CN114464760B - Electron transport layer material, semiconductor device and preparation method of electron transport layer material and semiconductor device - Google Patents
Electron transport layer material, semiconductor device and preparation method of electron transport layer material and semiconductor device Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Abstract
The application provides an electron transport layer material and a preparation method thereof, a semiconductor device and a preparation method thereof, and belongs to the field of semiconductor device manufacturing. The electron transport layer material comprises ZnAlO/rGO nano-composite, and the preparation method comprises the steps of preparing graphene oxide into sol, adding a guiding agent, a precipitating agent, zn salt and Al salt into the sol for heating reaction to prepare ZnAl-LDH/rGO, wherein the molar ratio of the Zn salt to the Al salt is (2:1) - (4:1); and calcining ZnAl-LDH/rGO to prepare the ZnAlO/rGO nanocomposite. The device prepared by the material can improve the phenomenon of unbalance injection of electrons and holes in the quantum dot layer of the device, thereby improving the efficiency of the device and prolonging the service life of the device.
Description
Technical Field
The present application relates to the field of semiconductor device manufacturing, and in particular, to an electron transport layer material and a preparation method thereof, a semiconductor device and a preparation method thereof.
Background
In the prior art, the phenomenon of unbalance injection of electrons and holes exists in a quantum dot layer in a semiconductor device, so that the efficiency and the service life of the device are greatly reduced.
Disclosure of Invention
The invention aims to provide an electron transport layer material and a preparation method thereof, a semiconductor device and a preparation method thereof, which can improve the phenomenon of unbalance injection of electrons and holes in a quantum dot layer, thereby improving the efficiency of the device and prolonging the service life of the device.
Embodiments of the present application are implemented as follows:
in a first aspect, embodiments of the present application provide an electron transport layer material comprising ZnAlO/rGO nanocomposite.
In the technical scheme, the electron transport layer material comprising the ZnAlO/rGO nano compound can effectively regulate and control the electron mobility in the electron transport layer.
In a second aspect, embodiments of the present application provide a method for preparing an electron transport layer material according to the embodiments of the first aspect, including the following steps:
preparing graphene oxide;
preparing graphene oxide into sol, adding a guiding agent, a precipitating agent, zn salt and Al salt into the sol, and carrying out heating reaction to obtain ZnAl-LDH/rGO, wherein the molar ratio of the Zn salt to the Al salt is (2:1) - (4:1);
and calcining ZnAl-LDH/rGO to prepare the ZnAlO/rGO nanocomposite.
In the technical scheme, the molar ratio of Zn salt to Al salt is controlled within the range of (2:1) - (4:1), so that the preparation of the ZnAl-LDH/rGO intermediate product with a crystal structure can be ensured, and on the basis, the ZnAlO/rGO nanocomposite capable of effectively regulating and controlling the electron mobility can be prepared by combining the process.
In some alternative embodiments, in the step of heating the reaction, the reaction temperature is 60-180 ℃ and the reaction time is 6-48 hours.
In the technical scheme, the reaction temperature and the reaction time are respectively controlled within the range of 60-180 ℃ and 6-48 hours, so that the prepared ZnAlO/rGO nano compound can be ensured to have better regulation and control performance on electron mobility.
In some alternative embodiments, in the step of preparing ZnAl-LDH/rGO, the graphene oxide has a mass of m1, the amount of total material of Zn salt and Al salt being m2, m1: m2 is (80 to 120): (0.01 to 0.014).
In the technical scheme, the mass of graphene oxide and the total mass of Zn salt and Al salt are controlled to be (80-120): in the range of (0.01-0.014), the regulation and control performance of the prepared ZnAlO/rGO nano-composite on electron mobility can be further optimized.
In some alternative embodiments, the directing agent comprises citrate;
optionally, the directing agent comprises at least one of citric acid, sodium citrate, sodium dihydrogen citrate, sodium monohydrogen citrate, or potassium citrate.
In the technical scheme, the guiding agent comprises citrate, and the types of the guiding agent are limited, so that ZnAl-LDH with a crystal structure can be better prepared, and graphene oxide can be better reduced to obtain reduced graphene oxide (rGO) through the reduction performance of the citrate.
In some alternative embodiments, the graphene oxide is prepared from graphite by a hydrothermal method, and the temperature of the water bath reaction is 15-30 ℃ and the time of the water bath reaction is 20-120 min in the preparation process of the hydrothermal method.
According to the technical scheme, the temperature and time of the water bath reaction are respectively controlled within the range of 15-30 ℃ and 20-120 min, so that the graphene oxide with a single layer and uniform particle size can be prepared better.
In some alternative embodiments, the step of calcining is performed under an atmosphere of a protective gas; the protective gas comprises oxygen, and at least one of inert gas, nitrogen and carbon dioxide;
optionally, in the protective gas, the volume ratio of oxygen is 5-25%.
