An alumina / zinc oxide co-doped polythiophene derivative conductive film, its preparation method and application

Abstract

This invention discloses an alumina / zinc oxide co-doped polythiophene derivative conductive film, its preparation method, and its applications. The preparation method includes the following steps: reacting diethylzinc vapor and water vapor with an initial polythiophene derivative film, repeating this process several times to obtain a zinc oxide-doped polythiophene derivative film; then reacting trimethylaluminum vapor and water vapor with the zinc oxide-doped polythiophene derivative film, repeating the above steps to obtain an alumina / zinc oxide co-doped polythiophene derivative film. This process eliminates the influence of the liquid phase environment on the morphology and structure of the polymer film, and also allows for precise control of the doping amount of various precursor molecules within the polymer matrix. The preparation method disclosed in this invention has the advantages of simple operation, controllable doping process, and stable structure and properties of the modified polymer film, significantly improving the electrical conductivity of the material after modification.

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronic materials technology, and relates to an aluminum oxide / zinc oxide co-doped polythiophene derivative conductive film, its preparation method and application. Background Technology

[0002] Organic / inorganic nanocomposites, composed of inorganic semiconductor nanocrystals (NCs) and organic conjugated polymers, have been actively studied over the past decade due to their potential applications in low-cost, large-area, and flexible electronic and optical devices. Integrating inorganic nanocrystals into a conjugated polymer matrix leverages the beneficial properties of both materials: the high electronic and optical properties of inorganic semiconductor nanocrystals and the excellent processability of organic polymers.

[0003] The preparation of organic / inorganic nanocomposites typically involves several methods. One method involves first preparing nanoscale metal oxide structures, then spin-coating a polymer onto these structures. However, metal oxide nanocrystals, due to their large specific surface area and high surface energy, tend to aggregate, hindering dispersion within the conjugated polymer and altering the mixture morphology, thus degrading device performance. Another method involves adding a metal oxide precursor to a polymer solution, then simultaneously casting and in-situ converting the precursor into a metal oxide within the polymer film. However, these processing conditions limit control over the morphology of the nano-donors / acceptors and interfacial affinity. Nanocomposites prepared using these methods are simply physical mixtures; the interactions between surfactants or ligands and nanocrystals are static and weak, such as van der Waals forces or Lewis acid-base interactions. These interactions are susceptible to variations in processing and usage conditions, leading to unstable performance in the nanocomposites. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides an alumina / zinc oxide co-doped polythiophene derivative conductive film, its preparation method, and its application, thereby solving the technical problems of easy aggregation of metal oxides on the surface of polythiophene derivative films obtained by current preparation processes, and the weak interaction between metal oxides and polythiophene derivative films.

[0005] This invention is achieved through the following technical solution:

[0006] A method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive thin film includes the following steps:

[0007] S1: Diethylzinc vapor and water vapor are repeatedly reacted with the initial polythiophene derivative film, and the product after the reaction is completed is purged with nitrogen gas;

[0008] S2: Trimethylaluminum vapor and water vapor are reacted with the product of step S1, and nitrogen is used to purge the product after the reaction is complete.

[0009] S3: Repeat steps S1 to S2 on the product after completing step S2 to obtain the alumina / zinc oxide co-doped polythiophene derivative film.

[0010] In step S1, the diethylzinc vapor and water vapor are repeatedly reacted with the initial polythiophene derivative film 5 to 30 times.

[0011] In step S3, the product from step S2 is subjected to steps S1 to S2 400 to 500 times.

[0012] Preferably, step S1 specifically comprises:

[0013] S11: Place the initial polythiophene derivative film in a closed reactor and purge the reactor with an inert gas. Then, introduce diethylzinc vapor and keep the diethylzinc vapor in the reactor for 60-65 seconds. Then, purge the reactor with nitrogen.

[0014] S12: Water vapor is introduced into the reactor after step S11, and the diethylzinc vapor and water vapor react with the initial polythiophene derivative film. After the reaction is completed, nitrogen gas is introduced into the reactor to purge the product after the reaction.

[0015] S13: Repeat steps S11 to S12 5 to 30 times.

[0016] Preferably, in step S11, the pressure in the sealed reactor is 40-60 Pa, and the flow rate of the inert gas is 40-60 sccm.

[0017] Preferably, in step S1, the diethylzinc vapor and water vapor are reacted with the initial polythiophene derivative film 10 times.

[0018] Preferably, step S2 specifically comprises:

[0019] S21: After completing step S1, trimethylaluminum vapor is introduced into the reactor and kept in the reactor for 60-65 seconds. The reactor is then purged with nitrogen.

[0020] S22: Water vapor is introduced into the reactor after step S21, and trimethylaluminum vapor and water vapor react with the product after step S1. After the reaction is completed, nitrogen gas is introduced into the reaction system to purge the product after the reaction.

