An alcohol dispersion of crosslinked polyethylene dioxythiophene, method of preparation and use

Abstract

The application relates to a cross-linked polyethylene dioxythiophene alcohol dispersion liquid, a preparation method and application, and belongs to the technical field of photoelectric materials. A cross-linking agent is added into a polyethylene dioxythiophene alcohol dispersion liquid, an epoxy group on the cross-linking agent and a p-anion high-fluorine sulfonic acid ion polymer in the polyethylene dioxythiophene alcohol dispersion liquid are cross-linked, a film formed by the cross-linked polyethylene dioxythiophene alcohol dispersion liquid forms a continuous three-dimensional network structure, resistance to alcohol solvents is realized, and the alcohol solution has better wettability on the surface of the cross-linked polymer film. The cross-linked polyethylene dioxythiophene alcohol dispersion liquid can be used in organic solar cells with different structures, and can be applied to other fields such as light-emitting diodes, electrochromism, bioelectronic and anti-static coating and the like.

Description

Technical Field

[0001] This invention belongs to the field of optoelectronic materials technology, and more specifically, relates to an alcohol dispersion of cross-linked polyethylene dioxythiophene, its preparation method, and its application. Background Technology

[0002] With the rapid development of optoelectronic devices, solution-processable conductive polymer materials such as poly(3,4-ethylenedioxythiophene) (PEDOT) are widely used in optoelectronics due to their advantages such as high conductivity, high transmittance in the visible light region, and versatility in processing methods. Among them, poly(styrene sulfonic acid) (PSS) as the water-soluble anion-resistant PEDOT:PSS was developed by Heraeus (Germany) and Agfa (Belgium) and has already been successfully commercialized. Solutions with different conductivity can be obtained by adjusting the ratio of anions and cations. However, PEDOT:PSS aqueous dispersions have disadvantages such as poor wettability, acidity, and easy hygroscopicity in film formation, which limits their application to some extent.

[0003] Addressing the issues with PEDOT:PSS aqueous solutions, patent CN114316223A discloses a novel conductive polyethylenedioxythiophene alcohol dispersion. The anion is a perfluorosulfonic acid ionomer (PFSA), and an alcohol solution is used as the solvent, solving the problems of wettability, acidity, and film hygroscopicity. This dispersion can be used as a hole transport layer in organic solar cells and can also be applied in other fields such as light-emitting diodes, antistatic coatings, electrochromic materials, thermoelectric materials, and bioelectronics. However, due to the alcohol solubility of the perfluorosulfonic acid ionomer, the film prepared from the conductive polyethylenedioxythiophene alcohol dispersion is also easily dissolved in the alcohol solvent. It can be washed away and dissolved by the subsequently coated alcohol-dispersed functional layer solution, leading to film damage and affecting device performance. This invention proposes adding a certain amount of crosslinking agent to the PEDOT:PFSA solution to improve the alcohol solubility resistance of the PEDOT:PFSA film, thereby meeting the application requirements of different scenarios. Summary of the Invention

[0004] To address the shortcomings and improvement needs of existing technologies, this invention discloses a crosslinked polyvinyldioxythiophene alcohol dispersion. To address the problem that films prepared from polyvinyldioxythiophene alcohol dispersions are easily dissolved in alcohol solutions, a certain amount of crosslinking agent is introduced into the alcohol dispersion. Under crosslinking action, a continuous three-dimensional network structure is formed within the prepared film, which resists dissolution and erosion by alcohol solutions. Furthermore, the surface of the crosslinked polymer film is smoother and has better wettability to alcohol solutions. By controlling the amount of crosslinking agent added, while maintaining the film's resistance to alcohol solubility, the optical and electrical properties of the crosslinked polymer film can be made comparable to the initial film properties, demonstrating good applicability in optoelectronic devices. This solves the problem of easy dissolution of films prepared from polyvinyldioxythiophene alcohol dispersions in alcohol solutions.

[0005] According to a first aspect of the present invention, a method for preparing a crosslinked polyethylene dioxythiophene alcohol dispersion is provided, characterized in that a crosslinking agent containing epoxy groups is added to the polyethylene dioxythiophene alcohol dispersion, wherein the polyethylene dioxythiophene comprises polyethylene dioxythiophene cationic and fluorinated sulfonic acid ion polymeric anionic; the epoxy groups on the crosslinking agent undergo a crosslinking reaction with the sulfonic acid groups on the fluorinated sulfonic acid ion polymeric anionic anionic to obtain the crosslinked polyethylene dioxythiophene alcohol dispersion.

