CN118215319A - High-performance quantum dot light emitting diode and preparation method thereof - Google Patents
High-performance quantum dot light emitting diode and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 claims abstract description 19
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
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- 239000002244 precipitate Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000005525 hole transport Effects 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
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- 239000000047 product Substances 0.000 claims description 14
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 8
- 229920000767 polyaniline Polymers 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000003573 thiols Chemical class 0.000 claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 5
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 7
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- 238000009776 industrial production Methods 0.000 abstract 1
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- 238000010586 diagram Methods 0.000 description 3
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- 230000005540 biological transmission Effects 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
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- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to the technical field of diode preparation, and in particular provides a high-performance quantum dot light emitting diode and a preparation method thereof. According to the invention, the thiol is utilized to modify the covalent organic framework material, the halogen perovskite quantum dots are grown in situ in the material, so that the environmental stability of the halogen perovskite quantum dots is effectively improved, and the quantum dot light emitting diode prepared by using the material is excellent in photoelectric property, simple in preparation method and beneficial to large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of diode preparation, in particular to a high-performance quantum dot light emitting diode and a preparation method thereof.
Background
Light Emitting Diodes (LEDs) are a type of solid state light source widely used in the display and lighting arts, and their principle of operation is based on the electroluminescent effect, i.e. when a current is passed through a semiconductor material, electrons recombine with holes to produce light. LED technology is favored because of its energy efficiency, long life, and environmental characteristics. In recent years, conventional semiconductor materials such as gallium arsenide have been widely used for manufacturing LEDs, but these materials have limitations in terms of optical color purity and color tunable range.
In recent years, halogen perovskite quantum dots are becoming a hot research material in the field of light emitting diodes due to their excellent photoelectric properties. The material has the characteristics of high light efficiency and wide band gap regulation and control, and can realize wide wavelength coverage from ultraviolet to infrared. In particular in QLED (quantum dot light emitting diode) applications, the halogen perovskite quantum dots exhibit a broader chromatographic coverage and a higher brightness than conventional quantum dots. However, halogen perovskite quantum dots still face some technical challenges in LED applications. The main disadvantages of the halogen perovskite quantum dot are environmental stability and large-scale synthesis problems, and the halogen perovskite quantum dot is easy to degrade under the influence of environmental factors such as humidity, oxygen, illumination and the like, so that the application life of the halogen perovskite quantum dot in the outdoor or high-humidity environment is limited. In addition, halogen perovskite materials may contain toxic elements such as lead, which may constitute a potential risk to the environment and human health.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides a high-performance quantum dot light-emitting diode and a preparation method thereof, wherein halogen perovskite quantum dots are generated in situ in a mercaptan modified covalent organic framework material, so that the environmental stability of the halogen perovskite quantum dots is improved, and the halogen perovskite quantum dots are used as a light-emitting layer to prepare the light-emitting diode with excellent light-emitting performance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a high-performance quantum dot light emitting diode which comprises an anode, a hole transport layer, a perovskite quantum dot light emitting layer, an electron transport layer and a cathode which are sequentially stacked, wherein the perovskite quantum dot light emitting layer is made of one or more PQDs@COFs.
Preferably, the anode is any one of indium tin oxide and fluorine doped tin oxide.
Preferably, the cathode is any one of aluminum and silver.
Preferably, the hole transport layer is made of poly (3, 4-ethylenedioxythiophene) polyaniline hydrochloride.
Preferably, the electron transport layer is any one of ZnO and TiO 2、SnO2.
