CN114464760A - Electron transport layer material and preparation method thereof, semiconductor device and preparation method thereof - Google Patents
Electron transport layer material and preparation method thereof, semiconductor device and preparation method thereof Download PDFInfo
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- 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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- 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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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 a ZnAlO/rGO nano compound, and the preparation method comprises the steps of preparing graphene oxide, preparing the graphene oxide into sol, adding a guiding agent, a precipitating agent, a Zn salt and an Al salt into the sol to carry out heating reaction, and preparing 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 nano composite. The device prepared by the material can improve the phenomenon of unbalanced injection of electrons and holes in a 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 application relates to the field of semiconductor device manufacturing, in particular to an electron transport layer material and a preparation method thereof, and a semiconductor device and a preparation method thereof.
Background
In the prior art, a quantum dot layer in a semiconductor device has the phenomenon of unbalanced electron and hole injection, so that the efficiency and the service life of the device are greatly reduced.
Disclosure of Invention
The present application is directed to an electron transport layer material and a method for manufacturing the same, and a semiconductor device and a method for manufacturing the same, which can improve the phenomenon of unbalanced injection of electrons and holes in a quantum dot layer, thereby improving the device efficiency and prolonging the device lifetime.
The embodiment of the application is realized as follows:
in a first aspect, embodiments of the present application provide an electron transport layer material comprising a ZnAlO/rGO nanocomposite.
In the technical scheme, the electron transport layer material comprising the ZnAlO/rGO nano composite 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 as provided in an embodiment of the first aspect, including the following steps:
preparing graphene oxide;
preparing graphene oxide into sol, adding a guiding agent, a precipitating agent, a Zn salt and an Al salt into the sol to carry out heating reaction, and preparing 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 nano composite.
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 a ZnAl-LDH/rGO intermediate product with a crystal structure can be prepared, and on the basis, the ZnAlO/rGO nano-composite capable of effectively regulating and controlling the electron mobility can be prepared by combining the process.
In some optional embodiments, in the step of heating for reaction, the reaction temperature is 60 to 180 ℃ and the reaction time is 6 to 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 h, so that the prepared ZnAlO/rGO nano composite has good regulation and control performance on the electron mobility.
In some alternative embodiments, in the step of preparing to obtain ZnAl-LDH/rGO, the mass of graphene oxide is m1, and the total mass of Zn salt and Al salt is m2, m 1: m2 is (80-120): (0.01-0.014).
In the technical scheme, the mass of the graphene oxide and the total amount of Zn salt and Al salt are controlled to be (80-120): (0.01-0.014), the regulation performance of the prepared ZnAlO/rGO nano composite on the 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 type of the guiding agent is limited, on one hand, the guiding agent is used for better preparing ZnAl-LDH with a crystal structure, and on the other hand, the graphene oxide can be better reduced through the reducibility of the citrate to obtain reduced graphene oxide (rGO).
In some optional embodiments, the graphene oxide is prepared from graphite by a hydrothermal method, and in the preparation process of the hydrothermal method, the temperature of the water bath reaction is 15-30 ℃, and the time of the water bath reaction is 20-120 min.
In the technical scheme, the temperature and the time of the water bath reaction are respectively controlled within the range of 15-30 ℃ and 20-120 min, so that the single-layer graphene oxide with uniform particle size can be better prepared.
In some alternative embodiments, the step of calcining is performed under an atmosphere of a protective gas; the protective gas comprises oxygen, and the protective gas further comprises at least one of an inert gas, nitrogen, and carbon dioxide;
optionally, the volume ratio of oxygen in the protective gas 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 meanwhile, ZnAlO can be prevented from being reduced; in addition, the volume ratio of oxygen in the protective gas is limited to be within the range of 5-25%, and the graphite material and ZnAlO can be better protected.
In a third aspect, embodiments of the present application provide a semiconductor device, including an electron transport layer made of the electron transport layer material provided in the embodiments of the first aspect or the electron transport layer material provided in the embodiments of the second aspect.