[0006] Preferably, the crosslinking agent is at least one selected from polyethylene glycol diglycidyl ether, (3-glycidylpropoxy)trimethoxysilane, (3-glycidylpropoxy)-1,1,3,3-tetramethyldisiloxane, terminal epoxy polysiloxane, resorcinol diglycidyl ether, and bisphenol diglycidyl ether.

[0007] Preferably, the volume of the crosslinking agent is 0.03%-2% of the volume of the alcohol dispersion;

[0008] Preferably, the volume of the crosslinking agent is 0.05%-0.5% of the volume of the alcohol dispersion.

[0009] Preferably, the crosslinking reaction takes 5-20 minutes.

[0010] Preferably, the molar ratio of the polyethylene dioxythiophene cationic polymer to the fluorinated sulfonic acid ionic polymer to the anionic polymer is 1:(2-7).

[0011] According to another aspect of the present invention, a cross-linked polyethylene dioxythiophene alcohol dispersion prepared by any one of the methods is provided.

[0012] According to another aspect of the present invention, the cross-linked polyethylene dioxythiophene alcohol dispersion is provided for use in the preparation of cross-linked polyethylene dioxythiophene alcohol films.

[0013] According to another aspect of the present invention, a cross-linked polyethylene dioxythiophene alcohol film obtained by the aforementioned application is provided.

[0014] Preferably, the conductivity of the thin film is 10. -7 -10 3 S cm -1 The work function is 4.8-5.6 eV.

[0015] According to another aspect of the present invention, the cross-linked polyethylene dioxythiophene alcohol film is provided for use in hole transport layers of organic solar cells, light-emitting diodes, electrochromic films, bioelectronic or antistatic coatings.

[0016] In summary, compared with the prior art, the above-described technical solutions conceived by this invention mainly possess the following technical advantages:

[0017] (1) The film prepared by the cross-linked polyethylene dioxythiophene alcohol dispersion provided by the present invention overcomes the problem of easy dissolution by alcohol. The initial polyethylene dioxythiophene alcohol dispersion (PEDOT:PFSA) has high solubility in alcohol solution, and the processed film is easily washed away and dissolved by alcohol solution. However, after cross-linking, a continuous network can be formed in the film to resist the erosion of alcohol solution.

[0018] (2) The crosslinked polyethylene dioxythiophene alcohol dispersion provided by this invention has excellent wettability, and the work function and conductivity of the prepared film are adjustable, being 4.8-5.6 eV and 10 eV, respectively. -7 -10 3 S cm -1 This cross-linked polymer film can be used as a hole transport layer in organic solar cells, effectively enabling the extraction and transport of hole carriers.

[0019] (3) The film prepared by the cross-linked polyethylene dioxythiophene alcohol dispersion provided by the present invention is smoother and more even than the initial state, and other dispersions using alcohol as solvent have better wettability on its surface.

[0020] (4) The cross-linked polyethylene dioxythiophene alcohol dispersion provided by the present invention has a simple synthesis process and can be applied to any substrate surface and other application fields such as light-emitting diodes, electrochromic, bioelectronics and antistatic coatings. Attached Figure Description

[0021] Figure 1 (a) in the figure is the chemical molecular structure of PEDOT:PFSA. Figure 1 (b) is a schematic diagram of the crosslinking reaction of the crosslinked polyethylene dioxythiophene alcohol dispersion of the present invention.

[0022] Figure 2(a) shows the absorption spectra of crosslinked PEDOT:PFSA (c-PEDOT:F) films at different crosslinking agent concentrations. Figure 2 (b) in the figure represents the conductivity of crosslinked PEDOT:PFSA films at different crosslinking agent concentrations.

[0023] Figure 3 These are comparison photos of c-PEDOT:F films before and after 5 minutes of alcohol immersion under different crosslinking agent concentrations.

[0024] Figure 4 These are the work function curves of c-PEDOT:F films under different crosslinking agent concentrations.

[0025] Figure 5 These are photographs of c-PEDOT:F films after 5 minutes of alcohol soaking at different crosslinking agent concentrations when using another crosslinking agent (3-glycidylpropoxy)trimethoxysilane.

