CN111490169B - Quantum dot light-emitting diode and preparation method thereof - Google Patents
Quantum dot light-emitting diode and preparation method thereof Download PDFInfo
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- CN111490169B CN111490169B CN201910074572.7A CN201910074572A CN111490169B CN 111490169 B CN111490169 B CN 111490169B CN 201910074572 A CN201910074572 A CN 201910074572A CN 111490169 B CN111490169 B CN 111490169B
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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]
- H10K50/11—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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- 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
- H10K50/166—Electron transporting layers comprising a multilayered structure
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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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
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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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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
- Led Devices (AREA)
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 [6,6] -phenyl-C61-butyrate combined on the surface of the quantum dot. The [6,6] -phenyl-C61-butyrate is modified on the surface of the carbon quantum dot, so that the electron mobility of the carbon quantum dot is improved, redundant holes can be effectively prevented from entering the carbon quantum dot layer, the carbon quantum dot layer is prevented from generating a fluorescence phenomenon, the carbon quantum dot layer is applied to a QLED device as an electron transport layer, and the electron transport rate of the QLED device can be improved.
Description
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, tiO 2 、MoO 3 Semiconductor 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 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 carbon quantum dots, and [6,6] -phenyl-C61-butyrate is combined on the surfaces of the carbon quantum dots.
The [6,6] -phenyl-C61-butyrate is modified on the surface of the carbon quantum dot, so that the electron mobility of the carbon quantum dot is improved, redundant holes can be effectively prevented from entering the carbon quantum dot layer, the carbon quantum dot layer is prevented from generating a fluorescence phenomenon, the carbon quantum dot layer is applied to a QLED device as an electron transport layer, and the electron transport rate of the QLED device can be improved.
A preparation method of a quantum dot light-emitting diode comprises the following steps:
providing a substrate and a carbon quantum dot solution, wherein [6,6] -phenyl-C61-butyrate is bound on the surface of the carbon quantum dot;
and depositing the carbon quantum dot solution on the surface of the substrate, and annealing to form a first layer.
The [6,6] -phenyl-C61-butyrate is modified on the surface of the carbon quantum dot, so that the electron mobility of the carbon quantum dot is improved, redundant holes can be effectively prevented from entering the carbon quantum dot layer, the carbon quantum dot layer is prevented from generating a fluorescence phenomenon, the carbon quantum dot layer is applied to a QLED device as an electron transport layer, and the electron transport rate of the QLED device can be improved. The first layer is prepared by a solution method, and the method has the advantages of simple process, good film forming property and good application prospect.
Drawings
Fig. 1 is a schematic structural diagram of a positive type structure device according to an embodiment of the present invention.
Detailed Description
The present invention provides a quantum dot light emitting diode and a method for manufacturing the same, and the present invention is further described in detail below in order to make the objects, technical solutions, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not 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 first layer comprising a carbon quantum dot having [6,6] -phenyl-C61-butyrate bonded to a surface of the carbon quantum dot.
The [6,6] -phenyl-C61-butyrate is modified on the surface of the carbon quantum dot, so that the electron mobility of the carbon quantum dot is improved, redundant holes can be effectively prevented from entering the carbon quantum dot layer, the carbon quantum dot layer is prevented from generating a fluorescence phenomenon, the carbon quantum dot layer is applied to a QLED device as an electron transport layer, and the electron transport rate of the QLED device can be improved.
In some embodiments, the material of the first layer consists of the carbon quantum dots and metal oxide nanoparticles. The conduction band of the oxide and the LUMO energy level matching performance of the carbon quantum dot modified by the [6,6] -phenyl-C61-butyrate are good, so that the injection and the transmission of electrons are facilitated.
In some embodiments, the quantum dot light emitting diode further comprises a stack disposed between the cathode and the quantum dot light emitting layer, the stack being disposed from a first layer and a second layer, the first layer comprising a material comprising [6,6] -phenyl-C61-butyrate-modified carbon quantum dots, the second layer comprising a material comprising metal oxide nanoparticles, the first layer disposed proximate to the quantum dot light emitting layer, the second layer disposed proximate to the cathode. By adopting the drop-in structure of the first layer and the second layer, the metal oxide nanoparticle/[ 6,6] -phenyl-C61-butyrate modified carbon quantum dot laminated structure has good energy level matching, and the electron transmission path and direction are stable, so that electrons can be transmitted to a quantum dot light-emitting layer, the light-emitting efficiency of a 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 abrupt change of the crystal lattice, and new crystal lattice is formed. When the doping amount of arsenic is too low, arsenic is lost during the reaction, and thus effective doping cannot be achieved. In some specific embodiments, the first layer has a thickness of 5 to 20nm; in some specific embodiments, the second layer has a thickness of 15 to 40nm.
