WO2021103471A1 - Self-assembling multi-dimensional quantum well cspbx3 perovskite nanocrystalline light-emitting diode - Google Patents

Self-assembling multi-dimensional quantum well cspbx3 perovskite nanocrystalline light-emitting diode Download PDF

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WO2021103471A1
WO2021103471A1 PCT/CN2020/093651 CN2020093651W WO2021103471A1 WO 2021103471 A1 WO2021103471 A1 WO 2021103471A1 CN 2020093651 W CN2020093651 W CN 2020093651W WO 2021103471 A1 WO2021103471 A1 WO 2021103471A1
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quantum well
cspbx
self
assembled
transport layer
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田建军
毕成浩
姚志伟
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北京科技大学
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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
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating

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  • the invention belongs to the field of nanotechnology and light-emitting display, and specifically relates to the preparation of self-assembled multidimensional quantum well cesium lead halide CsPbX 3 perovskite nanocrystalline electroluminescent diode, which is applied to the fields of light-emitting, lighting and display.
  • Semiconductor nanocrystals with quantum confinement effect exhibit unique physical and electronic properties, such as size efficiency, adjustable band gap, and multiple exciton effects. They have important applications and development prospects in the fields of optoelectronics, biology and energy. Among them, the preparation process of the colloidal semiconductor nanocrystalline solution is simple, the raw material cost is low, and the size and dimension can be adjusted through the chemical synthesis process, and the photoelectric characteristics can be well adjusted, showing great application potential.
  • the metal halide perovskite materials developed in recent years exhibit very superior photoelectric properties, such as high charge mobility, long carrier diffusion distance, and high quantum fluorescence yield. They have developed rapidly in the photovoltaic and luminescence fields.
  • metal halide perovskite solar cells exceeds 25%, and the highest external quantum dot efficiency of metal halide perovskite electroluminescent diodes also reaches 20%.
  • metal halide perovskite nanocrystals which have narrow luminous line width, higher luminous efficiency and close to 100% quantum dot fluorescence yield, which is a very superior luminescent material.
  • the metal halide perovskite nanocrystal prepared by the colloidal method has the advantages of adjustable spectrum, high luminous intensity, high color purity, long fluorescence life, and single light source can excite multicolor fluorescence. It is a new generation of electroluminescent diodes (Light -Emitting Diode, LED) is one of the most promising materials.
  • nanocrystals to prepare electroluminescent LEDs has the advantages of high energy efficiency, low cost and easy processing. It can be integrated into electroluminescent LEDs after solution processing, spin coating or inkjet printing and can be used as an effective exciton radiation recombination center , Is a new generation of luminescent materials used in solid-state lighting and full-color flat panel displays. Compared with traditional phosphor LED and organic electroluminescence LED, nanocrystalline electroluminescence LED has the advantages of wide color gamut, high color purity and low cost.
  • NTSC National Television System Committee
  • CsPbX 3 nanocrystals have been proven to have good fluorescent properties and have a good development prospect in electro-induced LEDs.
  • the biggest bottleneck and problem of CsPbX 3 nanocrystalline electro-induced LEDs is extremely poor stability. This is because of the intrinsic ionic crystal nature of CsPbX 3 and its weak lattice formation energy, resulting in very poor electrical, optical, and thermal stability of nanocrystals, and the lifespan of LED devices is very short, far below the requirements of actual application standards.
  • the external quantum efficiency of pure blue and pure red LEDs is very low. Therefore, it is of great significance to improve the stability of CsPbX 3 nanocrystals and the lifetime of LED devices.
  • the nanocrystalline self-assembly process can effectively eliminate the lattice distortion and defects in the nanocrystalline by preferentially growing low-dimensional structures, and then through the self-assembly of the later low-dimensional structures, and self-repair occurs during the assembly process.
  • the interface of different dimensions of nanocrystals is protected by organic ligands, which has high thermodynamic stability and stable energy state. Therefore, the present invention designs a self-assembled multidimensional quantum well cesium lead halide CsPbX 3 nanocrystalline electroluminescent diode.
  • the self-assembled multi-dimensional quantum well CsPbX 3 nanocrystals By adjusting the dimensions and composition of the self-assembled multi-dimensional quantum well CsPbX 3 nanocrystals, it is possible to achieve any emission spectrum within the visible light emission range of 400-700 nanometers; and the multi-dimensional quantum well structure CsPbX 3 nanocrystals have high fluorescence quantum yield and fewer defects;
  • the light-emitting diode has high luminous efficiency and external quantum efficiency, and good stability; the organic ligands in multiple dimensions eliminate the defect of poor stability of ionic crystals, greatly extend the service life of LED devices, and thus meet the requirements of actual use.
  • a self-assembled multi-dimensional quantum well CsPbX 3 perovskite nanocrystalline electroluminescent diode which is composed of transparent conductive oxide anode TOC (1), hole transport layer material HTL (2), multi-dimensional quantum well structure CsPbX 3 nanocrystalline light-emitting
  • the layer EL (3), the electron transport layer material ETL (4) and the metal cathode CL (5) are composed.
  • the specific preparation steps are as follows:
  • a self-assembled multidimensional quantum well CsPbX 3 nanocrystalline solution is prepared.
  • the two-dimensional CsPbX 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 20-40 nanometers.
  • Use an ice bath to quickly cool the reaction solution to 0 ⁇ 10°C, add ethyl acetate or tert-butanol, centrifuge the reaction solution, and then wash it with n-hexane for 3-5 times, after drying to obtain a self-assembled multidimensional quantum well structure CsPbX 3 nanometer crystal.
  • the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a self-assembled multidimensional quantum well CsPbX 3 nanocrystal solution with a molar concentration of 0.5 to 1.5.
  • the hole transport layer material with a molar concentration of 0.5 to 1.5 is spin-coated on the transparent conductive oxide anode TOC (1) and annealed at 100 to 150°C for 10 to 20 minutes to form a hole transport layer material with a thickness of 30 to 70 nanometers HTL(2).
  • the self-assembled multi-dimensional quantum well CsPbX 3 nanocrystal solution with a molar concentration of 0.5 ⁇ 1.5 is spin-coated on the hole transport layer material HTL(2), and annealed at 30 ⁇ 100°C for 20 ⁇ 50 minutes to form a thickness of 30 ⁇ 50 nm Nanocrystalline light-emitting layer EL(3).
  • the electron transport material with a molar concentration of 0.5 ⁇ 1.5 is spin-coated on the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline light-emitting layer EL(3), and annealed at 30 ⁇ 100°C for 5 ⁇ 20 minutes to obtain a thickness of 50 ⁇ 100 nm Electron transport layer ETL(4).
  • a metal cathode CL (5) with a thickness of 30-100 nanometers is deposited on the electron transport layer ETL (4) by vacuum thermal evaporation.
  • X in the CsPbX 3 is a halogen element, which is one of Cl, Br, I, or a mixed halogen of Cl and Br, and Br and I.
  • the transparent conductive oxide anode TOC (1) is indium-doped tin oxide (ITO) or fluorine-doped tin oxide (FTO).
  • the hole transport layer material HTL(2) is poly[bis(4-phenyl)(4-butylphenyl)amine] (abbreviation: P-TPD), 1,2,4,5-tetra( Trifluoromethyl)benzene (abbreviation: TFB), poly(9-vinylcarbazole) (abbreviation: PVK), poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (abbreviation: PETDOT: PSS), NiO, MgNiO, 4,4'-bis(9-carbazole)biphenyl (abbreviation: CBP), one or more of MoO 2 or WO 3.
  • P-TPD poly[bis(4-phenyl)(4-butylphenyl)amine]
  • TFB 1,2,4,5-tetra( Trifluoromethyl)benzene
  • PVK poly(9-vinylcarbazole)
  • PETDOT PSS
  • NiO M
  • the electron transport layer material ETL (4) is TiO 2 , ZnO, SnO 2 , AlZnO, MgZnO, Zn 2 SnO 4 , Nb 2 O 5 , In 2 O 3 , 8-hydroxyquinoline aluminum (abbreviation: Alq3) , 3-(Biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (abbreviation: TZA), 2-(4- Biphenyl)-5-phenyloxadiazole (abbreviation: PBD), 3',3”-diphenyl-3'H,3”H-dicyclopropano[1,9:52,60] rich One or more of Leene-C60-IH-3',3"-dimethyl dibutyrate (abbreviation: PCBM) or bromocresol purple sodium salt (abbreviation: BCP).
  • PCBM Leene-C60-IH-3',
  • the metal cathode CL (5) is one of silver, gold and aluminum.
  • the self-assembled multi-dimensional quantum well CsPbX 3 perovskite nanocrystals By adjusting the dimensions and composition of the self-assembled multi-dimensional quantum well CsPbX 3 perovskite nanocrystals, it is possible to achieve any emission spectrum in the visible light emission range of 400 to 700 nm; and the fluorescence quantum yield of the multidimensional quantum well structure CsPbX 3 perovskite nanocrystals High, low defects; high luminous efficiency and external quantum efficiency of electroluminescent diode LED, good stability; organic ligands in multiple dimensions eliminate the defects of poor stability of ionic crystals, greatly extend the service life of LED devices, and then Reaching the requirements of actual use is an important breakthrough in the field of metal halide perovskite luminescence.
  • Figure 1a is an electron micrograph of the cross section of the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline electroluminescent diode device of the present invention
  • Figure 1b is a schematic diagram of the device structure: 1 is a transparent conductive substrate TOC; 2 is a hole transport layer material HTL, 3 is a multidimensional quantum well structure CsPbX 3 nanocrystalline light-emitting layer EL, 4 is an electron transport layer material ETL, 5 is a metal cathode CL ;
  • FIG 2a is a self-assembled multi-dimensional quantum well CsPbX 3 nanocrystals of the present invention (50 nm) HRTEM micrograph
  • FIG. 2b is a self-assembled multi-dimensional quantum well CsPbX 3 nanocrystals of the present invention (10 nm) high-resolution transmission electron microscope photograph;
  • Figure 3 is a fluorescence spectrum of the self-assembled multidimensional quantum well CsPbX 3 nanocrystals of the present invention.
