CN113130780A - Composite film, preparation method thereof and light-emitting diode - Google Patents
Composite film, preparation method thereof and light-emitting diode Download PDFInfo
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Abstract
The invention belongs to the technical field of display, and particularly relates to a composite film, a preparation method thereof and a light-emitting diode. The preparation method provided by the invention comprises the following steps: mixing metal oxide nanoparticles and poly (3, 4-ethylenedioxythiophene): mixing poly (styrene sulfonic acid) in the solution to obtain a first mixed solution; depositing the first mixed solution on a substrate to obtain a composite film; wherein the metal oxide nanoparticles are selected from: at least one of yttrium oxide, zirconium dioxide and niobium pentoxide. Therefore, the prepared composite film has high density, can avoid electrode leakage current, has high film uniformity, has good hole transmission efficiency, and can be used for improving the light emitting performance of the light emitting diode.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a composite film, a preparation method thereof and a light-emitting diode.
Background
Quantum Dot Light Emitting Diodes (QLEDs) are a new display device using Quantum dots as Light Emitting layer materials applied to organic or polymer electroluminescent devices, and emit Light by injecting electrons and holes into a Light Emitting layer and by radiation recombination.
Poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid) (PEDOT: PSS) is a novel organic conductive material, and has the advantages of high conductivity, high optical transmittance, high coverage of a substrate and the like, so that the poly (styrenesulfonic acid) (PEDOT: PSS) is the most common hole injection layer material in QLED devices. However, PEDOT and PSS are weakly acidic materials and are prone to interface chemical corrosion damage. For example, when the substrate is an indium tin oxide electrode, indium ions diffuse into the hole injection layer due to acidic corrosion of PEDOT: PSS, causing bottom electrode leakage current.
Therefore, the current composite film, the preparation method thereof and the light emitting diode still need to be improved.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a composite film, and aims to solve the problem that leakage current is formed due to acidic corrosion of an ITO electrode in the application process of a conventional PEDOT/PSS hole injection layer.
The invention also provides a composite film and a light-emitting diode.
In order to achieve the above object, in a first aspect, the present invention provides a method for preparing a composite film, comprising the steps of:
mixing metal oxide nanoparticles and poly (3, 4-ethylenedioxythiophene): mixing poly (styrene sulfonic acid) in the solution to obtain a first mixed solution;
depositing the first mixed solution on a substrate to obtain the composite film;
wherein the metal oxide nanoparticles are selected from at least one of yttrium oxide, zirconium dioxide and niobium pentoxide.
The preparation method of the composite film provided by the invention comprises the following steps of mixing the mixture of metal oxide nano-particles and poly (3, 4-ethylenedioxythiophene): the first mixed solution of poly (styrene sulfonic acid) is deposited on the substrate to prepare the composite film, no special chemical reagent is needed to be added, and the operation is simple and controllable. According to the method, the metal oxide nanoparticles are compounded with PEDOT and PSS, the metal oxide nanoparticles are selected from at least one of yttrium oxide, zirconium dioxide and niobium pentoxide, holes generated in film forming of the PEDOT and PSS are effectively filled, a compact doped film layer is promoted to be formed, and the flatness of the surface of the film layer is improved. The composite film prepared by the method has high density, high film uniformity and good hole transmission efficiency, and can be used for improving the light emitting performance of the light emitting diode.
In a second aspect, the invention also provides a composite film, and the composite film is prepared by the preparation method.
The composite film provided by the invention is prepared by the preparation method, has the characteristics of high density, high film layer uniformity, good hole transmission efficiency and the like, and is beneficial to improving the hole injection efficiency of the light-emitting diode and improving the light-emitting performance of the light-emitting diode when being used as a hole injection layer to prepare the light-emitting diode.
In a third aspect, the present invention further provides a light emitting diode, including:
an anode, a cathode, a light emitting layer disposed between the anode and the cathode, a hole injection layer disposed between the anode and the light emitting layer;
wherein, the hole injection layer is prepared by the preparation method.
The hole injection layer of the light-emitting diode provided by the invention is the composite film prepared by the preparation method, and the light-emitting diode has good light-emitting performance.
