The present disclosure relates to the field of display technologies, and more particularly, to a manufacturing method of a graphene oxide film, an organic light-emitting diode (OLED), and a manufacturing method thereof.
Organic light-emitting diodes (organic light emission diodes, OLEDs) possess advantages of high brightness, a wide range of materials selection, low driving voltages, fully-cured active light emission, etc. Moreover, OLEDs possess advantages of high definition, wide viewing angles, and fast response time. OLEDs are thus display technologies and light sources with great potential. Luminous performance of OLEDs is mainly associate with energy-level matching between functional layers. However, traditional OLEDs have poor luminous efficiency and stability. Affinity between each functional layer is weak, such that the energy level matching between the functional layers is poor. Therefore, the luminous efficiency of the OLEDs is directly affected.
In summary, in existing OLEDs and manufacturing methods thereof, the energy level matching between the functional layers is poor because of the weak affinity between each functional layer. Therefore, the luminous efficiency of the OLEDs is directly affected.
In existing OLEDs and manufacturing methods thereof, the energy level matching between the functional layers is poor because of the weak affinity between each functional layer. Therefore, the luminous efficiency of the OLEDs is directly affected.
In a first aspect, an embodiment of the present disclosure provides a manufacturing method of a graphene oxide film, comprising:
a step S10 of providing a graphene oxide aqueous solution in an initial concentration which is a specific concentration, and dispersing the initial concentration to a first concentration by an ultraviolet reduction process to prepare a first graphene oxide solution;
a step S20 of putting the first graphene oxide solution into an ultrasonic cleaning apparatus and subjecting the first graphene oxide solution to a shaking water bath in the ultrasonic cleaning apparatus at a first temperature; and
a step S30 of coating the first graphene oxide solution, after being subjected to the shaking water bath, to form a graphene oxide film by a spin-coating process.
In the manufacturing method of the graphene oxide film, in the step S10, the first concentration is 0.06-0.2 times as much as the initial concentration.
In the manufacturing method of the graphene oxide film, in the step S20, the first temperature ranges from 20 to 40° C. and duration of subjecting the first graphene oxide solution to the shaking water bath ranges from 2 to 6 hours.
In the second aspect, an embodiment of the present disclosure further provides an organic light-emitting diode (OLED), comprising: a substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode stacked in sequence, wherein the hole injection layer is a graphene oxide layer, and the hole transport layer is any one of N,N′-diphenyl-N,N′-bis(3-tolyl)-1,1′-biphenyl-4,4′-diamine, 1,4-bis(diphenylamino) biphenyl, or N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine.
In the OLED, a concentration of a graphene oxide solution used in the graphene oxide layer ranges from 0.3 to 1 mg/ml.
In the third aspect, an embodiment of the present disclosure further provides a manufacturing method of an organic light-emitting diode (OLED), comprising:
a step S10 of forming an anode on a cleaned substrate by a magnetron sputtering process to obtain an anode substrate;
a step S20 of adjusting a concentration of a graphene oxide solution by an ultraviolet reduction process, and then coating the graphene oxide solution on the anode substrate by a spin coating process, and performing a drying treatment to form a hole injection layer; and
a step S30 of depositing a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode on the hole injection layer in sequence by evaporation processes.
In the manufacturing method of the OLED, the S20 further comprises:
a step S201 of providing a graphene oxide aqueous solution in an initial concentration which is a specific concentration and adjusting the concentration of the graphene oxide solution by the ultraviolet reduction process to prepare a first graphene oxide solution; and
a step S202 of subjecting the first graphene oxide solution to a shaking water bath via an ultrasonic cleaning instrument for 2-6 hours, wherein an ultrasonic process is controlled at 20-40° C., and then coating the first graphene oxide solution on the anode substrate, and performing the drying treatment to form the hole injection layer.
In the manufacturing method of the OLED, in the step S201, the first concentration is 0.06 to 0.2 times as much as the initial concentration.