  • Fig. 5 is a life test diagram of the self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline electroluminescent diode device of the present invention.
  • the two-dimensional CsPbX 3 nanosheets are gradually assembled into nanocrystals with a multi-dimensional quantum well structure, and the size of the nanocrystals is 20 nanometers.
  • the reaction solution was quickly cooled to 0°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane 3 times, and after drying, a self-assembled multidimensional quantum well structure CsPbX 3 nanocrystal was obtained.
  • the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a self-assembled multidimensional quantum well CsPbX 3 nanocrystal solution with a 0.5 molar concentration.
  • a hole transport precursor solution of 0.5 molar concentration was spin-coated on the transparent conductive oxide anode ITO, and annealed at 100° C. for 20 minutes to form a hole transport layer material P-TPD with a thickness of 30 nanometers.
  • a 0.5 molar self-assembled multidimensional quantum well CsPbX 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 30° C.
  • a nanocrystalline light-emitting layer EL with a thickness of 30 nanometers.
  • a 0.5 molar concentration of electron transport material ZnO precursor solution was spin-coated on the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline light-emitting layer, and annealed at 30° C. for 20 minutes to obtain an electron transport layer ZnO with a thickness of 50 nanometers.
  • a metal cathode Ag with a thickness of 30 nanometers was deposited on the electron transport layer ETL by vacuum thermal evaporation.
  • Table 1 shows the performance of different halogen self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline electroluminescent diodes.
  • the two-dimensional CsPbX 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers.
  • the reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbX 3 nanocrystal was obtained.
  • nanocrystals are then dissolved in n-octane, toluene or methylene chloride solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbX 3 nanocrystal solution.
  • a hole transport precursor solution with a 1.0 molar concentration was spin-coated on the transparent conductive oxide anode ITO, and annealed at 120° C. for 15 minutes to form a hole transport layer material P-TPD with a thickness of 50 nanometers.
  • a 1.0 molar self-assembled multidimensional quantum well CsPbX 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C.
  • the two-dimensional CsPbX 3 nanosheets are gradually assembled into nanocrystals with a multi-dimensional quantum well structure, and the size of the nanocrystals is 40 nanometers.
  • the reaction solution was quickly cooled to 10°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 5 times. After drying, a self-assembled multidimensional quantum well structure CsPbX 3 nanocrystal was obtained.
  • the nanocrystals are then dissolved in n-octane, toluene or dichloromethane solvents to form a 1.5 molar self-assembled multidimensional quantum well CsPbX 3 nanocrystal solution.
  • a hole transport precursor solution of 1.5 molar concentration was spin-coated on the transparent conductive oxide anode ITO, and annealed at 150° C. for 10 minutes to form a hole transport layer material P-TPD with a thickness of 70 nanometers.
  • the self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline solution with a concentration of 1.5 molar was spin-coated on the hole transport layer material and annealed at 100° C.
  • the two-dimensional CsPbI 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers.
  • the reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbI 3 nanocrystal was obtained.
  • the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystal solution.
  • a hole transport precursor solution with a 1.0 molar concentration was spin-coated on different transparent conductive oxide anodes, and annealed at 120° C. for 15 minutes to form a hole transport layer material P-TPD with a thickness of 50 nanometers.
  • a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C.
  • the two-dimensional CsPbI 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers.
  • the reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbI 3 nanocrystal was obtained.
  • the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystal solution.
  • Different hole transport precursor solutions of 1.0 molar concentration were spin-coated on the transparent conductive oxide anode ITO, and annealed at 120° C. for 15 minutes to form different hole transport layer materials with a thickness of 50 nanometers.
  • a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C.
  • the two-dimensional CsPbI 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers.
  • the reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbI 3 nanocrystal was obtained.
  • the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystal solution.
  • a 1.0 molar concentration of T-TPD hole transport precursor solution was spin-coated on the transparent conductive oxide anode ITO, and annealed at 120° C. for 15 minutes to form a hole transport layer material P-TPD with a thickness of 50 nanometers.
  • a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C.
  • nanocrystalline light-emitting layer with a thickness of 40 nanometers.
  • the precursor solutions of different electron transport materials with 1.0 molar concentration were spin-coated on the self-assembled multidimensional quantum well CsPbI 3 nanocrystalline light-emitting layer, and annealed at 80° C. for 10 minutes to obtain an electron transport layer with a thickness of 60 nanometers.
  • a metal cathode Ag with a thickness of 50 nm was deposited on the electron transport layer by vacuum thermal evaporation. As shown in Table 6.
  • the two-dimensional CsPbI 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers.
  • the reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbI 3 nanocrystal was obtained.
  • the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystal solution.
  • a 1.0 molar concentration of T-TPD hole transport precursor solution was spin-coated on the transparent conductive oxide anode ITO, and annealed at 120° C. for 15 minutes to form a hole transport layer material P-TPD with a thickness of 50 nanometers.
  • a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C.

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Abstract

A self-assembling multi-dimensional quantum well CsPbX3 perovskite nanocrystalline light-emitting diode, relating to the fields of nanotechnology and light-emitting display. The diode is composed of a transparent conductive oxide anode TOC (1), a hole transport layer material HTL (2), a multi-dimensional quantum well structure CsPbX3 nanocrystalline light-emitting layer EL (3), an electron transport layer material ETL (4), and a metal cathode CL (5). First using a chemical synthesis method to prepare a self-assembling multi-dimensional quantum well CsPbX3 nanocrystalline solution, then using a spin coating technique to spin coat the hole transport layer HTL (2), the CsPbX3 self-assembling multi-dimensional quantum well nanocrystalline solution, and the electron transport layer material ETL (4) onto the TOC (1) in sequence, and finally depositing the metal cathode CL (5) on the ETL (4) by means of a vacuum evaporation technique. In the present solution, by means of adjusting the dimensions and the composition of the self-assembling multi-dimensional quantum well CsPbX3 nanocrystals, any light emission spectrum within the visible light emission range of 400-700 nm can be implemented; the multi-dimensional quantum well CsPbX3 nanocrystals have a high fluorescence quantum yield and few defects; and the light-emitting diode has high light emission efficiency and external quantum efficiency, good stability, and a long service life.

Description

一种自组装多维量子阱CsPbX 3钙钛矿纳米晶电致发光二极管 A self-assembled multidimensional quantum well CsPbX 3Perovskite nanocrystalline electroluminescent diode 技术领域Technical field
本发明属于纳米科技和发光显示领域，具体涉及制备自组装多维量子阱铯铅卤化物CsPbX 3钙钛矿纳米晶电致发光二极管，应用于发光、照明和显示领域等。 The invention belongs to the field of nanotechnology and light-emitting display, and specifically relates to the preparation of self-assembled multidimensional quantum well cesium lead halide CsPbX 3 perovskite nanocrystalline electroluminescent diode, which is applied to the fields of light-emitting, lighting and display.
背景技术Background technique
具有量子限域效应的半导体纳米晶表现出独特的物理电子特性，如尺寸效率、带隙可调和多重激子效应等，在光电、生物和能源等领域中具有重要的应用和发展前景。其中胶体半导体纳米晶溶液的制备工艺简单，原料成本较低，且可以通过化学合成过程中调控尺寸和维度，很好的调控光电特性，表现出极大的应用潜力。近年来发展起来的金属卤化物钙钛矿材料，展现出非常优越的光电性能，如高电荷迁移率、载流子扩散距离长、量子荧光产率高等，在光伏、发光领域得到迅速发展。目前，金属卤化物钙钛矿太阳能电池的最高光电转换效率超过25％，金属卤化物钙钛矿电致发光二极管的外量子点效率最高也达到20％。制备成金属卤化物钙钛矿纳米晶，其发光线宽窄、发光效率更高和接近100％的量子点荧光产率，是一种非常优越的发光材料。而且，胶体法制备的金属卤化物钙钛矿纳米晶具有光谱可调，发光强度大、色纯度高、荧光寿命长，单光源可激发多色荧光等优势，是新一代电致发光二极管(Light-Emitting Diode，LED)最具发展潜力的材料之一。Semiconductor nanocrystals with quantum confinement effect exhibit unique physical and electronic properties, such as size efficiency, adjustable band gap, and multiple exciton effects. They have important applications and development prospects in the fields of optoelectronics, biology and energy. Among them, the preparation process of the colloidal semiconductor nanocrystalline solution is simple, the raw material cost is low, and the size and dimension can be adjusted through the chemical synthesis process, and the photoelectric characteristics can be well adjusted, showing great application potential. The metal halide perovskite materials developed in recent years exhibit very superior photoelectric properties, such as high charge mobility, long carrier diffusion distance, and high quantum fluorescence yield. They have developed rapidly in the photovoltaic and luminescence fields. At present, the highest photoelectric conversion efficiency of metal halide perovskite solar cells exceeds 25%, and the highest external quantum dot efficiency of metal halide perovskite electroluminescent diodes also reaches 20%. Prepared into metal halide perovskite nanocrystals, which have narrow luminous line width, higher luminous efficiency and close to 100% quantum dot fluorescence yield, which is a very superior luminescent material. Moreover, the metal halide perovskite nanocrystal prepared by the colloidal method has the advantages of adjustable spectrum, high luminous intensity, high color purity, long fluorescence life, and single light source can excite multicolor fluorescence. It is a new generation of electroluminescent diodes (Light -Emitting Diode, LED) is one of the most promising materials.