Drawings
FIG. 1 is a flow chart of a method for manufacturing a composite film according to an embodiment of the present invention;
FIG. 2 is a flowchart illustrating steps of preparing a mixed solution in a method for manufacturing a composite film according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a light emitting diode according to an embodiment of the present invention;
FIG. 4 is an AFM image of the hole injection layer of comparative example 1;
FIG. 5 is an AFM image of the hole injection layer of example 1;
FIG. 6 is an impedance profile of example 1, example 2 and comparative example 1;
reference numerals: an anode L01, a hole injection layer L02, a light emitting layer L03, and a cathode L04.
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.
A method for preparing a composite film, as shown in fig. 1, comprising the steps of:
s01, mixing the metal oxide nano particles and poly (3, 4-ethylenedioxythiophene): mixing poly (styrene sulfonic acid) in the solution to obtain a first mixed solution;
s02, depositing the first mixed solution on a substrate to obtain the composite film;
wherein the metal oxide nanoparticles are selected from: at least one of yttrium oxide, zirconium dioxide and niobium pentoxide.
The preparation method of the composite film provided by the embodiment of the invention comprises the following steps of mixing the mixture containing metal oxide nanoparticles and poly (3, 4-ethylenedioxythiophene): the first mixed solution of poly (styrene sulfonic acid) is deposited on the substrate to prepare the composite film, no special chemical reagent is needed to be added, and the operation is simple and controllable. PSS is compounded with metal oxide nano particles, and the metal oxide nano particles are selected from the following components: PSS film-forming, promotes to form the compact doping film layer, moreover, the radius of yttrium oxide, zirconium dioxide and niobium pentoxide is greater than free indium ion, thus prevented in the follow-up application process because the ITO electrode is corroded by the acid free indium ion diffusion and enter the hole injection layer, and then avoid the ITO electrode to form the leakage current. The composite film prepared by the method has high density and high film uniformity, and can be used for forming a hole injection layer of a light-emitting diode, so that the composite film has good hole transmission efficiency and can improve the light-emitting performance of the light-emitting diode.
In particular, the metal oxide nanoparticles are selected from: at least one of yttrium oxide, zirconium dioxide and niobium pentoxide. The yttrium oxide, the zirconium dioxide and the niobium pentoxide have good ductility, can promote the formation of PEDOT and PSS films, and can effectively fill holes on the PEDOT and PSS films in the film forming process, promote the formation of compact doped films and improve the flatness of the surfaces of the films, and meanwhile, the radiuses of the metal oxide nanoparticles are larger than that of indium ions, so that free indium ions are effectively prevented from entering the PEDOT and PSS films, and further an ITO electrode is prevented from forming leakage current; moreover, when the PEDOT/PSS film layer is doped with the metal oxide nanoparticles, and the composite film prepared by the method is used for forming a hole injection layer of the light-emitting diode, the quantity of hole injection in the light-emitting diode is increased, the efficiency of hole recombination with electrons in a light-emitting layer is improved, and the light-emitting performance of the light-emitting diode is improved; meanwhile, the metal oxides have good visible light transmittance, and cannot cause reduction influence on the light emission of the light-emitting device.
In one embodiment, the metal oxide nanoparticles have a particle size of 2 to 10 nm. When the particle size of the metal oxide nano particles is less than 2 nanometers, holes existing in a PEDOT (PSS) film layer cannot be effectively covered; when the particle size of the metal oxide nanoparticles is larger than 10 nanometers, aggregation and precipitation are easy to occur on a PEDOT (PSS) film layer, so that the effects of reducing the resistance and increasing the number of injected holes cannot be achieved.
The PEDOT: PSS is selected from commercial products or products prepared by means of the conventional technical means in the field, and the embodiment of the invention does not limit the PEDOT: PSS in particular.
Specifically, in step S01, metal oxide nanoparticles and poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid) was mixed in the solution to obtain a first mixed solution in which metal oxide nanoparticles and PEDOT: PSS were dispersed.
In the present specification, "solution" refers to a homogeneous, stable liquid, which may consist of one substance or may consist of at least two substances.
