CN114242920A - Indium phosphide quantum dot electroluminescent device based on tin oxide as electron injection layer and preparation thereof - Google Patents
Indium phosphide quantum dot electroluminescent device based on tin oxide as electron injection layer and preparation thereof Download PDFInfo
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- 238000002347 injection Methods 0.000 title claims abstract description 58
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- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 8
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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]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
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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
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- Nanotechnology (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the technical field of electroluminescent devices, and discloses an indium phosphide quantum dot electroluminescent device based on tin oxide as an electron injection layer and preparation thereof. The indium phosphide quantum dot electroluminescent device comprises an ITO substrate, an electron injection layer, an electron transport layer, an indium phosphide quantum dot light emitting layer, a hole transport layer, a hole injection layer and a metal anode which are sequentially stacked; the electron injection layer is tin dioxide. According to the invention, the tin dioxide material is used as the electron injection layer of the electroluminescent device, the electron injection is optimized, the preparation of the indium phosphide quantum dot electroluminescent device based on the tin dioxide material as the electron injection layer is realized by utilizing the high electron mobility of the tin dioxide material, the turn-on voltage of the quantum dot device is favorably reduced, the electroluminescent efficiency and the working life of the quantum dot device are improved, and the application of the quantum dot material in the fields of next generation display and illumination is promoted.
Description
Technical Field
The invention belongs to the technical field of indium phosphide quantum dot photoelectric devices, relates to an indium phosphide quantum dot electroluminescent device based on tin dioxide as an electron injection layer, and particularly relates to an indium phosphide quantum dot electroluminescent device and a preparation method thereof.
Background
In the field of electro-optical display, quantum dot display has attracted much attention from scientists because of its excellent properties such as wide spectral tunability, narrow full width at half maximum (FWHM), high color purity, etc., and is considered to be a very prominent candidate for the next generation of display technology. The performance of quantum dot light emitting diodes (QLEDs) has been rapidly developed, and especially the red, green and blue three-color light emitting performance of the cadmium-based QLED has been very close to the level of Organic Light Emitting Diodes (OLEDs). However, cadmium element has serious harm to human body and environment. Therefore, researchers have shifted their attention to more environmentally friendly quantum dot materials, and InP quantum dots are the most promising environmentally friendly materials to replace cadmium-based quantum dots due to their outstanding properties such as large bohr radius, wide spectral tunability, etc.
However, compared with the cadmium-based quantum dot light emitting diode, the InP quantum dot light emitting diode still has a large gap in performance and stability. Among the studies on InP quantum dots, the synthesis of InP quantum dots is often studied, for example: core-shell structure, choice of ligands, etc. The research on adjusting and optimizing the device structure of the InP quantum dot light-emitting diode is less.
The invention adopts the tin dioxide material as the electron injection layer of the indium phosphide quantum dot electroluminescent device, optimizes the electron injection of the device, realizes the preparation of the indium phosphide quantum dot electroluminescent device based on the tin dioxide material as the electron injection layer, is beneficial to reducing the turn-on voltage of the quantum dot device, improves the electroluminescent efficiency and the working life of the quantum dot device, and promotes the application of the quantum dot material in the fields of next generation display and illumination.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide an indium phosphide quantum dot electroluminescent device based on a tin dioxide material as an electron injection layer and a preparation method thereof. The invention adopts the tin dioxide material as the electron injection layer of the indium phosphide quantum dot electroluminescent device, optimizes the electron injection of the device and improves the efficiency of the indium phosphide quantum dot light-emitting diode device.
The purpose of the invention is realized by the following technical scheme:
an indium phosphide quantum dot electroluminescent device based on tin oxide as an electron injection layer comprises an ITO substrate, an electron injection layer, an electron transport layer, an indium phosphide quantum dot light-emitting layer, a hole transport layer, a hole injection layer and a metal anode which are sequentially stacked; the electron injection layer is tin dioxide.
The tin dioxide material comprises tin dioxide nanoparticles (the particle size is about 3-5 nm) with different particle sizes. The tin dioxide material is prepared into a film by adopting a spin coating process. The thickness of the electron injection layer is 30 to 50 nm.