利用纳米晶制备电致LED，具有能效高、成本低且易加工等优点，可以经过溶液加工、旋涂或喷墨印刷成膜后集成到电致发光LED中可以作为有效的激子辐射复合中心，是应用于固态照明和全色平板显示的新 一代发光材料。纳米晶电致LED与传统荧光粉LED及有机电致LED相比，具有色域广、色纯度高和低成本的优势。The use of nanocrystals to prepare electroluminescent LEDs has the advantages of high energy efficiency, low cost and easy processing. It can be integrated into electroluminescent LEDs after solution processing, spin coating or inkjet printing and can be used as an effective exciton radiation recombination center , Is a new generation of luminescent materials used in solid-state lighting and full-color flat panel displays. Compared with traditional phosphor LED and organic electroluminescence LED, nanocrystalline electroluminescence LED has the advantages of wide color gamut, high color purity and low cost.
1994年，Alivisatos等报道了CdSe纳米晶电致LED(Nature,1994,370,354-357)，外量子效率很低，小于1％。在接下来的20多年时间里，纳米晶电致LED的效率得到了很大的提升。2014年，Dai等报道了最高外量子效率超过20％的CdSe纳米晶LED(Nature,2014,515,96-99)。与Cd系硫族化合物纳米晶和有机染料相比，全无机铯铅卤化物钙钛矿CsPbX 3(X＝Cl,Br,I)纳米晶材具有更高的载流子迁移率、更窄的发光半峰宽(11-40nm)，并所展现出的更高色彩饱和度(色纯度)、更广的色域(150％国家电视系统委会(NTSC)标准色域)及更真实的显示效果。 In 1994, Alivisatos et al. reported that the CdSe nanocrystalline electro-induced LED (Nature, 1994, 370, 354-357) had a very low external quantum efficiency, less than 1%. In the next 20 years, the efficiency of nanocrystalline electroluminescent LEDs has been greatly improved. In 2014, Dai et al. reported the CdSe nanocrystalline LED with the highest external quantum efficiency exceeding 20% (Nature, 2014, 515, 96-99). Compared with Cd-based chalcogenide nanocrystals and organic dyes, all-inorganic cesium-lead halide perovskite CsPbX 3 (X=Cl,Br,I) nanocrystals have higher carrier mobility and narrower Luminous half-peak width (11-40nm), higher color saturation (color purity), wider color gamut (150% of the National Television System Committee (NTSC) standard color gamut) and more realistic display effect.
2015年，Protesescu等使用热注入的方法制备出CsPbX 3纳米晶(Nano Lett.2015,15,3692-3696)。纳米晶尺寸为4-15纳米，通过组分和纳米晶尺寸的共同调节，可以在410-700纳米范围内改变其发光光谱和带隙能，具有12-42纳米宽的发射光谱线、覆盖140％的NTSC标准色域、90％的荧光量子产率和1-24纳秒的荧光寿命。2017年，Liu等人(ACS Nano,2017,11,10373-10383)采用三正辛基膦(TOP)配体替换传统的油胺油酸配体，减少表面缺陷，实现CsPbI 3的荧光量子产率接近100％的红光发射。但由于TOP无法溶解其它的源，导致无法制备其他卤素源的纳米晶。2019年Zheng等采用双钝化配体，制备出荧光量子产率接近100％的绿光发射的CsPbBr 3纳米晶(ACS Appl.Mater.Interfaces,2019,11,25410-25416)。 In 2015, Protesescu et al. used heat injection to prepare CsPbX 3 nanocrystals (Nano Lett. 2015, 15, 3692-3696). The size of the nanocrystal is 4-15 nanometers. Through the joint adjustment of the composition and the size of the nanocrystal, its emission spectrum and band gap energy can be changed in the range of 410-700 nanometers. It has a wide emission spectrum line of 12-42 nanometers, covering 140 % NTSC standard color gamut, 90% fluorescence quantum yield and 1-24 nanosecond fluorescence lifetime. In 2017, Liu et al. (ACS Nano, 2017, 11, 10373-10383) used tri-n-octyl phosphine (TOP) ligand to replace the traditional oleylamine oleic acid ligand, reducing surface defects, and realizing the fluorescence quantum production of CsPbI 3. The rate of red light emission is close to 100%. However, because TOP cannot dissolve other sources, it is impossible to prepare nanocrystals of other halogen sources. In 2019, Zheng et al. used double passivation ligands to prepare green light emitting CsPbBr 3 nanocrystals with a fluorescence quantum yield close to 100% (ACS Appl.Mater.Interfaces, 2019,11,25410-25416).
然而，只有将高发光性能的铯铅卤化物纳米晶制备成电致LED，才能很好的应用于照明和显示领域。2015年，Song等(Advanced Materials,2015,27,7162)采用胶体CsPbX 3纳米晶制备出多层结构电致LED，发 射蓝绿光、绿光和橙光，其发光外量子效率分别是0.07％、0.12％和0.09％，发光亮度分别为742cd/m 2、742cd/m 2和742cd/m 2。这些器件的发光外量子效率还很低。2018年，Chiba等(Nature Photonics,2018,12,681-687)使用阴离子交换法，将绿光发射CsPbBr 3纳米晶通过碘化铵盐进行处理，实现了649nm的红光发射，并且制备了电致LED器件，最高外量子点效率达到21.3％。 However, only by preparing cesium-lead halide nanocrystals with high luminescence properties into electroluminescent LEDs, can they be well used in the field of lighting and display. In 2015, Song et al. (Advanced Materials, 2015, 27, 7162) used colloidal CsPbX 3 nanocrystals to prepare a multilayer structure electroluminescent LED, emitting blue-green light, green light and orange light, and their luminous external quantum efficiencies were 0.07%. , 0.12% and 0.09%, the luminous brightness is 742cd/m 2 , 742cd/m 2 and 742cd/m 2 respectively . The light-emitting external quantum efficiency of these devices is still very low. In 2018, Chiba et al. (Nature Photonics, 2018, 12, 681-687) used the anion exchange method to process the green light-emitting CsPbBr 3 nanocrystals with ammonium iodide to achieve red light emission at 649 nm, and prepared electroluminescent LEDs The device, the highest external quantum dot efficiency reached 21.3%.
到目前为止，铯铅卤化物钙钛矿CsPbX 3纳米晶被证明具有很好的荧光性能，在电致LED有很好的发展前景。但目，CsPbX 3纳米晶电致LED的最大瓶颈和问题就是极差的稳定性。这是因为CsPbX 3的本征离子晶体性质，其晶格形成能弱，造成纳米晶的电、光、热稳定性非常差，LED器件的寿命非常短，远远达不到实际应用标准要求。且纯蓝光、纯红LED的外量子效率非常低。因此，提高CsPbX 3纳米晶的稳定性和LED器件的寿命具有重要的意义。 So far, cesium-lead halide perovskite CsPbX 3 nanocrystals have been proven to have good fluorescent properties and have a good development prospect in electro-induced LEDs. However, the biggest bottleneck and problem of CsPbX 3 nanocrystalline electro-induced LEDs is extremely poor stability. This is because of the intrinsic ionic crystal nature of CsPbX 3 and its weak lattice formation energy, resulting in very poor electrical, optical, and thermal stability of nanocrystals, and the lifespan of LED devices is very short, far below the requirements of actual application standards. In addition, the external quantum efficiency of pure blue and pure red LEDs is very low. Therefore, it is of great significance to improve the stability of CsPbX 3 nanocrystals and the lifetime of LED devices.
纳米晶自组装工艺可以通过优先生长低维结构，再通过后期低维结构的自组装，并在组装过程中发生自修复，有效地消除纳米晶中的晶格畸变和缺陷。且纳米晶不同维度界面被有机配体保护，具有高的热力学稳定性和稳定的能量状态。为此，本发明设计一种自组装多维量子阱铯铅卤化物CsPbX 3纳米晶电致发光二极管。通过调控自组装多维量子阱CsPbX 3纳米晶的维度和成分就可以实现400～700纳米可见光发光范围内任意发光谱；而且多维量子阱结构CsPbX 3纳米晶的荧光量子产率高、缺陷少；电致发光二极管发光效率和外量子效率高、稳定性好；在多维度间的有机配体消除了离子晶体稳定性差的缺陷，极大延长了LED器件的使用寿命，进而达到实际使用的要求，是金属卤化物钙钛矿发光领域的一个重要突破。 The nanocrystalline self-assembly process can effectively eliminate the lattice distortion and defects in the nanocrystalline by preferentially growing low-dimensional structures, and then through the self-assembly of the later low-dimensional structures, and self-repair occurs during the assembly process. In addition, the interface of different dimensions of nanocrystals is protected by organic ligands, which has high thermodynamic stability and stable energy state. Therefore, the present invention designs a self-assembled multidimensional quantum well cesium lead halide CsPbX 3 nanocrystalline electroluminescent diode. By adjusting the dimensions and composition of the self-assembled multi-dimensional quantum well CsPbX 3 nanocrystals, it is possible to achieve any emission spectrum within the visible light emission range of 400-700 nanometers; and the multi-dimensional quantum well structure CsPbX 3 nanocrystals have high fluorescence quantum yield and fewer defects; The light-emitting diode has high luminous efficiency and external quantum efficiency, and good stability; the organic ligands in multiple dimensions eliminate the defect of poor stability of ionic crystals, greatly extend the service life of LED devices, and thus meet the requirements of actual use. An important breakthrough in the field of metal halide perovskite luminescence.