[0021] Preferably, in step 3, steps S1 to S2 are repeated 490 times.

[0022] Preferably, during the reaction process in steps S1 to S3, the temperature of the reaction system is 180 to 185°C.

[0023] Preferably, during the reaction process in steps S1 to S3, the pressure of the reaction system is 1000 to 2000 Pa.

[0024] An alumina / zinc oxide co-doped polythiophene derivative conductive film is prepared by the above method. In the alumina / zinc oxide co-doped polythiophene derivative conductive film, the mass ratio of alumina to zinc oxide is 1g:(4-24)g; the thickness of the alumina / zinc oxide composite layer on the surface of the alumina / zinc oxide co-doped polythiophene derivative conductive film is 4.5nm-5.5nm; and the conductivity of the alumina / zinc oxide co-doped polythiophene derivative conductive film is 0.50-1.16S / cm.

[0025] Applications of the aforementioned alumina / zinc oxide co-doped polythiophene derivative conductive films in optoelectronic devices.

[0026] Compared with the prior art, the present invention has the following beneficial technical effects:

[0027] A method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive film involves infiltrating diethylzinc and trimethylaluminum, precursors of alumina and zinc oxide, into an initial polythiophene derivative film substrate via vapor infiltration. Water vapor is then introduced, causing the precursors to react in situ with the water vapor to generate metal oxides. These metal oxides then react with functional groups in the polymer chain structure to form the alumina / zinc oxide co-doped polythiophene derivative conductive film. The infiltrated metal-organic precursors undergo chemical reactions in the subsurface region of the substrate, resulting in a novel hybrid material. The dispersed alumina promotes the nucleation and growth of zinc oxide. After periodic alumina doping, the relative intensity of the ZnO peak is weak, and the average grain size increases. A critical zinc oxide thickness exists between the alumina layers, which determines the formation of a highly conductive alumina / zinc oxide nanolayer. Therefore, the crystal arrangement, average size, and doping effect formed by the co-doping of the two oxides significantly improve the conductivity. Furthermore, the sulfur atoms on the thiophene ring in the polythiophene derivative combine with zinc atoms in AZO to form highly stable Zn-S bonds, significantly improving the electrical conductivity of the film while maintaining the morphological and structural stability of the film material. This process does not introduce solvent molecules, successfully eliminating the influence of the liquid phase environment on the morphology and structure of the polymer film, and also allows for precise control of the doping amounts of various precursor molecules within the polymer matrix. The preparation method disclosed in this invention has the advantages of simple operation, controllable doping process, and stable structure and properties of the modified polymer film, which greatly improves the electrical conductivity of the material after modification. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is a schematic flowchart of a method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive film according to the present invention.

[0030] Figure 2 The images show SEM images of the PBTTT-C14 (poly(2,5-bis(3-tetradecylthiophene-2-yl)thiopheno[3,2-b]thiophene) thin film before and after vapor phase permeation in Example 1 of the present invention; wherein, (a) is the PBTTT-C14 thin film without in-situ doping modification; and (b) is the PBTTT-C14 thin film after in-situ doping modification with AZO.

[0031] Figure 3The X-ray diffraction spectra of PBTTT-C14 / AZO films after Al2O3:ZnO(1:x) (x=30, 10 and 5) permeation cycling treatment with different VPI cycling ratios in Examples 1, 2 and 4 of the present invention are shown.

[0032] Figure 4 The IV curves of PBTTT-C14 / AZO films after permeation cycling treatment with Al2O3:ZnO(1:x) (x=30, 19, 10 and 5) with different VPI cycling ratios in Examples 1, 2, 3 and 4 of this invention are shown.

[0033] Figure 5 The figures show the conductivity variation curves of PBTTT-C14 / AZO films after permeation cycling treatment with Al2O3:ZnO(1:x) (x=30, 19, 10 and 5) with different VPI cycling ratios in Examples 1, 2, 3 and 4 of this invention. Detailed Implementation

[0034] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0035] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0036] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0037] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0038] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0039] like Figure 1 As shown, this invention provides a method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive film, comprising the following steps:

[0040] S1: Diethylzinc vapor and water vapor are repeatedly reacted with the initial polythiophene derivative film, and the product after the reaction is completed is purged with nitrogen gas;

[0041] Specifically:

[0042] S11: The initial polythiophene derivative film is placed in a closed reactor at a pressure of 40–60 Pa. The reactor is purged with an inert gas at a flow rate of 40–60 sccm. Helium or argon can be used as the inert gas. Nitrogen can also be used instead of helium. The closed reactor can be a gas-phase permeation device. Then, diethylzinc vapor is introduced and held in the reactor for 60–65 seconds, followed by purging with nitrogen.