Specifically, the quantum dot light emitting diode has a positive structure and an inversion 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 reflection 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 reflection 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.
In some embodiments, the obtained QLED is subjected to a packaging process, which may be performed by a common machine or by a manual method. Preferably, the oxygen content and the water content in the packaging treatment environment are both lower than 0.1 ppm 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 quantum dots with surfaces combined with [6,6] -phenyl-C61-butyrate, 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 a positive structure, wherein the method comprises the following steps:
s1, providing a substrate and a carbon quantum dot solution, wherein [6,6] -phenyl-C61-butyrate is bound to the surface of the carbon quantum dot;
s2, depositing the carbon quantum dot solution on the surface of the substrate, and annealing to form a first layer.
In the step S01, the substrate is determined according to the device structure (positive structure or negative structure).
For example, some embodiments of the present invention provide a method for preparing a positive-type quantum dot light emitting diode, 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;
or,
some embodiments of the present invention provide a method for preparing an inversion-structure 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 the surface of the second layer to form the first layer.
In the step S01, for the positive 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 a 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 inversion 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.
The [6,6] -phenyl-C61-butyrate is modified on the surface of the carbon quantum dot, so that the electron mobility of the carbon quantum dot is improved, redundant holes can be effectively prevented from entering the carbon quantum dot layer, the carbon quantum dot layer is prevented from generating a fluorescence phenomenon, the carbon quantum dot layer is applied to a QLED device as an electron transport layer, and the electron transport rate of the QLED device can be improved. The first layer is prepared by a solution method, and the method has the advantages of simple process, good film forming property and good application prospect.
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 an organic solvent at a metal salt concentration of 0.2M (mol/L) to 1M. The molar ratio of alkali liquor to metal ions is (1.8 to 4.5): 1, continuously adding alkali, adjusting the pH to be 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.
By reaction of metal salts with alkali liquors to give the hydroxides M (OH) x ，M(OH) x Condensation polymerization reaction is carried out, and MO is generated by dehydration x . So the dosage of the alkali liquor is adjusted according to the valence state of the metal ions. Such as when the metal ion is +2 (Zn) 2+ ) The molar 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 at (1.8 to 2.5): 1, oxide nanoparticles can be generated. Such as when the metal ion is +4 (Ti) 4+ 、Sn 4+ 、Zr 4+ ) The mol ratio of the alkali liquor to the metal ions is 4:1, keeping the molar ratio of the alkali liquor to the metal ions (3.5 to 4.5): 1, oxide nanoparticles can be generated. When the molar ratio of alkali liquor to metal ions is less than1.8:1 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>13. Too high a pH leads to a reduction in the hydrolysis and polycondensation rates 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, finally obtaining compact and dense oxide film with uniformly distributed particles on the surface of the film.
In some embodiments, in order to remove the solvent and make the metal oxide nano material more crystalline, the metal oxide precursor solution is deposited on the surface of the substrate, and then annealed at 250 ℃ to 300 ℃ to obtain the second layer.
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, in step S02 or step S13, a carbon source is dispersed in an organic solvent for solvothermal reaction, and the carbon quantum dots are prepared by washing and centrifuging. The oxygen-containing groups (such as carboxyl, carbonyl, hydroxyl, epoxy and the like) contained on the surface of the carbon quantum dot mainly retain the oxygen-containing groups mainly comprising hydroxyl after the solvothermal reaction. The hydroxyl bound on the surface of the carbon quantum dot can be subjected to esterification reaction with [6,6] -phenyl-C61-butyric acid to form [6,6] -phenyl-C61-butyric acid ester bound on the surface of the carbon quantum dot. 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 the adoption of the raw material containing the aromatic structure is beneficial to improving the conductivity of the carbon quantum dot. In some embodiments, the carbon source is dispersed in the organic solvent at a carbon source concentration of 0.5-2M, and the yield is low if the carbon source reactant concentration is less than 0.5M; 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 organic solvent is a high boiling point alkene such as 1-Octadecene (ODE), 1-hexadecene, 1-eicosene, and the like. In some embodiments, the temperature of the heating reaction is 60 ℃ to 90 ℃; the reaction time is 2 to 4 hours.