The electron transport layer is an inorganic nanoparticle material (such as more than one of zinc oxide, zinc magnesium oxide and titanium oxide) of metal oxide, and has the effects of electron injection and transport; in the case of preparing a film by solution processing, the solvent used may be ethanol, isopropanol, or the like. The material of the electron transport layer is preferably zinc magnesium oxide. The thickness of the electron transport layer is 40-70 nm.
The material of the indium phosphide quantum dot light-emitting layer comprises quantum dots with different core-shell structures and different particle sizes (such as 2nm, 4nm and 6nm), wherein the quantum dots comprise InP/ZnS with core-shell structures, InP/ZnSe/ZnS with core-shell structures and the like; the quantum dot material comprises red light, green light, blue light and other quantum dots, such as: the green InP/ZnS quantum dot has a core-shell structure.
The indium phosphide quantum dot light-emitting layer adopts a solution processing method (such as a spin coating process) to prepare a film, and the solvent is a single solvent of n-octane, toluene, xylene and chlorobenzene or a composite solvent of the single solvent and high-boiling-point ethers (such as m-phenyl dimethyl ether and dimethyl anisole) and the like.
The thickness of the indium phosphide quantum dot light-emitting layer is as follows: 20-35 nm.
The hole transport layer may be an aromatic compound or a carbazole-based compound having low ionization energy and an organometallic complex film, and is preferably 4,4',4 ″ -tris (carbazol-9-yl) triphenylamine.
The hole transport layer is specifically more than one of 4,4 '-tris (carbazole-9-yl) triphenylamine (TCTA), Poly (9, 9-dioctylfluorene-2, 7-diyl) -co (4,4' - (N- (4-sec-butylphenyl) diphenylamine)) (TFB), Poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) (Poly-TPD); preferably TCTA;
thickness of the hole transport layer: 30-60 nm.
The hole injection layer is a film formed by a conjugated or non-conjugated high-conductivity system with carbon or silicon as a main chain; preferably polyaniline, polythiophene, polypyrrole, or poly-p-phenylene vinylene film, or inorganic oxide material molybdenum oxide.
The metal anode layer comprises metal materials such as metal aluminum, gold, silver and the like or an alloy of more than two metals.
The preparation method of the indium phosphide quantum dot electroluminescent device based on tin oxide as the electron injection layer comprises the following steps:
1) carrying out oxygen plasma treatment on the ITO substrate, and then sequentially preparing a tin dioxide electron injection layer, an electron transmission layer and an indium phosphide quantum dot light-emitting layer on the ITO substrate by a solution processing process;
2) preparing a hole transport layer and a hole injection layer on the luminescent layer in sequence by a solution processing process or a vacuum evaporation process;
3) a metal anode is prepared on the hole injection layer.
The tin dioxide electron injection layer is prepared in sequence through a solution processing technology, and when the electron transport layer is prepared, the adopted solvent is more than one of ethanol and isopropanol;
when the indium phosphide quantum dot light-emitting layer is prepared by a solution processing technology, the solvent is one of n-octane, toluene, xylene and chlorobenzene or a composite solvent blended with more than one of m-phenyl dimethyl ether and dimethyl anisole.
The invention has the advantages and effects that:
the indium phosphide quantum dot electroluminescent device takes the tin dioxide material as the electron injection layer, the tin dioxide material is close to the work function of ITO, the injection of electrons is optimized, the electron mobility of the tin dioxide is high, the transmission of electrons is enhanced, the indium phosphide quantum dot electroluminescent device taking the tin dioxide material as the electron injection layer is realized, the turn-on voltage of the quantum dot device can be effectively reduced, the electroluminescent efficiency of the indium phosphide quantum dot electroluminescent device is improved, and the application of the quantum dot material in the fields of next generation display and illumination is promoted.
Drawings
FIG. 1 is a schematic structural diagram of an indium phosphide quantum dot electroluminescent device of the present invention; the solar cell comprises a 1-ITO substrate, a 2-electron injection layer, a 3-electron transport layer, a 4-indium phosphide quantum dot light-emitting layer, a 5-hole transport layer, a 6-hole injection layer and a 7-metal anode;
FIG. 2 is a graph of the performance of a green-emitting InP quantum dot electroluminescent device of example 1; a. b is a current density-voltage-luminance (J-V-I) graph and a current efficiency-current density (L-E) graph of the device prepared in example 1, respectively; c is the electroluminescence (E-L) spectrum of the device prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
The structure schematic diagram of the indium phosphide quantum dot electroluminescent device is shown in fig. 1, and the indium phosphide quantum dot electroluminescent device comprises an ITO substrate 1, an electron injection layer 2, an electron transport layer 3, an indium phosphide quantum dot light-emitting layer 4, a hole transport layer 5, a hole injection layer 6 and a metal anode 7 which are sequentially stacked; the electron injection layer 2 is tin dioxide.
