Conductive polymer composites with thermal stability and solvent resistance

Abstract

To provide a conductive polymer composite having excellent conductivity, and excellent thermal stability and solvent resistance, and a manufacturing friendly preparation method for preparing the same.SOLUTION: The disclosed composite contains a doped electron rich host thiophene conjugated polymer and a crosslinkable silane network. The disclosed method includes a host thiophene conjugated polymer and a crosslinkable silane precursor, allowing simultaneously introducing both the dopant and the rigid cross-linked siloxane network into a polymer system.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to PCT Application No. PCT / US2020 / 041851, filed July 13, 2020, U.S. Patent Application No. 17 / 000,012, filed August 21, 2020, and U.S. Patent Application No. 17 / 189,637, filed March 2, 2021, the entire contents of each of the foregoing patent applications being incorporated herein by reference.

[0002] (Technical field) FIELD OF THE DISCLOSURE The present disclosure generally relates to thermally stable and solvent resistant conductive polymer composites and methods for making the same. [Background technology]

[0003] Conjugated polymers (CPs) are widely used in all kinds of electronic devices. Doping has proven to be a powerful tool for improving the robust electrical conductivity of conjugated polymers (CPs) at high temperatures and / or in various solvent environments. However, organic doping is generally sensitive to external stimuli such as heat, moisture, and chemicals, which can cause a dedoping process. For example, thermal stress often induces and promotes conformational changes in polymer chains, further resulting in microscale or morphological disorder in conjugated polymer thin films. In doped thin films, this process is often accompanied by the release of dopant molecules, resulting in a decrease in electrical conductivity and degradation of device performance. Molecular dopants such as ferric chloride and F4TCNQ enable stable doping of poly(3-hexylthiophene) under ambient conditions, but their relatively small size makes them prone to diffusion at high temperatures, making them thermally unstable.

[0004] To achieve robust electrical conductivity in conjugated polymers (CPs) using conventional doping methods, designing novel dopants or developing new doping methods requires significant synthetic and processing efforts. Therefore, a simple, efficient design and manufacturing-friendly method for thermally stable and solvent-resistant doped systems is highly desirable. Summary of the Invention [Means for solving the problem]

[0005] The present disclosure provides a conductive polymer composite material having thermal stability and solvent resistance and a method for producing the same.

[0006] In one aspect, the present disclosure provides a thermally stable and solvent-resistant conductive polymer composite comprising a doped electron-rich host thiophene conjugated polymer and a crosslinked siloxane network.

[0007] In some embodiments, the crosslinked siloxane network is formed from a crosslinkable silane precursor having the following chemical formula:

[0008] [ka]

[0009] During the ceremony, n is an integer greater than 0, X is a monomer unit and can be oxygen, a urea group (N2H2CO-), C1-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl; R1, R2, R3, R4, R5, and R6 are each independently hydrogen, a halide group, a hydroxyl group, a carboxyl group, a C1-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl; At least three of R1, R2, R3, R4, R5, and R6 are selected from the group consisting of chloride groups, bromine groups, hydroxyl groups, and alkyloxyl groups; At least one of R1, R2, R3, R4, R5, and R6 comprises a dopant.

[0010] In some embodiments, the crosslinked siloxane network is formed from a crosslinkable silane precursor having the following chemical formula:

[0011] [ka]

[0012] During the ceremony, R7, R8, R9, and R 10 Each of these is a hydrogen, halide group, hydroxyl group, carboxyl group, C1-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl; R7, R8, R9, and R 10 at least three of are selected from the group consisting of chloride groups, bromine groups, hydroxyl groups, and alkyloxyl groups; R7, R8, R9, and R 10 At least one of the layers contains a dopant.

[0013] In some embodiments, the crosslinked siloxane network is formed from a combination of silane precursors, including at least one of the two crosslinkable silane precursors described above. In addition to either of the two crosslinkable silane precursors described above, the system may also include a non-crosslinkable silane precursor that is incapable of forming a crosslinked siloxane network.

[0014] In some embodiments, the crosslinked siloxane network is formed from a crosslinkable chlorosilane precursor having the formula:

[0015] [ka]

[0016] During the ceremony, n is an integer greater than 0 and less than or equal to 13.

[0017] In some embodiments, the crosslinked siloxane network is formed from a crosslinkable chlorosilane precursor having the formula:

[0018] [ka]

[0019] During the ceremony, R 11 is hydrogen, halide group, hydroxyl group, carboxyl group, C1-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl.