发明内容Summary of the invention
一种自组装多维量子阱CsPbX 3钙钛矿纳米晶电致发光二极管，是由透明导电氧化物阳极TOC(1)、空穴传输层材料HTL(2)、多维量子阱结构CsPbX 3纳米晶发光层EL(3)、电子传输层材料ETL(4)和金属阴极CL(5)组成。具体制备步骤如下： A self-assembled multi-dimensional quantum well CsPbX 3 perovskite nanocrystalline electroluminescent diode, which is composed of transparent conductive oxide anode TOC (1), hole transport layer material HTL (2), multi-dimensional quantum well structure CsPbX 3 nanocrystalline light-emitting The layer EL (3), the electron transport layer material ETL (4) and the metal cathode CL (5) are composed. The specific preparation steps are as follows:
首先制备自组装多维量子阱CsPbX 3纳米晶溶液。将卤化铅(PbX 2)、油酸(OA)、辛胺(OTA)三种化合物按照摩尔比1:0.3:0.6～1:0.5:1的比例混合，置于加热装置的容器中，搅拌、抽真空，并升温至100～150℃，获得0.5～1.5摩尔浓度的铅前驱体溶液；将碳酸铯(Cs 2CO 3)、油酸(OA)按照摩尔比1:0.4～1:0.6的比例，加入到十八烯(ODE)中，然后置于加热装置容器中，搅拌、抽真空，并升温至100～150℃，获得0.5～1.0摩尔浓度的铯前驱体溶液；在惰性气体保护条件下，铯前驱体溶液加热至100～150℃，注入0.5～1.5摩尔浓度的铅前驱体溶液。保温30～60秒，在此过程中，二维CsPbX 3纳米片逐步组装成多维量子阱结构的纳米晶，纳米晶尺寸为20～40纳米。采用冰浴快速降温反应溶液到0～10℃，加入乙酸乙酯或叔丁醇，对反应溶液进行离心，再用正己烷进行洗涤3-5次，干燥后获得自组装多维量子阱结构的CsPbX 3纳米晶。随后将这种纳米晶溶解到正辛烷、甲苯或二氯甲烷溶剂中形成0.5～1.5摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液。 First, a self-assembled multidimensional quantum well CsPbX 3 nanocrystalline solution is prepared. Mix the three compounds of lead halide (PbX 2 ), oleic acid (OA), and octylamine (OTA) in a molar ratio of 1:0.3:0.6 to 1:0.5:1, and place them in the container of the heating device, stir, Vacuum and raise the temperature to 100-150°C to obtain a 0.5-1.5 molar concentration of lead precursor solution; cesium carbonate (Cs 2 CO 3 ) and oleic acid (OA) in a molar ratio of 1:0.4 to 1:0.6 , Added to octadecene (ODE), then placed in a heating device container, stirred, vacuumed, and heated to 100-150℃, to obtain 0.5-1.0 molar concentration of cesium precursor solution; under inert gas protection conditions , The cesium precursor solution is heated to 100-150 DEG C, and 0.5-1.5 molar concentration of the lead precursor solution is injected. Keep holding for 30-60 seconds. During this process, the two-dimensional CsPbX 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 20-40 nanometers. Use an ice bath to quickly cool the reaction solution to 0～10℃, add ethyl acetate or tert-butanol, centrifuge the reaction solution, and then wash it with n-hexane for 3-5 times, after drying to obtain a self-assembled multidimensional quantum well structure CsPbX 3 nanometer crystal. Subsequently, the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a self-assembled multidimensional quantum well CsPbX 3 nanocrystal solution with a molar concentration of 0.5 to 1.5.
将0.5～1.5摩尔浓度的空穴传输层材料旋涂在透明导电氧化物阳极TOC(1)上，在100～150℃退火10～20分钟，形成厚度为30～70纳米的空穴传输层材料HTL(2)。The hole transport layer material with a molar concentration of 0.5 to 1.5 is spin-coated on the transparent conductive oxide anode TOC (1) and annealed at 100 to 150°C for 10 to 20 minutes to form a hole transport layer material with a thickness of 30 to 70 nanometers HTL(2).
将0.5～1.5摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液旋涂在空穴传输层材料HTL(2)上，在30～100℃退火20～50分钟，形成厚度为30～50纳米的纳米晶发光层EL(3)。 The self-assembled multi-dimensional quantum well CsPbX 3 nanocrystal solution with a molar concentration of 0.5～1.5 is spin-coated on the hole transport layer material HTL(2), and annealed at 30～100℃ for 20～50 minutes to form a thickness of 30～50 nm Nanocrystalline light-emitting layer EL(3).
将0.5～1.5摩尔浓度的电子传输材料旋涂在自组装多维量子阱CsPbX 3纳米晶发光层EL(3)上，在30～100℃下退火5～20分钟，获得厚度为50～100纳米的电子传输层ETL(4)。 The electron transport material with a molar concentration of 0.5～1.5 is spin-coated on the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline light-emitting layer EL(3), and annealed at 30～100℃ for 5～20 minutes to obtain a thickness of 50～100 nm Electron transport layer ETL(4).
采用真空热蒸发在电子传输层ETL(4)上沉积30～100纳米厚度的金属阴极CL(5)。A metal cathode CL (5) with a thickness of 30-100 nanometers is deposited on the electron transport layer ETL (4) by vacuum thermal evaporation.
进一步地，所述CsPbX 3中X为卤族元素，是Cl、Br、I一种，或者Cl和Br、Br和I混合卤素。 Further, X in the CsPbX 3 is a halogen element, which is one of Cl, Br, I, or a mixed halogen of Cl and Br, and Br and I.
进一步地，透明导电氧化物阳极TOC(1)为掺铟氧化锡(ITO)或者掺氟氧化锡(FTO)。Further, the transparent conductive oxide anode TOC (1) is indium-doped tin oxide (ITO) or fluorine-doped tin oxide (FTO).
进一步地，空穴传输层材料HTL(2)为聚[双(4-苯基)(4-丁基苯基)胺](简称：P-TPD)、1,2,4,5-四(三氟甲基)苯(简称：TFB)、聚(9-乙烯咔唑)(简称：PVK)、聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(简称：PETDOT:PSS)，NiO，MgNiO，4,4'-二(9-咔唑)联苯(简称：CBP)，MoO 2或WO 3中的一种或多种。 Further, the hole transport layer material HTL(2) is poly[bis(4-phenyl)(4-butylphenyl)amine] (abbreviation: P-TPD), 1,2,4,5-tetra( Trifluoromethyl)benzene (abbreviation: TFB), poly(9-vinylcarbazole) (abbreviation: PVK), poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (abbreviation: PETDOT: PSS), NiO, MgNiO, 4,4'-bis(9-carbazole)biphenyl (abbreviation: CBP), one or more of MoO 2 or WO 3.
进一步地，电子传输层材料ETL(4)为TiO 2，ZnO，SnO 2，AlZnO，MgZnO，Zn 2SnO 4，Nb 2O 5，In 2O 3，8-羟基喹啉铝(简称：Alq3)，3-(联苯-4-基)-5-(4-叔丁基苯基)-4-苯基-4H-1,2,4-三唑(简称：TZA)，2-(4-联苯基)-5-苯基恶二唑(简称：PBD)，3',3”-二苯基-3'H,3”H-二环丙烷并[1,9:52,60]富勒烯-C60-IH-3',3”-二丁酸二甲酯(简称：PCBM)或溴甲酚紫钠盐(简称：BCP)中的一种或多种。 Further, the electron transport layer material ETL (4) is TiO 2 , ZnO, SnO 2 , AlZnO, MgZnO, Zn 2 SnO 4 , Nb 2 O 5 , In 2 O 3 , 8-hydroxyquinoline aluminum (abbreviation: Alq3) , 3-(Biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (abbreviation: TZA), 2-(4- Biphenyl)-5-phenyloxadiazole (abbreviation: PBD), 3',3”-diphenyl-3'H,3”H-dicyclopropano[1,9:52,60] rich One or more of Leene-C60-IH-3',3"-dimethyl dibutyrate (abbreviation: PCBM) or bromocresol purple sodium salt (abbreviation: BCP).
进一步地，金属阴极CL(5)是银、金和铝中的一种。Further, the metal cathode CL (5) is one of silver, gold and aluminum.
本发明的有益技术效果：The beneficial technical effects of the present invention:
通过调控自组装多维量子阱CsPbX 3钙钛矿纳米晶的维度和成分就可以实现400～700纳米可见光发光范围内任意发光谱；而且多维量子阱结构CsPbX 3钙钛矿纳米晶的荧光量子产率高、缺陷少；电致发光二极管 LED发光效率和外量子效率高、稳定性好；在多维度间的有机配体消除了离子晶体稳定性差的缺陷，极大延长了LED器件的使用寿命，进而达到实际使用的要求，是金属卤化物钙钛矿发光领域的一个重要突破。 By adjusting the dimensions and composition of the self-assembled multi-dimensional quantum well CsPbX 3 perovskite nanocrystals, it is possible to achieve any emission spectrum in the visible light emission range of 400 to 700 nm; and the fluorescence quantum yield of the multidimensional quantum well structure CsPbX 3 perovskite nanocrystals High, low defects; high luminous efficiency and external quantum efficiency of electroluminescent diode LED, good stability; organic ligands in multiple dimensions eliminate the defects of poor stability of ionic crystals, greatly extend the service life of LED devices, and then Reaching the requirements of actual use is an important breakthrough in the field of metal halide perovskite luminescence.