[0043] S12: Continue to introduce water vapor into the reactor after completing step S11, and allow the diethylzinc vapor and water vapor to react with the initial polythiophene derivative film. After the reaction is completed, introduce nitrogen gas into the reactor and use nitrogen gas to purge the product after the reaction.

[0044] S13: Repeat steps S11 to S12 5 to 30 times.

[0045] In this application, the initial polythiophene derivative films were all prepared by solution casting, and the specific operations included:

[0046] a) The polythiophene derivative was completely dissolved in a good solvent, 1,2-dichlorobenzene, to obtain a mixed solution. The mixing ratio of the polythiophene derivative to the good solvent was 30 mg: 1 ml.

[0047] b) The mixed solution was coated onto a peelable carrier and dried by heating to obtain the initial film of polythiophene derivative.

[0048] S2: Trimethylaluminum vapor and water vapor are reacted with the product of step S1, and nitrogen is used to purge the product after the reaction is complete.

[0049] Specifically:

[0050] S21: After completing step S1, trimethylaluminum vapor is introduced into the reactor and kept in the reactor for 60-65 seconds. The reactor is then purged with nitrogen.

[0051] S22: Water vapor is introduced into the reactor after step S21, and trimethylaluminum vapor and water vapor react with the product after step S1. After the reaction is completed, nitrogen gas is introduced into the reaction system to purge the product after the reaction.

[0052] S3: Repeat steps S1 to S2 on the product obtained from step S2 to obtain the alumina / zinc oxide co-doped polythiophene derivative film; specifically, the product obtained from step S2 is subjected to steps S1 to S2 400 to 500 times.

[0053] During the reaction process in steps S1 to S3, the temperature of the reaction system is 180 to 185°C, and the pressure of the reaction system is 1000 to 2000 Pa.

[0054] In this invention, DEZ, TMA and H2O are loaded into a medicine bottle in a glove box, and then heated to vaporization by a heating mantle on the outside of the medicine bottle in an ALD device, thereby performing a gas phase permeation cycle.

[0055] An alumina / zinc oxide co-doped polythiophene derivative conductive film is prepared by the method of the present invention. In this conductive film, the mass ratio of alumina to zinc oxide is 1g:(4-24)g; the thickness of the alumina / zinc oxide composite layer on the surface of the alumina / zinc oxide co-doped polythiophene derivative conductive film is 4.5nm-5.5nm; and the conductivity of the prepared alumina / zinc oxide co-doped polythiophene derivative conductive film is 0.50-1.16S / cm.

[0056] This study employs an effective method for in-situ doping modification of initial polythiophene derivative films using vapor phase infiltration based on atomic layer deposition (ALD). Specifically, in the examples, multiple precursor vapor phase infiltration based on ALD is used to in-situ dope modify the polymer film PBTTT-C14. Precursor molecules are brought into contact with the polymer substrate and adsorbed into the polymer, where they diffuse and react with the polymer chains, significantly improving the film's conductivity while having minimal impact on its morphology. The resulting in-situ doped PBTTT-C14 conductive film represents a novel organic-inorganic hybrid material. Firstly, compared to traditional methods such as liquid-phase doping and self-assembly, vapor phase infiltration (VPI) is a material modification process based on atomic layer deposition (ALD). The doping process is controllable, and the modified polymer film exhibits stable structure and properties. In this process, vapor-phase precursor molecules infiltrate into the polymer matrix and react with functional groups in its framework structure, thereby preparing a novel organic-inorganic hybrid material.

[0057] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0058] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0059] Example 1

[0060] A method for preparing a conductive thin film of polythiophene derivative based on multiple precursor doping includes the following steps:

[0061] ① Clean the insulating glass sheet (1.5cm×1.5cm) several times with deionized water, acetone and alcohol in sequence using ultrasonic cleaning, and then let it dry for later use;

[0062] ② In the preparation of the initial film, 30 mg of PBTTT-C14 (poly(2,5-bis(3-tetradecylthiophene-2-yl)thiopheno[3,2-b]thiophene) was weighed using an electronic balance and then dissolved in 1 ml of 1,2-dichlorobenzene (DCB) to obtain a homogeneous solution. The resulting solution was then dropped onto a prepared glass slide and calcined at 70 °C for 12 h to obtain the initial PBTTT-C14 film.

[0063] ③ Finally, the prepared PBTTT-C14 initial film is placed in the reaction chamber of the atomic layer deposition (ALD) equipment, and in-situ doping modification is achieved by gas-phase permeation cycling with Al2O3 and ZnO precursors and H2O.