[0020] In some embodiments, the crosslinked siloxane network is formed from a crosslinkable chlorosilane precursor having the formula:

[0021] [ka]

[0022] In some embodiments, the doped electron-rich host thiophene-conjugated polymer comprises a p-type thiophene-conjugated polymer with an oxidation potential 0.4 V lower than Ag / AgCl.

[0023] Various embodiments disclosed herein relate to various host thiophene conjugated polymers that comprise the thermally stable and solvent resistant conductive polymer composites of the present disclosure. In some embodiments, the doped electron-rich host thiophene conjugated polymer comprises a copolymer represented by the following chemical formula:

[0024] [ka]

[0025] During the ceremony, a and b are integers of 0 or greater, The values ​​of a and b indicate the ratio of the two monomer units (but do not necessarily indicate the exact sequence of monomers in the polymer), n is an integer greater than 0, R 12 , R 13 , R 14 , and R 15 Each of the groups may be independently selected from the group consisting of, but not limited to, hydrogen, C-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl; R 12 , R 13 , R 14 , and R 15 At least one of the atoms is electron rich and has an excess of donating electrons.

[0026] In some embodiments, the doped electron-rich host thiophene conjugated polymer comprises a dioxythiophene copolymer represented by the following chemical formula:

[0027] [ka]

[0028] During the ceremony, a and b are integers of 0 or greater, The values ​​of a and b indicate the ratio of the two monomer units (but do not necessarily indicate the exact sequence of monomers in the polymer), n is an integer greater than 0, R 16 , R 17 , R 18 , and R 19 Each of the groups may be independently selected from the group consisting of, but not limited to, hydrogen, C-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl.

[0029] In some embodiments, the doped electron-rich host thiophene conjugated polymer comprises a dioxythiophene copolymer represented by the following chemical formula:

[0030] [ka]

[0031] During the ceremony, a and b are integers of 0 or greater, The values ​​of a and b indicate the ratio of the two monomer units (but do not necessarily indicate the exact sequence of monomers in the polymer), n is an integer greater than or equal to 0, R 20 , R 21 , R 22, and R 23 Each of the groups may be independently selected from the group consisting of, but not limited to, hydrogen, C-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl.

[0032] In some embodiments, the doped electron-rich host thiophene conjugated polymer comprises a dioxythiophene copolymer containing soluble 3,4-propylenedioxythiophene (ProDOT) units and electron-rich 3,4-ethylenedioxythiophene (EDOT) units, represented by the following chemical formula:

[0033] [ka]

[0034] where x is an integer greater than 0, y is an integer equal to or greater than 0, and n is an integer greater than 0. The values ​​of x and y indicate the ratio of two monomer units. However, the values ​​of x and y do not necessarily indicate the exact monomer sequence in the polymer. This means that the reaction may be regular or random polymerization. In some embodiments, the doped electron-rich host thiophene conjugated polymer is ProDOTx-EDOTy (P) with an average ratio of y:x in the range of 0-10. x E y An example of a PxEy polymer is PE3, whose sequence is, for example, PE-PEEEE-PEE-PEEEEE-PEEE... in the case of random polymerization, with an average y:x ratio of 3, and PEEE-PEEE-PEEE-PEEE-PEEE... in the case of regular polymerization.

[0035] In some embodiments, the doped electron-rich host thiophene conjugated polymer is a dioxythiophene copolymer P, represented by the formula above, where x=1 and y=1, 2, or 3. x E y Includes:

[0036] In another aspect, the present disclosure provides a method for producing a thermally stable and solvent-resistant conductive polymer composite. The method for producing a thermally stable and solvent-resistant conductive polymer composite according to the present disclosure includes the steps of preparing a crosslinkable silane precursor solution containing a crosslinkable silane precursor and a solvent; preparing an electron-rich host thiophene conjugated polymer solution containing an electron-rich host thiophene conjugated polymer and a solvent; and mixing the crosslinkable silane precursor solution with the electron-rich host thiophene conjugated polymer solution in a ratio of the crosslinkable silane precursor in the range of 0.1 to 90 wt % and reacting for a reaction time of up to 168 hours to produce a solution containing a conductive polymer composite. The method of the present disclosure also optionally includes, after the step of preparing the solution containing the conductive polymer composite, adding a hydrogen-bond blocking solvent to break hydrogen bonds and improve the consistency of the solution. The solution containing the conductive polymer composite thus produced can then be coated onto a substrate using conventional coating techniques to form a thin film of the thermally stable and solvent-resistant conductive polymer composite of the present disclosure.

