CN111384267B - Preparation method of graphene quantum dot film, light-emitting diode and preparation method of light-emitting diode - Google Patents
Preparation method of graphene quantum dot film, light-emitting diode and preparation method of light-emitting diode Download PDFInfo
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Abstract
The invention belongs to the technical field of display, and particularly relates to a preparation method of a graphene quantum dot film, a light-emitting diode and a preparation method of the light-emitting diode. The preparation method of the graphene quantum dot film comprises the following steps: providing a graphene quantum dot solution, mixing the graphene quantum dot solution with a treating agent for treatment, wherein the treating agent is an oxidant or a reducing agent, the treatment time is 10 s-1 h, obtaining a doped graphene quantum dot solution, and forming a film on the doped graphene quantum dot solution to obtain a doped graphene quantum dot film; or providing a graphene quantum dot solution, depositing the graphene quantum dot solution on a substrate, drying to obtain a graphene quantum dot film, and treating the graphene quantum dot film with a treating agent, wherein the treating agent is an oxidant or a reducing agent, and the treating time is 10 s-1 h to obtain the doped graphene quantum dot film.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a preparation method of a graphene quantum dot film, a light-emitting diode and a preparation method of the light-emitting diode.
Background
Quantum Dot Light Emitting diodes (QLEDs) and Organic Light Emitting Diodes (OLEDs) show great application prospects in the display field due to their characteristics of self-luminescence, fast response speed, high contrast, low power consumption, large viewing angle, flexibility and the like. In the research of these light emitting diodes, various high performance light emitting materials are layered endlessly, and since different light emitting materials have different energy level structures, in order to fully exert the performance of these light emitting materials, it is necessary to effectively inject and transport charge carriers, and it is necessary to continuously develop charge transport materials with different energy level structures to match the energy level structures of different light emitting materials. However, such development is difficult and complicated. Therefore, a charge transport material that can flexibly adjust its energy level structure is important.
As is known, graphene is a two-dimensional layered structure material with ultra-strong conductivity, the thickness of the graphene is usually from a few tenths to a few nanometers, the size of the graphene in the plane direction is usually from a few microns to a few tens of microns corresponding to a single-layer or two to three-layer graphene sheet, and the size of the graphene quantum dot in the plane direction is not more than 100 nanometers, so that the graphene has a quantum confinement effect, and therefore, the graphene has the general properties of quantum dots, namely, the size of the graphene can be adjusted along with the size. In summary, the graphene quantum dot has good conductivity and an energy level structure (including a conduction band, a valence band, a work function, and the like) which is adjustable along with the size. In addition, graphene quantum dots, like graphene, have a large number of oxygen-containing groups on the surface, for example: the graphene quantum dots have epoxy groups, hydroxyl groups and the like on a basal plane and a large number of carboxyl groups on a side surface, and the oxygen-containing groups enable the graphene quantum dots to have excellent solubility in an aqueous solvent (such as deionized water, methanol, ethanol, isopropanol and the like) and to be insoluble in a common organic solvent with low polarity (such as n-hexane, toluene, chlorobenzene, dichlorobenzene and the like).
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a preparation method of a graphene quantum dot film, a light-emitting diode and a preparation method thereof, and aims to solve the technical problem that the charge transmission effect of the existing light-emitting diode is not ideal.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a graphene quantum dot film on one hand, which comprises the following steps:
providing a graphene quantum dot solution, mixing the graphene quantum dot solution with a treating agent for treatment, wherein the treating agent is an oxidant or a reducing agent, the treatment time is 10 s-1 h, obtaining a doped graphene quantum dot solution, and forming a film on the doped graphene quantum dot solution to obtain a doped graphene quantum dot film; alternatively, the first and second electrodes may be,
providing a graphene quantum dot solution, depositing the graphene quantum dot solution on a substrate, drying to obtain a graphene quantum dot film, and treating the graphene quantum dot film with a treating agent, wherein the treating agent is an oxidant or a reducing agent, and the treating time is 10 s-1 h to obtain the doped graphene quantum dot film.
According to the preparation method of the graphene quantum dot film, the graphene quantum dot solution and the treating agent are mixed and processed to form a film, or the film-formed graphene quantum dot film and the treating agent are mixed and processed to obtain the graphene quantum dot film, because the oxidation-reduction potential of the graphene quantum dot is close to that of a standard hydrogen electrode, the oxidation or reduction of the graphene quantum dot by using an oxidation-reduction method is an effective method capable of changing the work function of the graphene quantum dot; if the graphene quantum dots and the reducing agent are mixed, electrons are obtained by the graphene quantum dots and the reducing agent, which is equivalent to n-type doping, so that the work function of the graphene quantum dots is reduced, and the obtained n-type doped graphene quantum dot film can be used as a hole transport layer of a light-emitting device; therefore, the graphene quantum dot film obtained by the preparation method can promote injection and transmission of charge carriers, and further improves the light emitting performance of the device.