附图说明Description of the drawings
图1a是本发明自组装多维量子阱CsPbX 3纳米晶电致发光二极管器件截面的电子显微照片； Figure 1a is an electron micrograph of the cross section of the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline electroluminescent diode device of the present invention;
图1b是器件结构示意图：1是透明导电基底TOC；2是空穴传输层材料HTL，3是多维量子阱结构CsPbX 3纳米晶发光层EL，4是电子传输层材料ETL，5是金属阴极CL； Figure 1b is a schematic diagram of the device structure: 1 is a transparent conductive substrate TOC; 2 is a hole transport layer material HTL, 3 is a multidimensional quantum well structure CsPbX 3 nanocrystalline light-emitting layer EL, 4 is an electron transport layer material ETL, 5 is a metal cathode CL ；
图2a是本发明的自组装多维量子阱CsPbX 3纳米晶的(50nm)高分辨透射显微镜照片，图2b是本发明的自组装多维量子阱CsPbX 3纳米晶的(10nm)高分辨透射显微镜照片； FIG 2a is a self-assembled multi-dimensional quantum well CsPbX 3 nanocrystals of the present invention (50 nm) HRTEM micrograph, FIG. 2b is a self-assembled multi-dimensional quantum well CsPbX 3 nanocrystals of the present invention (10 nm) high-resolution transmission electron microscope photograph;
图3是本发明的自组装多维量子阱CsPbX 3纳米晶的荧光谱图； Figure 3 is a fluorescence spectrum of the self-assembled multidimensional quantum well CsPbX 3 nanocrystals of the present invention;
图4是本发明的自组装多维量子阱CsPbX 3纳米晶电致发光二极管器件的电压-亮度-外量子效率图； 4 is a graph of voltage-luminance-external quantum efficiency of the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline electroluminescent diode device of the present invention;
图5是本发明的自组装多维量子阱CsPbX 3纳米晶电致发光二极管器件寿命测试图。 Fig. 5 is a life test diagram of the self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline electroluminescent diode device of the present invention.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细描述。应当理解，此处所描述的具体实施例仅仅用于解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions, and advantages of the present invention clearer, the following further describes the present invention in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention.
相反，本发明涵盖任何由权利要求定义的在本发明的精髓和范围上做的替代、修改、等效方法以及方案。进一步，为了使公众对本发明有 更好的了解，在下文对本发明的细节描述中，详尽描述了一些特定的细节部分。对本领域技术人员来说没有这些细节部分的描述也可以完全理解本发明。On the contrary, the present invention covers any alternatives, modifications, equivalent methods and schemes defined by the claims in the spirit and scope of the present invention. Further, in order to enable the public to have a better understanding of the present invention, in the following detailed description of the present invention, some specific details are described in detail. Those skilled in the art can fully understand the present invention without the description of these details.
实施例1Example 1
将卤化铅(PbX 2)、油酸(OA)、辛胺(OTA)三种化合物按照摩尔比1:0.3:0.6的比例混合，置于加热装置的容器中，搅拌、抽真空，并升温至100℃，获得0.5摩尔浓度的铅前驱体溶液；将碳酸铯(Cs 2CO 3)、油酸(OA)按照摩尔比1:0.4的比例，加入到十八烯(ODE)中，然后置于加热装置容器中，搅拌、抽真空，并升温至100℃，获得0.5摩尔浓度的铯前驱体溶液；在惰性气体保护条件下，铯前驱体溶液加热至100℃，注入0.5摩尔浓度的铅前驱体溶液。保温60秒，在此过程中，二维CsPbX 3纳米片逐步组装成多维量子阱结构的纳米晶，纳米晶尺寸为20纳米。采用冰浴快速降温反应溶液到0℃，加入乙酸乙酯或叔丁醇，对反应溶液进行离心，再用正己烷进行洗涤3次，干燥后获得自组装多维量子阱结构的CsPbX 3纳米晶。随后将这种纳米晶溶解到正辛烷、甲苯或二氯甲烷溶剂中形成0.5摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液。将0.5摩尔浓度的空穴传输前驱溶液旋涂在透明导电氧化物阳极ITO上，在100℃退火20分钟，形成厚度为30纳米的空穴传输层材料P-TPD。将0.5摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液旋涂在空穴传输层材料上，在30℃退火50分钟，形成厚度为30纳米的纳米晶发光层EL。将0.5摩尔浓度的电子传输材料ZnO前驱溶液旋涂在自组装多维量子阱CsPbX 3纳米晶发光层上，在30℃下退火20分钟，获得厚度为50纳米的电子传输层ZnO。采用真空热蒸发在电子传输层ETL上沉积30纳米厚度的金属阴极Ag。表1是不同卤素自组装多维量子阱CsPbX 3纳米晶电致发光二极管的性能。 Mix the three compounds of lead halide (PbX 2 ), oleic acid (OA), and octylamine (OTA) at a molar ratio of 1:0.3:0.6, and place them in a container of a heating device, stir, vacuum, and heat to 100°C, obtain a 0.5 molar lead precursor solution; add cesium carbonate (Cs 2 CO 3 ) and oleic acid (OA) to the octadecene (ODE) at a molar ratio of 1:0.4, and then place In the vessel of the heating device, stir, evacuate, and raise the temperature to 100°C to obtain a 0.5 molar cesium precursor solution; under inert gas protection, the cesium precursor solution is heated to 100°C, and 0.5 molar lead precursor is injected Solution. In the process of holding for 60 seconds, the two-dimensional CsPbX 3 nanosheets are gradually assembled into nanocrystals with a multi-dimensional quantum well structure, and the size of the nanocrystals is 20 nanometers. The reaction solution was quickly cooled to 0°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane 3 times, and after drying, a self-assembled multidimensional quantum well structure CsPbX 3 nanocrystal was obtained. Subsequently, the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a self-assembled multidimensional quantum well CsPbX 3 nanocrystal solution with a 0.5 molar concentration. A hole transport precursor solution of 0.5 molar concentration was spin-coated on the transparent conductive oxide anode ITO, and annealed at 100° C. for 20 minutes to form a hole transport layer material P-TPD with a thickness of 30 nanometers. A 0.5 molar self-assembled multidimensional quantum well CsPbX 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 30° C. for 50 minutes to form a nanocrystalline light-emitting layer EL with a thickness of 30 nanometers. A 0.5 molar concentration of electron transport material ZnO precursor solution was spin-coated on the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline light-emitting layer, and annealed at 30° C. for 20 minutes to obtain an electron transport layer ZnO with a thickness of 50 nanometers. A metal cathode Ag with a thickness of 30 nanometers was deposited on the electron transport layer ETL by vacuum thermal evaporation. Table 1 shows the performance of different halogen self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline electroluminescent diodes.
表1不同纳米晶电致发光二极管的性能Table 1 Performance of different nanocrystalline electroluminescent diodes
Figure PCTCN2020093651-appb-000001
Figure PCTCN2020093651-appb-000001
实施例2Example 2
将卤化铅(PbX 2)、油酸(OA)、辛胺(OTA)三种化合物按照摩尔比1:0.4:0.8的比例混合，置于加热装置的容器中，搅拌、抽真空，并升温至120℃，获得1.0摩尔浓度的铅前驱体溶液；将碳酸铯(Cs 2CO 3)、油酸(OA)按照摩尔比1:0.5的比例，加入到十八烯(ODE)中，然后置于加热装置容器中，搅拌、抽真空，并升温至120℃，获得0.7摩尔浓度的铯前驱体溶液；在惰性气体保护条件下，铯前驱体溶液加热至120℃，注入1.0摩尔浓度的铅前驱体溶液。保温40秒，在此过程中，二维CsPbX 3纳米片逐步组装成多维量子阱结构的纳米晶，纳米晶尺寸为30纳米。采用冰浴快速降温反应溶液到5℃，加入乙酸乙酯或叔丁醇，对反应溶液进行离心，再用正己烷进行洗涤4次，干燥后获得自组装多维量子阱结构的CsPbX 3纳米晶。随后将这种纳米晶溶解到正辛烷、甲苯或二氯甲烷溶剂中形成1.0摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液。将1.0摩尔浓度的空穴传输前驱溶液旋涂在透明导电氧化物阳极ITO上，在120℃退火15分钟，形成厚度为50纳米的空穴传输层材料P-TPD。将1.0摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液旋涂在空穴传输层材料上，在50℃退火30分钟，形成厚度为40纳米的纳米晶发光层。将1.0摩尔浓度的电子传输材料ZnO前驱溶液旋涂在自组装多维量子阱 CsPbX 3纳米晶发光层上，在80℃下退火10分钟，获得厚度为60纳米的电子传输层ZnO。采用真空热蒸发在电子传输层上沉积50纳米厚度的金属阴极Ag。表2是不同卤素自组装多维量子阱CsPbX 3纳米晶电致发光二极管的性能。 Mix the three compounds of lead halide (PbX 2 ), oleic acid (OA), and octylamine (OTA) in a molar ratio of 1:0.4:0.8, and place them in the container of the heating device, stir, vacuum, and heat to 120℃, obtain a 1.0 molar lead precursor solution; add cesium carbonate (Cs 2 CO 3 ) and oleic acid (OA) to the octadecene (ODE) at a molar ratio of 1:0.5, and then place In the vessel of the heating device, stir, evacuate, and raise the temperature to 120°C to obtain a cesium precursor solution of 0.7 molar concentration; under inert gas protection, the cesium precursor solution is heated to 120°C, and 1.0 molar concentration of lead precursor is injected Solution. In the process of holding for 40 seconds, the two-dimensional CsPbX 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers. The reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbX 3 nanocrystal was obtained. The nanocrystals are then dissolved in n-octane, toluene or methylene chloride solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbX 3 nanocrystal solution. A hole transport precursor solution with a 1.0 molar concentration was spin-coated on the transparent conductive oxide anode ITO, and annealed at 120° C. for 15 minutes to form a hole transport layer material P-TPD with a thickness of 50 nanometers. A 1.0 molar self-assembled multidimensional quantum well CsPbX 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C. for 30 minutes to form a nanocrystalline light-emitting layer with a thickness of 40 nanometers. A 1.0 molar concentration of electron transport material ZnO precursor solution was spin-coated on the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline light-emitting layer, and annealed at 80° C. for 10 minutes to obtain an electron transport layer ZnO with a thickness of 60 nanometers. A metal cathode Ag with a thickness of 50 nm was deposited on the electron transport layer by vacuum thermal evaporation. Table 2 shows the performance of different halogen self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline electroluminescent diodes.