In the technical scheme, the protective gas is arranged and the type of the protective gas is limited, so that the graphite material is prevented from being oxidized, and ZnAlO is prevented from being reduced; in addition, the volume ratio of oxygen in the protective gas is limited to be in the range of 5-25%, so that a better protective effect can be achieved on the graphite material and ZnAlO.
In a third aspect, embodiments of the present application provide a semiconductor device, including an electron transport layer made of a material such as the material of the electron transport layer provided in the embodiment of the first aspect or the material of the electron transport layer manufactured by the method for manufacturing the material of the electron transport layer provided in the embodiment of the second aspect.
In the above technical scheme, the material of the electron transport layer in the semiconductor device is limited, so as to effectively regulate and control the electron mobility in the electron transport layer, thereby improving the phenomenon of unbalance injection of electrons and holes in the quantum dot layer of the semiconductor device, and further prolonging the service life of the device while improving the efficiency of the device.
In a fourth aspect, embodiments of the present application provide a method for manufacturing a semiconductor device according to the embodiments of the third aspect, including preparing an electron transport layer using a ZnAlO/rGO composite nanomaterial.
In the technical scheme, the electron transport layer is prepared by adopting the ZnAlO/rGO composite nano material, and the semiconductor device for effectively regulating and controlling the electron mobility in the electron transport layer can be prepared.
In some alternative embodiments, the method comprises the steps of:
preparing an anode on the surface of a substrate;
preparing a hole injection layer on the surface of the anode;
preparing a hole transport layer on the surface of the hole injection layer;
preparing a quantum dot layer on the surface of the hole transport layer;
preparing an electron transport layer on the surface of the quantum dot layer by adopting a ZnAlO/rGO composite nano material;
and preparing a cathode on the surface of the electron transport layer, and packaging.
According to the technical scheme, the semiconductor device can be prepared by adopting the preparation process, meanwhile, the electron transport layer is prepared on the surface of the quantum dot layer by adopting the ZnAlO/rGO composite nano material, and the electron mobility of the electron transport layer of the prepared semiconductor device can be effectively regulated and controlled.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for preparing an electron transport layer material according to an embodiment of the present application;
fig. 2 is a schematic structural diagram of a QLED device using ZnAlO/rGO composite nanomaterial as ETL according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In addition, in the description of the present application, unless otherwise indicated, "one or more" means "a plurality of" means two or more; the range of the values a to b includes the two end values "a" and "b", and the "measurement unit" in the values a to b+measurement unit "represents the" measurement unit "of both the values a and b.
An electron transport layer material, a preparation method thereof, a device and a preparation method thereof are described in detail below.
In the working mechanism of the semiconductor device, a process of injecting electrons and holes from a carrier transmission layer to a quantum dot layer is involved, wherein the carrier transmission layer consists of a Hole Transmission Layer (HTL) and an Electron Transmission Layer (ETL), and the injection efficiency of holes and electrons, whether the injection is balanced or not and the blocking effect on reverse carriers are all related to the carrier mobility of a transmission layer material and the energy level structure of the transmission layer material.
In the prior art, the electron mobility in the electron transport layer is too fast or too slow due to the lower controllability of the electron mobility, so that the electron and hole injection in the quantum dot layer are unbalanced, and the efficiency and the service life of the semiconductor device are greatly reduced.
The inventor researches and discovers that the reduced graphene oxide (rGO) serving as one of carbon materials has excellent electron transmission performance; the layered double oxide ZnAlO has the advantages of adjustable composition, controllable structure and good stability, and the two are combined to easily realize controllable transmission of electrons.
In a first aspect, embodiments of the present application provide an electron transport layer material comprising ZnAlO/rGO nanocomposite.
In the application, the electron transport layer material comprising the ZnAlO/rGO nano compound can effectively regulate and control the electron mobility in the electron transport layer.
In a second aspect, referring to fig. 1, an embodiment of the present application provides a method for preparing an electron transport layer material according to the embodiment of the first aspect, including the following steps:
preparing graphene oxide;
preparing graphene oxide into sol, adding a guiding agent, a precipitating agent, zn salt and Al salt into the sol, and carrying out heating reaction to obtain ZnAl-LDH/rGO, wherein the molar ratio of the Zn salt to the Al salt is (2:1) - (4:1);
and calcining ZnAl-LDH/rGO to prepare the ZnAlO/rGO nanocomposite.
In the present application, the molar ratio of Zn salt to Al salt is controlled in the range of (2:1) to (4:1), for example, but not limited to, the molar ratio is 2: 1. 3:1 and 4:1 or any point value or range value between any two; and by combining the process, the ZnAlO/rGO nano-composite which can effectively regulate and control the electron mobility can be prepared.