Preferably, the PQDs@COFs are prepared by in-situ generation of halogen perovskite quantum dots by covalent organic framework materials, and the preparation method comprises the following steps:
① . Vinyl COFs synthesis: adding 0.08 mmoL of 1,3, 5-tris (4-aminophenyl) benzene and 0.12 mmoL of 2, 5-divinyl-1, 4-phthalaldehyde into a centrifuge tube of 50mL, adding 10mL acetonitrile, carrying out ultrasonic treatment for 5-10 min, continuously adding 1mL concentration of acetic acid solution of 12 mol/L, shaking vigorously on a vortex mixer for 10 s, standing for 3 d, centrifuging at 10000-12000 rpm to separate precipitate, washing with tetrahydrofuran and ethanol for three times alternately, and drying at 60 ℃ in a vacuum drying oven for 12g to obtain vinyl COFs;
② . Thiol modification COFs: weighing 200 mg parts of vinyl COFs prepared in step ①, placing the vinyl COFs in a Schlenk tube, adding 4 mL DMF parts under the protection of nitrogen, continuously adding 0.5-0.6 mL of 0.1 mol/L of 4-thiobenzoic acid DMF solution, adding 10mg benzophenone as a photoinitiator, placing the Schlenk tube under a 365 nm UV lamp, irradiating for 24 hours, maintaining the temperature at room temperature, centrifuging at 10000-12000 rpm after the reaction is finished, separating out a product, washing the product with acetone three times, and placing the product in a vacuum drying oven at 60 ℃ for drying 12 g to obtain thiol-modified COFs;
③ . Pqds@cofs synthesis: and (3) weighing 200 mg of thiol-modified COFs prepared in step ②, dispersing in 10mL DMF, adding 0.1 mmoL PbX 2, 200W of ultrasonic dispersion 10min, magnetically stirring at 300-400 rpm at room temperature for 6h, centrifugally collecting precipitate at 8000 rpm, redispersing in 4 mL dichloromethane, adding 0.2 mL of ethanol solution containing 0.1 mmoL CsX under the condition of magnetically stirring at 400-500 rpm at room temperature, stirring for 6-10 h, centrifugally separating precipitate at 10000-12000 rpm after the reaction is completed, washing the precipitate three times by using DMF, and drying 12 g at 60 ℃ in a vacuum drying oven to obtain PQDs@COFs.
Preferably, in the step ③, X of PbX 2 and CsX is any one of Cl, br, and I.
The invention also provides a preparation method of the high-performance quantum dot light emitting diode, which specifically comprises the following steps:
s1, dissolving poly (3, 4-ethylenedioxythiophene) polyaniline hydrochloride in water to obtain a concentration of 1.5-1.8wt%, and forming a hole transport layer with a thickness of 30-50 nm on the surface of an anode by a spraying technology;
S2, dispersing one or more PQDs@COFs prepared in the step S1 in methylene dichloride with the concentration of 50 mg/100 mL, and spin-coating to form a perovskite quantum dot luminescent layer with the thickness of 10-20 nm on the surface of the hole transport layer prepared in the step S1;
S3, selecting one of ZnO, tiO 2 or SnO 2, dispersing in water with the concentration of 60 mg/100 mL, and spin-coating on the surface of the perovskite quantum dot luminescent layer prepared in the step S2 to form an electron transport layer with the thickness of 20-40 nm;
S4, depositing aluminum or silver on the electron transport layer manufactured in the step S3 in a thermal evaporation or sputtering mode to form a cathode of 30-50 nm, namely synthesizing the high-performance quantum dot light-emitting diode.
The beneficial effects obtained by the invention are as follows:
the high-performance quantum dot light-emitting diode adopts the halogen perovskite quantum dot as a light-emitting layer material, has remarkable light efficiency and color purity, can cover broadband wavelengths from ultraviolet to infrared, and realizes wider color display. The thiol modified Covalent Organic Framework (COFs) is adopted to stabilize the halogen perovskite quantum dot, so that the environmental stability under high humidity and high oxidation environment is obviously improved, the service life is prolonged, and the halogen perovskite quantum dot is suitable for outdoor or high humidity environment application. Meanwhile, the preparation process is simple, the danger of high-temperature hot injection is avoided, the use of harmful substances is reduced, and the potential risks to the environment and human health are reduced. The invention also ensures the consistency of the highly controllable production process and the product quality through the detailed preparation method, so that the invention is suitable for various applications such as high definition display screens, high-efficiency illumination, advanced photoelectric equipment and the like.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only of the invention and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a quantum dot light emitting diode according to examples 1 to 3 and comparative example 1 of the present invention;
FIG. 2 is a transmission electron micrograph of PQDs@COFs prepared in example 1;
FIG. 3 is a graph showing fluorescence stability of PQDs@COFs prepared in examples 1-3 and PQDs prepared in comparative example 1;
FIG. 4 is an electroluminescent diagram of the Quantum dot light emitting diode prepared in examples 1-3;
Fig. 5 is a voltage-current-luminance curve of the quantum dot light emitting diode prepared in example 1.