[0064] Specifically, the initial polythiophene derivative film is placed in the reaction chamber of a gas phase infiltration device, the pressure of the reaction chamber is controlled at 40 Pa, and an inert gas is introduced at a flow rate of 40 sccm; then, Al2O3 and ZnO precursors and H2O are used to perform gas phase infiltration cycling to achieve in-situ doping modification.

[0065] The ZnO permeation cycle is first performed as follows: ZnO precursor vapor, diethylzinc (DEZ) vapor, is pulsed into the reaction chamber for 0.08 s and held for 60 s, followed by a 60 s N2 purging step to remove excess precursor molecules. Then, H2O is pulsed into the reaction chamber for 0.02 s, exposing the polymer matrix to the precursor for 60 s, and finally, N2 is purged for 60 s. The ZnO permeation cycle is repeated a total of 5 times.

[0066] Then, an Al2O3 permeation cycle is performed, specifically as follows: Al2O3 precursor vapor, trimethylaluminum (TMA) vapor, is pulsed into the reaction chamber for 0.02 s, exposing the polymer matrix to the precursor for 60 s. Finally, N2 is used to purge for 60 s to remove excess precursor molecules. Then, H2O is pulsed into the reaction chamber for 0.02 s and held there for 60 s, followed by N2 purging for 60 s to remove further excess precursor molecules.

[0067] The ZnO and Al2O3 infiltration processes were repeated 500 times to obtain an alumina / zinc oxide co-doped (poly(2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene) conductive film (PBTTT-C14 / AZO film).

[0068] The SEM image of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment is shown in [image missing]. Figure 2 ,Depend on Figure 2Comparing (a) and (b), it can be seen that after AZO infiltration doping, very dense metal oxide nanospheres appear on the surface of the PBTTT-C14 film and are distributed very evenly. This is because the modification of the polymer matrix is ​​carried out from top to bottom during the gas phase infiltration process. At the same time, the gas phase infiltration process is a derivative of the atomic layer deposition process. Therefore, oxides will be deposited on the surface of the polymer matrix during the infiltration process.

[0069] The X-ray diffraction spectrum of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment is shown in the figure. Figure 3 .

[0070] The IV curve of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment is shown in [reference needed]. Figure 4 .

[0071] The conductivity values ​​of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment are shown in [reference needed]. Figure 5 .

[0072] Example 2

[0073] A method for preparing a conductive thin film based on in-situ doped polythiophene derivative includes the following steps:

[0074] ① Clean the insulating glass sheet (1.5cm×1.5cm) several times with deionized water, acetone and alcohol in sequence using ultrasonic cleaning, and then let it dry for later use;

[0075] ② In the process of preparing the initial film, 30 mg of PBTTT-C14 was weighed using an electronic balance, and then dissolved in 1 ml of 1,2-dichlorobenzene (DCB) to obtain a homogeneous solution. The resulting solution was then dropped onto a prepared glass slide and calcined at 70 °C for 12 h to obtain the initial PBTTT-C14 film.

[0076] ③ Finally, the prepared PBTTT-C14 initial film is placed in the reaction chamber of the ALD device, and in-situ doping modification is achieved by gas-phase permeation cycling with Al2O3 and ZnO precursors and H2O.

[0077] Specifically, the initial polythiophene derivative film is placed in the reaction chamber of a gas phase infiltration device, the pressure of the reaction chamber is controlled at 40 Pa, and an inert gas is introduced at a flow rate of 40 sccm; then, Al2O3 and ZnO precursors and H2O are used to perform gas phase infiltration cycling to achieve in-situ doping modification.

[0078] The ZnO permeation cycle is first performed, specifically as follows: ZnO precursor vapor, diethylzinc (DEZ) vapor, is pulsed into the reaction chamber for 0.08 s and held for 60 s, followed by a 60 s N2 purging step to remove excess precursor molecules. Then, H2O is pulsed into the reaction chamber for 0.02 s, exposing the polymer matrix to the precursor for 60 s, and finally, a 60 s N2 purging is performed. The ZnO permeation cycle is repeated 10 times.

[0079] Then, an Al2O3 permeation cycle is performed, specifically as follows: Al2O3 precursor vapor, trimethylaluminum (TMA) vapor, is pulsed into the reaction chamber for 0.02 s, exposing the polymer matrix to the precursor for 60 s. Finally, N2 is used to purge for 60 s to remove excess precursor molecules. Then, H2O is pulsed into the reaction chamber for 0.02 s and held there for 60 s, followed by N2 purging for 60 s to remove further excess precursor molecules.

[0080] The ZnO and Al2O3 infiltration processes were repeated 480 times to prepare an alumina / zinc oxide co-doped (poly(2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene) conductive film (PBTTT-C14 / AZO film).

[0081] The X-ray diffraction spectrum of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment is shown in the figure. Figure 3 .

[0082] The IV curve of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment is shown in [reference needed]. Figure 4 .