The solvent is used as a medium for dispersing the metal oxide nanoparticles and the PEDOT: PSS, and is preferably a liquid medium which can fully dissolve the PEDOT: PSS and prevent the metal oxide nanoparticles from agglomerating in a mixing process or a subsequent film forming process.
As an embodiment, metal oxide nanoparticles and poly (3, 4-ethylenedioxythiophene): in the step of mixing poly (styrenesulfonic acid) in solution, the metal oxide nanoparticles and the poly (3, 4-ethylenedioxythiophene): the weight ratio of poly (styrene sulfonic acid) is (1-10) to (1-20).
When the dosage of the metal oxide nano particles is less than the weight range, holes existing in a PEDOT (PSS) film layer cannot be effectively covered, and the leakage current phenomenon is easy to generate; when the amount of the metal oxide nanoparticles is larger than the above weight range, aggregation and precipitation are easily caused on the PEDOT/PSS film layer, and the effect of the metal oxide nanoparticles cannot be effectively exerted.
As an embodiment, as shown in fig. 2, the first mixed solution is obtained by:
s011, adding the metal oxide nanoparticles into a second mixed solution containing ammonium ions, and carrying out first mixing treatment to obtain a metal oxide precursor solution;
s012, poly (3, 4-ethylenedioxythiophene): and carrying out second mixing treatment on the third mixed solution of the poly (styrene sulfonic acid) and the metal oxide precursor solution to obtain the first mixed solution.
The solvent of the PEDOT PSS solution is generally water, however, the solubility of the metal oxide nanoparticles in water is low, which is not favorable for forming a uniform mixed solution. Compared with the scheme of directly adding the metal oxide nanoparticles into the PEDOT/PSS solution or the scheme of firstly dispersing the metal oxide nanoparticles into water and then adding the PEDOT/PSS solution, the embodiment of the invention dissolves the metal oxide nanoparticles into the ammonium ion-containing solution and then mixes the metal oxide nanoparticles with the PEDOT/PSS solution, so that on one hand, the metal oxide and the PEDOT/PSS solution are promoted to be fully mixed, the uniformity of the mixed solution is greatly improved, and the high-uniformity composite film is favorably formed; on the other hand, the solution containing ammonium ions is alkaline, and when the alkaline solution is mixed with a PEDOT/PSS solution, the PEDOT/PSS solution can be neutralized to a certain degree, so that the acidic corrosivity of the PEDOT/PSS solution is reduced.
In step S011, the second mixed solution contains ammonium ions, and in some embodiments, the second mixed solution is an ammonium salt aqueous solution and/or ammonia water. Wherein the ammonium salt is water-soluble ammonium salt, including but not limited to ammonium nitrate, ammonium nitrite, ammonium chloride and the like. In some embodiments, the concentration of ammonium ions in the second mixed solution is 0.5-3 mg/mL. Too low ammonium ion concentration can result in too slow reaction rate, insufficient dissolution of metal oxide nanoparticles, and ineffective neutralization of PSS; if the concentration of the ammonium ions is too high, the ammonium ions are not easy to completely remove in the subsequent heating process, and the ammonium ions remain in the PEDOT/PSS layer, which causes the resistance to be increased and the hole injection efficiency to be reduced. .
The metal oxides such as yttrium oxide, zirconium dioxide and niobium pentoxide are compounded with ammonium in the ammonium ion solution to form a water-soluble metal oxide precursor. With yttrium oxide (Y)2O3) For example, the reaction in aqueous ammonia and the thermal decomposition of the reaction product have the following equations:
Y2O3+2NH3·H2O→2(NH4)YO2+H2O
obviously, by dissolving the metal oxide nanoparticles in the ammonium ion-containing solution, the reaction product (metal oxide precursor) can be decomposed again under heating to form the metal oxide, and the by-products are ammonia and water, so that no impurity is introduced into the composite film prepared by the embodiment of the present invention.
The first mixing treatment may employ at least one of heat treatment, ultrasonic dispersion and mechanical stirring to promote sufficient dissolution of the metal oxide nanoparticles and accelerate the reaction rate.