It is noted that the inventor researches and discovers that the mole ratio of Zn salt to Al salt is controlled within the range of (2:1) - (4:1), so that the preparation of the ZnAl-LDH/rGO intermediate product with a crystal structure can be ensured; when the intermediate product is ZnAl-LDH/rGO with a crystal structure, the prepared ZnAlO/rGO composite nano material can be ensuredThe material has controllable performance on electron mobility. However, when the molar ratio of Zn salt to Al salt is outside this range, the components of ZnO, al are prepared 2 O 3 Zn-doped Al 2 O 3 Or a mixed material of ZnO doped with Al, instead of ZnAl-LDH/rGO of crystalline structure.
It can be understood that in order to prepare the ZnAlO/rGO nano-composite with better regulation and control effect on electron mobility, the reaction temperature and time in the heating reaction process can be regulated and controlled.
The inventors have further studied and found that in the step of heating the reaction, the reaction temperature is 60 to 180 ℃, for example, but not limited to, the reaction temperature is 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, and 160 ℃ or any one point value or any range value between the two; the reaction time is 6 to 48 hours, such as, but not limited to, a reaction time of 6 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 45 hours, and 48 hours, or a range of values therebetween.
In the embodiment, the reaction temperature and the reaction time are respectively controlled within the range of 60-180 ℃ and 6-48 hours, so that the prepared ZnAlO/rGO nano compound can be ensured to have better regulation and control performance on electron mobility.
It can be understood that the ZnAlO/rGO nano-composite prepared by combining proper reaction temperature and proper reaction time can have better regulation and control effect on electron mobility.
As an example, in the step of heating the reaction, the reaction temperature is 80 ℃ and the reaction time is 12 hours.
On the basis, in order to further optimize the regulation and control performance of the ZnAlO/rGO nano compound on electron mobility, the ratio of the total substances m2 of the graphene oxide m1, zn salt and Al salt can be regulated and controlled.
As an example, in the step of preparing ZnAl-LDH/rGO, the mass of graphene oxide is m1, the total mass of Zn salt and Al salt is m2, m1: m2 is (80 to 120): (0.01-0.014), such as but not limited to m1: m2 is 80:0.01, 80:0.011, 80:0.012, 80:0.013, 80:0.014, 100:0.01, 100:0.011, 100:0.012, 100:0.013, 100:0.014, 120:0.01, 120:0.011, 120:0.012, 120:0.013 and 120: any one point value or any range value between any two of 0.014.
In this embodiment, the ratio of the mass m1 of graphene oxide to the total mass m2 of Zn salt and Al salt is controlled to (80 to 120): in the range of (0.01-0.014), the regulation and control performance of the prepared ZnAlO/rGO nano-composite on electron mobility can be further optimized.
It is understood that the amounts of the directing agent and the precipitant may also be regulated in the process of regulating the ratio of the mass m1 of graphene oxide, the amount m2 of the total substance of Zn salt and Al salt.
As an example, in the step of preparing ZnAl-LDH/rGO, the ratio of the mass of graphene oxide to the mass of the director is (1.8 to 2.2): 1, the ratio of the mass of graphene oxide to the mass of the precipitant is (80-120): 0.05.
on this basis, the concentration of the sol can be optimized for better preparation of ZnAl-LDH with a crystal structure.
As an example, in the step of configuring graphene oxide into a sol, the concentration of the sol is 0.4 to 0.6mg/mL, for example, but not limited to, a concentration of the sol is any one point value or a range value between any two of 0.4mg/mL, 0.5mg/mL and 0.6 mg/mL.
It will be appreciated that the kind of directing agent may be adapted in order to better prepare ZnAl-LDH having a crystal structure.
As one example, the directing agent includes citrate; optionally, the directing agent comprises at least one of citric acid, sodium citrate, sodium dihydrogen citrate, sodium monohydrogen citrate, or potassium citrate.
In this embodiment, the guiding agent includes citrate, and the kind of the guiding agent is limited, so that ZnAl-LDH having a crystal structure is better prepared on the one hand, and graphene oxide can be better reduced to obtain reduced graphene oxide (rGO) through the reducing property of citrate on the other hand.
On this basis, the precipitants, zn salts and Al salts may be selected according to the requirements known in the art.
As an example, the precipitant may be an alkaline substance known in the art; the Zn salt may be an acid salt of Zn and a hydrate thereof; the Al salt may be an acid salt of Al and a hydrate thereof.
For ease of understanding, specific kinds of precipitants, zn salts and Al salts may be described.
As an example, the precipitant may be urea, na 2 CO 3 、NaHCO 3 、NaOH、K 2 CO 3 、KHCO 3 、KOH、NH 3 H 2 At least one of O; the Zn salt can be ZnCl 2 、ZnSO 4 And Zn (NO) 3 ) 2 And at least one of its crystalline water-containing related compounds; the Al salt may be AlCl 3 、Al 2 (SO 4 ) 3 And Al (NO) 3 ) 3 And at least one of its crystalline water-containing related compounds.