Description of the reference numerals: 1. anode 2, hole transport layer 3, perovskite quantum dot luminescent layer 4, electron transport layer 5, cathode.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples, but the present invention is not limited to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Unless otherwise specified, the chemical reagents involved in the present invention are all commercially available.
Example 1: the embodiment provides a high-performance quantum dot light emitting diode, the structure of which is shown in fig. 1, and the quantum dot light emitting diode comprises an anode 1, a hole transport layer 2, a perovskite quantum dot light emitting layer 3, an electron transport layer 4 and a cathode 5 which are sequentially stacked.
The PQDs@COFs is prepared by generating halogen perovskite quantum dots in situ by a covalent organic framework material, and the preparation method comprises the following steps:
① . Vinyl COFs synthesis: adding 0.08 mmoL of 1,3, 5-tris (4-aminophenyl) benzene and 0.12 of mmoL of 2, 5-divinyl-1, 4-phthalaldehyde into a centrifuge tube of 50mL, adding 10mL of acetonitrile, performing ultrasonic treatment on 5 min by 200W, continuing to add acetic acid solution with the concentration of 12 mol/L of 1mL, shaking 10 s vigorously on a vortex mixer, standing 3d, centrifuging to separate precipitate by 100000 rpm, washing three times alternately by using tetrahydrofuran and ethanol, and drying 12 g at 60 ℃ in a vacuum drying oven to obtain vinyl COFs;
② . Thiol modification COFs: weighing 200mg vinyl COFs prepared in step ①, placing the vinyl COFs in a Schlenk tube, adding 4 mL DMF under the protection of nitrogen, continuously adding 0.5 mL of 0.1 mol/L of 4-thiobenzoic acid DMF solution, adding 10mg benzophenone as a photoinitiator, placing the Schlenk tube under a 365 nm UV lamp, irradiating for 24 hours, maintaining the temperature at room temperature, centrifuging the reaction product through 10000 rpm, washing the product three times by using acetone, and drying the product in a vacuum drying oven at 60 ℃ for 12 g to obtain the thiol-modified COFs;
③ . Pqds@cofs synthesis: 200. 200mg of thiol-modified COFs prepared in step ② are weighed and dispersed in 10mL DMF, 0.1 mmoL PbBr 2 is added, 200W of ultrasonic dispersion is carried out for 10min, 300-rpm is magnetically stirred at room temperature for 6h, 8000 rpm is used for centrifugally collecting precipitate and redispersing the precipitate in 4-mL dichloromethane, 0.2-mL of ethanol solution containing 0.1-mmoL CsBr is added under the condition of continuously 400-rpm magnetic stirring at room temperature, 6-h is stirred, precipitate is separated through 10000-rpm centrifugation after the reaction is completed, the precipitate is washed three times by DMF, and the precipitate is placed in a vacuum drying oven at 60 ℃ for drying 12-g, thus obtaining PQDs@COFs.
The embodiment also provides a preparation method of the high-performance quantum dot light emitting diode, which specifically comprises the following steps:
S1, dissolving poly (3, 4-ethylenedioxythiophene) polyaniline hydrochloride in water to obtain a concentration of 1.5wt%, and forming a 30 nm-thick hole transport layer 2 on the surface of an indium tin oxide anode 1 by a spraying technology;
s2, dispersing PQDs@COFs in dichloromethane with the concentration of 50 mg/100 mL, and spin-coating the surface of the hole transport layer 2 prepared in the step S1 to form a perovskite quantum dot luminescent layer 3 with the thickness of 10 nm;
S3, znO is selected to be dispersed in water, the concentration is 60 mg/100 mL, and the surface of the perovskite quantum dot luminescent layer 3 manufactured in the step S2 is spin-coated to form an electron transport layer 4 with the thickness of 20 nm;
S4, depositing aluminum on the electron transport layer 4 prepared in the step S3 through thermal evaporation to form a cathode 5 of 30-50 nm, namely the high-performance quantum dot light-emitting diode is synthesized.
Example 2: the embodiment provides a high-performance quantum dot light emitting diode, which comprises an anode 1, a hole transport layer 2, a perovskite quantum dot light emitting layer 3, an electron transport layer 4 and a cathode 5 which are sequentially stacked.