In some embodiments, the first mixing process comprises:
sequentially stirring and ultrasonically treating the second mixed solution added with the metal oxide nanoparticles;
wherein the rotating speed of the stirring treatment is 2000-3000 rpm, and the time of the stirring treatment is 10-30 minutes;
the power of ultrasonic treatment is 100-400W, and the time of ultrasonic treatment is 10-60 minutes.
Through the comprehensive effect of the plurality of process conditions, the metal oxide nanoparticles can be fully dissolved in the solution, and the smoothness and the flatness of the subsequent film formation are improved.
In some embodiments, the weight ratio of the metal oxide nanoparticles to the ammonium ions in the metal oxide precursor solution is 1 (3-8).
Within the range, the complete dissolution of the metal oxide nano particles can be fully promoted, a uniform metal oxide precursor solution is formed, the acidity of PEDOT (PSS) can be effectively pre-neutralized, and the function of protecting the anode is achieved. When the weight ratio of the metal oxide nanoparticles to the ammonium ions in the ammonium ion-containing solution is more than 1:3, too few ammonium ions are available, the metal oxide nanoparticles cannot be effectively dissolved, and effective acidic neutralization is performed on PEDOT: PSS; when the weight ratio of the metal oxide nanoparticles to the ammonium ions in the ammonium ion-containing solution is less than 1:8, the amount of the ammonium ions is too large, which results in an increase in the film resistance of the prepared composite film and a decrease in the hole transport efficiency.
In step S012, a polymer composition containing poly (3, 4-ethylenedioxythiophene): the step of subjecting the third mixed solution of poly (styrenesulfonic acid) and the metal oxide precursor solution to the second mixing treatment can be performed by referring to the conventional procedures in the art, poly (3, 4-ethylenedioxythiophene): the adding sequence and the mixing temperature of the poly (styrene sulfonic acid) solution and the metal oxide precursor solution can be flexibly adjusted according to the actual situation.
In some embodiments, the solvent of the third mixed solution is water, which has good transparency, which facilitates the formation of a uniform composite film.
In some embodiments, the poly (3, 4-ethylenedioxythiophene): the concentration of the poly (styrene sulfonic acid) is 10-60 mg/mL;
the concentration of the metal oxide precursor is 3-10 mg/mL.
Therefore, the film layer with a flat and smooth surface is obtained.
Specifically, in step S02, the first mixed solution is deposited on a substrate to prepare a composite film.
The substrate can be a rigid substrate or a flexible substrate and is used as a substrate material for preparing the composite film, and the specific structure of the substrate refers to a product actually produced.
The deposition method can be spin coating, dip coating, evaporation, ink jet printing, magnetron sputtering or chemical vapor deposition.
As one embodiment, the step of depositing the first mixed solution on a substrate includes:
spin-coating the first mixed solution on the substrate at a rotation speed of 2000rpm to 4000 rpm;
wherein the spin coating time is 10-30 seconds.
The mixed solution is spin-coated at the rotating speed of 2000-4000 rpm, so that a smooth film layer with uniform thickness is formed. The rotation speed is too fast, the time is too short, the thickness of the formed film layer is too thin, the film layer is easily broken down by the starting voltage in the application process, and sufficient hole injection into the light-emitting layer cannot be provided. The rotating speed is too slow, and the starting voltage of the device is increased and the energy consumption of the device is increased if the time is too long.
As an embodiment, the step of depositing the first mixed solution on the substrate further includes:
annealing treatment is carried out at 120-180 ℃.
In some embodiments, the composite film is annealed at 120-180 ℃ for 20-60 minutes to ensure good performance of the composite film. When the annealing temperature is higher than 180 ℃, the film is overheated to curl, and the film is easy to fall off or separate, so that the resistance of the whole device is increased; when the annealing temperature is lower than 120 ℃, the metal oxide precursor cannot be decomposed into the metal oxide and ammonia gas, resulting in a decrease in the hole transport rate of the thin film.
Based on the technical scheme, the embodiment of the invention also provides the composite film and the light-emitting diode.
A composite film is prepared by the preparation method.