The invention provides a light-emitting diode, which comprises an anode, a cathode and a light-emitting layer positioned between the anode and the cathode, wherein a hole transport layer is arranged between the anode and the light-emitting layer, and the hole transport layer is a p-type doped graphene quantum dot film obtained by the preparation method of the graphene quantum dot film; and/or the presence of a gas in the gas,
an electron transport layer is arranged between the cathode and the light-emitting layer, and the electron transport layer is the n-type doped graphene quantum dot film obtained by the preparation method of the graphene quantum dot film.
In the light emitting diode provided by the invention, the p-type doped graphene quantum dot film obtained by the preparation method of the special graphene quantum dot film is arranged between the anode and the light emitting layer and is used as the hole transport layer, and/or the n-type doped graphene quantum dot film obtained by the preparation method of the special graphene quantum dot film is arranged between the cathode and the light emitting layer and is used as the electron transport layer. The p-type doped graphene quantum dot film or the n-type doped graphene quantum dot film can promote injection and transmission of charge carriers, and further improve the light emitting performance of the device.
Finally, the invention provides a method for preparing a light-emitting diode, which comprises the following steps:
providing a substrate;
preparing a p-type doped graphene quantum dot film on the substrate as a hole transport layer by adopting the preparation method of the graphene quantum dot film; and/or the presence of a gas in the gas,
the preparation method of the graphene quantum dot film is adopted to prepare the n-type doped graphene quantum dot film on the substrate as an electron transport layer.
The preparation method of the quantum dot light-emitting diode provided by the invention has the advantages of simple process and low cost, and the p-type doped graphene quantum dot film is directly prepared on the substrate by adopting the preparation method of the special graphene quantum dot film provided by the invention to be used as the hole transmission layer, and/or the n-type doped graphene quantum dot film is prepared by adopting the preparation method of the special graphene quantum dot film provided by the invention to be used as the electron transmission layer. The p-type doped graphene quantum dot film or the n-type doped graphene quantum dot film can promote injection and transmission of charge carriers, and the luminous performance of the finally prepared device is remarkably improved.
Drawings
Fig. 1 is a flow chart of a method for preparing a graphene quantum dot film according to the present invention;
fig. 2 is a flow chart of another preparation method of the graphene quantum dot film of the present invention;
fig. 3 is a schematic structural diagram of a quantum dot light-emitting diode according to embodiment 1 of the present invention;
fig. 4 is a schematic structural diagram of a quantum dot light emitting diode in embodiment 2 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On one hand, the embodiment of the invention provides a preparation method of a graphene quantum dot film, as shown in fig. 1, the preparation method comprises the following steps:
s01: providing a graphene quantum dot solution;
s02: mixing the graphene quantum dot solution with a treating agent, wherein the treating agent is an oxidant or a reducing agent, and the treating time is 10 s-1 h, so as to obtain a doped graphene quantum dot solution;
s03: and forming a film by using the doped graphene quantum dot solution to obtain the doped graphene quantum dot film.
Alternatively, as shown in fig. 2, the method comprises the following steps:
e01: providing a graphene quantum dot solution;
e02: depositing the graphene quantum dot solution on a substrate, and drying to obtain a graphene quantum dot film;
e03: and treating the graphene quantum dot film by using a treating agent, wherein the treating agent is an oxidant or a reducing agent, and the treating time is 10 s-1 h, so as to obtain the doped graphene quantum dot film.
In the two methods for preparing the graphene quantum dot thin films provided by the embodiment of the invention, the graphene quantum dot solution and the treating agent are mixed and processed to form a film, or the film-formed graphene quantum dot thin film and the treating agent are mixed and processed to obtain the film, because the oxidation-reduction potential of the graphene quantum dot is close to the oxidation-reduction potential of the standard hydrogen electrode, the oxidation or reduction of the graphene quantum dot by using the oxidation-reduction method is an effective method for changing the work function of the graphene quantum dot; if the graphene quantum dots and the reducing agent are mixed, electrons are obtained by the graphene quantum dots and the reducing agent, which is equivalent to n-type doping, so that the work function of the graphene quantum dots is reduced, and the obtained n-type doped graphene quantum dot film can be used as a hole transport layer of a light-emitting device; therefore, the graphene quantum dot film obtained by the preparation method can promote injection and transmission of charge carriers, and further improves the light emitting performance of the device.
In the embodiment of the invention, the graphene quantum dots are oxidized or reduced by using a redox method to effectively change the work function of the graphene quantum dots, the redox method is realized by mixing and contacting the graphene quantum dots with an oxidant or a reducing agent, a graphene quantum dot solution and a treating agent are mixed for treatment and then a film is formed, or the treating agent is used for treating a graphene quantum dot film; for treating the graphene quantum dot film by using the treating agent, the graphene quantum dot film is formed and then is immersed in an oxidant solution or a reducing agent solution; the surface of the graphene quantum dot film may be covered with an oxidant solution or a reducing agent solution. After the two materials interact for a period of time, the oxidant or reducing agent solution residue on the surface of the graphene quantum dot film is cleaned by deionized water to be used as a charge transport layer (namely a hole transport layer or an electron transport layer). The work function of the graphene quantum dot film is influenced by the mixing time of the graphene quantum dot film and an oxidant or reducing agent solution, and within a certain time range, the longer the graphene quantum dot film is soaked in the oxidant solution after being formed into a film, the larger the work function of the graphene quantum dot film is; the longer the infiltration time of the graphene quantum dots in a reducing agent solution after film formation is, the smaller the work function of the graphene quantum dots is; when the time range is exceeded, the work function change of the graphene quantum dot film basically tends to saturation, so that in the embodiment of the invention, the graphene quantum dot solution (or the graphene quantum dot film) is mixed with the oxidant or the reducing agent for treatment for 10 s-1 h, the graphene quantum dot structure is not influenced in the time range, the work function of the graphene quantum dot can be adjusted, and the obtained p-type doped graphene quantum dot film or n-type doped graphene quantum dot can be better used as a charge transport layer.