In the manufacturing method of the OLED, in the step S30, an evaporation rate of the light-emitting layer is between 1-4 Å/s, an evaporation rate of the electron injection layer is between 0.1-0.3 Å/s, and an evaporation rate of the cathode is between 1-5 Å/s.
In the manufacturing method of the OLED, in the step S30, material of the light-emitting layer is tris(8-hydroxyquinoline) aluminum, material of the electron injection layer is LiF, and material of the cathode is Al.
Compared with the prior art, the manufacturing method of the graphene oxide film, the OLED, and the manufacturing method thereof provided by the present disclosure employ different concentrations of the graphene oxide solution as a hole injection layers and employ specific types of hole transport layers, which are beneficial to the injection and transport of holes and further increase luminous efficiency of OLED.
The present disclosure provides a manufacturing method of a graphene oxide film, an OLED, and a manufacturing method thereof. In order to make purposes, technical solutions, and effects of the application to be clearer and more specific, the present disclosure is further described with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are only used to explain the present disclosure, and are not intended to limit the present disclosure.
As shown in
a step S10 of providing a graphene oxide aqueous solution in an initial concentration which is a specific concentration and dispersing the initial concentration to a first concentration by an ultraviolet reduction process to prepare a first graphene oxide solution.
Specifically, the step S10 further includes the following:
First, a specific concentration of graphene oxide aqueous solution is obtained from commercial sources. The specific concentration may be 5 mg/ml. Then, the initial concentration of the graphene oxide solution is dispersed to a first concentration by an ultraviolet reduction process to prepare a first graphene oxide solution. The concentration of the first concentration is 0.06 to 0.2 times as much as the initial concentration. Preferably, when the initial concentration is set to 5 mg/ml, the first concentration ranges from 0.3 mg/ml to 1 mg/ml. Preferably, the initial concentration of the graphene oxide solution is dispersed into a graphene oxide solution A having a solution concentration of 0.3 mg/ml, a graphene oxide solution B having a solution concentration of 0.5 mg/ml, and an Graphene solution C having a solution concentration of 1 mg/ml.
a step S20 of putting the first graphene oxide solution into an ultrasonic cleaning apparatus and subjecting the first graphene oxide solution to a shaking water bath in the ultrasonic cleaning apparatus at a first temperature.
Specifically, the step S20 further includes the following:
Afterwards, the first graphene oxide solution is put into an ultrasonic cleaning apparatus and is subjected to the shaking water bath at the first temperature. The first temperature ranges from 20 to 40° C. and duration of subjecting the first graphene oxide solution to the shaking water bath ranges from 2 to 6 hours. Preferably, the first graphene oxide solution includes the graphene oxide solution A, the graphene oxide solution B, and the graphene oxide solution C.
A step S30 of coating the first graphene oxide solution after being subjected to the shaking bath to form a graphene oxide film by a spin-coating process.
Specifically, the step S30 further includes the following:
Finally, the first graphene oxide solution after being subject to the shaking bath is coated to form a graphene oxide film by the spin-coating process. Preferably, the graphene oxide film includes a film prepared from the graphene oxide solution A, a film prepared from the graphene oxide solution B, and a film prepared from the graphene oxide solution C.
As shown in
Preferably, the substrate 11 is a glass substrate.
Specifically, the anode 12 is preferably indium tin oxide (ITO).
Specifically, when the graphene oxide of the graphene oxide layer is in an oxidized state, the sp2 hybrid conjugation of graphene itself will be destroyed which results in the lack of freely moving 7E electrons. The graphene oxide is in an insulated state and have a wide energy gap, about 3.5 eV or more. When the graphene oxide of the graphene oxide layer is in a reduced state, freely moving 7E electrons can be generated in a conjugated region, which is in a conductive state. The use of graphene oxide as a hole injection layer effectively increases an injection rate of holes, thereby increasing a light emission rate of the OLED.
Specifically, the concentration of the graphene oxide solution used for the graphene oxide layer ranges from 0.3 mg/ml to 1 mg/ml. Preferably, the concentration of the graphene oxide solution used for the graphene oxide layer is 0.3 mg/ml, or 0.5 mg/ml, or 1 mg/ml.