The composite film provided by the embodiment of the invention is prepared by the preparation method, has the characteristics of high density, high film layer uniformity, good hole transmission efficiency and the like, and is favorable for improving the hole injection efficiency of the light-emitting diode and the light-emitting performance of the light-emitting diode when being used as a hole injection layer to prepare the light-emitting diode.
A light emitting diode, as shown in fig. 3, comprising:
an anode and a cathode arranged oppositely;
a light emitting layer disposed between the anode and the cathode;
a hole injection layer disposed between the anode and the light emitting layer;
wherein, the hole injection layer is prepared by the preparation method.
According to the light-emitting diode provided by the embodiment of the invention, the hole injection layer is the composite film prepared by the preparation method, and the light-emitting diode has good light-emitting performance.
The anode may be selected from anodes conventional in the art, such as indium tin oxide electrodes, zinc indium oxide, and the like. In one embodiment, the anode is an ITO electrode. In some embodiments, the hole injection layer with the thickness of 20-40 nm is too thick, so that the starting voltage of the device is increased, and the energy consumption of the device is increased. The hole injection layer is too thin, which is easily broken down by the activation voltage, and does not provide sufficient hole injection into the light emitting layer.
The structure of the light emitting diode can refer to the conventional technology in the field, in some embodiments, the light emitting diode is in a positive structure, and an anode is connected with a substrate to serve as a bottom electrode; in some embodiments, the light emitting diode is an inverted structure, and the cathode is connected to the substrate as a bottom electrode. Furthermore, besides the cathode, the anode, the luminescent layer, the electron transport layer and other functional film layers, a hole transport layer, a hole injection layer, a hole blocking layer and other hole functional layers can be arranged between the anode and the luminescent layer, and an electron injection layer, an electron blocking layer and other electronic functional layers can be arranged between the cathode and the luminescent layer, so that the flexible adjustment can be carried out according to the product requirements.
The light emitting diode can be prepared by referring to the conventional operation in the field, such as sequentially depositing a hole injection layer, a light emitting layer, a cathode and the like on an anode. The deposition can be carried out by methods conventional in the art, such as spin coating, dip coating, evaporation, ink jet printing, magnetron sputtering, or chemical vapor deposition.
In order that the above details of the implementation and operation of the present invention will be clearly understood by those skilled in the art, and the advanced performance of the composite film, the preparation method thereof and the light emitting diode according to the embodiments of the present invention will be remarkably shown, the implementation of the present invention will be exemplified by the following embodiments.
Example 1
The embodiment prepares the light emitting diode, and specifically comprises the following steps:
(1) sticking a 3M adhesive tape to the surface of the indium tin oxide conductive anode in a specific pattern, uniformly covering the part which is not stuck with zinc powder, then corroding the part of the indium tin oxide conductive anode with dilute hydrochloric acid, then removing the 3M adhesive tape, respectively carrying out ultrasonic cleaning on the etched indium tin oxide conductive anode with a detergent, ultrapure water, acetone and isopropanol, and carrying out ultraviolet ozone treatment to obtain an anode sheet.
(2) Adding 0.001g of yttrium oxide into 10g of ammonia water solution, rapidly and violently stirring for 10 minutes at 2000r/min, and then carrying out ultrasonic treatment for 15 minutes at 100W ultrasonic power to form yttrium oxide precursor solution;
and mixing the yttrium oxide precursor solution with a PEDOT (Poly ethylene glycol Ether-butyl ether) PSS (PolyEthylene Ether) aqueous solution to obtain a mixed solution.
Spin-coating the mixed solution on an anode plate at a speed of 2000r/min for 10 seconds, and then annealing at 120 ℃ for 20 minutes to form a hole injection layer; the weight ratio of the yttrium oxide nanoparticles to PEDOT to PSS in the hole injection layer was 1: 2.
(3) And sequentially forming a light-emitting layer, an electron transport layer, an electron injection layer and a cathode on the hole injection layer by evaporation.