In the above technical solution, the material of the electron transport layer in the semiconductor device is limited to effectively regulate and control the electron mobility in the electron transport layer, so as to improve the phenomenon of unbalanced injection of electrons and holes in the quantum dot layer of the semiconductor device, and further improve the device efficiency and prolong the service life of the device.
In a fourth aspect, embodiments of the present application provide a method for manufacturing a semiconductor device as provided in the third aspect, including preparing an electron transport layer using ZnAlO/rGO composite nanomaterial.
In the technical scheme, the electron transport layer is prepared from the ZnAlO/rGO composite nano material, so that the semiconductor device capable of effectively regulating and controlling the electron mobility in the electron transport layer can be prepared.
In some alternative embodiments, the following steps are included:
preparing an anode on the surface of the 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 transmission 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 then packaging.
In the technical scheme, 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 transport layer of the prepared semiconductor device can realize effective regulation and control on the electron mobility.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a process flow diagram of a method for preparing an electron transport layer material according to an embodiment of the present disclosure;
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 clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In addition, in the description of the present application, the meaning of "a plurality" of "one or more" means two or more unless otherwise specified; the range of "numerical value a to numerical value b" includes both values "a" and "b", and "unit of measure" in "numerical value a to numerical value b + unit of measure" represents both "unit of measure" of "numerical value a" and "numerical value b".
The following describes an electron transport layer material, a method for manufacturing the same, a device, and a method for manufacturing the same in embodiments of the present application.
In the working mechanism of the semiconductor device, a process of injecting electrons and holes from a carrier transport layer to a quantum dot layer simultaneously is involved, wherein the carrier transport layer consists of a Hole Transport Layer (HTL) and an Electron Transport Layer (ETL), and the injection efficiency, the injection balance and the blocking effect of holes and electrons on reverse carriers are related to the carrier mobility and the energy level structure of the transport layer material.
In the prior art, due to the fact that the controllability of the electron mobility is low in the electron transport layer, the electron mobility is too fast or too slow, so that the injection of electrons and holes in the quantum dot layer is unbalanced, and the efficiency and the service life of a semiconductor device are greatly reduced.
The inventor researches and discovers that reduced graphene oxide (rGO) as one of carbon materials has excellent electron transport performance; the layered bimetal oxide ZnAlO has the advantages of adjustable composition, controllable structure and good stability, and the combination of the two can easily realize the controllable transmission of electrons.
In a first aspect, embodiments of the present application provide an electron transport layer material comprising a ZnAlO/rGO nanocomposite.
In the application, the electron transport layer material comprising the ZnAlO/rGO nano composite can realize effective regulation and control on 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 as provided in an embodiment of the first aspect, including the following steps:
preparing graphene oxide;
preparing graphene oxide into sol, adding a guiding agent, a precipitating agent, a Zn salt and an Al salt into the sol to carry out heating reaction, and preparing 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 nano composite.
In the present application, the molar ratio of the Zn salt to the Al salt is controlled within the range of (2: 1) to (4: 1), for example, but not limited to, a molar ratio of 2: 1. 3: 1 and 4: 1 or a range between any two; and the ZnAlO/rGO nano composite capable of effectively regulating and controlling the electron mobility can be prepared by combining the process.
It should be noted that the inventors have found that the molar ratio of the Zn salt to the Al salt is controlled to be (2: 1) to (4: 1)In the range, the preparation of ZnAl-LDH/rGO intermediate products with crystal structures can be ensured; and when the intermediate product is ZnAl-LDH/rGO with a crystal structure, the prepared ZnAlO/rGO composite nano material can be ensured to have controllable performance on electron mobility. However, when the molar ratio of the Zn salt to the Al salt is out of this range, the composition prepared is ZnO, Al2O3Zn-doped Al2O3Or a mixed material of Al-doped ZnO instead of ZnAl-LDH/rGO with a crystal structure.