The PQDs@COFs is prepared by generating halogen perovskite quantum dots in situ by a covalent organic framework material, and the preparation method comprises the following steps:
① . Vinyl COFs synthesis: adding 0.08mmoL of 1,3, 5-tris (4-aminophenyl) benzene and 0.12 mmoL of 2, 5-divinyl-1, 4-phthalaldehyde into a centrifuge tube of 50 mL, adding 10mL of acetonitrile, performing ultrasonic treatment on the mixture by 200W of 8 min, continuing to add acetic acid solution with the concentration of 12 mol/L of 1 mL, shaking the mixture vigorously on a vortex mixer for 10 s, standing the mixture for 3 d, centrifuging the mixture by 12000 rpm to separate precipitate, washing the precipitate by using tetrahydrofuran and ethanol for three times alternately, and drying the precipitate in a vacuum drying oven at 60 ℃ for 12 g to obtain vinyl COFs;
② . Thiol modification COFs: weighing 200 mg vinyl COFs prepared in step ①, placing the vinyl COFs in a Schlenk tube, adding 4 mL DMF under the protection of nitrogen, continuously adding 0.6 mL of 0.1 mol/L of 4-thiobenzoic acid DMF solution, adding 10 mg benzophenone as a photoinitiator, placing the Schlenk tube under a 365 nm UV lamp, irradiating for 24 hours, maintaining the temperature at room temperature, centrifuging the reaction product through 12000 rpm, washing the product three times by using acetone, and drying the product in a vacuum drying oven at 60 ℃ for 12 g to obtain the thiol-modified COFs;
③ . Pqds@cofs synthesis: 200 mg of thiol-modified COFs prepared in step ② was weighed and dispersed in 10 mL DMF, 0.1 mmoL PbI 2 was added, 200W of ultrasonic dispersion was conducted for 10 min, the precipitate was collected by centrifugation at 400 and rpm at room temperature for 6h, 8000 rpm and redispersed in 4 mL dichloromethane, 0.2 mL of ethanol solution containing 0.1 and mmoL CsI was added under continuous 500rpm magnetic stirring at room temperature, 8h was stirred, the precipitate was separated by centrifugation through 12000 rpm after completion of the reaction, the precipitate was washed three times with DMF, and 12 g was dried at 60℃in a vacuum oven to obtain PQDs@COFs.
The embodiment also provides a preparation method of the high-performance quantum dot light emitting diode, which specifically comprises the following steps:
S1, dissolving poly (3, 4-ethylenedioxythiophene) polyaniline hydrochloride in water to obtain a concentration of 1.8wt%, and forming a hole transport layer 2 with a thickness of 40 nm on the surface of a fluorine-doped tin oxide anode 1 by a spraying technology;
S2, dispersing PQDs@COFs in dichloromethane with the concentration of 50 mg/100 mL, and spin-coating the surface of the hole transport layer 2 prepared in the step S1 to form a perovskite quantum dot luminescent layer 3 with the thickness of 20 nm;
s3, tiO 2 is selected to be dispersed in water, the concentration is 60 mg/100 mL, and the perovskite quantum dot luminescent layer 3 prepared in the step S2 is spin-coated on the surface to form an electron transport layer 4 with the thickness of 30 nm;
And S4, depositing silver on the electron transport layer 4 prepared in the step S3 by sputtering to form a cathode 5 of 40 nm, namely synthesizing the high-performance quantum dot light-emitting diode.
Example 3: the embodiment provides a high-performance quantum dot light emitting diode, which comprises an anode 1, a hole transport layer 2, a perovskite quantum dot light emitting layer 3, an electron transport layer 4 and a cathode 5 which are sequentially stacked.