[0083] The conductivity values ​​of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment are shown in [reference needed]. Figure 5 .

[0084] Example 3

[0085] A method for preparing a conductive thin film based on in-situ doped polythiophene derivative includes the following steps:

[0086] ① Clean the insulating glass sheet (1.5cm×1.5cm) several times with deionized water, acetone and alcohol in sequence using ultrasonic cleaning, and then let it dry for later use;

[0087] ② In the process of preparing the initial film, 30 mg of PBTTT-C14 was weighed using an electronic balance, and then dissolved in 1 ml of 1,2-dichlorobenzene (DCB) to obtain a homogeneous solution. The resulting solution was then dropped onto a prepared glass slide and calcined at 70 °C for 12 h to obtain the initial PBTTT-C14 film.

[0088] ③ Finally, the prepared PBTTT-C14 initial film is placed in the reaction chamber of the ALD device, and in-situ doping modification is achieved by gas-phase permeation cycling with Al2O3 and ZnO precursors and H2O.

[0089] Specifically, the initial polythiophene derivative film is placed in the reaction chamber of a gas phase infiltration device, the pressure of the reaction chamber is controlled at 40 Pa, and an inert gas is introduced at a flow rate of 40 sccm; then, Al2O3 and ZnO precursors and H2O are used to perform gas phase infiltration cycling to achieve in-situ doping modification.

[0090] The ZnO permeation cycle was first performed, specifically as follows: ZnO precursor vapor, diethylzinc (DEZ) vapor, was pulsed into the reaction chamber for 0.08 s and held for 60 s, followed by a 60 s N2 purging step to remove excess precursor molecules. Then, H2O was pulsed into the reaction chamber for 0.02 s, exposing the polymer matrix to the precursor for 60 s, and finally, a 60 s N2 purging was performed. The ZnO permeation cycle was repeated a total of 19 times.

[0091] Then, an Al2O3 permeation cycle is performed, specifically as follows: Al2O3 precursor vapor, trimethylaluminum (TMA) vapor, is pulsed into the reaction chamber for 0.02 s, exposing the polymer matrix to the precursor for 60 s. Finally, N2 is used to purge for 60 s to remove excess precursor molecules. Then, H2O is pulsed into the reaction chamber for 0.02 s and held there for 60 s, followed by N2 purging for 60 s to remove further excess precursor molecules.

[0092] The ZnO and Al2O3 infiltration processes were repeated 480 times to prepare an alumina / zinc oxide co-doped (poly(2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene) conductive film (PBTTT-C14 / AZO film).

[0093] The IV curve of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment is shown in [reference needed]. Figure 4 .

[0094] The conductivity values ​​of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment are shown in [reference needed]. Figure 5 .

[0095] Example 4

[0096] A method for preparing a conductive thin film based on in-situ doped polythiophene derivative includes the following steps:

[0097] ① Clean the insulating glass sheet (1.5cm×1.5cm) several times with deionized water, acetone and alcohol in sequence using ultrasonic cleaning, and then let it dry for later use;

[0098] ② In the preparation of the initial film, 30 mg of PBTTT-C14 was weighed using an electronic balance and then dissolved in 1 ml of 1,2-dichlorobenzene (DCB) to obtain a homogeneous solution. The resulting solution was then dropped onto a prepared glass slide and calcined at 70 °C for 12 h to obtain the initial PBTTT-C14 film.

[0099] ③ Finally, the prepared PBTTT initial film is placed in the reaction chamber of the ALD device, and in-situ doping modification is achieved by gas-phase permeation cycling with Al2O3 and ZnO precursors and H2O.

[0100] Specifically, the initial polythiophene derivative film is placed in the reaction chamber of a gas phase infiltration device, the pressure of the reaction chamber is controlled at 40 Pa, and an inert gas is introduced at a flow rate of 40 sccm; then, Al2O3 and ZnO precursors and H2O are used to perform gas phase infiltration cycling to achieve in-situ doping modification.

[0101] The ZnO permeation cycle is first performed as follows: ZnO precursor vapor, diethylzinc (DEZ) vapor, is pulsed into the reaction chamber for 0.08 s and held for 60 s, followed by a 60 s N2 purging step to remove excess precursor molecules. Then, H2O is pulsed into the reaction chamber for 0.02 s, exposing the polymer matrix to the precursor for 60 s, and finally, the chamber is purged with N2 for 60 s. The ZnO permeation cycle is repeated a total of 30 times.

[0102] Then, an Al2O3 permeation cycle is performed, specifically as follows: Al2O3 precursor vapor, trimethylaluminum (TMA) vapor, is pulsed into the reaction chamber for 0.02 s, exposing the polymer matrix to the precursor for 60 s. Finally, N2 is used to purge for 60 s to remove excess precursor molecules. Then, H2O is pulsed into the reaction chamber for 0.02 s and held there for 60 s, followed by N2 purging for 60 s to remove further excess precursor molecules.