Specifically, material of the light-emitting layer 15 is preferably tris(8-hydroxyquinoline) aluminum (Alq3).
Specifically, material of the electron transport layer 16 is preferably tris(8-hydroxyquinoline) aluminum (Alq3).
Specifically, material of the electron injection layer is preferably LiF.
Specifically, material of the cathode is preferably Al.
The OLEDs provided in the embodiments of the present disclosure employ different concentrations of graphene oxide films as hole injection layers and employ specific hole transport layers, which greatly increases conductivity of the OLEDs and further increases light-emitting efficiency of the OLED.
As shown in
a step S10 of forming an anode 22 on a cleaned substrate by a magnetron sputtering process to obtain an anode substrate 21.
Specifically, the step S10 further includes the following:
First, a substrate 21 is provided. The substrate 21 is preferably a glass substrate. After being rinsed with distilled water and ethanol, the substrate 21 is immersed in isopropyl alcohol for one night, and is then dried for use. Then, an anode 22 is formed on the substrate 21 by the magnetron sputtering process to obtain an anode substrate. Material of the anode 22 is conductive ITO glass and has a sputtering rate of 0.2 nm/s. Afterwards, the anode substrate is rinsed with deionized water, then the anode substrate is rinsed with warm water for 30-50 min, dried, and is finally washed in an ion cleaner for 6-15 min. The use of plasma treatment here is to increase work function of the ITO surface to 4-8 eV or more, and increase the interface contact between the anode substrate and the subsequent organic functional layer, as shown in
A step S20 of adjusting a concentration of a graphene oxide solution by an ultraviolet reduction process, and then coating the graphene oxide solution on the anode substrate by a spin coating process, and performing a drying treatment to form a hole injection layer 23.
Specifically, the step S20 further includes the following:
First, a specific concentration of graphene oxide aqueous solution is obtained from commercial sources. The specific concentration may be 5 mg/ml. Then, the initial concentration of the graphene oxide solution is dispersed to a first concentration by an ultraviolet reduction process to prepare a first graphene oxide solution. The concentration of the first concentration is 0.06 to 0.2 times as much as the initial concentration. Preferably, when the initial concentration is set to 5 mg/ml, the first concentration ranges from 0.3 mg/ml to 1 mg/ml. Preferably, the initial concentration of the graphene oxide solution is dispersed into a graphene oxide solution A having a solution concentration of 0.3 mg/ml, a graphene oxide solution B having a solution concentration of 0.5 mg/ml, and a graphene oxide solution C having a solution concentration of 1 mg/ml. Afterwards, the first graphene oxide solution is subjected to a shaking water bath via an ultrasonic cleaning instrument for 2-6 hours. The ultrasonic process is controlled at 20-40° C., and then different concentrations of the graphene oxide solutions (equal amounts) are coated on three of the anode substrates via the spin coating process. Three batches of the sample were prepared and dried to obtain the hole injection layer 23, as shown in the
A step S30 of depositing a hole transport layer 24, a light-emitting layer 25, an electron transport layer 26, an electron injection layer 27, and a cathode 28 on the hole injection layer 23 in sequence by evaporation processes.
Specifically, the step S30 further includes the following:
First, the anode substrate that is spin-coated with graphene oxide is fixed on a mask plate, transferred to a vacuum evaporation chamber, and vacuumed using a molecular pump. Until the degree of vacuum is lower than 4.0×10−4 Pa to 6.5×10−4 Pa, a hole transport layer 24 is deposited on the hole injection layer 23. The hole transport layer 24 is N,N′-diphenyl-N,N′-bis(3-tolyl)-1,1′-biphenyl-4,4′-diamine (TPD), 1,4-bis(diphenylamino) biphenyl (DDB), and N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine (NPB). Thereafter, a light-emitting layer 25, an electron transporting layer 26, an electron injection layer 27, and a cathode 28 are deposited on the hole transporting layer 24 in sequence. Finally, OLEDs with different concentrations of graphene oxide and OLEDs that correspond to different hole transport layers are obtained, as shown in
An evaporation rate of the light-emitting layer 25 is between 1 to 4 Å/s. Material of the light-emitting layer 25 is preferably tris(8-hydroxyquinoline) aluminum (Alq3). Material of the electron transport layer 26 is preferably tris(8-hydroxyquinoline) aluminum (Alq3). An evaporation rate of the electron injection layer 27 is between 0.1 to 0.3 Å/s. Material of the electron injection layer is preferably LiF. An evaporation rate of the cathode 28 is between 1 to 5 Å/s. Material of the cathode 28 is preferably Al.
