sulfonate. In some embodiments, the zirconium salt is selected from soluble inorganic or organic zirconium salts, such as, but not limited to, one or more of zirconium acetate, zirconium nitrate, zirconium chloride, and zirconium sulfate. In some embodiments, the organic solvent is selected from one or more of ethylene glycol methyl ether, propylene glycol methyl ether, isopropanol, ethanol, propanol, butanol, and acetone, but is not limited thereto.
In some embodiments, the metal salt is dissolved in the organic solvent at a metal salt concentration of 0.2M (mol/L) to 1M. According to the molar ratio of alkali liquor to metal ions (1.8-4.5): 1, continuously adding alkali, adjusting the pH value to 12-13, and mixing for 4-6 h at the temperature of 60-90 ℃. In some embodiments, the alkaline solution is selected from the group consisting of ammonia, potassium hydroxide, sodium hydroxide, lithium hydroxide, ethanolamine, ethylene glycol, diethanolamine, triethanolamine, and ethylenediamine, but is not limited thereto.
Formation of the hydroxide M (OH) by reaction of a metal salt with a basex，M(OH)xCondensation polymerization reaction is carried out, and MO is generated by dehydrationx. Therefore, the dosage of the alkali liquor is specifically adjusted according to the valence state of the metal ions. Such as when the metal ion is +2 (Zn)2+) The mol ratio of the alkali liquor to the metal ions is 2: 1, so that the molar ratio of the alkali liquor to the metal ions is kept between 1.8 and 2.5: 1, oxide nanoparticles can be generated. Such as when the metal ion is +4 (Ti)4+、Sn4+、Zr4+) The mol ratio of the alkali liquor to the metal ions is 4: 1, so that the molar ratio of the alkali liquor to the metal ions is kept between (3.5 and 4.5): 1, oxide nanoparticles can be generated. When the molar ratio of the alkali liquor to the metal ions is less than 1.8: 1 or 3.5: 1, pH<When 12 hours, alkali liquor is insufficient, metal salt is excessive, and reaction is insufficient; greater than 2.5: 1 or 4.5: 1, pH>At 13, too high a pH will result in a slow hydrolysis and polycondensation rate of the sol in the system. Optimally, the molar ratio of the alkali liquor to the metal ions is kept between 1.8 and 4.5: 1, compact and compact oxide film and surface particles of the film can be finally obtainedThe distribution is uniform.
In some embodiments, the second layer is obtained by annealing at 250-300 ℃ after depositing the metal oxide precursor solution on the substrate surface in order to remove the solvent and to make the metal oxide nanomaterial more crystalline.
In some embodiments, the first layer is formed to a thickness of 15 to 40nm by adjusting the amount of the metal oxide precursor.
In some embodiments, the carbon source and the arsenic source are mixed and heated in a solvent, washed, and separated to produce arsenic doped carbon quantum dots in step S02 or step S13. In some embodiments, the carbon source is an organic carboxylic acid containing an aromatic structure, such as phthalic acid, terephthalic acid, benzoic acid, salicylic acid, caffeic acid, and the like, but is not limited thereto. The carbon source adopts organic carboxylic acid with an aromatic structure, and the conjugated large pi bond in the aromatic ring has good electron transport capacity, so that the adoption of the raw material containing the aromatic structure is beneficial to improving the conductivity of the carbon quantum dot. In some specific embodiments, carbon quantum dots with small and uniform particle size can be prepared by mixing a carbon source and an arsenic source in a solvent according to a carbon source concentration of 0.5-2M. If the concentration of the carbon source reactant is less than 0.5M, the yield is low; if the concentration of the carbon source reactant is more than 2M, the solvothermal reaction is insufficient, and the carbonization degree is not thorough. In some embodiments, the arsenic source is arsenic acid (H)3AsO4) Meta-arsenic acid (HAsO)3) And the like are not limited thereto. In some specific embodiments, the organic solvent B is a high-boiling alkane such as 1-Octadecene (ODE), 1-hexadecene, 1-eicosene, etc. In some embodiments, the molar ratio of carbon to arsenic is 1: (0.01-0.1), when the doping amount of arsenic reaches a certain value (more than 0.1), the solid solubility of arsenic in the carbon quantum dots reaches saturation, and when the doping amount continues to increase, arsenic is concentrated on the surfaces of the carbon quantum dot crystal grains to form a new phase, so that the effective specific surface area of the nano carbon quantum dots is reduced; the increase of the doping amount causes the lattice to be mutated, and a new lattice is formed. When the doping amount of arsenic is too low, arsenic is lost in the reaction process, and effective doping cannot be realized; in thatIn some specific embodiments, the heating temperature is 60-90 ℃ and the time is 2-4 h.