In some embodiments, PCBM ([ 6,6] -phenyl-C61-butanoate) is dispersed in an organic solvent, added to a base solution, and stirred at an elevated temperature to form a solution of PCBA ([ 6,6] -phenyl-C61-butanoate). The molar ratio of the alkali liquor to the PCBM is (1 to 1.5): 1; pH =12 to 13. The temperature is 60-90 ℃; stirring for 2h to 3 h. The molar ratio of the alkali liquor to the PCBM is (1 to 1.5): at 1, PCBM may be hydrolyzed to PCBA. When the molar ratio is small, the PCBM is excessive and can not be fully hydrolyzed into PCBA; when the molar ratio is too large, the alkali liquor is excessive, and the rate of the hydrolysis reaction is slowed down. Optimally, the molar ratio of the alkali liquor to the PCBM is kept to (1 to 1.5): 1.
in some embodiments, an alkaline PCBA-containing solution is mixed with carbon quantum dots and heated to produce quantum dots with surface-bound [6,6] -phenyl-C61-butyrate. The heating temperature is 60-90 ℃, and the time is 2-3 h. Mixing the PCBA solution and the carbon quantum dots according to the molar ratio of the PCBA to the carbon quantum dots of 1 to 2: 1.
In some embodiments, for better solvent removal, the annealing temperature is 100 ℃ to 120 ℃ after arsenic doped carbon quantum dots are deposited on the substrate.
In some embodiments, the first layer with the thickness of 5 to 20nm is formed by adjusting the dosage 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 carbon quantum dot layered structure of titanium oxide/surface-bound [6,6] -phenyl-C61-butyrate will be described as an example.
An appropriate amount of titanium acetate was added to 50 ml of ethanol to form a solution having a total concentration of 0.5M. Dissolved at 70 ℃ with stirring. Adding a solution of potassium hydroxide dissolved in 10ml of ethanol (molar ratio of potassium hydroxide to titanium ions is 3.5-4.5: 1, pH = 12), and continuing stirring at 70 ℃ for 4 h to form an oxide solution.
An appropriate amount of benzoic acid was dissolved in 50 ml of ODE to form a 1M solution. And transferring the solution to a polytetrafluoroethylene inner container, placing the inner container in a reaction kettle, screwing the reaction kettle tightly, sealing the reaction kettle, 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 are prepared and dispersed in normal hexane.
Dispersing a proper amount of PCBM into 10ml of ethanol, adding a solution of potassium hydroxide dissolved in 10ml of ethanol (the molar ratio of sodium hydroxide to PCBM is 1-1.5: 1, and the pH is = 12), and stirring at 70 ℃ for 2h to form a PCBA solution.
And (2) uniformly mixing the carbon quantum dot solution and the PCBA solution (the molar ratio is PCBA: carbon quantum dot =1 to 2: 1), and continuously stirring for 2 hours at 70 ℃ to form a [6,6] -phenyl-C61-butyrate modified carbon quantum dot solution.
Finally, spin-coating the oxide solution on the treated substrate by a spin coater and annealing at 250 ℃; and dripping the [6,6] -phenyl-C61-butyrate modified carbon quantum dot solution on a substrate, spin-coating at 150 ℃, and annealing to form a film, thereby forming a titanium oxide/[ 6,6] -phenyl-C61-butyrate modified carbon quantum dot laminated structure.
Example two:
the preparation of a carbon quantum dot layered structure of zinc oxide/surface bound [6,6] -phenyl-C61-butyrate is described as an example.
An appropriate amount of zinc nitrate was added to 50 ml of methanol to form a solution having a total concentration of 0.5M. Dissolved at 60 ℃ with stirring. A solution of ethanolamine dissolved in 10ml of methanol (molar ratio of ethanolamine to zinc ion: 3.5-4.5: 1, pH = 12) was added, and stirring was continued at 60 ℃ for 4 hours to form an oxide solution.
An appropriate amount of phthalic acid was dissolved in 50 ml of 1-hexadecene to form a 1M solution. 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 carbon quantum dots are prepared and dispersed in n-octane.
Dispersing appropriate amount of PCBM in 10ml of methanol, adding solution of ethanolamine dissolved in 10ml of methanol (molar ratio of ethanolamine to PCBM is 1-1.5: 1, pH = 12), and stirring at 60 deg.C for 2h to obtain PCBA solution.
And (2) uniformly mixing the carbon quantum dot solution and the PCBA solution (the molar ratio is PCBA: carbon quantum dot =1 to 2: 1), and continuously stirring for 2 hours at 60 ℃ to form a [6,6] -phenyl-C61-butyrate modified carbon quantum dot solution.
Finally, spin-coating the oxide solution on the treated substrate by a spin coater and annealing at 250 ℃; and dripping the [6,6] -phenyl-C61-butyrate modified carbon quantum dot solution on a substrate, spin-coating at 150 ℃, and annealing to form a film, thereby forming a zinc oxide/[ 6,6] -phenyl-C61-butyrate modified carbon quantum dot laminated structure.
Example three:
the preparation of a carbon quantum dot stack structure with tin oxide/surface bound [6,6] -phenyl-C61-butyrate is described as an example.