It will be appreciated that the appropriate types of reactants cooperate with one another to facilitate the reaction.
As an example, the precipitant is urea, the Zn salt is Zn (NO 3 ) 2 ·6H 2 O and Al salt is Al (NO) 3 ) 3 ·9H 2 O。
It is understood that the temperature and time during calcination can be controlled in order to better prepare ZnAlO/rGO nanocomposite from the intermediate ZnAl-LDH/rGO.
As an example, in the calcination process, the calcination temperature is 200 to 800 ℃, such as, but not limited to, the reaction temperature is 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, and 800 ℃ or any one point value or any range value between the two; the calcination time is 1 to 8 hours, such as, but not limited to, the reaction time being any one of 1h, 2h, 3h, 4h, 5h, 6h, 7h, and 8h or a range between any two.
In the embodiment, the calcination temperature and the calcination time are controlled within the ranges of 200-800 ℃ and 1-8 hours respectively, and interlayer ions and water molecules in the ZnAl-LDH can be removed better, so that the ZnAlO/rGO nanocomposite with better performance is prepared.
It is understood that ZnAlO/rGO nanocomposite materials with better performance can be prepared by proper calcination temperature and proper calcination time.
As an example, in the calcination process, the calcination temperature is 400 ℃ and the calcination time is 2 hours.
It should be noted that researchers have found that under high temperature conditions, if the oxygen content is too high, it can result in the graphite material being directly oxidized by oxygen; if the oxygen content is low, the ZnAlO composite oxide is reduced by the C element in rGO; in order to ensure that the intermediate ZnAl-LDH/rGO can form ZnAlO/rGO nanocomposite material by a calcination step, the calcination conditions can be optimized.
As an example, the step of calcining is performed under an atmosphere of a protective gas; the protective gas includes oxygen, and at least one of inert gas, nitrogen, and carbon dioxide.
In this embodiment, the protective gas is provided and the type of protective gas is limited, so that the oxidation of the graphite material can be prevented, the reduction of ZnAlO can be prevented, and the intermediate product ZnAl-LDH/rGO can be ensured to form the ZnAlO/rGO nanocomposite through the calcination step.
It will be appreciated that the oxygen content of the protective gas may be regulated in order to better protect the graphite material as well as the ZnAlO.
As an example, the volume ratio of oxygen in the protective gas is 5-25%, such as, but not limited to, any one point value or a range value between any two of 5%, 10%, 15%, 20% and 25% by volume.
In the embodiment, the protective gas can play a better role in protecting the graphite material and the ZnAlO, so that the prepared ZnAlO/rGO nanocomposite material has better quality.
It is understood that in the step of preparing graphene oxide, a specific preparation process is not limited.
As an example, in the step of preparing graphene oxide, graphite, potassium permanganate, and concentrated sulfuric acid are mixed and then subjected to a hydrothermal reaction; then adding hydrogen peroxide for reduction until the solution is bright yellow; and finally, filtering, washing and drying the prepared graphene oxide.
It can be understood that the temperature and time of the water bath reaction can be regulated and controlled in order to prepare graphene oxide with better quality.
As an example, in the preparation process of the hydrothermal method, the temperature of the water bath reaction is 15-30 ℃, such as, but not limited to, the reaction temperature is any one point value or a range value between any two of 15 ℃, 20 ℃, 25 ℃ and 30 ℃; the water bath reaction time is 20-120 min, such as, but not limited to, any one point value or range value between any two of 20min, 40min, 60min, 80min, 100min and 120min.
In the embodiment, the temperature of the water bath reaction and the time of the water bath reaction are respectively controlled within the ranges of 15-30 ℃ and 20-120 min, so that the preparation of the single-layer high-quality graphene oxide with uniform particle size can be ensured.
It is understood that the quality of the prepared graphene oxide can be further improved by combining an appropriate reaction temperature and an appropriate reaction time.
As an example, in the preparation of the hydrothermal method, the reaction temperature is 20 ℃ and the reaction time is 60min.
It should be noted that the process of mixing concentrated sulfuric acid is involved in the step of preparing graphene oxide, and the preparation process can be optimized for safety.
As an example, when the mixing of the concentrated sulfuric acid is performed, the reaction system is subjected to an ice-water bath treatment.
In this embodiment, it is possible to prevent danger caused by a large amount of heat released when the concentrated sulfuric acid is mixed, thereby securing the safety of the preparation process.
On the basis, the mass ratio of graphite, potassium permanganate and concentrated sulfuric acid can be regulated and controlled according to the quality of the prepared graphene oxide.