表2不同纳米晶电致发光二极管的性能Table 2 Performance of different nanocrystalline electroluminescent diodes
Figure PCTCN2020093651-appb-000002
Figure PCTCN2020093651-appb-000002
实施例3Example 3
将卤化铅(PbX 2)、油酸(OA)、辛胺(OTA)三种化合物按照摩尔比1:0.5:1的比例混合，置于加热装置的容器中，搅拌、抽真空，并升温至150℃，获得1.5摩尔浓度的铅前驱体溶液；将碳酸铯(Cs 2CO 3)、油酸(OA)按照摩尔比1:0.6的比例，加入到十八烯(ODE)中，然后置于加热装置容器中，搅拌、抽真空，并升温至150℃，获得1.0摩尔浓度的铯前驱体溶液；在惰性气体保护条件下，铯前驱体溶液加热至150℃，注入1.5摩尔浓度的铅前驱体溶液。保温30秒，在此过程中，二维CsPbX 3纳米片逐步组装成多维量子阱结构的纳米晶，纳米晶尺寸为40纳米。采用冰浴快速降温反应溶液到10℃，加入乙酸乙酯或叔丁醇，对反应溶液进行离心，再用正己烷进行洗涤5次，干燥后获得自组装多维量子阱结构的CsPbX 3纳米晶。随后将这种纳米晶溶解到正辛烷、甲苯或二氯甲烷 溶剂中形成1.5摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液。将1.5摩尔浓度的空穴传输前驱溶液旋涂在透明导电氧化物阳极ITO上，在150℃退火10分钟，形成厚度为70纳米的空穴传输层材料P-TPD。将1.5摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液旋涂在空穴传输层材料上，在100℃退火20分钟，形成厚度为50纳米的纳米晶发光层。将1.5摩尔浓度的电子传输材料ZnO前驱溶液旋涂在自组装多维量子阱CsPbX 3纳米晶发光层上，在100℃下退火5分钟，获得厚度为100纳米的电子传输层ZnO。采用真空热蒸发在电子传输层上沉积100纳米厚度的金属阴极Ag。表3是不同卤素自组装多维量子阱CsPbX 3纳米晶电致发光二极管的性能。 Mix the three compounds of lead halide (PbX 2 ), oleic acid (OA), and octylamine (OTA) at a molar ratio of 1:0.5:1, and place them in the container of the heating device, stir, vacuum, and heat to 150℃, obtain a 1.5 molar lead precursor solution; add cesium carbonate (Cs 2 CO 3 ) and oleic acid (OA) to the octadecene (ODE) at a molar ratio of 1:0.6, and then place In the vessel of the heating device, stir, evacuate, and raise the temperature to 150°C to obtain a 1.0 molar cesium precursor solution; under inert gas protection, the cesium precursor solution is heated to 150°C, and 1.5 molar lead precursor is injected Solution. In the process of holding for 30 seconds, the two-dimensional CsPbX 3 nanosheets are gradually assembled into nanocrystals with a multi-dimensional quantum well structure, and the size of the nanocrystals is 40 nanometers. The reaction solution was quickly cooled to 10°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 5 times. After drying, a self-assembled multidimensional quantum well structure CsPbX 3 nanocrystal was obtained. The nanocrystals are then dissolved in n-octane, toluene or dichloromethane solvents to form a 1.5 molar self-assembled multidimensional quantum well CsPbX 3 nanocrystal solution. A hole transport precursor solution of 1.5 molar concentration was spin-coated on the transparent conductive oxide anode ITO, and annealed at 150° C. for 10 minutes to form a hole transport layer material P-TPD with a thickness of 70 nanometers. The self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline solution with a concentration of 1.5 molar was spin-coated on the hole transport layer material and annealed at 100° C. for 20 minutes to form a nanocrystalline light-emitting layer with a thickness of 50 nanometers. A 1.5 molar concentration of electron transport material ZnO precursor solution was spin-coated on the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline light-emitting layer, and annealed at 100° C. for 5 minutes to obtain an electron transport layer ZnO with a thickness of 100 nanometers. Vacuum thermal evaporation is used to deposit a metal cathode Ag with a thickness of 100 nm on the electron transport layer. Table 3 shows the performance of different halogen self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline electroluminescent diodes.
表3不同纳米晶电致发光二极管的性能Table 3 Performance of different nanocrystalline electroluminescent diodes
Figure PCTCN2020093651-appb-000003
Figure PCTCN2020093651-appb-000003
实施例4Example 4
将卤化铅(PbI 2)、油酸(OA)、辛胺(OTA)三种化合物按照摩尔比1:0.4:0.8的比例混合，置于加热装置的容器中，搅拌、抽真空，并升温至120℃，获得1.0摩尔浓度的铅前驱体溶液；将碳酸铯(Cs 2CO 3)、油酸(OA)按照摩尔比1:0.5的比例，加入到十八烯(ODE)中，然后置于加热装置容器中，搅拌、抽真空，并升温至120℃，获得0.7摩尔浓度的铯前驱体溶液；在惰性气体保护条件下，铯前驱体溶液加热至120℃， 注入1.0摩尔浓度的铅前驱体溶液。保温40秒，在此过程中，二维CsPbI 3纳米片逐步组装成多维量子阱结构的纳米晶，纳米晶尺寸为30纳米。采用冰浴快速降温反应溶液到5℃，加入乙酸乙酯或叔丁醇，对反应溶液进行离心，再用正己烷进行洗涤4次，干燥后获得自组装多维量子阱结构的CsPbI 3纳米晶。随后将这种纳米晶溶解到正辛烷、甲苯或二氯甲烷溶剂中形成1.0摩尔浓度的自组装多维量子阱CsPbI 3纳米晶溶液。将1.0摩尔浓度的空穴传输前驱溶液旋涂在不同透明导电氧化物阳极上，在120℃退火15分钟，形成厚度为50纳米的空穴传输层材料P-TPD。将1.0摩尔浓度的自组装多维量子阱CsPbI 3纳米晶溶液旋涂在空穴传输层材料上，在50℃退火30分钟，形成厚度为40纳米的纳米晶发光层。将1.0摩尔浓度的电子传输材料ZnO前驱溶液旋涂在自组装多维量子阱CsPbI 3纳米晶发光层上，在80℃下退火10分钟，获得厚度为60纳米的电子传输层ZnO。采用真空热蒸发在电子传输层上沉积50纳米厚度的金属阴极Ag。结果如表4所示 Mix the three compounds of lead halide (PbI 2 ), oleic acid (OA), and octylamine (OTA) in a molar ratio of 1:0.4:0.8, and place them in the container of the heating device, stir, vacuum, and heat to 120℃, obtain a 1.0 molar lead precursor solution; add cesium carbonate (Cs 2 CO 3 ) and oleic acid (OA) to the octadecene (ODE) at a molar ratio of 1:0.5, and then place In the vessel of the heating device, stir, evacuate, and raise the temperature to 120°C to obtain 0.7 molar concentration of cesium precursor solution; under inert gas protection, heat the cesium precursor solution to 120°C, and inject 1.0 molar concentration of lead precursor Solution. In the process of holding for 40 seconds, the two-dimensional CsPbI 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers. The reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbI 3 nanocrystal was obtained. Subsequently, the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystal solution. A hole transport precursor solution with a 1.0 molar concentration was spin-coated on different transparent conductive oxide anodes, and annealed at 120° C. for 15 minutes to form a hole transport layer material P-TPD with a thickness of 50 nanometers. A 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C. for 30 minutes to form a nanocrystalline light-emitting layer with a thickness of 40 nanometers. A 1.0 molar concentration of electron transport material ZnO precursor solution was spin-coated on the self-assembled multidimensional quantum well CsPbI 3 nanocrystalline light-emitting layer, and annealed at 80° C. for 10 minutes to obtain an electron transport layer ZnO with a thickness of 60 nanometers. A metal cathode Ag with a thickness of 50 nm was deposited on the electron transport layer by vacuum thermal evaporation. The results are shown in Table 4
表4不同TOC对发光二极管性能影响Table 4 The impact of different TOC on the performance of light-emitting diodes
Figure PCTCN2020093651-appb-000004
Figure PCTCN2020093651-appb-000004
实施例5Example 5
将卤化铅(PbI 2)、油酸(OA)、辛胺(OTA)三种化合物按照摩尔比1:0.4:0.8的比例混合，置于加热装置的容器中，搅拌、抽真空，并升温至120℃，获得1.0摩尔浓度的铅前驱体溶液；将碳酸铯(Cs 2CO 3)、油酸(OA)按照摩尔比1:0.5的比例，加入到十八烯(ODE)中，然后置于加热装置容器中，搅拌、抽真空，并升温至120℃，获得0.7摩尔浓度的铯前驱体溶液；在惰性气体保护条件下，铯前驱体溶液加热至120℃， 注入1.0摩尔浓度的铅前驱体溶液。保温40秒，在此过程中，二维CsPbI 3纳米片逐步组装成多维量子阱结构的纳米晶，纳米晶尺寸为30纳米。采用冰浴快速降温反应溶液到5℃，加入乙酸乙酯或叔丁醇，对反应溶液进行离心，再用正己烷进行洗涤4次，干燥后获得自组装多维量子阱结构的CsPbI 3纳米晶。随后将这种纳米晶溶解到正辛烷、甲苯或二氯甲烷溶剂中形成1.0摩尔浓度的自组装多维量子阱CsPbI 3纳米晶溶液。将1.0摩尔浓度的不同空穴传输前驱溶液旋涂在透明导电氧化物阳极ITO上，在120℃退火15分钟，形成厚度为50纳米的不同空穴传输层材料。将1.0摩尔浓度的自组装多维量子阱CsPbI 3纳米晶溶液旋涂在空穴传输层材料上，在50℃退火30分钟，形成厚度为40纳米的纳米晶发光层。将1.0摩尔浓度的电子传输材料ZnO前驱溶液旋涂在自组装多维量子阱CsPbI 3纳米晶发光层上，在80℃下退火10分钟，获得厚度为60纳米的电子传输层ZnO。采用真空热蒸发在电子传输层上沉积50纳米厚度的金属阴极Ag。