In the embodiment of the invention, if the treating agent is an oxidant, the obtained doped graphene quantum dot film is a p-type doped graphene quantum dot film. And if the treating agent is a reducing agent, the obtained doped graphene quantum dot film is an n-type doped graphene quantum dot film.
The graphene quantum dot is a two-dimensional layered structure material with super-strong conductivity, the thickness of the graphene quantum dot is from a few tenths of nanometers to a few nanometers, the graphene quantum dot corresponds to a single layer or two to three layers of graphene sheets, the plane size is smaller than 100 nanometers, the graphene quantum dot has a quantum confinement effect, the graphene quantum dot has good conductivity and an energy level structure which can be adjusted along with the size, the semiconductor characteristics of the graphene quantum dot, especially the work function, can be increased along with the reduction of the size of the graphene quantum dot, or can be reduced along with the increase of the size, so that the proper size of the graphene quantum dot can be selected according to the energy level structure of a luminescent material, and the injection and the transmission of charge carriers are promoted. Although the work function of the graphene quantum dot can be adjusted by changing the size, the change range of the work function is relatively small, generally between 3.8eV and 5eV, and the requirements of many luminescent materials cannot be met, so that the graphene quantum dot is important as a charge transport layer for further expanding the work function adjustment range.
Since the oxidation-reduction potential of the graphene quantum dot is close to that of the standard hydrogen electrode, the oxidation or reduction of the graphene quantum dot by using the oxidation-reduction method is an effective method for changing the work function of the graphene quantum dot. Because, if the graphene quantum dots are oxidized (i.e., p-type doped graphene quantum dots), the graphene quantum dots lose electrons and generate holes, which is equivalent to p-type doping, so that the work function of the graphene quantum dots is increased, and the obtained p-type doped graphene quantum dots serve as a hole transport layer; if the graphene quantum dots are reduced (namely n-type doped graphene quantum dots), electrons are obtained by the graphene quantum dots, namely n-type doping, so that the work function of the graphene quantum dots is reduced, the obtained n-type doped graphene quantum dots are used as an electron transport layer, the material structure of the graphene quantum dots is not changed by oxidation or reduction of the graphene quantum dots, the electron structure of the graphene quantum dot material is changed, hole sites or electrons are generated by the graphene quantum dot material, and therefore injection and transport of charge carriers can be promoted.
In one embodiment of the invention, the graphene quantum dot solution is deposited on a substrate, is dried, and is then mixed with an oxidant for 10 s-1 h, so that the obtained graphene quantum dot film is a p-type doped graphene quantum dot film. At this time, the oxidizing agent is selected from at least one of perchlorate, permanganate, dichromate, bromate, sodium peroxide, gold chloride, perbromic acid, ferrate, nitric acid, and concentrated sulfuric acid; the plane size of the graphene quantum dots in the graphene quantum dot solution is 2-30nm, and the plane size of the p-type doped graphene quantum dots in the obtained p-type doped graphene quantum dot film is 2-30 nm.
In another embodiment of the invention, the graphene quantum dot solution is deposited on a substrate, and is dried, and then is mixed with a reducing agent for 10 s-1 h, so that the obtained graphene quantum dot film is an n-type doped graphene quantum dot film. At this time, the reducing agent is selected from at least one of potassium hydroxide, sodium hydroxide, barium hydroxide, calcium hydroxide, and magnesium hydroxide; the plane size of the graphene quantum dots in the graphene quantum dot solution is 40-100nm, and the plane size of the n-type doped graphene quantum dots in the obtained n-type doped graphene quantum dot film is 40-100 nm.
The effect of changing the work function of the graphene quantum dot film is influenced by the oxidizing property of an oxidant and the reducing property of a reducing agent, and generally speaking, the stronger the oxidizing property of the oxidant is, the larger the work function is; the stronger the reducing agent is, the smaller the work function is. In an embodiment of the invention, the oxidant is preferably ferrate, the time for mixing the graphene quantum dots with the oxidant can be 1-10 minutes, and the work function of the ferrate-treated graphene quantum dots can reach 5.4 eV. In another embodiment of the invention, the reducing agent is preferably potassium hydroxide, the time for mixing the graphene quantum dots with the oxidizing agent can be 1-10 minutes, and the work function of the graphene quantum dots treated by the potassium hydroxide can reach 4.0eV or less.