The PQDs@COFs is prepared by generating halogen perovskite quantum dots in situ by a covalent organic framework material, and the preparation method comprises the following steps:
① . Vinyl COFs synthesis: adding 0.08 mmoL of 1,3, 5-tris (4-aminophenyl) benzene and 0.12 mmoL of 2, 5-divinyl-1, 4-phthalaldehyde into a centrifuge tube of 50mL, adding 10mL of acetonitrile, performing ultrasonic treatment on 10min by 200W, continuing to add acetic acid solution with the concentration of 12 mol/L of 1mL, shaking 10 s vigorously on a vortex mixer, standing 3d, centrifuging to separate precipitate by 11000 rpm, washing three times alternately by using tetrahydrofuran and ethanol, and drying 12 g at 60 ℃ in a vacuum drying oven to obtain vinyl COFs;
② . Thiol modification COFs: weighing 200 mg vinyl COFs prepared in step ①, placing the vinyl COFs in a Schlenk tube, adding 4 mL DMF under the protection of nitrogen, continuously adding 0.5mL of 0.1 mol/L of 4-thiobenzoic acid DMF solution, adding 10 mg benzophenone as a photoinitiator, placing the Schlenk tube under a 365 nm UV lamp, irradiating for 24 hours, maintaining the temperature at room temperature, centrifuging 11000 rpm after the reaction is finished, separating out a product, washing the product three times by using acetone, and drying the product in a vacuum drying oven at 60 ℃ for 12 g to obtain the thiol-modified COFs;
③ . Pqds@cofs synthesis: 200 mg of thiol-modified COFs prepared in step ② is weighed and dispersed in 10 mL DMF, 0.1 mmoL PbCl 2 of 200W of ultrasonic dispersion 10 min is added, 350-rpm of magnetic stirring is carried out at room temperature for 6 h,8000 rpm of centrifugation is carried out to collect precipitate, the precipitate is redispersed in 4-mL of dichloromethane, 0.2-mL of ethanol solution containing 0.1-mmoL CsCl is added under the condition of continuous 400-500 rpm of magnetic stirring at room temperature, 10 h of stirring is carried out, after the reaction is completed, the precipitate is separated through 11000-rpm centrifugation, DMF is used for cleaning the precipitate three times, and the precipitate is placed in a vacuum drying box at 60 ℃ to be dried for 12 g, thus obtaining PQDs@COFs.
The embodiment also provides a preparation method of the high-performance quantum dot light emitting diode, which specifically comprises the following steps:
S1, dissolving poly (3, 4-ethylenedioxythiophene) polyaniline hydrochloride in water to obtain a concentration of 1.6wt%, and forming a 50 nm-thick hole transport layer 2 on the surface of an indium tin oxide anode 1 by a spraying technology;
S2, dispersing PQDs@COFs in dichloromethane with the concentration of 50 mg/100 mL, and spin-coating the surface of the hole transport layer 2 prepared in the step S1 to form a perovskite quantum dot luminescent layer 3 with the thickness of 15 nm;
S3, snO 2 is selected to be dispersed in water, the concentration is 60 mg/100 mL, and the surface of the perovskite quantum dot luminescent layer 3 prepared in the step S2 is spin-coated to form an electron transport layer 4 with the thickness of 40 nm;
And S4, silver is deposited on the electron transport layer 4 prepared in the step S3 in a thermal evaporation or sputtering mode to form the cathode 5 of 50 nm, namely the high-performance quantum dot light-emitting diode is synthesized.
Comparative example 1: this comparative example proposes a high performance quantum dot light emitting diode which differs from example 1 only in that no thiol is added to modify COFs, and the remaining components, component contents, experimental procedure are the same as example 1. The quantum dot light emitting diode comprises an anode 1, a hole transport layer 2, a perovskite quantum dot light emitting layer 3, an electron transport layer 4 and a cathode 5 which are sequentially stacked.
PQDs is a method for generating halogen perovskite quantum dots by supersaturation precipitation, and the preparation method comprises the following steps:
① . PQDs synthesis: 0.1 mmoL PbBr 2 is added to 10mL DMF, 10min is dispersed by 200W ultrasonic, 300 rpm is stirred magnetically at room temperature for 6 hours, sediment is collected by centrifugation at 8000 rpm and redispersed in 4 mL dichloromethane, 0.2 mL ethanol solution containing 0.1 mmoL CsBr is added under the condition of continuous 400 rpm magnetic stirring at room temperature, 6 h is stirred, sediment is separated by centrifugation through 10000 rpm after the reaction is completed, the sediment is washed three times by DMF, and the sediment is placed in a vacuum drying oven and dried at 60 ℃ for 12 g to obtain PQDs.