In some embodiments, the annealing temperature is 100 ℃ to 120 ℃ after depositing arsenic doped carbon quantum dots on the substrate for better solvent removal.
In some embodiments, the first layer is formed to a thickness of 5 to 20nm by adjusting the amount of the arsenic-doped carbon quantum dots.
The present invention will be described in detail below with reference to examples.
Example one
The preparation of a titanium oxide/arsenic doped carbon quantum dot stack structure is described as an example.
An appropriate amount of titanium acetate was added to 50ml of ethanol to form a solution having a total concentration of 0.5M. Dissolve with stirring at 70 ℃. Adding a solution of potassium hydroxide dissolved in 10ml of ethanol (the molar ratio of potassium hydroxide to titanium ions is 3.5-4.5: 1, the pH value is 12), and continuing stirring at 70 ℃ for 4 hours to form a precursor solution A.
An appropriate amount of benzoic acid and n-arsenic acid was dissolved in 50ml of ODE to form a 1M solution (molar ratio, carbon: arsenic 1: 0.01-0.1). And transferring the solution to a polytetrafluoroethylene inner container, placing the polytetrafluoroethylene inner container in a reaction kettle, screwing the reaction kettle tightly, sealing, and placing the reaction kettle in a preheated oven, wherein the reaction temperature is 250 ℃ and the reaction time is 3 hours. After the reaction is finished, acetone is used for precipitation, cleaning and centrifugation are carried out, and the arsenic-doped carbon quantum dots are prepared and dispersed in normal hexane.
Finally, spin-coating the precursor solution A on the treated substrate by a spin coater and annealing at 250 ℃; and dripping the arsenic-doped carbon quantum dot solution onto a substrate, spin-coating at 150 ℃, and annealing to form a film to form a titanium oxide/arsenic-doped carbon quantum dot laminated structure.
Example two
The preparation of a zinc oxide/arsenic doped carbon quantum dot stack structure is described as an example.
An appropriate amount of zinc nitrate was added to 50ml of methanol to form a solution having a total concentration of 0.5M. Dissolved at 60 ℃ with stirring. Adding a solution of ethanolamine dissolved in 10ml of methanol (the molar ratio of ethanolamine to zinc ions is 3.5-4.5: 1, the pH value is 12), and continuing stirring at 60 ℃ for 4h to form a precursor solution A.
An appropriate amount of phthalic acid and meta-arsenic acid was dissolved in 50ml of 1-hexadecene to form a 1M solution (molar ratio, carbon: arsenic 1: 0.01 to 0.1). And transferring the solution to a polytetrafluoroethylene inner container, placing the polytetrafluoroethylene inner container in a reaction kettle, screwing the reaction kettle tightly, sealing, and placing the reaction kettle in a preheated oven, wherein the reaction temperature is 250 ℃ and the reaction time is 3 hours. After the reaction is finished, acetone is used for precipitation, cleaning and centrifugation are carried out, and the carbon quantum dots doped with arsenic are prepared and dispersed in n-octane.
Finally, spin-coating the precursor solution A on the treated substrate by a spin coater and annealing at 250 ℃; and dripping the arsenic-doped carbon quantum dot solution onto a substrate, spin-coating at 150 ℃ and annealing to form a film, thereby forming a zinc oxide/arsenic-doped carbon quantum dot laminated structure.
EXAMPLE III
The preparation of a tin oxide/arsenic doped carbon quantum dot stack structure is described as an example.
An appropriate amount of tin chloride was added to 50ml of ethylene glycol methyl ether to form a solution having a total concentration of 0.5M. Dissolved at 80 ℃ with stirring. Adding a solution of lithium hydroxide dissolved in 10ml of ethylene glycol monomethyl ether (the molar ratio of lithium hydroxide to tin ions is 3.5-4.5: 1, and the pH value is 12), and continuously stirring at 80 ℃ for 4 hours to form a precursor solution A.