结果如表5所示： Mix the three compounds of lead halide (PbI 2 ), oleic acid (OA), and octylamine (OTA) in a molar ratio of 1:0.4:0.8, and place them in the container of the heating device, stir, vacuum, and heat to 120℃, obtain a 1.0 molar lead precursor solution; add cesium carbonate (Cs 2 CO 3 ) and oleic acid (OA) to the octadecene (ODE) at a molar ratio of 1:0.5, and then place In the vessel of the heating device, stir, evacuate, and raise the temperature to 120°C to obtain 0.7 molar concentration of cesium precursor solution; under inert gas protection, heat the cesium precursor solution to 120°C, and inject 1.0 molar concentration of lead precursor Solution. In the process of holding for 40 seconds, the two-dimensional CsPbI 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers. The reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbI 3 nanocrystal was obtained. Subsequently, the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystal solution. Different hole transport precursor solutions of 1.0 molar concentration were spin-coated on the transparent conductive oxide anode ITO, and annealed at 120° C. for 15 minutes to form different hole transport layer materials with a thickness of 50 nanometers. A 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C. for 30 minutes to form a nanocrystalline light-emitting layer with a thickness of 40 nanometers. A 1.0 molar concentration of electron transport material ZnO precursor solution was spin-coated on the self-assembled multidimensional quantum well CsPbI 3 nanocrystalline light-emitting layer, and annealed at 80° C. for 10 minutes to obtain an electron transport layer ZnO with a thickness of 60 nanometers. A metal cathode Ag with a thickness of 50 nm was deposited on the electron transport layer by vacuum thermal evaporation. The results are shown in Table 5:
表5不同空穴传输层材料对发光二极管性能影响Table 5 The effect of different hole transport layer materials on the performance of light-emitting diodes
Figure PCTCN2020093651-appb-000005
Figure PCTCN2020093651-appb-000005
实施例6Example 6
将卤化铅(PbI 2)、油酸(OA)、辛胺(OTA)三种化合物按照摩尔比1:0.4:0.8的比例混合，置于加热装置的容器中，搅拌、抽真空，并升温至120℃，获得1.0摩尔浓度的铅前驱体溶液；将碳酸铯(Cs 2CO 3)、油酸(OA)按照摩尔比1:0.5的比例，加入到十八烯(ODE)中，然后置于加热装置容器中，搅拌、抽真空，并升温至120℃，获得0.7摩尔浓度的铯前驱体溶液；在惰性气体保护条件下，铯前驱体溶液加热至120℃，注入1.0摩尔浓度的铅前驱体溶液。保温40秒，在此过程中，二维CsPbI 3纳米片逐步组装成多维量子阱结构的纳米晶，纳米晶尺寸为30纳米。采用冰浴快速降温反应溶液到5℃，加入乙酸乙酯或叔丁醇，对反应溶液进行离心，再用正己烷进行洗涤4次，干燥后获得自组装多维量子阱结构的CsPbI 3纳米晶。随后将这种纳米晶溶解到正辛烷、甲苯或二氯甲烷溶剂中形成1.0摩尔浓度的自组装多维量子阱CsPbI 3纳米晶溶液。将1.0摩尔浓度的T-TPD空穴传输前驱溶液旋涂在透明导电氧化物阳极ITO上，在120℃退火15分钟，形成厚度为50纳米的空穴传输层材料P-TPD。将1.0摩尔浓度的自组装多维量子阱CsPbI 3纳米晶溶液旋涂在空穴传输层材料上，在50℃退火30分钟，形成厚度为40纳米的纳米晶发光层。将1.0摩尔浓度的不同电子传输材料前驱溶液旋涂在自组装多维量子阱CsPbI 3纳米晶发光层上，在80℃下退火10分钟，获得厚度为60纳米的电子传输层。采用真空热蒸发在电子传输层上沉积50纳米厚度的金属阴极Ag。如表6所示。 Mix the three compounds of lead halide (PbI 2 ), oleic acid (OA), and octylamine (OTA) in a molar ratio of 1:0.4:0.8, and place them in the container of the heating device, stir, vacuum, and heat to 120℃, obtain a 1.0 molar lead precursor solution; add cesium carbonate (Cs 2 CO 3 ) and oleic acid (OA) to the octadecene (ODE) at a molar ratio of 1:0.5, and then place In the vessel of the heating device, stir, evacuate, and raise the temperature to 120°C to obtain a cesium precursor solution of 0.7 molar concentration; under inert gas protection, the cesium precursor solution is heated to 120°C, and 1.0 molar concentration of lead precursor is injected Solution. In the process of holding for 40 seconds, the two-dimensional CsPbI 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers. The reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbI 3 nanocrystal was obtained. Subsequently, the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystal solution. A 1.0 molar concentration of T-TPD hole transport precursor solution was spin-coated on the transparent conductive oxide anode ITO, and annealed at 120° C. for 15 minutes to form a hole transport layer material P-TPD with a thickness of 50 nanometers. A 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C. for 30 minutes to form a nanocrystalline light-emitting layer with a thickness of 40 nanometers. The precursor solutions of different electron transport materials with 1.0 molar concentration were spin-coated on the self-assembled multidimensional quantum well CsPbI 3 nanocrystalline light-emitting layer, and annealed at 80° C. for 10 minutes to obtain an electron transport layer with a thickness of 60 nanometers. A metal cathode Ag with a thickness of 50 nm was deposited on the electron transport layer by vacuum thermal evaporation. As shown in Table 6.
表6不同电子传输层对发光二极管性能影响Table 6 The influence of different electron transport layers on the performance of light-emitting diodes
Figure PCTCN2020093651-appb-000006
Figure PCTCN2020093651-appb-000006
实施例7Example 7
将卤化铅(PbI 2)、油酸(OA)、辛胺(OTA)三种化合物按照摩尔比1:0.4:0.8的比例混合，置于加热装置的容器中，搅拌、抽真空，并升温至120℃，获得1.0摩尔浓度的铅前驱体溶液；将碳酸铯(Cs 2CO 3)、油酸(OA)按照摩尔比1:0.5的比例，加入到十八烯(ODE)中，然后置于加热装置容器中，搅拌、抽真空，并升温至120℃，获得0.7摩尔浓度的铯前驱体溶液；在惰性气体保护条件下，铯前驱体溶液加热至120℃，注入1.0摩尔浓度的铅前驱体溶液。保温40秒，在此过程中，二维CsPbI 3纳米片逐步组装成多维量子阱结构的纳米晶，纳米晶尺寸为30纳米。采用冰浴快速降温反应溶液到5℃，加入乙酸乙酯或叔丁醇，对反应溶液 进行离心，再用正己烷进行洗涤4次，干燥后获得自组装多维量子阱结构的CsPbI 3纳米晶。随后将这种纳米晶溶解到正辛烷、甲苯或二氯甲烷溶剂中形成1.0摩尔浓度的自组装多维量子阱CsPbI 3纳米晶溶液。将1.0摩尔浓度的T-TPD空穴传输前驱溶液旋涂在透明导电氧化物阳极ITO上，在120℃退火15分钟，形成厚度为50纳米的空穴传输层材料P-TPD。将1.0摩尔浓度的自组装多维量子阱CsPbI 3纳米晶溶液旋涂在空穴传输层材料上，在50℃退火30分钟，形成厚度为40纳米的纳米晶发光层。将1.0摩尔浓度的电子传输材料ZnO前驱溶液旋涂在自组装多维量子阱CsPbI 3纳米晶发光层上，在80℃下退火10分钟，获得厚度为60纳米的电子传输层ZnO。采用真空热蒸发在电子传输层上沉积50纳米厚度的不同金属阴极。如表7所示。 Mix the three compounds of lead halide (PbI 2 ), oleic acid (OA), and octylamine (OTA) in a molar ratio of 1:0.4:0.8, and place them in the container of the heating device, stir, vacuum, and heat to 120℃, obtain a 1.0 molar lead precursor solution; add cesium carbonate (Cs 2 CO 3 ) and oleic acid (OA) to the octadecene (ODE) at a molar ratio of 1:0.5, and then place In the vessel of the heating device, stir, evacuate, and raise the temperature to 120°C to obtain a cesium precursor solution of 0.7 molar concentration; under inert gas protection, the cesium precursor solution is heated to 120°C, and 1.0 molar concentration of lead precursor is injected Solution. In the process of holding for 40 seconds, the two-dimensional CsPbI 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, and the size of the nanocrystals is 30 nanometers. The reaction solution was quickly cooled to 5°C in an ice bath, ethyl acetate or tert-butanol was added, the reaction solution was centrifuged, and then washed with n-hexane for 4 times. After drying, a self-assembled multidimensional quantum well structure CsPbI 3 nanocrystal was obtained. Subsequently, the nanocrystals are dissolved in n-octane, toluene or dichloromethane solvents to form a 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystal solution. A 1.0 molar concentration of T-TPD hole transport precursor solution was spin-coated on the transparent conductive oxide anode ITO, and annealed at 120° C. for 15 minutes to form a hole transport layer material P-TPD with a thickness of 50 nanometers. A 1.0 molar self-assembled multidimensional quantum well CsPbI 3 nanocrystalline solution was spin-coated on the hole transport layer material, and annealed at 50° C. for 30 minutes to form a nanocrystalline light-emitting layer with a thickness of 40 nanometers. A 1.0 molar concentration of electron transport material ZnO precursor solution was spin-coated on the self-assembled multidimensional quantum well CsPbI 3 nanocrystalline light-emitting layer, and annealed at 80° C. for 10 minutes to obtain an electron transport layer ZnO with a thickness of 60 nanometers. Vacuum thermal evaporation is used to deposit different metal cathodes with a thickness of 50 nanometers on the electron transport layer. As shown in Table 7.