It can be understood that the reaction temperature and time in the heating reaction process can be regulated and controlled in order to prepare the ZnAlO/rGO nano composite which has a better regulation and control effect on the electron mobility.
The inventors further investigated and found that, in the step of heating reaction, the reaction temperature is 60 to 180 ℃, for example, but not limited to, the reaction temperature is any one of 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, and 160 ℃, or a range value between any two; the reaction time is 6-48 h, for example, but not limited to, the reaction time is any one of 6h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 20h, 25h, 30h, 35h, 40h, 45h and 48h or a range value between any two of the two.
In the embodiment, the reaction temperature and the reaction time are respectively controlled within the range of 60-180 ℃ and 6-48 h, so that the prepared ZnAlO/rGO nano composite has better regulation and control performance on the electron mobility.
It can be understood that the ZnAlO/rGO nano-composite prepared by combining the appropriate reaction temperature and the appropriate reaction time can have better regulation and control effect on the 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 performance of the prepared ZnAlO/rGO nano composite on the electron mobility, the ratio of the total substance amount m2 of graphene oxide m1, Zn salt and Al salt can be regulated.
As an example, in the step of preparing ZnAl-LDH/rGO, the mass of graphene oxide is m1, and the total amount of Zn salt and Al salt is m2, m 1: m2 is (80-120): (0.01 to 0.014), for example but not limited to m 1: 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 of 0.014 or a range value between any two.
In the embodiment, the ratio of the mass m1 of the graphene oxide to the total mass m2 of the Zn salt and the Al salt is controlled to be (80-120): (0.01-0.014), the regulation performance of the prepared ZnAlO/rGO nano composite on the electron mobility can be further optimized.
It can be understood that in the process of regulating the ratio of the mass m1 of the graphene oxide to the total mass m2 of the Zn salt and the Al salt, the dosage of the guiding agent and the precipitating agent can be regulated.
As an example, in the step of preparing ZnAl-LDH/rGO, the ratio of the mass of graphene oxide to the mass of the guiding agent is (1.8-2.2): 1, the ratio of the mass of the graphene oxide to the mass of the precipitant is (80-120): 0.05.
on the basis, the concentration of the sol can be optimized in order to better prepare ZnAl-LDH with a crystal structure.
As an example, in the step of configuring the graphene oxide into a sol, the concentration of the sol is 0.4-0.6 mg/mL, such as but not limited to any one of the values of the concentration of the sol being 0.4mg/mL, 0.5mg/mL and 0.6mg/mL or the range value between any two of the values.
It will be appreciated that the type of directing agent may be adjusted in order to better prepare the ZnAl-LDH having a crystal structure.
As an example, 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 this embodiment, the guiding agent includes citrate, and the kind of the guiding agent is limited, on one hand, the guiding agent is used for better preparing the ZnAl-LDH with the crystal structure, and on the other hand, the graphene oxide can be better reduced by the reduction of the citrate to obtain the reduced graphene oxide (rGO).
On this basis, the precipitant, the Zn salt and the Al salt can be selected according to the requirements well known in the art.
As an example, the precipitating agent may be an alkaline substance known in the art; the Zn salt can be acid salt of Zn and hydrate thereof; the Al salt may be an acid salt of Al and a hydrate thereof.
For ease of understanding, specific types of precipitants, Zn salts, and Al salts may be illustrated.
As an example, the precipitant may be urea, Na2CO3、NaHCO3、NaOH、K2CO3、KHCO3、KOH、NH3H2At least one of O; the Zn salt may be ZnCl2、ZnSO4And Zn (NO)3)2And related compounds containing water of crystallization; the Al salt may be AlCl3、Al2(SO4)3And Al (NO)3)3And a water-of-crystallization-related compound thereof.
It will be appreciated that the interaction of the appropriate species of reactants is more favourable to the reaction.
As an example, the precipitating agent is urea, the Zn salt is Zn (NO)3)2·6H2O and Al salt is Al (NO)3)3·9H2O。
It can be understood that the temperature and time during calcination can be adjusted and controlled in order to better prepare the ZnAlO/rGO nanocomposite material from the intermediate product ZnAl-LDH/rGO.