Example 2
The embodiment prepares the light emitting diode, and specifically comprises the following steps:
(1) and (2) sticking a 3M adhesive tape to the surface of the zinc tin oxide conductive anode in a specific pattern, uniformly covering the non-sticking part with zinc powder, then corroding the part of the zinc tin oxide conductive anode with dilute hydrochloric acid, then removing the 3M adhesive tape, then respectively carrying out ultrasonic cleaning on the etched zinc tin oxide conductive anode with a detergent, ultrapure water, acetone and isopropanol, and carrying out ultraviolet ozone treatment to obtain the anode sheet.
(2) Adding 0.005g of zirconium dioxide into 50g of ammonia water solution, rapidly and violently stirring for 30 minutes at 3000r/min, and then carrying out ultrasonic treatment for 50 minutes at 400W of ultrasonic power to form a zirconium dioxide precursor solution;
and mixing the zirconium dioxide precursor solution with a PEDOT (Polytetrafluoroethylene-PSS) aqueous solution to obtain a mixed solution.
Spin-coating the mixed solution on an anode sheet at the speed of 4000r/min for 30 seconds, and then annealing at 180 ℃ for 50 minutes to form a hole injection layer; the weight ratio of zirconium dioxide nanoparticles to PEDOT: PSS in the hole injection layer was 2: 5.
(3) And sequentially forming a light-emitting layer, an electron transport layer, an electron injection layer and a cathode on the hole injection layer by evaporation.
Example 3
The embodiment prepares the light emitting diode, and specifically comprises the following steps:
(1) and (2) sticking a 3M adhesive tape to the surface of the indium zinc oxide conductive anode in a specific pattern, uniformly covering the non-sticking part with zinc powder, then corroding the part of the indium zinc oxide conductive anode with dilute hydrochloric acid, then removing the 3M adhesive tape, then respectively carrying out ultrasonic cleaning on the etched indium zinc oxide conductive anode with a detergent, ultrapure water, acetone and isopropanol, and carrying out ultraviolet ozone treatment to obtain an anode sheet.
(2) Adding 0.003g of ruthenium trioxide into 30g of ammonia water solution, rapidly and violently stirring for 20 minutes at 1500r/min, and then carrying out ultrasonic treatment for 30 minutes at 200W ultrasonic power to form ruthenium trioxide precursor solution;
and mixing the ruthenium trioxide precursor solution with a PEDOT (Poly ethylene terephthalate) PSS (Poly ethylene styrene) aqueous solution to obtain a mixed solution.
Spin-coating the mixed solution on an anode plate at the speed of 3000r/min for 20 seconds, and then annealing at the temperature of 150 ℃ for 40 minutes to form a hole injection layer; the weight ratio of the ruthenium trioxide nanoparticles to PEDOT to PSS in the hole injection layer was 1: 4.
(3) And sequentially forming a light-emitting layer, an electron transport layer, an electron injection layer and a cathode on the hole injection layer by evaporation.
Comparative example 1
This comparative example differs from example 1 in that: and (3) in the step (2), the mixed solution is PEDOT and PSS aqueous solution, and the PEDOT and PSS aqueous solution is spin-coated on the anode piece to prepare the hole injection layer. The rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
Performance testing
1. The performance of the light emitting diodes prepared in comparative example 1 and example 1 was tested, and the test results are shown in table 1.
The results show that the light emitting intensity and the light emitting efficiency of the light emitting diode of the example 1 are better than those of the comparative example 1, and the starting voltage and the leakage current of the light emitting diode of the example 1 are obviously lower than those of the comparative example 1, which indicates that the light emitting diode provided by the embodiment of the invention overcomes the defects of PEDOT: the PSS hole injection layer has the problem of leakage current caused by acidic corrosion of an ITO electrode in the application process, and meanwhile, the luminous performance of the PSS hole injection layer is obviously improved.
TABLE 1
| Luminous intensity (cd) | Luminous efficiency (%) | Starting voltage (V) | Leakage current (A) | |
| Example 1 | 450 | 65 | 4 | 0.02 |
| Comparative example 1 | 210 | 31 | 6 | 0.1 |
2. The surface topography of the hole injection layers prepared in comparative example 1 and example 1 was scanned using an Atomic Force Microscope (AFM). Fig. 4 is an AFM image of the hole injection layer of comparative example 1, and fig. 5 is an AFM image of the hole injection layer of example 1, showing that the surface of the hole injection layer of example 1 is more planarized and smoother, indicating that by doping PEDOT with a metal oxide such as yttria: PSS is beneficial to preparing a hole injection layer with a flat and smooth surface.