As an example, in the step of preparing graphene oxide, the ratio of the mass of graphite to the mass of potassium permanganate is (1:2) - (1:4), such as, but not limited to, the ratio of the mass of graphite to the mass of potassium permanganate is 1: 2. 1:3 and 1:4 or a range value between any two of the point values; the ratio of the mass of graphite to the volume of concentrated sulfuric acid is (1:23) to (1:25), such as, but not limited to, the ratio of the mass of graphite to the volume of concentrated sulfuric acid is 1: 23. 1:24 and 1:25 or a range value between any one or two of them.
It is understood that the reaction system has a proper capacity, which is more favorable for the reaction.
As an example, in the step of preparing graphene oxide, the mass of graphite is 0.5g.
In a third aspect, referring to fig. 2, an embodiment of the present application provides a semiconductor device, including an electron transport layer made of a material such as the electron transport layer material provided in the embodiment of the first aspect or an electron transport layer made of an electron transport layer material made by the method for manufacturing an electron transport layer material provided in the embodiment of the second aspect.
In the application, the material of the electron transport layer in the semiconductor device is limited, so as to effectively regulate and control the electron mobility in the electron transport layer, thereby improving the phenomenon of unbalance injection of electrons and holes in the quantum dot layer of the semiconductor device, and further, prolonging the service life of the device while improving the efficiency of the device.
Note that the specific kind of the semiconductor device including the electron transport layer made of the material such as one of the electron transport layer materials provided in the embodiments of the first aspect or the electron transport layer made of the electron transport layer material made of the material such as the embodiment of the second aspect is not limited, and the semiconductor device may be a QLED device, or may be any one of an OLED device and a PSC device.
In a fourth aspect, embodiments of the present application provide a method for manufacturing a semiconductor device according to the embodiments of the third aspect, including preparing an electron transport layer using a ZnAlO/rGO composite nanomaterial.
In the application, the electron transport layer is prepared by adopting the ZnAlO/rGO composite nano material, and the semiconductor device for effectively regulating and controlling the electron mobility in the electron transport layer can be prepared.
It is understood that the fabrication process of the semiconductor device may be performed according to standards well known in the art.
As an example, a method of manufacturing a semiconductor device includes the steps of:
preparing an anode on the surface of a substrate;
preparing a hole injection layer on the surface of the anode;
preparing a hole transport layer on the surface of the hole injection layer;
preparing a quantum dot layer on the surface of the hole transport layer;
preparing an electron transport layer on the surface of the quantum dot layer by adopting a ZnAlO/rGO composite nano material;
and preparing a cathode on the surface of the electron transport layer, and packaging.
In the embodiment, the semiconductor device can be prepared by adopting the preparation process, and meanwhile, the electron transport layer is prepared on the surface of the quantum dot layer by adopting the ZnAlO/rGO composite nano material, so that the electron mobility of the electron transport layer of the prepared semiconductor device can be effectively regulated and controlled.
It is understood that the specific material of the quantum dot layer is not limited, and materials known in the art may be used.
As one example, the quantum dot layer may include, but is not limited to, one or more of group IIB-VIA compounds, group IIIA-VA compounds, group IIB-VA compounds, group IIIA-VIA compounds, group IVA-VIA compounds, group IB-IIIA-VIA compounds, group IIB-IVA-VIA compounds, or group IVA simple substances.
On this basis, materials corresponding to the structures in the semiconductor device can be all materials known in the art.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
A method for preparing an electron transport layer material, comprising the steps of:
s1, taking 0.5g of graphite and 1.5g of potassium permanganate as raw materials, and adding 12mL of concentrated sulfuric acid into the raw materials under an ice water bath for mixing; then reacting for 60min at the temperature of 20 ℃ to obtain graphene oxide slurry; and adding hydrogen peroxide into the slurry until the solution is bright yellow, and sequentially performing the steps of filtering, washing and drying to obtain the graphene oxide.
S2, 100mg of graphene oxide is weighed and dissolved in 200mL of deionized water, the graphene oxide is prepared into a sol with the concentration of 0.5mg/mL, and 50mg of citric acid, 0.05mmol of urea and 0.009mmol of Zn (NO) are added into the sol 3 ) 2 ·6H 2 O、0.003mmolAl(NO 3 ) 3 ·9H 2 O, adopting a hydrothermal method to react for 12 hours at 80 ℃ to prepare the ZnAl-LDH/rGO nano compound.
And S3, grinding the prepared ZnAl-LDH/rGO nano compound in a mortar, transferring the ground compound into a square boat, transferring the square boat into a tube furnace, introducing oxygen and argon mixed shielding gas with the oxygen volume ratio of 15%, and calcining at 400 ℃ for 2 hours to prepare the ZnAlO/rGO nano compound.