As an example, during the calcination, the calcination temperature is 200 to 800 ℃, such as but not limited to, a reaction temperature of any one of 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, and 800 ℃, or a range value between any two; the calcination time is 1 to 8 hours, for example, but not limited to, the reaction time is any one of 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours and 8 hours or a range between any two of the two.
In the embodiment, the calcination temperature and the calcination time are respectively controlled within the range of 200-800 ℃ and 1-8 h, interlayer ions and water molecules in ZnAl-LDH can be well removed, and the ZnAlO/rGO nano composite material with good performance is prepared.
It is understood that appropriate calcination temperatures combined with appropriate calcination times can produce ZnAlO/rGO nanocomposites with better properties.
As an example, in the calcination process, the calcination temperature is 400 ℃ and the calcination time is 2 h.
It should be noted that researchers have found that at high temperatures, if the oxygen content is too high, the graphite material is directly oxidized by oxygen; if the oxygen content is low, the ZnAlO composite oxide is reduced by C elements in the rGO; in order to ensure that the intermediate product ZnAl-LDH/rGO can form the ZnAlO/rGO nano composite material through the calcining step, the calcining condition can be optimized.
As an example, the step of calcining is performed under an atmosphere of a protective gas; the protective gas comprises oxygen and the protective gas further comprises at least one of an inert gas, nitrogen and carbon dioxide.
In the embodiment, protective gas is arranged and the type of the protective gas is limited, so that the graphite material can be prevented from being oxidized and simultaneously ZnAlO can be prevented from being reduced, and the intermediate product ZnAl-LDH/rGO can be formed into the ZnAlO/rGO nano composite material through a calcining 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 the oxygen in the protective gas is 5-25%, such as but not limited to 5%, 10%, 15%, 20% and 25% or any value or range between any two.
In the embodiment, the protective gas can play a better protective role on the graphite material and ZnAlO, so that the ZnAlO/rGO nano composite material prepared by the method has better quality.
It is understood that, in the step of preparing graphene oxide, the 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 to reduce until the solution is bright yellow; and finally, filtering, washing and drying the prepared graphene oxide.
It can be understood that, in order to prepare graphene oxide with better quality, the temperature and time of the water bath reaction can be regulated.
As an example, in the preparation process of the hydrothermal method, the temperature of the water bath reaction is 15 to 30 ℃, such as but not limited to any one of the reaction temperature of 15 ℃, 20 ℃, 25 ℃ and 30 ℃ or a range value between any two of the reaction temperature; the time of the water bath reaction is 20-120 min, for example, but not limited to, the reaction time is any one value or a range between any two of 20min, 40min, 60min, 80min, 100min and 120 min.
In the embodiment, the temperature of the water bath reaction and the time of the water bath reaction are respectively controlled within the range of 15-30 ℃ and 20-120 min, so that the single-layer high-quality graphene oxide with uniform particle size can be prepared.
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 process of the hydrothermal method, the reaction temperature is 20 ℃ and the reaction time is 60 min.
It should be noted that, the step of preparing graphene oxide involves a process of mixing concentrated sulfuric acid, and the preparation process may be optimized for safety.
As an example, when mixing concentrated sulfuric acid is performed, the reaction system is subjected to an ice-water bath treatment.
In the embodiment, the danger caused by a large amount of heat released when the concentrated sulfuric acid is mixed can be prevented, so that the safety of the preparation process is guaranteed.
On the basis, in consideration of the quality of the prepared graphene oxide, the mass ratio of graphite, potassium permanganate and concentrated sulfuric acid can be regulated and controlled.
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) to (1: 4), for example, 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 between any two; the ratio of the mass of graphite to the volume of concentrated sulfuric acid is (1: 23) to (1: 25), for example, 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 between any two.
It can be understood that the reaction system has appropriate capacity, which is more favorable for the reaction.