Example 1
Selecting a device structure shown in FIG. 1, carrying out ultrasonic cleaning on an ITO substrate for 10 minutes by respectively using a cleaning solution, deionized water and isopropanol, cleaning surface pollutants, drying the surface pollutants by using high-pressure nitrogen, carrying out surface modification on the surface pollutants by using oxygen plasma, and then spin-coating tin dioxide (with the particle size of about 3-5 nm) in a nitrogen glove box to form an electron injection layer (with the thickness of 40nm), wherein the used solvent is ethanol; spin-coating zinc magnesium oxide on tin dioxide as electron transport layer (thickness-50 nm) with ethanol as solvent, spin-coating green-light indium phosphide quantum dot material on zinc magnesium oxide to prepare quantum dot light-emitting layer (green-light InP/ZnS quantum dot with core-shell structure) with n-octane (thickness-30 nm), and vacuum evaporating in 3 × 10 chamber-4Pa) vapor deposition of hole transportA transmission layer 4,4' -tris (carbazole-9-yl) triphenylamine (thickness of 50nm) and a hole injection layer MoOx(thickness-10 nm) and metal electrode Al (thickness-150 nm), finally, adhering the glass packaging sheet with epoxy resin and carrying out ultraviolet curing packaging.
FIG. 2 is a graph of the performance of a green-emitting InP quantum dot electroluminescent device of example 1; a. b is a current density-voltage-luminance (J-V-I) graph and a current efficiency-current density (L-E) graph of the device prepared in example 1, respectively; c is the electroluminescence (E-L) spectrum of the device prepared in example 1.
Example 2
Selecting a device structure shown in figure 1, adopting an ITO substrate, respectively ultrasonically cleaning the ITO substrate by using a cleaning solution, deionized water and isopropanol for 10 minutes, cleaning surface pollutants, drying the ITO substrate by using high-pressure nitrogen, performing surface modification on the ITO substrate by using oxygen plasma, then spraying tin dioxide on the ITO substrate by using a spraying method as an electron injection layer (the thickness is 40nm), using ethanol as a solvent, transferring the substrate into a nitrogen glove box, then spin-coating zinc magnesium oxide on the tin dioxide substrate as an electron transmission layer (the thickness is 50nm), using ethanol as a solvent, spin-coating a green-light indium phosphide quantum dot material on the zinc magnesium oxide to prepare a quantum dot light emitting layer, using n-octane as a solvent (the thickness is 30nm), and finally performing high-vacuum evaporation in a high-vacuum evaporation bin (3 multiplied by 10 and the thickness is 30nm)-4Pa) respectively evaporating a hole transport layer 4,4' -tri (carbazole-9-yl) triphenylamine (thickness is 50nm) and a hole injection layer MoOx(thickness-10 nm) and metal electrode Al (thickness-150 nm), finally, adhering the glass packaging sheet with epoxy resin and carrying out ultraviolet curing packaging.
Claims (8)
1. An indium phosphide quantum dot electroluminescent device based on tin oxide as an electron injection layer, characterized in that: the ITO substrate, the electron injection layer, the electron transport layer, the indium phosphide quantum dot light emitting layer, the hole transport layer, the hole injection layer and the metal anode are sequentially stacked; the electron injection layer is tin dioxide.
2. An indium phosphide quantum dot electroluminescent device based on tin oxide as an electron injection layer as set forth in claim 1, characterized in that: the tin dioxide is tin dioxide nanoparticles, and the particle size is 3-5 nm;
the electron transport layer is more than one of zinc oxide, zinc magnesium oxide and titanium oxide, and the thickness of the electron transport layer is 40-70 nm;
the material of the indium phosphide quantum dot light-emitting layer comprises InP/ZnS quantum dots with a core-shell structure and InP/ZnSe/ZnS quantum dots; the quantum dots are red light quantum dots, green light quantum dots and blue light quantum dots;
the thickness of the indium phosphide quantum dot light-emitting layer is 20-35 nm.