[0026] Figure 6 (a) is a schematic diagram of the semi-transparent organic solar cell of the present invention (c-PEDOT: F as the hole transport layer). Figure 6 (b) in the figure shows the current density-voltage (JV) curves of the corresponding device structure before and after the addition of the reflector.

[0027] Figure 7 (a) is a schematic diagram of the top-incident organic solar cell of the present invention (c-PEDOT: F is used as the hole transport layer). Figure 7 (b) in the figure is the current density-voltage (JV) curve of the corresponding device structure. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0029] In this invention, a crosslinked polyethylene dioxythiophene alcohol dispersion is prepared by adding a crosslinking agent to the dispersion. The epoxy groups on the crosslinking agent react with the anionic perfluorosulfonic acid ion polymer in the polyethylene dioxythiophene alcohol dispersion. The film made from the crosslinked polyethylene dioxythiophene alcohol dispersion forms a continuous three-dimensional network structure, thereby achieving resistance to alcohol solvents and providing better wettability of alcohol solutions on the surface of the crosslinked polymer film. Figure 1 (a) in the figure is the chemical molecular structure of PEDOT:PFSA. Figure 1(b) in the diagram is a schematic diagram of the crosslinking reaction of the crosslinked polyethylene dioxythiophene alcohol dispersion of the present invention. Figure 1 As shown in (b), the intersection of the network structure reflects the cross-linking reaction between the epoxy groups at both ends of the cross-linking agent PEGDE and the sulfonic acid groups on the anionic PFSA.

[0030] In some embodiments, the polyvinyldioxythiophene alcohol dispersion contains cationic polyvinyldioxythiophene and anionic perfluorosulfonic acid ionomer in a molar ratio of 1:(2-7).

[0031] In some embodiments, the crosslinking agent contains two or more epoxy groups in its molecular structure, or at least contains trimethoxysilane and epoxy groups simultaneously; such as polyethylene glycol diglycidyl ether, (3-glycidylpropoxy)trimethoxysilane, (3-glycidylpropoxy)-1,1,3,3-tetramethyldisiloxane, terminal epoxy polysiloxane, resorcinol diglycidyl ether, bisphenol diglycidyl ether, etc.

[0032] In some embodiments, the sulfonic acid groups on the high-fluorine sulfonic acid ionomer react chemically with the epoxy groups on the crosslinking agent for a reaction time of 5-20 minutes.

[0033] In some embodiments, the concentration of the crosslinking agent is 0.03 v / v% to 2 v / v, preferably 0.05 v / v% to 0.3 v / v.

[0034] The films prepared by spin coating, doctor blade coating, and slot coating in this invention have a continuous network structure, which can resist the dissolution damage of alcohol solvents. The alcohols are C1-C10 fatty alcohols, alicyclic alcohols, or aromatic alcohols. The surface of the cross-linked polymer film is smoother and more even, and the alcohol solution has better wettability on its surface.

[0035] In some embodiments, the cross-linked polymer film has an electrical conductivity of 10. -7 -10 3 S cm -1 Its work function is 4.8-5.6 eV. It can be used to prepare organic solar cells, light-emitting diodes, electrochromic materials, bioelectronics, and antistatic coatings.

[0036] The following are specific embodiments.

[0037] Example 1

[0038] The synthesis process of the crosslinked polyethylene dioxythiophene alcohol dispersion (c-PEDOT:F) of the present invention is as follows: 6 mL of PDEOT:F stock solution was filtered twice through a 0.8 μm filter and then dispensed into 6 glass bottles. Subsequently, polyethylene glycol diglycidyl ether (PEGDE) was added to the bottles at volume ratios of 0, 0.03 v / v%, 0.05 v / v%, 0.1 v / v%, 0.5 v / v%, 1 v / v%, and 2 v / v, respectively. The mixed solution was then placed in an ultrasonic cleaner and sonicated for 10 minutes to ensure uniform mixing.

[0039] Crosslinked PEDOT:F films were fabricated using spin coating on clean glass substrates via dynamic spin coating at a speed of 1500 rpm. After spin coating, the films were annealed at 100°C for 3 minutes to completely evaporate the alcohol solvent. The film thicknesses at different concentrations are shown in Table 1. The absorption curves and conductivity of the crosslinked PEDOT:F films at different concentrations are shown in Table 1. Figure 2 As shown in (a) and (b) in the figure, by Figure 2 As shown in (a), the absorption curve of the c-PEDOT:F film hardly changes with the concentration of the crosslinking agent in the wavelength range of 350-1000 nm. Figure 2 As shown in (b), the conductivity of the c-PEDOT:F film gradually decreases with increasing crosslinking agent concentration. This indicates that introducing an insulating crosslinking agent into PEDOT:F does not affect the optical properties of the film, but it does have an adverse effect on the film's conductivity.