As an example, in the step of preparing graphene oxide, the mass of graphite is 0.5 g.
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 the electron transport layer material provided in the embodiment of the first aspect or the 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 to realize effective regulation and control of the electron mobility in the electron transport layer, so that the phenomenon of unbalanced injection of electrons and holes in a quantum dot layer of the semiconductor device is improved, and further, the service life of the device can be prolonged while the efficiency of the device is improved.
It should be noted that, the kind of the semiconductor device including the electron transport layer made of the electron transport layer material provided in the embodiment of the first aspect or the electron transport layer made of the electron transport layer material prepared by the method of preparing the electron transport layer material provided in 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 as provided in the third aspect, including preparing an electron transport layer using ZnAlO/rGO composite nanomaterial.
In the application, the electron transport layer is prepared from the ZnAlO/rGO composite nano material, so that the semiconductor device capable of 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 a standard 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 the 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 transmission 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 then 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 transport layer of the prepared semiconductor device can realize effective regulation and control on the electron mobility.
It is to be 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.
In addition, materials known in the art can be used for materials corresponding to the structures in the semiconductor device.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
A preparation method of an electron transport layer material comprises the following steps:
s1, taking 0.5g of graphite and 1.5g of potassium permanganate as raw materials, adding 12mL of concentrated sulfuric acid into the raw materials in an ice-water bath, and 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 then sequentially filtering, washing and drying to obtain the graphene oxide.
S2 dissolving 100mg of graphene oxide in 200mL of deionized water to prepare sol with the concentration of 0.5mg/mL, and adding 50mg of citric acid, 0.05mmol of urea and 0.009mmol of Zn (NO) into the sol3)2·6H2O、0.003mmolAl(NO3)3·9H2And O, reacting for 12 hours at 80 ℃ by adopting a hydrothermal method to prepare the ZnAl-LDH/rGO nano-composite.
S3, grinding the prepared ZnAl-LDH/rGO nano composite in a mortar, transferring the ground composite into a square boat, transferring the square boat into a tube furnace, introducing oxygen and argon mixed protective gas with the oxygen volume ratio of 15%, and calcining at 400 ℃ for 2 hours to prepare the ZnAlO/rGO nano composite.
Example 2
A method for preparing an electron transport layer material, which is different from example 1 only in that: adding 0.008 mmoleZn (NO)3)2·6H2O、0.004mmolAl(NO3)3·9H2O。
Example 3
A method for preparing an electron transport layer material, which is different from example 1 only in that: adding 0.0096mmolZn (NO)3)2·6H2O、0.0024mmolAl(NO3)3·9H2O。
Example 4
A method for preparing an electron transport layer material, which is different from example 1 only in that: and reacting for 48 hours at 60 ℃ by adopting a hydrothermal method to obtain the ZnAl-LDH/rGO nano-composite.
Example 5
A method for preparing an electron transport layer material, which is different from example 1 only in that: and reacting for 6 hours at 180 ℃ by adopting a hydrothermal method to prepare the ZnAl-LDH/rGO nano-composite.
Example 6
A method for preparing an electron transport layer material, which is different from example 1 only in that: and reacting for 50 hours at 55 ℃ by adopting a hydrothermal method to obtain the ZnAl-LDH/rGO nano-composite.
Example 7
A method for preparing an electron transport layer material, which is different from example 1 only in that: the ZnAl-LDH/rGO nano-composite is prepared by a hydrothermal method at 185 ℃ for 5 h.
Example 8
A method for preparing an electron transport layer material, which is different from the electron transport layer material of example 1 only in that: weighing 80mg of graphene, and adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2The amount of O total substances was 0.01 mmol.
Example 9
A method for preparing an electron transport layer material, which is different from example 1 only in that: weighing 80mg of graphene, and adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2The amount of total O was 0.014 mmol.
Example 10
A method for preparing an electron transport layer material, which is different from example 1 only in that: weighing 120mg of graphene, and adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2The amount of O total substances was 0.01 mmol.