3. Taking the mixed solution prepared in step (2) of example 1 and example 2 and PEDOT of comparative example 1: and respectively dripping the PSS aqueous solution on the conductive surfaces of the glassy carbon electrodes, waiting for drying, taking the saturated calomel electrode as a reference electrode, taking the glassy carbon electrode as a working electrode to be inserted into the prepared electrolyte, connecting the other end of the electrode to an electrochemical workstation, and giving out voltage through the electrochemical workstation to obtain an impedance spectrogram. Fig. 6 is a graph of the impedance of examples 1, 2 and 1, showing that the resistance of examples 1 and 2 is significantly reduced compared to comparative example 1, indicating that by doping PEDOT with a metal oxide such as yttrium oxide: PSS is favorable for reducing the resistance of the hole injection layer.
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 (10)
1. The preparation method of the composite film is characterized by comprising the following steps of:
mixing metal oxide nanoparticles and poly (3, 4-ethylenedioxythiophene): mixing poly (styrene sulfonic acid) in the solution to obtain a first mixed solution;
depositing the first mixed solution on a substrate to obtain the composite film;
wherein the metal oxide nanoparticles are selected from: at least one of yttrium oxide, zirconium dioxide and niobium pentoxide.
2. The production method according to claim 1, wherein the first mixed solution is obtained by:
adding the metal oxide nanoparticles into a second mixed solution containing ammonium ions, and carrying out first mixing treatment to obtain a metal oxide precursor solution;
adding a mixture containing poly (3, 4-ethylenedioxythiophene): and carrying out second mixing treatment on the third mixed solution of the poly (styrene sulfonic acid) and the metal oxide precursor solution to obtain the first mixed solution.
3. The production method according to claim 2, wherein the second mixed solution is an ammonium salt solution and/or aqueous ammonia;
optionally, in the metal oxide precursor solution, the mass ratio of the metal oxide nanoparticles to the ammonium ions is 1 (3-8).
4. The production method according to claim 2, wherein the first mixing process includes:
sequentially stirring and ultrasonically treating the second mixed solution added with the metal oxide nanoparticles;
wherein the rotating speed of the stirring treatment is 2000-3000 rpm, and the time of the stirring treatment is 10-30 minutes;
the power of ultrasonic treatment is 100-400W, and the time of ultrasonic treatment is 10-60 minutes.
5. The production method according to claim 2, wherein the second mixing treatment is performed such that the poly (3, 4-ethylenedioxythiophene): the concentration of the poly (styrene sulfonic acid) is 10-60 mg/mL;
the concentration of the metal oxide precursor is 3-10 mg/mL.
6. The production method according to any one of claims 1 to 5, wherein the step of depositing the first mixed solution on a substrate includes:
spin-coating the first mixed solution on the substrate at a rotation speed of 2000rpm to 4000 rpm;
wherein the spin coating time is 10-30 seconds.
7. The production method according to any one of claims 1 to 5, characterized in that the step of depositing the first mixed solution on a substrate further comprises, after:
annealing treatment is carried out at 120-180 ℃.
8. The production method according to any one of claims 1 to 5, characterized in that metal oxide nanoparticles and poly (3, 4-ethylenedioxythiophene): in the step of mixing poly (styrenesulfonic acid) in a solvent, the metal oxide nanoparticles and the poly (3, 4-ethylenedioxythiophene): the weight ratio of poly (styrene sulfonic acid) is (1-10) to (1-20).
9. A composite film produced by the production method according to any one of claims 1 to 8.
10. A light emitting diode, comprising:
an anode and a cathode arranged oppositely;
a light emitting layer disposed between the anode and the cathode;
a hole injection layer disposed between the anode and the light emitting layer;
wherein the hole injection layer is produced by the production method according to any one of claims 1 to 8.
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Application publication date: 20210716 |