[0103] The ZnO and Al2O3 infiltration processes were repeated 500 times to obtain an alumina / zinc oxide co-doped (poly(2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene) conductive film (PBTTT-C14 / AZO film).

[0104] The X-ray diffraction spectrum of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment is shown in the figure. Figure 3 .Depend on Figure 3It can be seen that when ZnO is doped into PBTTT-C14, the (102) peak at 2θ = 39.1° corresponds to the wurtzite-type ZnS structure. This means that the Zn atoms in the dopant molecule react with the S atoms in PBTTT-C14. In addition, the ZnO and a small amount of ZnS particles generated in the film achieve "double doping" of the polymer film. During the process of Al2O3 and ZnO doping of the polymer, no Al-S diffraction peaks were observed, indicating that S atoms do not react with Al atoms. In this doping process, ZnO, Al2O3 and a small amount of ZnS particles achieve "multiple doping" of the polymer film. Therefore, the XRD results show that the VPI process successfully introduced ZnO particles, Al2O3 particles and ZnS particles into the PBTTT-C14 film and produced a strong doping effect on the PBTTT-C14 film.

[0105] The IV curve of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment is shown in [reference needed]. Figure 4 .Depend on Figure 4 It is evident that the conductivity of the PBTTT-C14 conductive film modified by multiple precursors increases to varying degrees with different ZnO cycle numbers. This confirms the feasibility of using multiple vapor-phase infiltration for in-situ doping modification of the initial PBTTT-C14 film, as described in this patent.

[0106] The conductivity values ​​of the alumina / zinc oxide co-doped polythiophene derivative conductive film prepared in this embodiment are shown in [reference needed]. Figure 5 .Depend on Figure 5 It can be seen that the conductivity increases with the increase of the proportion of Al2O3, and the conductivity of the PBTTT-C14 / AZO film reaches 1.16 S·cm when the Al2O3:ZnO ratio is 1:10. -1 The conductivity of PBTTT-C14 / AZO and undoped PBTTT-C14 thin film is 7.93 × 10⁻⁶. -8 S·cm -1 Compared to the previous method, the conductivity increased by eight orders of magnitude. It is clear that using AZO as a dopant for in-situ doping modification of the initial PBTTT film significantly improves the conductivity of the substrate material.

[0107] In Examples 1-4 above, the initial PBTTT-C14 film is a porous polymer material, which can be effectively modified by in-situ doping via vapor phase infiltration. Given the significant differences observed in the samples before and after infiltration doping, DEZ and TMA precursor molecules are more likely to interact with the functional groups of the polymer in some way, thereby facilitating electronic conduction. See also Figure 2It can be seen that when ZnO is doped with PBTTT-C14, the (102) peak at 2θ = 39.1° corresponds to the wurtzite-type ZnS structure. This means that the Zn atoms in the dopant molecule react with the S atoms in PBTTT-C14. In addition, the ZnO and a small amount of ZnS particles generated in the film achieve "double doping" of the polymer film. The two react, and the sulfur atoms on the thiophene ring have lone pairs of electrons, which combine with zinc to form Zn-S bonds, changing the electronic state and thus improving the conductivity. The conductivity of the modified PBTTT-C14 film is increased by 8 orders of magnitude compared with its initial film sample, and its conductivity can reach 1.16 S / cm. Therefore, the conductive film based on in-situ doped polythiophene derivative can be well applied to the fabrication and development of various electronic devices, such as field-effect transistors, light-emitting diodes, and solar photovoltaic panels.

[0108] Example 5

[0109] A method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive thin film includes the following steps:

[0110] S1: The initial polythiophene derivative film is repeatedly reacted with diethylzinc vapor and water vapor, and the product after the reaction is completed is purged with nitrogen gas; the reaction is repeated 5 times; specifically:

[0111] S11: The initial polythiophene derivative film is placed in the gas phase permeation device reactor with a pressure of 40 Pa. The reactor is purged with argon gas and helium gas at a flow rate of 40 sccm. Then, diethylzinc vapor is introduced and kept in the reactor for 60 s. The reactor is then purged with nitrogen gas.

[0112] S12: Continue to introduce water vapor into the reactor after completing step S11, and allow the diethylzinc vapor and water vapor to react with the initial polythiophene derivative film. After the reaction is complete, introduce nitrogen gas into the reactor and use nitrogen gas to purge the product after the reaction.