[0040] Table 1. PEDOT:F film thickness at different crosslinking agent concentrations.

[0041]

[0042] Example 2

[0043] Crosslinked PEDOT:F films were fabricated using spin coating on clean ITO glass via dynamic spin coating at a speed of 1500 rpm. After spin coating, the films were annealed at 100°C for 3 minutes to completely evaporate the alcohol solvent. Half of the crosslinked PEDOT:F films at different concentrations were immersed in an ethanol solution, while the other half was exposed to air. Comparative photographs of the films before and after 5 minutes of immersion are shown below. Figure 3 As shown. By Figure 3 It can be seen that the film without the crosslinking agent PEGDE dissolves in ethanol, while the film with the crosslinking agent maintains its integrity. The optimal crosslinking agent concentration range is 0.05%-0.5%. The work function test results are as follows... Figure 4 As shown, by Figure 4 It can be seen that the work function of c-PEDOT:F film decreases with increasing crosslinking agent concentration.

[0044] Example 3

[0045] The synthesis process of the crosslinked polyvinyldioxythiophene alcohol dispersion described in this invention can use other types of crosslinking agents, such as (3-glycidylpropoxy)trimethoxysilane, (3-glycidylpropoxy)-1,1,3,3-tetramethyldisiloxane, terminal epoxy polysiloxane, resorcinol diglycidyl ether, bisphenol diglycidyl ether, etc. Taking (3-glycidylpropoxy)trimethoxysilane (GOPS) as an example, the preparation of the crosslinked PEDOT:F solution is achieved as follows: 1 mL of PEDOT:F stock solution is filtered twice through a 0.8 μm filter and placed in a glass bottle. Crosslinking agent GOPS is added in volume ratios of 0, 0.1 v / v%, 0.5 v / v%, 1 v / v%, 1.5 v / v%, and 2 v / v. The mixed solution is then placed in an ultrasonic cleaner and sonicated for 10 minutes to ensure uniform mixing.

[0046] Films were fabricated using spin coating. Different concentrations of crosslinked PEDOT:F were prepared on clean glass by dynamic spin coating at a speed of 1500 rpm. After spin coating, the films were annealed at 100°C for 3 minutes to completely evaporate the alcohol solvent. Half of each crosslinked PEDOT:F film at different concentrations was immersed in an ethanol solution, while the other half was exposed to air. Comparison of the final images after immersion for 5 minutes is shown in the accompanying photographs. Figure 5 As shown, by Figure 5 It can be seen that the film without the crosslinking agent GOPS is dissolved in ethanol, while the film with the crosslinking agent can maintain good integrity.

[0047] Example 4

[0048] The thin film prepared from the cross-linked polyethylene dioxythiophene alcohol dispersion described in this invention can be directly used as the hole transport layer of a semi-transparent organic solar cell.

[0049] (1) Synthesis of crosslinked polyethylene dioxythiophene alcohol dispersion: Repeat the same steps as in Example 1, wherein the crosslinking agent concentration is 0.05 v / v.

[0050] (2) Fabrication of semi-transparent organic solar cells: The device structure of semi-transparent organic solar cells is as follows: Figure 6 As shown in (a), the different functional layers in the device structure are glass / ITO / PEI-Zn / PM6:BTP-eC9:PC 71 BM / c-PEDOT:F / AgNWs. Wherein, ITO glass is the cathode layer, PEI-Zn is the electron transport layer, and PM6:BTP-eC9:PC 71 BM is used as the light-absorbing active layer, c-PEDOT:F as the hole transport layer, and AgNWs as the anode layer. The specific preparation method is as follows:

[0051] Cut transparent indium tin oxide (ITO) glass substrates were sequentially ultrasonically cleaned with deionized water (detergent), acetone, and isopropanol for 15 minutes each. A PEI-Zn electron transport layer solution was then spin-coated onto the cleaned ITO glass substrate at a spin speed of 1500 rpm. The substrate was then annealed at 150°C for 15 minutes. Two spin-coating cycles were performed to obtain a 100 nm PEI-Zn electron transport layer. PM6:BTP-eC9:PC was then spin-coated onto the above substrate. 71 The BM active layer solution (total concentration 19.8 mg / mL, mass ratio 1:1:0.2, solvent chlorobenzene, additive 0.5% DIO) was spin-coated at 1500 rpm and annealed at 100°C for 10 minutes. c-PEDOT:F was then spin-coated onto the active layer at 3000 rpm and annealed at 100°C for 2 minutes. Finally, the AgNWs solution was spin-coated. 3 mL of AgNWs stock solution was diluted with ethanol at a volume ratio of 1:3, centrifuged at 2500 rpm, and the supernatant was collected to obtain the desired AgNWs electrode solution. Two layers were spin-coated sequentially at 1500 rpm and annealed at 100°C for 2 minutes in a nitrogen glove box. The resulting AgNWs thin film electrode had a sheet resistance of 16 Ω / sq.

[0052] The current density-voltage ratio of the organic solar cell fabricated using the method described in this example is as follows: Figure 6 In (b), the current density-voltage curve was measured using a solar simulator and a digital source meter. Here, "reflector" represents the reflector; adding a reflector above the top electrode of the AgNWs facilitates secondary absorption of light by the active layer. Without a reflector, the open-circuit voltage V... OC =0.81V, short-circuit current density J SC =18.66mA / cm 2 The fill factor FF = 0.70 and the efficiency PCE = 10.61% are shown. After adding the reflector, the open-circuit voltage V... OC =0.82V, short-circuit current density J SC =23.15mA / cm 2 The fill factor FF = 0.69 and the efficiency PCE = 13.11%.

[0053] Example 5

[0054] The thin film prepared by the cross-linked polyethylene dioxythiophene alcohol dispersion of the present invention can be directly used as the hole transport layer of a top-incident organic solar cell.

[0055] (1) Synthesis of crosslinked polyethylene dioxythiophene alcohol dispersion: Repeat the same steps as in Example 1, wherein the crosslinking agent concentration is 0.05 v / v.

[0056] (2) Fabrication of top-incidence organic solar cells: The device structure of top-incidence organic solar cells is as follows: Figure 7 As shown in (a), the different functional layers in the device structure are glass / Ag / PEI-Zn / PM6:BTP-eC9:PC 71 BM / c-PEDOT:F / AgNWs. Where Ag is the cathode layer, PEI-Zn is the electron transport layer, and PM6:BTP-eC9:PC 71 BM is used as the light-absorbing active layer, c-PEDOT:F as the hole transport layer, and AgNWs as the anode layer. The specific preparation method is as follows:

[0057] The cut glass was ultrasonically cleaned sequentially with deionized water (dishwashing liquid), acetone, and isopropanol for 15 minutes each. Ag at a density of 70 nm was then vapor-deposited onto the cleaned glass in a vacuum chamber at a pressure of 2.6 × 10⁻⁶. -7 Torr. A PEI-Zn electron transport layer solution was then spin-coated at 1500 rpm, followed by annealing at 150°C for 15 minutes. Two spin-coatings were performed to obtain a 100 nm PEI-Zn electron transport layer. PM6:BTP-eC9:PC was then spin-coated onto the above substrate. 71 The BM active layer solution (total concentration 19.8 mg / mL, mass ratio 1:1:0.2, solvent chlorobenzene, additive 0.5% DIO) was spin-coated at 1500 rpm and annealed at 100°C for 10 minutes. c-PEDOT:F was then spin-coated onto the active layer at 3000 rpm and annealed at 100°C for 2 minutes. Finally, the AgNWs solution was spin-coated. 3 mL of AgNWs stock solution was diluted with ethanol at a volume ratio of 1:3, centrifuged at 2500 rpm, and the supernatant was collected to obtain the desired AgNWs electrode solution. Two layers were spin-coated sequentially at 1500 rpm and annealed at 100°C for 2 minutes in a nitrogen glove box. The resulting AgNWs thin film electrode had a sheet resistance of 16 Ω / sq.

[0058] The current density-voltage ratio of the organic solar cell fabricated using the method described in this example is as follows: Figure 7 In (b), the current density-voltage curve was measured using a solar simulator and a digital source meter. Incident light enters from the top of the battery, and the battery open-circuit voltage V... OC =0.83V, short-circuit current density J SC =24.87mA / cm 2 The fill factor FF = 0.72 and the efficiency PCE = 14.86%.