Example 2
A method for producing an electron transport layer material, which differs from example 1 only in that: 0.008mmolZn (NO) 3 ) 2 ·6H 2 O、0.004mmolAl(NO 3 ) 3 ·9H 2 O。
Example 3
A method for producing an electron transport layer material, which differs from example 1 only in that: adding 0.0096mmolZn (NO) 3 ) 2 ·6H 2 O、0.0024mmolAl(NO 3 ) 3 ·9H 2 O。
Example 4
A method for producing an electron transport layer material, which differs from example 1 only in that: the ZnAl-LDH/rGO nano compound is prepared by adopting a hydrothermal method to react for 48 hours at 60 ℃.
Example 5
A method for producing an electron transport layer material, which differs from example 1 only in that: the ZnAl-LDH/rGO nano compound is prepared by adopting a hydrothermal method to react for 6 hours at 180 ℃.
Example 6
A method for producing an electron transport layer material, which differs from example 1 only in that: the ZnAl-LDH/rGO nano compound is prepared by adopting a hydrothermal method to react for 50 hours at 55 ℃.
Example 7
A method for producing an electron transport layer material, which differs from example 1 only in that: the ZnAl-LDH/rGO nano compound is prepared by adopting a hydrothermal method to react for 5 hours at 185 ℃.
Example 8
A method for producing an electron transport layer material, which differs from example 1 only in that: 80mg of graphene was weighed and Zn (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The amount of O total material was 0.01mmol.
Example 9
A method for producing an electron transport layer material, which differs from example 1 only in that: 80mg of graphene was weighed and Zn (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The amount of O total substance was 0.014mmol.
Example 10
A method for producing an electron transport layer material, which differs from example 1 only in that: 120mg of graphene was weighed and Zn (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The amount of O total material was 0.01mmol.
Example 11
A method for producing an electron transport layer material, which differs from example 1 only in that: 120mg of graphene was weighed and Zn (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The amount of O total substance was 0.014mmol.
Example 12
A method for producing an electron transport layer material, which differs from example 1 only in that: 80mg of graphene was weighed and Zn (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The amount of O total material was 0.008mmol.
Example 13
A method for producing an electron transport layer material, which differs from example 1 only in that: 80mg of graphene was weighed and Zn (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The amount of O total material was 0.016mmol.
Example 14
A method for producing an electron transport layer material, which differs from example 1 only in that: 120mg of graphene was weighed and Zn (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The amount of O total material was 0.008mmol.
Example 15
A method for producing an electron transport layer material, which differs from example 1 only in that: 120mg of graphene was weighed and Zn (NO 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 The amount of O total material was 0.016mmol.
Example 16
A method for producing an electron transport layer material, which differs from example 1 only in that: and (3) reacting for 120min at the temperature of 15 ℃ to obtain graphene oxide slurry.
Example 17
A method for producing an electron transport layer material, which differs from example 1 only in that: and (3) reacting for 20min at the temperature of 30 ℃ to obtain graphene oxide slurry.
Example 18
A method for producing an electron transport layer material, which differs from example 1 only in that: and (3) reacting for 125min at the temperature of 10 ℃ to obtain graphene oxide slurry.
Example 19
A method for producing an electron transport layer material, which differs from example 1 only in that: and (3) reacting for 15min at the temperature of 35 ℃ to obtain graphene oxide slurry.
Example 20
A method for producing an electron transport layer material, which differs from example 1 only in that: transferring the ark into a tube furnace, and introducing oxygen and argon mixed shielding gas with the oxygen volume ratio of 5 percent.
Example 21
A method for producing an electron transport layer material, which differs from example 1 only in that: transferring the ark into a tube furnace, and introducing oxygen and argon mixed shielding gas with the oxygen volume ratio of 25 percent.
Example 22
A method for producing an electron transport layer material, which differs from example 1 only in that: transferring the ark into a tube furnace, and introducing oxygen and argon mixed shielding gas with the oxygen volume ratio of 3 percent.
Example 23
A method for producing an electron transport layer material, which differs from example 1 only in that: the ark was transferred to a tube furnace and oxygen and argon mixed shielding gas was introduced with an oxygen volume ratio of 28%.
Comparative example 1
A method for producing an electron transport layer material, which differs from example 1 only in that: adding 0.006mmolZn (NO) 3 ) 2 ·6H 2 O、0.006mmolAl(NO 3 ) 3 ·9H 2 O。
Comparative example 2
A method for producing an electron transport layer material, which differs from example 1 only in that: adding 0.01mmolZn (NO) 3 ) 2 ·6H 2 O、0.002mmolAl(NO 3 ) 3 ·9H 2 O。
Preparation example 1
A spin coating PEDOT on an ITO glass substrate: PSS, the revolution is 4000 r/min-6000 r/min, and the spin coating is completed and then heat treatment is carried out for 20-30 min at 150 ℃.
B, 30mgTFB is taken and dissolved in 1mL of chlorobenzene solvent, and stirred and ultrasonically mixed; spin-coating the prepared TFB chlorobenzene solution on PEDOT: on the PSS layer, the revolution is 2000r/min to 4000r/min, and after spin coating is completed, the spin coating is subjected to heat treatment at 150 ℃ for 20 to 30min.