[0113] S2: Trimethylaluminum vapor and water vapor are reacted with the zinc oxide-doped polythiophene derivative film, and the product after the reaction is completed is purged with nitrogen gas; specifically:

[0114] S21: After completing step S1, trimethylaluminum vapor is introduced into the reactor and kept in the reactor for 60 seconds. The reactor is then purged with nitrogen.

[0115] S22: Water vapor is introduced into the reactor after step S21, and trimethylaluminum vapor and water vapor react with the product after step S1. After the reaction is completed, nitrogen gas is introduced into the reaction system to purge the product after the reaction.

[0116] S3: Repeat steps S1 to S2 on the product obtained from step S2 to obtain the alumina / zinc oxide co-doped polythiophene derivative film. The number of times steps S1 to S2 are repeated is 490.

[0117] During the reaction process in steps S1 to S3, the temperature of the reaction system is 180℃ and the pressure of the reaction system is 1000Pa.

[0118] In this embodiment, the mass ratio of aluminum oxide to zinc oxide in the alumina / zinc oxide co-doped polythiophene derivative conductive film is 1g:4g; the thickness of the alumina / zinc oxide composite layer on the surface of the alumina / zinc oxide co-doped polythiophene derivative conductive film is 4.5nm; and the conductivity of the prepared alumina / zinc oxide co-doped polythiophene derivative conductive film is 0.50S / cm.

[0119] Example 6

[0120] A method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive thin film includes the following steps:

[0121] S1: The initial polythiophene derivative film is repeatedly reacted with diethylzinc vapor and water vapor, and the product after the reaction is completed is purged with nitrogen gas; the reaction is repeated 9 times; specifically:

[0122] S11: The initial polythiophene derivative film is placed in the gas phase permeation device reactor with a pressure of 44 Pa. The reactor is purged with argon and helium at a flow rate of 45 sccm. Then, diethylzinc vapor is introduced and kept in the reactor for 63 s. The reactor is then purged with nitrogen.

[0123] S12: Continue to introduce water vapor into the reactor after completing step S11, and allow the diethylzinc vapor and water vapor to react with the initial polythiophene derivative film. After the reaction is complete, introduce nitrogen gas into the reactor and use nitrogen gas to purge the product after the reaction.

[0124] S2: Trimethylaluminum vapor and water vapor are reacted with the zinc oxide-doped polythiophene derivative film, and the product after the reaction is completed is purged with nitrogen gas; specifically:

[0125] S21: After completing step S1, trimethylaluminum vapor is introduced into the reactor and kept in the reactor for 63 seconds. The reactor is then purged with nitrogen.

[0126] S22: Water vapor is introduced into the reactor after step S21, and trimethylaluminum vapor and water vapor react with the product after step S1. After the reaction is completed, nitrogen gas is introduced into the reaction system to purge the product after the reaction.

[0127] S3: Repeat steps S1 to S2 on the product obtained from step S2 to obtain the alumina / zinc oxide co-doped polythiophene derivative film. The number of times steps S1 to S2 are repeated is 480.

[0128] During the reaction process in steps S1 to S3, the temperature of the reaction system is 183℃ and the pressure of the reaction system is 1300Pa.

[0129] In this embodiment, the mass ratio of aluminum oxide to zinc oxide in the alumina / zinc oxide co-doped polythiophene derivative conductive film is 1g:10g; the thickness of the alumina / zinc oxide composite layer on the surface of the alumina / zinc oxide co-doped polythiophene derivative conductive film is 4.7nm; and the conductivity of the prepared alumina / zinc oxide co-doped polythiophene derivative conductive film is 0.56S / cm.

[0130] Example 7

[0131] A method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive thin film includes the following steps:

[0132] S1: The initial polythiophene derivative film is repeatedly reacted with diethylzinc vapor and water vapor, and the product after the reaction is completed is purged with nitrogen gas; the reaction is repeated 15 times; specifically:

[0133] S11: The initial polythiophene derivative film is placed in the gas phase permeation device reactor with a pressure of 50 Pa. The reactor is purged with argon gas and helium gas at a flow rate of 55 sccm. Then, diethylzinc vapor is introduced and kept in the reactor for 65 s. The reactor is then purged with nitrogen gas.

[0134] S12: Continue to introduce water vapor into the reactor after completing step S11, and allow the diethylzinc vapor and water vapor to react with the initial polythiophene derivative film. After the reaction is complete, introduce nitrogen gas into the reactor and use nitrogen gas to purge the product after the reaction.

[0135] S2: Trimethylaluminum vapor and water vapor are reacted with the zinc oxide-doped polythiophene derivative film, and the product after the reaction is completed is purged with nitrogen gas; specifically:

[0136] S21: After completing step S1, trimethylaluminum vapor is introduced into the reactor and kept in the reactor for 65 seconds. The reactor is then purged with nitrogen.