表7不同金属阴极材料Table 7 Different metal cathode materials
Figure PCTCN2020093651-appb-000007
Figure PCTCN2020093651-appb-000007

Claims (6)

  1. 一种自组装多维量子阱CsPbX 3钙钛矿纳米晶电致发光二极管，其特征在于是由透明导电氧化物阳极TOC(1)、空穴传输层材料HTL(2)、多维量子阱结构CsPbX 3纳米晶发光层EL(3)、电子传输层材料ETL(4)和金属阴极CL(5)组成；具体制备步骤如下： A self-assembled multi-dimensional quantum well CsPbX 3 perovskite nanocrystalline electroluminescent diode, which is characterized in that it is composed of a transparent conductive oxide anode TOC (1), a hole transport layer material HTL (2), and a multi-dimensional quantum well structure CsPbX 3 Nanocrystalline light-emitting layer EL (3), electron transport layer material ETL (4) and metal cathode CL (5) are composed; the specific preparation steps are as follows:
    (1)首先制备自组装多维量子阱CsPbX 3钙钛矿纳米晶溶液；将卤化铅(PbX 2)、油酸(OA)、辛胺(OTA)三种化合物按照摩尔比1:0.3:0.6～1:0.5:1的比例混合，置于加热装置的容器中，搅拌、抽真空，并升温至100～150℃，获得0.5～1.5摩尔浓度的铅前驱体溶液；将碳酸铯(Cs 2CO 3)、油酸(OA)按照摩尔比1:0.4～1:0.6的比例，加入到十八烯(ODE)中，然后置于加热装置容器中，搅拌、抽真空，并升温至100～150℃，获得0.5～1.0摩尔浓度的铯前驱体溶液；在惰性气体保护条件下，铯前驱体溶液加热至100～150℃，注入0.5～1.5摩尔浓度的铅前驱体溶液，保温30～60秒；在此过程中，二维CsPbX 3纳米片逐步组装成多维量子阱结构的纳米晶，纳米晶尺寸为20～40纳米；采用冰浴快速降温反应溶液到0～10℃，加入乙酸乙酯或叔丁醇，对反应溶液进行离心，再用正己烷进行洗涤3-5次，干燥后获得自组装多维量子阱结构的CsPbX 3纳米晶，随后将这种纳米晶溶解到正辛烷、甲苯或二氯甲烷溶剂中形成0.5～1.5摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液； (1) First, prepare the self-assembled multidimensional quantum well CsPbX 3 perovskite nanocrystal solution; combine the three compounds of lead halide (PbX 2 ), oleic acid (OA), and octylamine (OTA) according to the molar ratio of 1:0.3:0.6~ Mix at a ratio of 1:0.5:1, place it in the container of the heating device, stir, evacuate, and raise the temperature to 100-150°C to obtain a 0.5-1.5 molar concentration of the lead precursor solution; add cesium carbonate (Cs 2 CO 3 ), oleic acid (OA) is added to the octadecene (ODE) in a molar ratio of 1:0.4～1:0.6, and then placed in the heating device container, stirred, vacuumed, and heated to 100～150℃ , To obtain a cesium precursor solution with a molar concentration of 0.5 to 1.0; under inert gas protection, the cesium precursor solution is heated to 100-150°C, and a lead precursor solution with a molar concentration of 0.5 to 1.5 is injected, and the temperature is maintained for 30 to 60 seconds; During this process, the two-dimensional CsPbX 3 nanosheets are gradually assembled into nanocrystals with a multidimensional quantum well structure, the size of the nanocrystals is 20-40 nanometers; an ice bath is used to quickly cool the reaction solution to 0-10℃, and ethyl acetate or tert-butyl is added. Alcohol, the reaction solution is centrifuged, and then washed with n-hexane for 3-5 times. After drying, the self-assembled multi-dimensional quantum well structure of CsPbX 3 nanocrystals are obtained, and then the nanocrystals are dissolved in n-octane, toluene or dichloride A self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline solution with a molar concentration of 0.5 to 1.5 is formed in a methane solvent;
    (2)将0.5～1.5摩尔浓度的空穴传输层材料旋涂在透明导电氧化物阳极TOC(1)上，在100～150℃退火10～20分钟，形成厚度为30～70纳米的空穴传输层HTL(2)；(2) Spin-coating the hole transport layer material with a molar concentration of 0.5 to 1.5 on the transparent conductive oxide anode TOC (1), annealing at 100 to 150°C for 10 to 20 minutes to form holes with a thickness of 30 to 70 nanometers Transport layer HTL(2);
    (3)将0.5～1.5摩尔浓度的自组装多维量子阱CsPbX 3纳米晶溶液旋涂在空穴传输层HTL(2)上，在30～100℃退火20～50分钟，形成厚度为30～50纳米的纳米晶发光层EL(3)； (3) The self-assembled multi-dimensional quantum well CsPbX 3 nanocrystalline solution with a molar concentration of 0.5 to 1.5 is spin-coated on the hole transport layer HTL (2), and annealed at 30 to 100°C for 20 to 50 minutes to form a thickness of 30 to 50 Nano-nanocrystalline light-emitting layer EL(3);
    (4)将0.5～1.5摩尔浓度的电子传输材料旋涂在自组装多维量子阱 CsPbX 3纳米晶发光层EL(3)上，在30～100℃下退火5～20分钟，获得厚度为50～100纳米的电子传输层ETL(4)； (4) The electron transport material with a molar concentration of 0.5 to 1.5 is spin-coated on the self-assembled multidimensional quantum well CsPbX 3 nanocrystalline light-emitting layer EL (3), and annealed at 30 to 100°C for 5 to 20 minutes to obtain a thickness of 50 to 100nm electron transport layer ETL(4);
    (5)采用真空热蒸发在电子传输层ETL(4)上沉积30～100纳米厚度的金属阴极CL(5)。(5) A metal cathode CL (5) with a thickness of 30-100 nanometers is deposited on the electron transport layer ETL (4) by vacuum thermal evaporation.
  2. 如权利要求1所述的自组装多维量子阱CsPbX 3钙钛矿纳米晶电致发光二极管，其特征在于CsPbX 3中X为卤族元素，是Cl、Br、I一种，或者Cl和Br、Br和I混合卤素。 The self-assembled multidimensional quantum well CsPbX 3 perovskite nanocrystalline electroluminescent diode according to claim 1, wherein X in CsPbX 3 is a halogen element, which is one of Cl, Br, I, or Cl and Br, Br and I are mixed with halogens.
  3. 根据权利要求1所述的自组装多维量子阱CsPbX 3钙钛矿纳米晶电致发光二极管，其特征在于透明导电氧化物阳极TOC(1)为掺铟氧化锡(ITO)或者掺氟氧化锡(FTO)。 The self-assembled multidimensional quantum well CsPbX 3 perovskite nanocrystalline electroluminescent diode according to claim 1, wherein the transparent conductive oxide anode TOC (1) is indium-doped tin oxide (ITO) or fluorine-doped tin oxide ( FTO).
  4. 根据权利要求1所述的自组装多维量子阱CsPbX 3钙钛矿纳米晶电致发光二极管，其特征在于空穴传输层材料HTL(2)为聚[双(4-苯基)(4-丁基苯基)胺](简称：P-TPD)、1,2,4,5-四(三氟甲基)苯(简称：TFB)、聚(9-乙烯咔唑)(简称：PVK)、聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(简称：PETDOT:PSS)，NiO，MgNiO，4,4'-二(9-咔唑)联苯(简称：CBP)，MoO 2或WO 3中的一种或多种。 The self-assembled multidimensional quantum well CsPbX 3 perovskite nanocrystalline electroluminescent diode according to claim 1, wherein the hole transport layer material HTL (2) is poly[bis(4-phenyl)(4-butyl) Phenyl)amine] (abbreviation: P-TPD), 1,2,4,5-tetrakis(trifluoromethyl)benzene (abbreviation: TFB), poly(9-vinylcarbazole) (abbreviation: PVK), Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (abbreviation: PETDOT:PSS), NiO, MgNiO, 4,4'-bis(9-carbazole) biphenyl (abbreviation: CBP), one or more of MoO 2 or WO 3.
  5. 根据权利要求1所述的自组装多维量子阱CsPbX 3钙钛矿纳米晶电致发光二极管，其特征在于电子传输层材料ETL(4)为TiO 2，ZnO，SnO 2，AlZnO，MgZnO，Zn 2SnO 4，Nb 2O 5，In 2O 3，8-羟基喹啉铝(简称：Alq3)，3-(联苯-4-基)-5-(4-叔丁基苯基)-4-苯基-4H-1,2,4-三唑(简称：TZA)，2-(4-联苯基)-5-苯基恶二唑(简称：PBD)，3',3”-二苯基-3'H,3”H-二环丙烷并[1,9:52,60]富勒烯-C60-IH-3',3”-二丁酸二甲酯(简称：PCBM)或溴甲酚紫钠盐(简称：BCP)中的一种或多种。 The self-assembled multidimensional quantum well CsPbX 3 perovskite nanocrystalline electroluminescent diode according to claim 1, wherein the electron transport layer material ETL (4) is TiO 2 , ZnO, SnO 2 , AlZnO, MgZnO, Zn 2 SnO 4 , Nb 2 O 5 , In 2 O 3 , 8-hydroxyquinoline aluminum (abbreviation: Alq3), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4- Phenyl-4H-1,2,4-triazole (abbreviation: TZA), 2-(4-biphenyl)-5-phenyloxadiazole (abbreviation: PBD), 3',3”-diphenyl -3'H,3”H-dicyclopropano[1,9:52,60]fullerene-C60-IH-3',3”-dimethyl dibutyrate (abbreviation: PCBM) or bromine One or more of cresol purple sodium salt (abbreviation: BCP).
  6. 根据权利要求1所述的自组装多维量子阱CsPbX 3钙钛矿纳米晶电致发光二极管，其特征在于金属阴极CL(5)是银、金和铝中的一种。 The self-assembled multidimensional quantum well CsPbX 3 perovskite nanocrystalline electroluminescent diode according to claim 1, wherein the metal cathode CL (5) is one of silver, gold and aluminum.
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