Specifically, when a p-type doped graphene quantum dot is used as a hole transport layer, its work function should be as close to the top valence band level or HOMO level of the light emitting material as possible, so the planar size of the p-type doped graphene quantum dot is preferably 2 to 30nm, more preferably 2 to 10 nm; when the n-type doped graphene quantum dot is used as an electron transport layer, the work function should be as close as possible to the conduction band bottom level or LUMO level of the light emitting material, and thus the planar size of the n-type doped graphene quantum dot is preferably 40 to 100nm, more preferably 70 to 100 nm.
Further, in the preparation method of the graphene quantum dot film provided by the embodiment of the invention, the concentration of the graphene quantum dots in the graphene quantum dot solution is 2-15 mg/ml; the temperature of the drying treatment is 50-100 ℃; the drying time is 0.5-2 h.
In a specific embodiment of the present invention, an effective method for graphene quantum dot thin film oxidation reduction is as follows: (1) preparing a graphene quantum dot solution, and dissolving the graphene quantum dots in absolute ethyl alcohol, wherein the concentration is 2-15 mg/ml; (2) depositing a graphene quantum dot film on a substrate, and then baking for 0.5-2 hours at 70 ℃; (3) preparing an oxidant solution or a reducing agent solution in advance, and dissolving the oxidant solution or the reducing agent solution into deionized water if the substances are salts; if the substances are solutions, the substances are directly used; (4) immersing the substrate into an oxidant solution or a reducing agent solution, and keeping for 10 s-1 h; or dropping an oxidant or a reducing agent solution on the surface of the graphene quantum dot film, and keeping soaking for 10 s-1 h; (5) and washing away oxidant or reducing agent solution residues on the surface of the graphene quantum dot film by using deionized water, and drying in weak nitrogen flow to finally obtain the hole transport layer or the electron transport layer.
On the other hand, the embodiment of the invention provides a light emitting diode, which comprises an anode, a cathode and a light emitting layer positioned between the anode and the cathode, wherein a hole transport layer is arranged between the anode and the light emitting layer, and the hole transport layer is a p-type doped graphene quantum dot film obtained by the preparation method of the graphene quantum dot film in the embodiment of the invention; and/or the presence of a gas in the gas,
an electron transport layer is arranged between the cathode and the light emitting layer, and the electron transport layer is the n-type doped graphene quantum dot film obtained by the preparation method of the graphene quantum dot film in the embodiment of the invention.
In the light emitting diode provided by the embodiment of the present invention, the p-type doped graphene quantum dot film obtained by the method for preparing a graphene quantum dot film specific to the embodiment of the present invention is disposed between the anode and the light emitting layer as the hole transport layer, and/or the n-type doped graphene quantum dot film obtained by the method for preparing a graphene quantum dot film specific to the embodiment of the present invention is disposed between the cathode and the light emitting layer as the electron transport layer. The p-type doped graphene quantum dot film or the n-type doped graphene quantum dot film can promote injection and transmission of charge carriers, and further improve the light emitting performance of the device.
Preferably, a small-sized (preferably 2-10nm) graphene quantum dot is taken as an object, the object is subjected to strong oxidant treatment, so as to serve as a hole transport material, that is, a hole transport layer arranged between the anode and the light-emitting layer is the p-type doped graphene quantum dot film, the work function of the p-type doped graphene quantum dot can reach 5.4eV, and from the aspect of energy level matching, a suitable light-emitting material can be a red/green quantum dot (such as CdSe/CdS/ZnS, ZnCdSeS, CsPbBr, CuInS and the like), and then the light-emitting diode is a quantum dot light-emitting diode; alternatively, red/green organic luminescent material (e.g., DCJT [ 4- (Dicyanomethylene) -2-methyl-6- (1,1,7, 7-tetramethyljunolidyl-9-enyl) -4H-pyran,2- [ 2-methyl-6- [2- (2,3,6, 7-tetrahydro-1, 1,7, 7-tetramethyl-1H, 5H-benzo [ ij)]Quinolizin-9-yl) ethenyl]-4H-pyran-4-ylidene]Malononitrile, Ir (piq)3【Tris[2-(4-n-hexylphenyl)quinoline)]Iridium (III), tris (1- (4-N-hexylphenyl) -isoquinoline-C2, N) iridium (III), Ir (ppy)3【Tris[2-(p-tolyl)pyridine]Iridium (III), tris [2- (p-tolyl) pyridine-C2, N) iridium (III) ], Ir (mppy)3) Tris (2-phenylpyridine) iridium (iii), Tris (2-phenylpyridine) iridium (ir), red/green polymeric luminescent materials, for example: MEH-PPV [ Poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene ]](ii) a Poly [2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylacetylene]】、SY-PPV【Poly[{2,5-di(3',7'-dimethyloctyloxy)-1,4-phenylene-vinylene}-co-{3-(4'-(3”,7”-di methyloctyloxy)phenyl)-1,4-phenylenevinylene}-co-{3-(3'-(3',7'-dimethyloctyloxy)p henyl)-1,4-phenylenevinylene}]Poly [ {2, 5-bis (3',7' -dimethyloctyloxy) -1, 4-phenylacetylene } -co- {3- (4'- (3 ", 7" -dimethyloctyloxy) phenyl) -1, 4-phenylacetylene } -co- {3- (3' - (3 ", 7" -dimethyloctyloxy) phenyl) -1, 4-phenylacetylene }]Etc. at this time, light emissionThe diode is an organic light emitting diode.