[0137] S22: Water vapor is introduced into the reactor after step S21, and trimethylaluminum vapor and water vapor react with the product after step S1. After the reaction is completed, nitrogen gas is introduced into the reaction system to purge the product after the reaction.

[0138] S3: Repeat steps S1 to S2 on the product obtained from step S2 to obtain the alumina / zinc oxide co-doped polythiophene derivative film. The number of times steps S1 to S2 are repeated is 430.

[0139] During the reaction process in steps S1 to S3, the temperature of the reaction system is 185℃ and the pressure of the reaction system is 1800Pa.

[0140] In this embodiment, the mass ratio of aluminum oxide to zinc oxide in the alumina / zinc oxide co-doped polythiophene derivative conductive film is 1g:20g; the thickness of the alumina / zinc oxide composite layer on the surface of the alumina / zinc oxide co-doped polythiophene derivative conductive film is 5.0nm; and the conductivity of the prepared alumina / zinc oxide co-doped polythiophene derivative conductive film is 1.00S / cm.

[0141] Example 8

[0142] A method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive thin film includes the following steps:

[0143] S1: The initial polythiophene derivative film is repeatedly reacted with diethylzinc vapor and water vapor, and the product after the reaction is completed is purged with nitrogen gas; the reaction is repeated 30 times; specifically:

[0144] S11: The initial polythiophene derivative film is placed in the gas phase permeation device reactor with a pressure of 60 Pa. The reactor is purged with argon and helium at a flow rate of 60 sccm. Then, diethylzinc vapor is introduced and kept in the reactor for 65 s. The reactor is then purged with nitrogen.

[0145] S12: Continue to introduce water vapor into the reactor after completing step S11, and allow the diethylzinc vapor and water vapor to react with the initial polythiophene derivative film. After the reaction is complete, introduce nitrogen gas into the reactor and use nitrogen gas to purge the product after the reaction.

[0146] S2: Trimethylaluminum vapor and water vapor are reacted with the zinc oxide-doped polythiophene derivative film, and the product after the reaction is completed is purged with nitrogen gas; specifically:

[0147] S21: After completing step S1, trimethylaluminum vapor is introduced into the reactor and kept in the reactor for 65 seconds. The reactor is then purged with nitrogen.

[0148] S22: Water vapor is introduced into the reactor after step S21, and trimethylaluminum vapor and water vapor react with the product after step S1. After the reaction is completed, nitrogen gas is introduced into the reaction system to purge the product after the reaction.

[0149] S3: Repeat steps S1 to S2 on the product obtained from step S2 to obtain the alumina / zinc oxide co-doped polythiophene derivative film. The number of times steps S1 to S2 are repeated is 400.

[0150] During the reaction process in steps S1 to S3, the temperature of the reaction system is 185℃ and the pressure of the reaction system is 2000Pa.

[0151] In this embodiment, the mass ratio of aluminum oxide to zinc oxide in the aluminum oxide / zinc oxide co-doped polythiophene derivative conductive film is 1g:24g; the thickness of the aluminum oxide / zinc oxide composite layer on the surface of the aluminum oxide / zinc oxide co-doped polythiophene derivative conductive film is 5.5nm; and the conductivity of the prepared aluminum oxide / zinc oxide co-doped polythiophene derivative conductive film is 1.2S / cm.

[0152] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

[0153] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for producing an electrically conductive thin film of an aluminum / zinc oxide co-doped polythiophene derivative, characterized by, The method comprises the following steps: S1: repeatedly reacting diethyl zinc vapor and water vapor with the initial polythiophene derivative film, and purging the product after the reaction with nitrogen; S2: reacting trimethylaluminum vapor and water vapor with the product after step S1, and purging the product after the reaction with nitrogen; S3: repeatedly performing steps S1-S2 on the product after step S2 to obtain the aluminum oxide / zinc oxide co-doped polythiophene derivative film; In step S3, the product after step S2 is repeatedly subjected to steps S1-S2 for 400-500 times; In step S1, the polythiophene derivative initial film is placed in a sealed reactor, the reactor is purged with an inert gas, then diethyl zinc vapor is introduced into the reactor and kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; 2. The method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive thin film according to claim 1, characterized in that, In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; 3. The method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive thin film according to claim 1, characterized in that, In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; 4. The method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive thin film according to claim 1, characterized in that, In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; 5. The method for preparing an alumina / zinc oxide co-doped polythiophene derivative conductive thin film according to claim 1, characterized in that, In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; 6. An electrically conductive thin film of an aluminum / zinc oxide co-doped polythiophene derivative, characterized in that, In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65 seconds, and then the reactor is purged with nitrogen; In step S2, trimethylaluminum vapor is introduced into the reactor after step S1, and the trimethylaluminum vapor is kept in the reactor for 60-65

Images