An appropriate amount of tin chloride was added to 50 ml 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 (molar ratio of lithium hydroxide to tin ions is 3.5-4.5: 1, pH = 12), and stirring at 80 ℃ for 4 hours to form an oxide solution.
An appropriate amount of terephthalic acid was dissolved in 50 ml of 1-eicosene to form a 1M solution. 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 carbon quantum dots are prepared and dispersed in n-decane.
Dispersing a proper amount of PCBM into 10ml of ethylene glycol monomethyl ether, adding a solution of lithium hydroxide dissolved in 10ml of ethylene glycol monomethyl ether (the molar ratio of the lithium hydroxide to the PCBM is 1-1.5: 1, and the pH is = 12), and stirring at 80 ℃ for 2h to form a PCBA solution.
And (2) uniformly mixing the carbon quantum dot solution and the PCBA solution (the molar ratio is PCBA: carbon quantum dot =1 to 2: 1), and continuously stirring for 2 hours at 80 ℃ to form a [6,6] -phenyl-C61-butyrate modified carbon quantum dot solution.
Finally, spin-coating the oxide solution on the treated substrate by a spin coater and annealing at 250 ℃; and dripping the [6,6] -phenyl-C61-butyrate modified carbon quantum dot solution onto a substrate, spin-coating at 150 ℃, and annealing to form a film, thereby forming a tin oxide/[ 6,6] -phenyl-C61-butyrate modified carbon quantum dot laminated structure.
Claims (12)
1. 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 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 carbon quantum dots, and [6,6] -phenyl-C61-butyrate is combined on the surfaces of the carbon quantum dots; the carbon quantum dot with the [6,6] -phenyl-C61-butyrate bound on the surface is prepared by the esterification reaction of the carbon quantum dot with the hydroxyl bound on the surface and the [6,6] -phenyl-C61-butyric acid.
2. The quantum dot light-emitting diode of claim 1, wherein the material of the first layer consists of the carbon quantum dots and metal oxide nanoparticles.
3. The quantum dot light emitting diode of claim 1, further comprising a stack of layers disposed between a cathode and a quantum dot light emitting layer, the stack of layers being disposed from a first layer and a second layer, the material of the first layer comprising the carbon quantum dots, the material of the second layer comprising metal oxide nanoparticles, the first layer disposed proximate the quantum dot light emitting layer, the second layer disposed proximate the cathode.
4. The qd-led of claim 3, wherein the material of the first layer is the carbon qds and the material of the second layer is metal oxide nanoparticles.
5. The qd-led of claim 3, wherein the thickness of the first layer is 5-20nm; and/or the presence of a gas in the gas,
the thickness of the second layer is 15-40nm.
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 like 2 、ZrO 2 And SnO 2 One or more of (a).
7. A preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
providing a substrate and a carbon quantum dot solution, wherein [6,6] -phenyl-C61-butyrate is bound on the surface of the carbon quantum dot;
depositing the carbon quantum dot solution on the surface of the substrate, and annealing to form a first layer; the carbon quantum dot with the [6,6] -phenyl-C61-butyrate bound on the surface is prepared by carrying out esterification reaction on the carbon quantum dot with the hydroxyl bound on the surface and the [6,6] -phenyl-C61-butyric acid; the quantum dot light emitting diode further comprises a cathode and a quantum dot light emitting layer, and the first layer is arranged between the cathode and the quantum dot light emitting layer.
8. The method of claim 7, comprising the steps of:
providing an anode substrate, wherein a quantum dot light-emitting layer is arranged on the surface of the anode substrate;
providing a solution of carbon quantum dots, wherein [6,6] -phenyl-C61-butyrate is combined on the surface of the carbon quantum dots, depositing the solution 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; or,
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 carbon quantum dots, wherein [6,6] -phenyl-C61-butyrate is combined on the surface of the carbon quantum dots, depositing the solution of the carbon quantum dots on the surface of a second layer, and annealing to form a first layer.
9. The method according to claim 8, wherein the carbon quantum dot having the hydroxyl group bound to the surface thereof is prepared by providing a carbon quantum dot having a hydroxyl group bound to the surface thereof, mixing [6,6] -phenyl-C61-butyric acid with the carbon quantum dot, and heating the mixture under alkaline conditions.
10. The production method according to claim 9,
the heating is carried out at 60-90 ℃.
11. The method for preparing the carbon quantum dots according to claim 9, wherein the method for preparing the carbon quantum dots comprises the steps of:
and dispersing a carbon source in a first solvent, and carrying out solvothermal reaction to obtain the carbon quantum dot.
12. The method according to claim 11, 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 presence of a gas in the gas,
the first solvent is selected from one or more of 1-Octadecene (ODE), 1-hexadecene and 1-eicosene.
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