The method is characterized in that large-size (preferably 70-100nm) graphene quantum dots are used as objects, strong reducing agent treatment is carried out on the large-size graphene quantum dots to be used as electron transport materials, namely an electron transport layer arranged between a cathode and a light-emitting layer is the n-type doped graphene quantum dot thin film, the work function of the n-type doped graphene quantum dots can reach 4.0eV or less, and from the aspect of energy level matching, suitable light-emitting materials are mainly quantum dots (such as CdSe/CdS/ZnS, CdSe @ ZnS, CuInS, InP/ZnS, CsPbBr and the like), and then the light-emitting diode is a quantum dot light-emitting diode.
Further, in the light emitting diode according to the embodiment of the present invention, a hole injection layer is disposed between the anode and the hole transport layer; and/or an electron injection layer is arranged between the cathode and the electron transport layer.
Furthermore, in the embodiment of the present invention, the light emitting diode is a quantum dot light emitting diode, and the light emitting layer is a quantum dot light emitting layer; or, the light emitting diode is an organic light emitting diode, and the light emitting layer is an organic light emitting layer.
On the other hand, the embodiment of the invention also provides a preparation method of the light-emitting diode, which comprises the following steps:
e01: providing a substrate;
e02: preparing a p-type doped graphene quantum dot film on the substrate as a hole transport layer by adopting the preparation method of the graphene quantum dot film; and/or the presence of a gas in the gas,
the preparation method of the graphene quantum dot film provided by the embodiment of the invention is adopted to prepare the n-type doped graphene quantum dot film on the substrate as an electron transport layer.
The preparation method of the quantum dot light-emitting diode provided by the embodiment of the invention has the advantages of simple process and low cost, and the p-type doped graphene quantum dot film prepared by the preparation method of the graphene quantum dot film special for the embodiment of the invention is directly adopted on the substrate to be used as the hole transmission layer, and/or the n-type doped graphene quantum dot film prepared by the preparation method of the graphene quantum dot film special for the embodiment of the invention is used as the electron transmission layer. The p-type doped graphene quantum dot film or the n-type doped graphene quantum dot film can promote injection and transmission of charge carriers, and the luminous performance of the finally prepared device is remarkably improved.
Specifically, for the substrate in step E01, for preparing a hole transport layer composed of a p-type doped graphene quantum dot film on the substrate, if the surface of the substrate is provided with an anode, the substrate is an anode substrate, directly preparing a hole transport layer composed of a p-type doped graphene quantum dot film on the anode, subsequently preparing a quantum dot light-emitting layer on the hole transport layer, then preparing an electron transport layer on the quantum dot light-emitting layer, and finally preparing a cathode on the electron transport layer; if the surface of the substrate is provided with the quantum dot light emitting layer, the substrate is a cathode substrate, a hole transport layer consisting of the p-type doped graphene quantum dot film is directly prepared on the quantum dot light emitting layer, a hole injection layer is subsequently prepared on the hole transport layer, and finally an anode is prepared on the hole injection layer.
For preparing an electron transport layer composed of an n-type doped graphene quantum dot film on the substrate, if a cathode is arranged on the surface of the substrate, the substrate is a cathode substrate, the electron transport layer composed of the n-type doped graphene quantum dot film is directly prepared on the cathode, a quantum dot light emitting layer is subsequently prepared on the electron transport layer, a hole transport layer is prepared on the quantum dot light emitting layer, and finally an anode is prepared on the hole transport layer; if the surface of the substrate is provided with the quantum dot light emitting layer, the substrate is an anode substrate, an electron transmission layer consisting of the n-type doped graphene quantum dot film is directly prepared on the quantum dot light emitting layer, an electron injection layer is subsequently prepared on the electron transmission layer, and finally a cathode is prepared on the electron injection layer.
The step E02: the hole transport layer is formed by preparing the p-type doped graphene quantum dot film or the electron transport layer is formed by preparing the n-type doped graphene quantum dot film, and the specific method refers to the preparation method of the graphene quantum dot film.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A quantum dot light emitting diode is structurally shown in FIG. 3, and comprises the following components in sequence from bottom to top: the light-emitting diode comprises a substrate 101, an anode 102, a hole transport layer 103 consisting of p-type doped graphene quantum dots, a quantum dot light-emitting layer 104, an electron transport layer 105 and a cathode 106.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
(1) preparing a graphene quantum dot solution: dissolving 10 nm-graphene quantum dots in absolute ethyl alcohol, wherein the concentration is 8 mg/ml; preparing a potassium perchlorate aqueous solution: dissolving potassium perchlorate into deionized water with the concentration of 5 mM;
(2) depositing a graphene quantum dot film on a substrate with an ITO anode pattern by using a solution method, and then baking for 1 hour at 70 ℃;
(3) immersing the substrate obtained in the step (2) into a potassium perchlorate solution, soaking for 1 minute, and then taking out; washing away potassium perchlorate solution residues on the surface of the graphene quantum dot film by using deionized water, and drying in weak nitrogen flow to obtain a hole transport layer consisting of p-type doped graphene quantum dots;
(4) depositing CdSe/CdS/ZnS quantum dots on the surface of the hole transport layer by a solution method in a nitrogen environment to be used as a quantum dot light emitting layer, wherein the thickness of the CdSe/CdS/ZnS quantum dots is 25nm, and then annealing for 10 minutes at 100 ℃;
(5) depositing ZnO nanoparticles as an electron transport layer on the quantum dot light-emitting layer by a solution method in a nitrogen environment, wherein the thickness of the ZnO nanoparticles is 30nm, and then annealing the ZnO nanoparticles for 30 minutes at 80 ℃;
(6) al is evaporated on the electron transport layer as a cathode and has a thickness of 100 nm.