The comparative example also provides a preparation method of the high-performance quantum dot light emitting diode, which specifically comprises the following steps:
S1, dissolving poly (3, 4-ethylenedioxythiophene) polyaniline hydrochloride in water to obtain a concentration of 1.5wt%, and forming a 30 nm-thick hole transport layer 2 on the surface of an indium tin oxide anode 1 by a spraying technology;
s2, dispersing PQDs in dichloromethane with the concentration of 50 mg/100 mL, and spin-coating the surface of the hole transport layer 2 prepared in the step S1 to form a perovskite quantum dot luminescent layer 3 with the thickness of 10 nm;
S3, znO is selected to be dispersed in water, the concentration is 60 mg/100 mL, and the surface of the perovskite quantum dot luminescent layer 3 manufactured in the step S2 is spin-coated to form an electron transport layer 4 with the thickness of 20 nm;
S4, depositing aluminum on the electron transport layer 4 prepared in the step S3 through thermal evaporation to form a cathode 5 of 30-50 nm, namely the high-performance quantum dot light-emitting diode is synthesized.
Experimental example 1: the PQDs@COFs micro-morphology prepared in example 1 was observed using a transmission electron microscope.
FIG. 2 is a transmission electron microscope image of PQDs@COFs prepared in example 1, wherein PQDs is uniformly dispersed in a COFs material, the particle size of PQDs is about 8 nm, the COFs material can effectively improve the environmental stability of PQDs, and meanwhile, the excellent luminous performance of PQDs can be maintained.
Experimental example 2: the PQDs@COFs prepared in examples 1 to 3 and PQDs prepared in comparative example 1 were dispersed in water, respectively, and 100 mg/L of quantum dot solution was prepared, and the fluorescence intensity of the solution was recorded every 5 days.
FIG. 3 is a graph showing the fluorescence stability profiles of PQDs@COFs prepared in examples 1-3 and PQDs prepared in comparative example 1. As shown in the graph, PQDs@COFs prepared in examples 1-3 have higher stability in water and lower fluorescence intensity, while PQDs prepared in comparative example 1 is rapidly decomposed in water and has lower stability, which indicates that the structural stability of the perovskite quantum dots can be effectively improved by encapsulating the halogen perovskite quantum dots by thiol-modified covalent organic framework materials.
Experimental example 3: the electroluminescent patterns of the quantum dot light emitting diodes prepared in examples 1 to 3 were tested.
Fig. 4 is an electroluminescent diagram of the qd led prepared in examples 1 to 3, in which the CsPbI 3 PQDs-based qd led prepared in example 1 emits green light, the CsPbI 3 PQDs-based qd led prepared in example 2 emits red light, the CsPbCl 3 PQDs-based qd led prepared in example 1 emits blue-violet light, and the half-width is narrow and the optical properties are excellent.
Experimental example 4: the voltage-current-luminance curve of the quantum dot light emitting diode prepared in example 1 was tested.
Fig. 5 is a voltage-current-brightness curve of the quantum dot light emitting diode prepared in example 1, and as shown in the figure, the light emitting diode has a low turn-on voltage of 3.4V, the light emitting intensity and current increase with increasing voltage, and can emit higher light emitting intensity at higher voltage of 8.8V, and has excellent light emitting performance.
The invention and its embodiments have been described above without limitation, and the practical application is not limited thereto. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (8)
1. The high-performance quantum dot light-emitting diode is characterized by comprising an anode, a hole transport layer, a perovskite quantum dot light-emitting layer, an electron transport layer and a cathode which are sequentially stacked, wherein the perovskite quantum dot light-emitting layer is made of one or more PQDs@COFs.
2. The high performance qd led of claim 1, wherein said anode is any one of indium tin oxide and fluorine doped tin oxide.
3. The high performance qd led of claim 2, wherein said cathode is any one of aluminum and silver.
4. A high performance qd-led as recited in claim 3 wherein said hole transport layer is poly (3, 4-ethylenedioxythiophene) polyaniline hydrochloride.
5. The high performance quantum dot light emitting diode of claim 4, wherein the electron transport layer is any one of ZnO, tiO 2、SnO2.