Preferably, the manufacturing method of an OLED provided in the embodiments of the present disclosure obtains OLEDs of 9 different embodiments. Details are described as follows:
The OLED A1 includes a hole injection layer that is prepared from a 0.3 mg/ml of the graphene oxide solution and a hole transporting layer that is prepared from N,N′-diphenyl-N,N′-bis(3-tolyl)-1,1′-biphenyl-4,4′-diamine (TPD). The OLED A2 includes a hole injection layer that is prepared from a 0.5 mg/ml of the graphene oxide solution and a hole-transporting layer that is prepared from N,N′-diphenyl-N,N′-bis(3-tolyl)-1,1′-biphenyl-4,4′-diamine. The OLED A3 includes a hole injection layer that is prepared from 1 mg/ml of the graphene oxide solution and a hole transport layer that is prepared from N,N′-diphenyl-N,N′-bis(3-tolyl)-1,1′-biphenyl-4,4′-diamine (TPD).
The OLED B1 includes a hole injection layer that is prepared from a 0.3 mg/ml of the graphene oxide solution and a hole transport layer that is prepared from 1,4-bis(diphenylamino) biphenyl (DDB). The OLED B2 includes a hole injection layer that is prepared from a 0.5 mg/ml of the graphene oxide solution and a hole transport layer that is prepared from 1,4-bis(diphenylamino) biphenyl (DDB). The OLED B3 includes a hole injection layer prepared from 1 mg/ml of the graphene oxide solution and a hole transport layer that is prepared from 1,4-bis(diphenylamino) biphenyl (DDB).
The OLED C1 includes a hole injection layer that is prepared from 0.3 mg/ml of the graphene oxide solution and a hole transport layer that is prepared from N,N′-diphenyl-N,N′-bis(3-tolyl)-1,1′-biphenyl-4,4′-diamine (NPB). The OLED C2 includes a hole injection layer that is prepared from 0.5 mg/ml of the graphene oxide solution and a hole transport layer that is prepared from N,N′-diphenyl-N,N′-bis(3-tolyl)-1,1′-biphenyl-4,4′-diamine (NPB). The OLED C3 includes a hole injection layer that is prepared from 1 mg/ml of the graphene oxide solution and a hole transport layer that is prepared from N,N′-diphenyl-N,N′-bis(3-tolyl)-1,1′-biphenyl-4,4′-diamine.
As shown in
As shown in
As shown in
In summary, in combination with the experimental results of
The OLEDs and manufacturing methods provided in the embodiments of the present disclosure comprehensively compare the effects of the graphene oxide solution concentrations and the material choices of the hole transport layer on the light-emitting efficiency of the OLED in the nine embodiments, which is beneficial to the increase of luminous efficiency of the OLED.
The manufacturing method of the graphene oxide film, the OLED, and the manufacturing method thereof provided by the present disclosure employ different concentrations of the graphene oxide solution as hole injection layers and employ specific types of hole transport layers, which are beneficial to the injection and transport of holes and further increase luminous efficiency of OLED.
It can be understood that one of ordinarily skill in the art can carry out changes and modifications to the described embodiment according to technical solutions and technical concepts of the present application, and all such changes and modifications are considered encompassed in the scope of protection defined by the claims of the present application.
Filing Document | Filing Date | Country | Kind |
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PCT/CN2019/125080 | 12/13/2019 | WO | 00 |