C spin coating CdSe/ZnS quantum dot layer on the TFB, and the rotation number is 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano compound prepared in the embodiment 2 on the quantum dot layer, wherein the revolution is 2000-4000 r/min;
e, evaporating Al electrodes, packaging, and finishing the preparation of the QLED device.
Preparation example 2
A spin coating PEDOT on an ITO glass substrate: PSS, the revolution is 4000 r/min-6000 r/min, and the spin coating is completed and then heat treatment is carried out for 20-30 min at 150 ℃.
B, 30mgTFB is taken and dissolved in 1mL of chlorobenzene solvent, and stirred and ultrasonically mixed; spin-coating the prepared TFB chlorobenzene solution on PEDOT: on the PSS layer, the revolution is 2000r/min to 4000r/min, and after spin coating is completed, the spin coating is subjected to heat treatment at 150 ℃ for 20 to 30min.
C spin coating CdSe/ZnS quantum dot layer on the TFB, and the rotation number is 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano-composite prepared in the embodiment 1 on the quantum dot layer, wherein the rotation number is 2000-4000 r/min;
e, evaporating Al electrodes, packaging, and finishing the preparation of the QLED device.
Preparation example 3
A spin coating PEDOT on an ITO glass substrate: PSS, the revolution is 4000 r/min-6000 r/min, and the spin coating is completed and then heat treatment is carried out for 20-30 min at 150 ℃.
B, 30mgTFB is taken and dissolved in 1mL of chlorobenzene solvent, and stirred and ultrasonically mixed; spin-coating the prepared TFB chlorobenzene solution on PEDOT: on the PSS layer, the revolution is 2000r/min to 4000r/min, and after spin coating is completed, the spin coating is subjected to heat treatment at 150 ℃ for 20 to 30min.
C spin coating CdSe/ZnS quantum dot layer on the TFB, and the rotation number is 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano compound prepared in the embodiment 3 on the quantum dot layer, wherein the revolution is 2000-4000 r/min;
e, evaporating Al electrodes, packaging, and finishing the preparation of the QLED device.
Preparation example 4
A spin coating PEDOT on an ITO glass substrate: PSS, the revolution is 4000 r/min-6000 r/min, and the spin coating is completed and then heat treatment is carried out for 20-30 min at 150 ℃.
B, 30mgTFB is taken and dissolved in 1mL of chlorobenzene solvent, and stirred and ultrasonically mixed; spin-coating the prepared TFB chlorobenzene solution on PEDOT: on the PSS layer, the revolution is 2000r/min to 4000r/min, and after spin coating is completed, the spin coating is subjected to heat treatment at 150 ℃ for 20 to 30min.
C spin coating CdSe/ZnS quantum dot layer on the TFB, and the rotation number is 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano compound prepared in the comparative example 1 on the quantum dot layer, wherein the revolution is 2000-4000 r/min;
e, evaporating Al electrodes, packaging, and finishing the preparation of the QLED device.
Preparation example 5
A spin coating PEDOT on an ITO glass substrate: PSS, the revolution is 4000 r/min-6000 r/min, and the spin coating is completed and then heat treatment is carried out for 20-30 min at 150 ℃.
B, 30mgTFB is taken and dissolved in 1mL of chlorobenzene solvent, and stirred and ultrasonically mixed; spin-coating the prepared TFB chlorobenzene solution on PEDOT: on the PSS layer, the revolution is 2000r/min to 4000r/min, and after spin coating is completed, the spin coating is subjected to heat treatment at 150 ℃ for 20 to 30min.
C spin coating CdSe/ZnS quantum dot layer on the TFB, and the rotation number is 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano compound prepared in the comparative example 2 on the quantum dot layer, wherein the revolution is 2000-4000 r/min;
e, evaporating Al electrodes, packaging, and finishing the preparation of the QLED device.
Preparation example 6
OLED devices were prepared using the ZnAlO/rGO nanocomposite prepared in example 2.
Preparation example 7
PSC devices were fabricated using the ZnAlO/rGO nanocomposites prepared in example 2.
Test example 1
It should be noted that the preparation examples 1 to 5 are different only in that the ZnAlO/rGO nanocomposite used is different, and the devices prepared in preparation examples 1 to 5 are tested for External Quantum Efficiency (EQE) and service life.
The detection method of the External Quantum Efficiency (EQE) and the service life of the device is as follows:
in preparation of preparation examples 1 to 5, after the step of spin-coating the ZnAlO/rGO nanocomposite on the quantum dot layer is completed, znO is spin-coated on the quantum dot layer of another device, respectively, to serve as a control example of preparation examples 1 to 5, and then detection is performed on preparation examples 1 to 5 and respective control examples.