6. The high performance quantum dot light emitting diode of claim 5, wherein the pqds@cofs is prepared by in situ generating halogen perovskite quantum dots from covalent organic framework materials, and the preparation method comprises the following steps:
① . Vinyl COFs synthesis: adding 0.08 mmoL of 1,3, 5-tris (4-aminophenyl) benzene and 0.12 mmoL of 2, 5-divinyl-1, 4-phthalaldehyde into a centrifuge tube of 50mL, adding 10mL acetonitrile, carrying out ultrasonic treatment for 5-10 min, continuously adding 1mL concentration of acetic acid solution of 12 mol/L, shaking vigorously on a vortex mixer for 10 s, standing for 3 d, centrifuging at 10000-12000 rpm to separate precipitate, washing with tetrahydrofuran and ethanol for three times alternately, and drying at 60 ℃ in a vacuum drying oven for 12g to obtain vinyl COFs;
② . Thiol modification COFs: weighing 200 mg parts of vinyl COFs prepared in step ①, placing the vinyl COFs in a Schlenk tube, adding 4 mL DMF parts under the protection of nitrogen, continuously adding 0.5-0.6 mL of 0.1 mol/L of 4-thiobenzoic acid DMF solution, adding 10mg benzophenone as a photoinitiator, placing the Schlenk tube under a 365 nm UV lamp, irradiating for 24 hours, maintaining the temperature at room temperature, centrifuging at 10000-12000 rpm after the reaction is finished, separating out a product, washing the product with acetone three times, and placing the product in a vacuum drying oven at 60 ℃ for drying 12 g to obtain thiol-modified COFs;
③ . Pqds@cofs synthesis: and (3) weighing 200 mg of thiol-modified COFs prepared in step ②, dispersing in 10mL DMF, adding 0.1 mmoL PbX 2, 200W of ultrasonic dispersion 10min, magnetically stirring at 300-400 rpm at room temperature for 6h, centrifugally collecting precipitate at 8000 rpm, redispersing in 4 mL dichloromethane, adding 0.2 mL of ethanol solution containing 0.1 mmoL CsX under the condition of magnetically stirring at 400-500 rpm at room temperature, stirring for 6-10 h, centrifugally separating precipitate at 10000-12000 rpm after the reaction is completed, washing the precipitate three times by using DMF, and drying 12 g at 60 ℃ in a vacuum drying oven to obtain PQDs@COFs.
7. The high performance qd-led of claim 6, wherein in step ③, X of PbX 2 and CsX is any one of Cl, br, I.
8. A method for preparing a high performance quantum dot light emitting diode according to any one of claims 1 to 7, comprising the steps of:
s1, dissolving poly (3, 4-ethylenedioxythiophene) polyaniline hydrochloride in water to obtain a concentration of 1.5-1.8wt%, and forming a hole transport layer with a thickness of 30-50 nm on the surface of an anode by a spraying technology;
S2, dispersing one or more PQDs@COFs prepared in the step S1 in methylene dichloride with the concentration of 50 mg/100 mL, and spin-coating to form a perovskite quantum dot luminescent layer with the thickness of 10-20 nm on the surface of the hole transport layer prepared in the step S1;
S3, selecting one of ZnO, tiO 2 or SnO 2, dispersing in water with the concentration of 60 mg/100 mL, and spin-coating on the surface of the perovskite quantum dot luminescent layer prepared in the step S2 to form an electron transport layer with the thickness of 20-40 nm;
S4, depositing aluminum or silver on the electron transport layer manufactured in the step S3 in a thermal evaporation or sputtering mode to form a cathode of 30-50 nm, namely synthesizing the high-performance quantum dot light-emitting diode.
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| CN117440699A (en) * | 2023-10-24 | 2024-01-23 | 西南交通大学 | Perovskite light-emitting diode and preparation method thereof |
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| CN117440699A (en) * | 2023-10-24 | 2024-01-23 | 西南交通大学 | Perovskite light-emitting diode and preparation method thereof |
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| Title |
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| JIEJUN REN 等: "《In situ passivation and thiol-mediated anchoring of perovskite quantum dots in mesoporous covalent-organic frameworks》", 《 CHEMICAL ENGINEERING JOURNAL》, vol. 454, no. 140285, 15 February 2023 (2023-02-15), pages 1 - 12 * |
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