Example 11
A method for preparing an electron transport layer material, which is different from example 1 only in that: weighing 120mg of graphene, and adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2The amount of total O was 0.014 mmol.
Example 12
A method for preparing an electron transport layer material, which is different from example 1 only in that: weighing 80mg of graphene, and adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2The total O content was 0.008 mmol.
Example 13
A method for preparing an electron transport layer material, which is different from example 1 only in that: weighing 80mg of graphene, and adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2The amount of O total substances was 0.016 mmol.
Example 14
A method for preparing an electron transport layer material, which is different from example 1 only in that: weighing 120mg of graphene, and adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2The total O content was 0.008 mmol.
Example 15
A method for preparing an electron transport layer material, which is different from the electron transport layer material of example 1 only in that: weighing 120mg of graphene, and adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2The amount of O total substances was 0.016 mmol.
Example 16
A method for preparing an electron transport layer material, which is different from example 1 only in that: and reacting at 15 ℃ for 120min to obtain graphene oxide slurry.
Example 17
A method for preparing an electron transport layer material, which is different from example 1 only in that: and reacting for 20min at the temperature of 30 ℃ to obtain graphene oxide slurry.
Example 18
A method for preparing an electron transport layer material, which is different from example 1 only in that: and reacting at the temperature of 10 ℃ for 125min to obtain graphene oxide slurry.
Example 19
A method for preparing an electron transport layer material, which is different from example 1 only in that: and reacting for 15min at the temperature of 35 ℃ to obtain graphene oxide slurry.
Example 20
A method for preparing an electron transport layer material, which is different from example 1 only in that: the ark is transferred into a tube furnace and oxygen and argon mixed protective gas with the oxygen volume ratio of 5 percent is introduced.
Example 21
A method for preparing an electron transport layer material, which is different from example 1 only in that: the ark is transferred into a tube furnace and oxygen and argon mixed protective gas with the oxygen volume ratio of 25 percent is introduced.
Example 22
A method for preparing an electron transport layer material, which is different from example 1 only in that: the ark is transferred into a tube furnace and oxygen and argon mixed protective gas with the oxygen volume ratio of 3 percent is introduced.
Example 23
A method for preparing an electron transport layer material, which is different from example 1 only in that: the ark is transferred into a tube furnace and oxygen and argon mixed protective gas with the oxygen volume ratio of 28 percent is introduced.
Comparative example 1
A method for preparing an electron transport layer material, which is different from example 1 only in that: adding 0.006mmol Zn (NO)3)2·6H2O、0.006mmolAl(NO3)3·9H2O。
Comparative example 2
A method for preparing an electron transport layer material, which is different from example 1 only in that: adding 0.01mmol Zn (NO)3)2·6H2O、0.002mmolAl(NO3)3·9H2O。
Preparation example 1
A, spin coating PEDOT on an ITO glass substrate: PSS, the revolution number is 4000 r/min-6000 r/min, and after the spin coating is finished, the heat treatment is carried out for 20-30 min at the temperature of 150 ℃.
B, dissolving 30mgTFB in 1mL of chlorobenzene solvent, stirring and ultrasonically mixing; spin-coating the prepared TFB chlorobenzene solution on PEDOT: and (3) performing heat treatment on the PSS layer at 150 ℃ for 20-30 min after the rotation number is 2000-4000 r/min.
C spin-coating CdSe/ZnS quantum dot layer on TFB at 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano-composite prepared in the embodiment 2 on a quantum dot layer, wherein the revolution is 2000-4000 r/min;
e, evaporating an Al electrode, packaging, and finishing the preparation of the QLED device.
Preparation example 2
A, spin coating PEDOT on an ITO glass substrate: PSS, the revolution number is 4000 r/min-6000 r/min, and after the spin coating is finished, the heat treatment is carried out for 20-30 min at the temperature of 150 ℃.