3. An indium phosphide quantum dot electroluminescent device based on tin oxide as an electron injection layer as set forth in claim 2, characterized in that: the electron transport layer is zinc magnesium oxide.
4. An indium phosphide quantum dot electroluminescent device based on tin oxide as an electron injection layer as set forth in claim 1, characterized in that: the hole transport layer is more than one of 4,4 '-tris (carbazole-9-yl) triphenylamine, poly (9, 9-dioctylfluorene-2, 7-diyl) -co (4,4' - (N- (4-sec-butylphenyl) diphenylamine)), poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine);
the thickness of the hole transport layer is 30-60 nm;
the hole injection layer is made of more than one of polyaniline, polythiophene, polypyrrole, poly (p-phenylene vinylene) or molybdenum oxide;
the thickness of the hole injection layer is 6-12 nm.
5. An indium phosphide quantum dot electroluminescent device based on tin oxide as an electron injection layer as defined in claim 4, characterized in that: the hole transport layer is 4,4' -tris (carbazole-9-yl) triphenylamine; the hole injection layer is molybdenum oxide.
6. An indium phosphide quantum dot electroluminescent device based on tin oxide as an electron injection layer as set forth in claim 1, characterized in that: the metal anode layer comprises more than one of metal aluminum, gold and silver.
7. The method for preparing the indium phosphide quantum dot electroluminescent device based on tin oxide as the electron injection layer according to any one of claims 1 to 6, wherein the method comprises the following steps: the method comprises the following steps:
1) carrying out oxygen plasma treatment on the ITO substrate, and then sequentially preparing a tin dioxide electron injection layer, an electron transmission layer and an indium phosphide quantum dot light-emitting layer on the ITO substrate by a solution processing process;
2) preparing a hole transport layer and a hole injection layer on the luminescent layer in sequence by a solution processing process or a vacuum evaporation process;
3) a metal anode is prepared on the hole injection layer.
8. The method for preparing an indium phosphide quantum dot electroluminescent device based on tin oxide as an electron injection layer as claimed in claim 7, wherein: the tin dioxide electron injection layer is prepared in sequence through a solution processing technology, and when the electron transport layer is prepared, the adopted solvent is more than one of ethanol and isopropanol;
when the indium phosphide quantum dot light-emitting layer is prepared by a solution processing technology, the solvent is one of n-octane, toluene, xylene and chlorobenzene or a composite solvent blended with more than one of m-phenyl dimethyl ether and dimethyl anisole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111340780.0A CN114242920B (en) | 2021-11-12 | 2021-11-12 | Indium phosphide quantum dot electroluminescent device based on tin oxide as electron injection layer and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111340780.0A CN114242920B (en) | 2021-11-12 | 2021-11-12 | Indium phosphide quantum dot electroluminescent device based on tin oxide as electron injection layer and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114242920A true CN114242920A (en) | 2022-03-25 |
| CN114242920B CN114242920B (en) | 2024-06-25 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713098A (en) * | 2017-10-26 | 2019-05-03 | 乐金显示有限公司 | Light emitting diode and luminaire including the light emitting diode |
| CN108075043B (en) * | 2016-11-15 | 2019-11-01 | 乐金显示有限公司 | Light emitting diode with quantum dots and the luminous display unit for using the diode |
| CN112397665A (en) * | 2020-11-05 | 2021-02-23 | 上海大学 | Inverted organic electroluminescent device and preparation method thereof |
| CN113493219A (en) * | 2020-04-07 | 2021-10-12 | 香港理工大学深圳研究院 | Tin dioxide quantum dot material, preparation method thereof and photoelectric device |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108075043B (en) * | 2016-11-15 | 2019-11-01 | 乐金显示有限公司 | Light emitting diode with quantum dots and the luminous display unit for using the diode |
| CN109713098A (en) * | 2017-10-26 | 2019-05-03 | 乐金显示有限公司 | Light emitting diode and luminaire including the light emitting diode |
| CN113493219A (en) * | 2020-04-07 | 2021-10-12 | 香港理工大学深圳研究院 | Tin dioxide quantum dot material, preparation method thereof and photoelectric device |
| CN112397665A (en) * | 2020-11-05 | 2021-02-23 | 上海大学 | Inverted organic electroluminescent device and preparation method thereof |
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