[0059] Example 6

[0060] The film prepared from the cross-linked polyethylene dioxythiophene alcohol dispersion of the present invention is used to prepare an antistatic coating by a blade coating process. After the antistatic coating is applied, the surface of the product has a certain degree of ionicity, which can reduce the surface resistivity and form a channel for static charge leakage. The method for preparing the antistatic coating is as follows:

[0061] (1) Synthesis of cross-linked polyethylene dioxythiophene alcohol dispersion: The same steps as described in Example 1 were repeated, and the synthesized cross-linked polyethylene dioxythiophene alcohol dispersion was used to prepare a film with a conductivity of 7.2 × 10⁻⁶. -3 S / cm.

[0062] (2) Specific preparation process of antistatic coating: 2.5×7.5cm 2 The glass was ultrasonically cleaned sequentially with deionized water (detergent), acetone, and isopropanol for 15 minutes. The clean glass was placed on a coating stage with a substrate temperature of 50°C. 50 μL of cross-linked polyethylene dioxythiophene alcohol dispersion was applied, with a slit height of 150 μm and a coating speed of 10 mm / s. After one coat, the glass was heated at 100°C for 3 minutes. Under these conditions, the coating was repeated 1–30 times in alternating directions. The resulting film thickness was adjustable between 30 and 10,000 nm, and the sheet resistance was within 10. 3 -10 8 Adjustable between Ω.

[0063] In summary, the conductive polyethylene dioxythiophene alcohol dispersion provided by this invention is not only simple to synthesize and easy to process, but also compatible with various processing surfaces and processes. Furthermore, the films prepared from the dispersion have shown great application potential in device structures such as organic solar cells, antistatic coatings, and thermoelectric devices.

[0064] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing an alcohol dispersion of cross-linked polyethylene dioxythiophene, characterized in that, A crosslinking agent containing epoxy groups is added to an alcohol dispersion of polyethylene dioxythiophene, wherein the alcohol dispersion of polyethylene dioxythiophene comprises polyethylene dioxythiophene cationic polymer and high-fluorine sulfonic acid ion polymer anionic polymer; the epoxy groups on the crosslinking agent undergo a crosslinking reaction with the sulfonic acid groups on the high-fluorine sulfonic acid ion polymer anionic polymer to obtain a crosslinked alcohol dispersion of polyethylene dioxythiophene.

2. The method for preparing the cross-linked polyethylene dioxythiophene alcohol dispersion as described in claim 1, characterized in that, The crosslinking agent is at least one of polyethylene glycol diglycidyl ether, (3-glycidylpropoxy)trimethoxysilane, (3-glycidylpropoxy)-1,1,3,3-tetramethyldisiloxane, terminal epoxy polysiloxane, resorcinol diglycidyl ether, and bisphenol diglycidyl ether.

3. The method for preparing the cross-linked polyethylene dioxythiophene alcohol dispersion as described in claim 1, characterized in that, The volume of the crosslinking agent is 0.03% - 2% of the volume of the alcohol dispersion.

4. The method for preparing the cross-linked polyethylene dioxythiophene alcohol dispersion as described in claim 3, characterized in that, The volume of the crosslinking agent is 0.05% - 0.5% of the volume of the alcohol dispersion.

5. The method for preparing the cross-linked polyethylene dioxythiophene alcohol dispersion as described in claim 1, characterized in that, The cross-linking reaction takes 5-20 minutes.

6. The method for preparing the cross-linked polyethylene dioxythiophene alcohol dispersion as described in claim 1, characterized in that, The molar ratio of the polyethylene dioxythiophene cationic polymer to the anionic polymer is 1:(2-7).

7. The alcohol dispersion of cross-linked polyethylene dioxythiophene prepared by the method according to any one of claims 1-6.

8. The application of the alcohol dispersion of cross-linked polyethylene dioxythiophene as described in claim 7 in the preparation of cross-linked polyethylene dioxythiophene films.

9. The cross-linked polyethylene dioxythiophene film obtained by the application as described in claim 8.

10. The cross-linked polyethylene dioxythiophene film as described in claim 9, characterized in that, The conductivity of the thin film is 10. -7 -10 3 S cm -1 The work function is 4.8-5.6 eV.

11. The application of the cross-linked polyethylene dioxythiophene film as described in claim 9 or 10 in the hole transport layer of organic solar cells, light-emitting diodes, electrochromic films, or antistatic coatings.

Images