TABLE 1 EQE and Life detection results for preparation examples 1 to 5
As can be seen from Table 1, when the molar ratio of Zn to Al is in the range of (2:1) to (4:1), the EQE of the prepared QLED device is improved and the service life of the device is prolonged compared with that of the comparative example; however, when the molar ratio of Zn to Al is not in the range of (2:1) - (4:1), the EQE of the prepared QLED device is reduced and the service life of the device is reduced compared with that of the comparative example.
In addition, as can be seen from preparation examples 1 to 3, when the molar ratio of Zn to Al is 3: and 1, the EQE and the service life of the prepared QLED device are improved to the greatest extent.
Test example 2
The OLED device prepared in preparation example 6 was subjected to detection of luminance and luminosity efficiency.
The detection method of the brightness and the efficiency of the OLED device comprises the following steps:
in the preparation of preparation example 6, after the step of spin-coating the ZnAlO/rGO nanocomposite on the quantum dot layer was completed, znO was spin-coated on the quantum dot layer of another device, respectively, as a control example of preparation example 6, and then preparation example 6 and its control example were examined.
TABLE 2 Brightness and photometric efficiency test results for preparation example 6
As can be seen from table 2, when the molar ratio of Zn to Al is 2:1, the brightness and efficiency of the prepared OLED device are better than those of the comparison example.
Test example 3
The PSC device prepared in preparation example 7 was subjected to detection of photoelectric conversion efficiency.
The method for detecting the efficiency of the PSC device comprises the following steps:
in the preparation of preparation example 7, after the step of spin-coating the ZnAlO/rGO nanocomposite on the quantum dot layer was completed, znO was spin-coated on the quantum dot layer of another device, respectively, as a control example of preparation example 7, and then preparation example 6 and its control example were examined.
TABLE 3 photoelectric conversion efficiency detection results of PREPARATIVE EXAMPLE 7
As can be seen from table 3, when the molar ratio of Zn to Al is 2:1, the efficiency of the PSC device prepared is obviously better than that of the control example.
In summary, the electron transport layer material, the preparation method thereof, the device and the preparation method thereof can improve the phenomenon of unbalance injection of electrons and holes in the quantum dot layer, thereby improving the efficiency of the device and prolonging the service life of the device.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
Claims (11)
1. A method for preparing an electron transport layer material, comprising the steps of:
preparing graphene oxide;
preparing graphene oxide into sol, adding a guiding agent, a precipitating agent, zn salt and Al salt into the sol, and carrying out heating reaction to obtain ZnAl-LDH/rGO, wherein the molar ratio of the Zn salt to the Al salt is (2:1) - (4:1);
and calcining the ZnAl-LDH/rGO to prepare the ZnAlO/rGO nanocomposite.
2. The method for producing an electron transport layer material according to claim 1, wherein in the step of heating reaction, the reaction temperature is 60 to 180 ℃ and the reaction time is 6 to 48 hours.
3. The method for producing an electron transport layer material according to claim 1, wherein in the step of producing ZnAl-LDH/rGO, the graphene oxide has a mass of m1, the total mass of the Zn salt and the Al salt is m2, and the mass of m1: m2 is (80 to 120): (0.01 to 0.014).
4. The method of producing an electron transport layer material according to claim 1, wherein the directing agent comprises citrate.
5. The method of claim 4, wherein the directing agent comprises at least one of citric acid, sodium citrate, sodium dihydrogen citrate, sodium monohydrogen citrate, or potassium citrate.
6. The method for preparing the electron transport layer material according to claim 1, wherein the graphene oxide is prepared from graphite by a hydrothermal method, and the temperature of water bath reaction is 15-30 ℃ and the time of water bath reaction is 20-120 min in the preparation process of the hydrothermal method.
7. The method for producing an electron transport layer material according to any one of claims 1 to 6, wherein the step of calcining is performed under an atmosphere of a protective gas; the protective gas includes oxygen, and the protective gas further includes at least one of inert gas, nitrogen, and carbon dioxide.
8. The method for producing an electron transport layer material according to claim 7, wherein the volume ratio of the oxygen in the protective gas is 5 to 25%.
9. A semiconductor device comprising an electron transporting layer made of the electron transporting layer material according to any one of claims 1 to 8.
10. A method of fabricating the semiconductor device of claim 9, wherein the electron transport layer is fabricated using ZnAlO/rGO nanocomposite.
11. The method of manufacturing a semiconductor device according to claim 10, comprising the steps of:
preparing an anode on the surface of a substrate;
preparing a hole injection layer on the surface of the anode;
preparing a hole transport layer on the surface of the hole injection layer;
preparing a quantum dot layer on the surface of the hole transport layer;
preparing the electron transport layer on the surface of the quantum dot layer by adopting a ZnAlO/rGO nano compound;
and preparing a cathode on the surface of the electron transport layer, and packaging.
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