An appropriate amount of terephthalic acid and n-arsenic acid were dissolved in 50ml of ODE to form a 1M solution (molar ratio, carbon: arsenic 1: 0.01-0.1). And transferring the solution to a polytetrafluoroethylene inner container, placing the polytetrafluoroethylene inner container in a reaction kettle, screwing the reaction kettle tightly, sealing, and placing the reaction kettle in a preheated oven, wherein the reaction temperature is 250 ℃ and the reaction time is 3 hours. After the reaction is finished, acetone is used for precipitation, cleaning and centrifugation are carried out, and the arsenic-doped carbon quantum dots are prepared and dispersed in n-decane.
Finally, spin-coating the precursor solution A on the treated substrate by a spin coater and annealing at 250 ℃; and dripping the arsenic-doped carbon quantum dot solution onto a substrate, spin-coating at 150 ℃, and annealing to form a film to form a tin oxide/arsenic-doped carbon quantum dot laminated structure.

Claims (10)

1. The quantum dot light-emitting diode comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, and is characterized by further comprising a first layer arranged between the cathode and the quantum dot light-emitting layer, wherein the material of the first layer comprises arsenic-doped carbon quantum dots.
2. The quantum dot light-emitting diode of claim 1, wherein the material of the first layer consists of arsenic doped carbon quantum dots and metal oxide nanoparticles.
3. The quantum dot light-emitting diode of claim 1, further comprising a second layer disposed on top of the first layer, the second layer disposed proximate to the cathode, the material of the second layer comprising metal oxide nanoparticles.
4. The qd-led of claim 3, wherein the material of the second layer is metal oxide nanoparticles and the material of the first layer is arsenic doped carbon quantum dots.
5. The qd-led of claim 3, wherein the thickness of the first layer is 5-20 nm; and/or the presence of a gas in the gas,
the thickness of the second layer is 15-40 nm.
6. The qd-led of any one of claims 3 to 5, wherein the metal oxide nanoparticles in the second layer are selected from ZnO, TiO and the like2、ZrO2And SnO2One or more of (a).
7. The qd-led of any one of claims 1 to 5, wherein the molar ratio of the arsenic element to the carbon element in the arsenic-doped carbon qd is (0.01-0.1): 1.
8. a preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
providing an anode substrate, wherein a quantum dot light-emitting layer is arranged on the surface of the anode substrate;
providing a solution containing arsenic-doped carbon quantum dots, depositing the solution containing arsenic-doped carbon quantum dots on the surface of the quantum dot light-emitting layer, and annealing to form a first layer;
depositing a metal oxide precursor salt solution on the surface of the first layer, and annealing to form a second layer; alternatively, providing a cathode substrate;
depositing a metal oxide precursor salt solution on the surface of the cathode substrate, and annealing to form a second layer; providing a solution containing arsenic-doped carbon quantum dots, depositing the solution containing arsenic-doped carbon quantum dots on the surface of the second layer, and annealing to form the first layer.
9. The method of claim 8, wherein the arsenic-doped carbon quantum dot is obtained by mixing a carbon source and an arsenic source in a first solvent and heating the mixture, wherein the carbon source is an organic carboxylic acid containing an aromatic structure.
10. The method according to claim 9, wherein the carbon source is one or more selected from the group consisting of phthalic acid, terephthalic acid, benzoic acid, salicylic acid, and caffeic acid; and/or, the first solvent is selected from one or more of 1-Octadecene (ODE), 1-hexadecene and 1-eicosene; and/or the presence of a gas in the gas,
and mixing a carbon source and an arsenic source in a first solvent, and heating at 60-90 ℃ to obtain the arsenic-doped carbon quantum dot.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102849724A (en) * 2012-10-12 2013-01-02 上海交通大学 Preparation method of water-soluble carbon quantum dots
CN103107287A (en) * 2013-02-19 2013-05-15 中国科学院理化技术研究所 Application of heteroatom-doped carbon quantum dots in solar cell
AU2018201157A1 (en) * 2018-02-16 2019-09-05 Brilliant Lighting (Aust) Pty Ltd A Fan

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102849724A (en) * 2012-10-12 2013-01-02 上海交通大学 Preparation method of water-soluble carbon quantum dots
CN103107287A (en) * 2013-02-19 2013-05-15 中国科学院理化技术研究所 Application of heteroatom-doped carbon quantum dots in solar cell
AU2018201157A1 (en) * 2018-02-16 2019-09-05 Brilliant Lighting (Aust) Pty Ltd A Fan

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