Example 2
A quantum dot light emitting diode is structurally shown in FIG. 4, and comprises the following components in sequence from bottom to top: the light-emitting diode comprises a substrate 201, a cathode 202, an electron transport layer 203 consisting of n-type doped graphene quantum dots, a quantum dot light-emitting layer 204, a hole transport layer 205, a hole injection layer 206 and an anode 207.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
(1) preparing a graphene quantum dot solution: dissolving 80 nm-graphene quantum dots in absolute ethyl alcohol, wherein the concentration is 8 mg/ml; preparation of an aqueous potassium hydroxide solution: dissolving potassium hydroxide into deionized water with the concentration of 8 mM;
(2) depositing a graphene quantum dot film on a substrate with an ITO cathode pattern by using a solution method, and then baking for 1 hour at 70 ℃;
(3) immersing the substrate obtained in the step (2) into a potassium hydroxide solution, soaking for 2 minutes, and then taking out; washing away potassium hydroxide solution residues on the surface of the graphene quantum dot film by using deionized water, and drying in weak nitrogen flow to obtain an electron transport layer consisting of n-type doped graphene quantum dots;
(4) depositing CdSe/CdS/ZnS quantum dots on the surface of the electron transport layer by a solution method in a nitrogen environment to be used as a quantum dot light emitting layer, wherein the thickness of the CdSe/CdS/ZnS quantum dots is 25nm, and then annealing for 10 minutes at 100 ℃;
(5) transferring the substrate into a vapor deposition chamber, and vacuumizing to 10 DEG-5Evaporating 30nm NPB on the surface of the quantum dot light-emitting layer as a hole transport layer below Pa;
(6) evaporating 10nm HAT-CN on the surface of the hole transport layer to be used as a hole injection layer;
(7) 100nm Ag was vapor-deposited on the hole injection layer as an anode.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (12)
1. A preparation method of a p-type doped graphene quantum dot film is characterized by comprising the following steps:
providing a graphene quantum dot solution with the plane size of 2-30nm of graphene quantum dots, mixing the graphene quantum dot solution with a treating agent, wherein the treating agent is an oxidant, the treating time is 10 s-1 h, obtaining a p-type doped graphene quantum dot solution, and forming a film on the p-type doped graphene quantum dot solution to obtain a p-type doped graphene quantum dot film; alternatively, the first and second electrodes may be,
providing a graphene quantum dot solution with the plane size of 2-30nm of graphene quantum dots, depositing the graphene quantum dot solution on a substrate, drying to obtain a graphene quantum dot film, and treating the graphene quantum dot film with a treating agent which is an oxidant for 10 s-1 h to obtain the p-type doped graphene quantum dot film.
2. The method of claim 1, wherein the oxidizing agent is selected from at least one of perchlorate, permanganate, dichromate, bromate, sodium peroxide, gold chloride, perbromic acid, ferric acid, nitric acid, and concentrated sulfuric acid.
3. The method of claim 2, wherein the oxidizing agent is ferrate and the treatment time is 1 to 10 minutes.
4. The preparation method according to any one of claims 1 to 3, wherein the graphene quantum dot concentration in the graphene quantum dot solution is 2 to 15 mg/ml; and/or the presence of a gas in the gas,
the temperature of the drying treatment is 50-100 ℃; and/or the presence of a gas in the gas,
the drying time is 0.5-2 h.
5. A preparation method of an n-type doped graphene quantum dot film is characterized by comprising the following steps:
providing a graphene quantum dot solution with the plane size of graphene quantum dots being 40-100nm, mixing the graphene quantum dot solution with a treating agent for treatment, wherein the treating agent is a reducing agent, the treatment time is 10 s-1 h, so as to obtain an n-type doped graphene quantum dot solution, and forming a film on the n-type doped graphene quantum dot solution so as to obtain an n-type doped graphene quantum dot film; alternatively, the first and second electrodes may be,
providing a graphene quantum dot solution with the plane size of graphene quantum dots being 40-100nm, depositing the graphene quantum dot solution on a substrate, drying to obtain a graphene quantum dot film, and treating the graphene quantum dot film with a treating agent, wherein the treating agent is a reducing agent, and the treating time is 10 s-1 h to obtain the n-type doped graphene quantum dot film.
6. The method according to claim 5, wherein the reducing agent is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, barium hydroxide, calcium hydroxide and magnesium hydroxide.