B, dissolving 30mgTFB in 1mL of chlorobenzene solvent, stirring and ultrasonically mixing; spin-coating the prepared TFB chlorobenzene solution on PEDOT: and (3) performing heat treatment on the PSS layer at 150 ℃ for 20-30 min after the rotation number is 2000-4000 r/min.
C spin-coating CdSe/ZnS quantum dot layer on TFB at 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano-composite prepared in the embodiment 1 on a quantum dot layer at the revolution of 2000-4000 r/min;
e, evaporating an Al electrode, packaging, and finishing the preparation of the QLED device.
Preparation example 3
A, spin coating PEDOT on an ITO glass substrate: PSS, the revolution number is 4000 r/min-6000 r/min, and after the spin coating is finished, the heat treatment is carried out for 20-30 min at the temperature of 150 ℃.
B, dissolving 30mgTFB in 1mL of chlorobenzene solvent, stirring and ultrasonically mixing; spin-coating the prepared TFB chlorobenzene solution on PEDOT: and (3) performing heat treatment on the PSS layer at 150 ℃ for 20-30 min after the rotation number is 2000-4000 r/min.
C spin-coating CdSe/ZnS quantum dot layer on TFB at 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano-composite prepared in the embodiment 3 on a quantum dot layer, wherein the revolution is 2000-4000 r/min;
e, evaporating an Al electrode, packaging, and finishing the preparation of the QLED device.
Preparation example 4
A, spin coating PEDOT on an ITO glass substrate: PSS, the revolution number is 4000 r/min-6000 r/min, and after the spin coating is finished, the heat treatment is carried out for 20-30 min at the temperature of 150 ℃.
B, dissolving 30mgTFB in 1mL of chlorobenzene solvent, stirring and ultrasonically mixing; spin-coating the prepared TFB chlorobenzene solution on PEDOT: and (3) performing heat treatment on the PSS layer at 150 ℃ for 20-30 min after the rotation number is 2000-4000 r/min.
C spin-coating CdSe/ZnS quantum dot layer on TFB at 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano-composite prepared in the comparative example 1 on a quantum dot layer, wherein the revolution is 2000-4000 r/min;
e, evaporating an Al electrode, packaging, and finishing the preparation of the QLED device.
Preparation example 5
A, spin coating PEDOT on an ITO glass substrate: PSS, the revolution number is 4000 r/min-6000 r/min, and after the spin coating is finished, the heat treatment is carried out for 20-30 min at the temperature of 150 ℃.
B, dissolving 30mgTFB in 1mL of chlorobenzene solvent, stirring and ultrasonically mixing; spin-coating the prepared TFB chlorobenzene solution on PEDOT: and (3) performing heat treatment on the PSS layer at 150 ℃ for 20-30 min after the rotation number is 2000-4000 r/min.
C spin-coating CdSe/ZnS quantum dot layer on TFB at 2000-4000 r/min.
D, spin-coating the ZnAlO/rGO nano-composite prepared in the comparative example 2 on a quantum dot layer, wherein the revolution is 2000-4000 r/min;
e, evaporating an Al electrode, packaging, and finishing the preparation of the QLED device.
Preparation example 6
An OLED device was prepared using the ZnAlO/rGO nanocomposite prepared in example 2.
Preparation example 7
The ZnAlO/rGO nano-composite prepared in example 2 is used for preparing a PSC device.
Test example 1
It should be noted that the differences between the preparation examples 1 to 5 are only the differences between the ZnAlO/rGO nano-composites, and the External Quantum Efficiency (EQE) and the service life of the devices prepared in the preparation examples 1 to 5 are detected.
The method for detecting the External Quantum Efficiency (EQE) and the service life of the device is as follows:
in the preparation of preparation examples 1 to 5, 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 as a control example of preparation examples 1 to 5, and then the preparation examples 1 to 5 and the respective control examples were examined.
TABLE 1 EQE and Life test results of 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 device lifetime is prolonged as compared with the comparative example; however, when the molar ratio of Zn to Al is not in the range of (2: 1) to (4: 1), the QLED device obtained is reduced in EQE and the device lifetime as compared with the comparative example.