7. The method of claim 6, wherein the reducing agent is potassium hydroxide and the treatment time is 1 to 10 minutes.
8. The preparation method according to any one of claims 5 to 7, wherein the graphene quantum dot concentration in the graphene quantum dot solution is 2 to 15 mg/ml; and/or the presence of a gas in the gas,
the temperature of the drying treatment is 50-100 ℃; and/or the presence of a gas in the gas,
the drying time is 0.5-2 h.
9. A light-emitting diode comprises an anode, a cathode and a light-emitting layer positioned between the anode and the cathode, and is characterized in that a hole transport layer is arranged between the anode and the light-emitting layer, and the hole transport layer is the p-type doped graphene quantum dot film obtained by the preparation method of the p-type doped graphene quantum dot film according to any one of claims 1 to 4; and/or the presence of a gas in the gas,
an electron transport layer is arranged between the cathode and the light-emitting layer, and the electron transport layer is the n-type doped graphene quantum dot film obtained by the preparation method of the n-type doped graphene quantum dot film according to any one of claims 5 to 8.
10. The light-emitting diode according to claim 9, wherein a hole transport layer provided between the anode and the light-emitting layer is the p-type doped graphene quantum dot thin film, and the light emission is performedThe material of the layer is selected from at least one of CdSe/CdS/ZnS, ZnCdSeS, CsPbBr and CuInS, or from DCJT and Ir (piq)3、Ir(ppy)3、Ir(mppy)3At least one of MEH-PPV and SY-PPV; alternatively, the first and second electrodes may be,
the electron transport layer arranged between the cathode and the light-emitting layer is the n-type doped graphene quantum dot film, and the material of the light-emitting layer is selected from at least one of CdSe/CdS/ZnS, CdSe @ ZnS, CuInS, InP/ZnS and CsPbBr.
11. The light-emitting diode according to claim 9, wherein a hole injection layer is provided between the anode and the hole transport layer; and/or the presence of a gas in the gas,
an electron injection layer is arranged between the cathode and the electron transport layer; and/or the presence of a gas in the gas,
the light-emitting layer is a quantum dot light-emitting layer or an organic light-emitting layer.
12. A preparation method of a light-emitting diode is characterized by comprising the following steps:
providing a substrate;
preparing a p-type doped graphene quantum dot film on the substrate as a hole transport layer by adopting the preparation method of the p-type doped graphene quantum dot film according to any one of claims 1 to 4; and/or the presence of a gas in the gas,
preparing the n-type doped graphene quantum dot film on the substrate as an electron transport layer by adopting the preparation method of the n-type doped graphene quantum dot film according to any one of claims 5 to 8.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102176382A (en) * | 2011-01-31 | 2011-09-07 | 中国科学院上海硅酸盐研究所 | Method for preparing grapheme-quantum dot composite film and solar battery structured by using same |
| CN103769583A (en) * | 2014-03-03 | 2014-05-07 | 上海交通大学 | Preparation method of gold nanoparticle modified by graphene quantum dots |
| CN104291321A (en) * | 2014-07-28 | 2015-01-21 | 长春工业大学 | Preparation method for graphene quantum dot film |
| CN105355787A (en) * | 2015-10-29 | 2016-02-24 | 上海师范大学 | Novel solar cell device and preparation method thereof |
| CN106477558A (en) * | 2015-08-25 | 2017-03-08 | 深圳粤网节能技术服务有限公司 | The preparation method of the graphene quantum dot of different oxygen content, graphene quantum dot and fluorescent material |
| CN106715519A (en) * | 2014-09-16 | 2017-05-24 | 默克专利有限公司 | Conjugated polymers |
| CN107431211A (en) * | 2014-11-06 | 2017-12-01 | 威廉马歇莱思大学 | By the method for various carbon sources manufacture graphene quantum dot |
| CN107732273A (en) * | 2017-09-28 | 2018-02-23 | 上海博暄能源科技有限公司 | A kind of preparation method of graphene quantum dot modified proton exchange film |
| CN107768331A (en) * | 2016-08-23 | 2018-03-06 | 三星电子株式会社 | Radiator structure and the method that manufactures the radiator structure using graphene quantum dot |
| CN107768379A (en) * | 2017-09-01 | 2018-03-06 | 河北大学 | A kind of low-power consumption charge trapping memory based on graphene oxide quantum dot and preparation method thereof |
| CN108047662A (en) * | 2017-12-13 | 2018-05-18 | 天津宝兴威科技股份有限公司 | A kind of preparation method of graphene quantum dot enhanced film |
| CN108147403A (en) * | 2018-03-07 | 2018-06-12 | 湖南大学 | A kind of preparation method of graphene oxide quantum dot and products thereof |
| CN108359451A (en) * | 2018-01-12 | 2018-08-03 | 湖北民族学院 | Graphene quantum dot and preparation method thereof |
| CN108767122A (en) * | 2018-05-28 | 2018-11-06 | 福州大学 | The preparation and its application of the mesoporous titanium dioxide film material of modified by graphene quantum dot |
| CN108779128A (en) * | 2016-03-15 | 2018-11-09 | 默克专利有限公司 | Organic semiconductor |
| CN108855040A (en) * | 2018-06-29 | 2018-11-23 | 江苏弗瑞仕环保科技有限公司 | The preparation method of the Dy doping ZnO catalysis material of modified by graphene quantum dot |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120068154A1 (en) * | 2010-09-16 | 2012-03-22 | Samsung Led Co., Ltd. | Graphene quantum dot light emitting device and method of manufacturing the same |
| KR101462901B1 (en) * | 2012-11-29 | 2014-11-20 | 성균관대학교산학협력단 | Light emtting device using graphene quantum dot and organic light emitting device including the same |
| CN103212394B (en) * | 2013-04-09 | 2014-11-05 | 太原理工大学 | Process for preparing oxidized graphene/titanium dioxide composite material with high visible-light activity at low temperature |
| CN103738941A (en) * | 2013-11-14 | 2014-04-23 | 盐城增材科技有限公司 | Graphene quantum dot preparation method |
| KR20160025337A (en) * | 2014-08-27 | 2016-03-08 | 성균관대학교산학협력단 | Light emtting device using graphene quantum dot and preparing method of the same |
| CN106554008A (en) * | 2015-09-18 | 2017-04-05 | 上海新池能源科技有限公司 | A kind of method that catalyst auxiliary prepares graphene quantum dot |
| CN108101039B (en) * | 2016-11-25 | 2019-08-16 | 中国科学院化学研究所 | A kind of method of graphene oxide size separation |
| CN107302017B (en) * | 2017-08-14 | 2020-04-10 | 武汉天马微电子有限公司 | Organic light-emitting display panel and device |
| CN107758644B (en) * | 2017-10-13 | 2019-08-20 | 杭州高烯科技有限公司 | A kind of method that super-pressure thermal reduction prepares graphene film |
| CN107651671B (en) * | 2017-10-13 | 2019-10-15 | 杭州高烯科技有限公司 | A kind of method and a kind of preparation method of super flexible high thermal conductivity graphene film of catalyzed graphitization |
-
2018
- 2018-12-29 CN CN201811638395.2A patent/CN111384267B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102176382A (en) * | 2011-01-31 | 2011-09-07 | 中国科学院上海硅酸盐研究所 | Method for preparing grapheme-quantum dot composite film and solar battery structured by using same |
| CN103769583A (en) * | 2014-03-03 | 2014-05-07 | 上海交通大学 | Preparation method of gold nanoparticle modified by graphene quantum dots |
| CN104291321A (en) * | 2014-07-28 | 2015-01-21 | 长春工业大学 | Preparation method for graphene quantum dot film |
| CN106715519A (en) * | 2014-09-16 | 2017-05-24 | 默克专利有限公司 | Conjugated polymers |
| CN107431211A (en) * | 2014-11-06 | 2017-12-01 | 威廉马歇莱思大学 | By the method for various carbon sources manufacture graphene quantum dot |
| CN106477558A (en) * | 2015-08-25 | 2017-03-08 | 深圳粤网节能技术服务有限公司 | The preparation method of the graphene quantum dot of different oxygen content, graphene quantum dot and fluorescent material |
| CN105355787A (en) * | 2015-10-29 | 2016-02-24 | 上海师范大学 | Novel solar cell device and preparation method thereof |
| CN108779128A (en) * | 2016-03-15 | 2018-11-09 | 默克专利有限公司 | Organic semiconductor |
| CN107768331A (en) * | 2016-08-23 | 2018-03-06 | 三星电子株式会社 | Radiator structure and the method that manufactures the radiator structure using graphene quantum dot |
| CN107768379A (en) * | 2017-09-01 | 2018-03-06 | 河北大学 | A kind of low-power consumption charge trapping memory based on graphene oxide quantum dot and preparation method thereof |
| CN107732273A (en) * | 2017-09-28 | 2018-02-23 | 上海博暄能源科技有限公司 | A kind of preparation method of graphene quantum dot modified proton exchange film |
| CN108047662A (en) * | 2017-12-13 | 2018-05-18 | 天津宝兴威科技股份有限公司 | A kind of preparation method of graphene quantum dot enhanced film |
| CN108359451A (en) * | 2018-01-12 | 2018-08-03 | 湖北民族学院 | Graphene quantum dot and preparation method thereof |
| CN108147403A (en) * | 2018-03-07 | 2018-06-12 | 湖南大学 | A kind of preparation method of graphene oxide quantum dot and products thereof |
| CN108767122A (en) * | 2018-05-28 | 2018-11-06 | 福州大学 | The preparation and its application of the mesoporous titanium dioxide film material of modified by graphene quantum dot |
| CN108855040A (en) * | 2018-06-29 | 2018-11-23 | 江苏弗瑞仕环保科技有限公司 | The preparation method of the Dy doping ZnO catalysis material of modified by graphene quantum dot |
Non-Patent Citations (1)
| Title |
|---|
| Jiangsheng Xie等.Enhanced Electronic Properties of SnO2 via Electron Transfer from Graphene Quantum Dots for Efficient Perovskite Solar Cells.《ACS nano》.2017,第9176页-9182页. * |
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