In addition, it is clear from preparation examples 1 to 3 that when the molar ratio of Zn to Al is 3: 1, the EQE and the service life of the prepared QLED device are both improved to the maximum extent.
Test example 2
The OLED device prepared in preparation example 6 was subjected to luminance and luminosity efficiency detection.
The method for detecting 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 is completed, ZnO is spin-coated on the quantum dot layer of another device, respectively, as a comparative example of preparation example 6, and then the preparation example 6 and the comparative example thereof are tested.
Table 2 results of luminance and luminous efficiency measurements of preparation example 6
| Group of | Zn：Al | Luminance (cd/m)2) | Luminous efficiency (cd/A) |
| Preparation example 6 | 2：1 | 520 | 4.3 |
| Comparative example 6 | 450 | 3.2 |
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 comparative example.
Test example 3
The PSC device prepared in preparation example 7 was subjected to detection of photoelectric conversion efficiency.
The PSC device performance efficiency detection method comprises the following steps:
when the preparation of preparation example 7 was performed, 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 comparative example of preparation example 7, and then the preparation example 6 and the comparative example thereof were examined.
Table 3 photoelectric conversion efficiency test results of preparation example 7
| Group of | Zn：Al | Photoelectric conversion efficiency (%) |
| Preparation example 6 | 2：1 | 10.2 |
| Comparative example 6 | 7.8 |
As can be seen from table 3, when the molar ratio of Zn to Al is 2: 1, the efficiency of the prepared PSC device is significantly better than the control.
In summary, the electron transport layer material, the preparation method thereof, the device and the preparation method thereof according to the embodiments of the present application can improve the phenomenon of unbalanced injection of electrons and holes in the quantum dot layer, thereby improving the device efficiency and prolonging the service life of the device.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (10)
1. An electron transport layer material comprising a ZnAlO/rGO nanocomposite.
2. A method of preparing an electron transport layer material according to claim 1, comprising the steps of:
preparing graphene oxide;
preparing the graphene oxide into sol, adding a guiding agent, a precipitating agent, a Zn salt and an Al salt into the sol to perform a heating reaction, and preparing 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 nano composite.
3. The method for preparing an electron transport layer material according to claim 2, wherein in the step of heating reaction, the reaction temperature is 60-180 ℃ and the reaction time is 6-48 h.
4. The method for preparing the material for the electron transport layer according to claim 2, wherein in the step of preparing ZnAl-LDH/rGO, the mass of the graphene oxide is m1, the total mass of the Zn salt and the Al salt is m2, and the mass of the Zn salt and the Al salt is m 1: m2 is (80-120): (0.01-0.014).
5. The method for preparing an electron transport layer material according to claim 2, wherein 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.
6. The method for preparing the electron transport layer material according to claim 2, wherein the graphene oxide is prepared from graphite by a hydrothermal method, and in the preparation process of the hydrothermal method, the temperature of the water bath reaction is 15-30 ℃, and the time of the water bath reaction is 20-120 min.
7. The method for producing an electron transport layer material according to any one of claims 2 to 6, wherein the calcining is performed in an atmosphere of a protective gas; the protective gas comprises oxygen, the protective gas further comprising at least one of an inert gas, nitrogen, and carbon dioxide;
optionally, the volume ratio of the oxygen in the protective gas is 5-25%.
8. A semiconductor device, comprising an electron transport layer made of the electron transport layer material according to claim 1 or the electron transport layer material prepared by the method according to any one of claims 2 to 7.
9. A method for manufacturing a semiconductor device according to claim 8, wherein the electron transport layer is manufactured using the ZnAlO/rGO composite nanomaterial.
10. A method for manufacturing a semiconductor device according to claim 9, comprising the steps of:
preparing an anode on the surface of the 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 the ZnAlO/rGO composite nano material;
and preparing a cathode on the surface of the electron transport layer, and then packaging.
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