[0037] In some embodiments, the solvent for preparing the solution of the crosslinkable silane precursor and the solvent for preparing the solution of the electron-rich host thiophene conjugated polymer are selected from one or more aprotic solvents, such as chloroform, dichloromethane, nitromethane, or toluene.

[0038] In some embodiments, a hydrogen bond blocking solvent is a solvent that can be used to break hydrogen bonds. Examples of hydrogen bond blocking solvents include alcohols and acetone.

[0039] In some embodiments, the present invention relates to devices or machines incorporating thin films of the conductive polymer composites of the present disclosure.

[0040] Particular features of various embodiments of the present technology are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present technology will be obtained by reference to the following detailed description that sets forth illustrative embodiments in which the principles of the invention are utilized, and the accompanying drawings. [Brief explanation of the drawings]

[0041] [Figure 1] Figure 1 is a scheme of the components of the conductive polymer composite of the present disclosure. Figure 1(A) shows a scheme of a crosslinked siloxane network formed by a crosslinkable silane precursor. Figure 1(B) is a simplified diagram of the crosslinked siloxane network. Figure 1(C) shows a scheme of a host thiophene conjugated polymer (CP). Figure 1(D) is a scheme of a conductive polymer composite including a host CP and a crosslinked siloxane network. [Figure 2] Figure 2 shows AFM phase images of pure PE3-hosted CP (Figure 2(A)) and C6-Si / PE3 (Figure 2(B)). [Figure 3] Figure 3 shows AFM phase images of L6-Si / PE3 (Figure 3(A)) and F-Si / PE3 (Figure 3(B)). [Figure 4] Figure 4 shows the IR spectra of the C6-Si / PE3 thin film, the L6-Si / PE3 thin film, and the pure PE3 thin film. [Figure 5] FIG. 5 shows the IR spectra of the C6-Si / PE3 composite thin film as spin-coated, after annealing at 373 K for 30 min, and after annealing at 373 K for 60 min. [Figure 6] FIG. 6 shows a comparison of the electrical conductivities of three silane / PE3 composites (C6-Si / PE3, L6-Si / PE3, and F-Si / PE3) at various silane precursor concentrations. [Figure 7] Figure 7 shows AFM phase images of C6-Si / PE3 composites containing various concentrations of C6-Si, with C6-Si concentrations of approximately 72 wt% (Figure 7(A)), approximately 56 wt% (Figure 7(B)), approximately 39 wt% (Figure 7(C)), and approximately 24 wt% (Figure 7(D)), respectively. [Figure 8] FIG. 8 shows the normalized UV-vis absorption spectra of the composite thin films including pure PE3, C6-Si / PE3, L6-Si / PE3, and F-Si / PE3. [Figure 9] FIG. 9 shows a comparison of the electrical conductivity of different silane / PE3 composites before (left) and after (right) annealing at 393 K. [Figure 10] Figure 10 shows the normalized in situ UV-Vis absorption spectra of various silane / PE3 composites at temperatures increasing from 293 K to 453 K: Figure 10(A) for C6-Si / PE3, Figure 10(B) for L6-Si / PE3, and Figure 10(C) for F-Si / PE3. [Figure 11] FIG. 11 shows a comparison of the optical density ratio (OD at 550 nm / OD at 1600 nm) at elevated temperatures for various silane / PE3 composites. [Figure 12] FIG. 12 shows the normalized conductivity of various silane / PE3 composites at 353 K for 6 hours. [Figure 13] Figure 13 shows the IR spectra of the C6-Si / PE3 composite (Figure 13(A)), C10-Si / PE3 composite (Figure 13(B)), and CM-Si / PE3 composite (Figure 13(C)) before annealing (as spin-coated), after annealing at 373 K for 30 minutes, and after annealing at 373 K for 60 minutes. [Figure 14] FIG. 14 shows a comparison of the conductivity of various polymer PxEy host CPs (PE1, PE2, and PE3) and the conductive polymer composite CM-Si / PxEy containing them. [Figure 15] FIG. 15 shows a comparison of the normalized conductivity of CM-Si / PxEy composites with various PxEy host CPs (PE1, PE2, and PE3) at 353 K for 24 h. [Figure 16]Figure 16 shows the normalized UV-Vis absorption spectra of CM-Si / PxEy composites with various PxEy host polymers as the temperature increases from 293 K to 453 K. Figure 16(A) shows the CM-Si / PE3 composite, Figure 16(B) shows the CM-Si / PE2 composite, and Figure 16(C) shows the CM-Si / PE1 composite. [Figure 17] FIG. 17 shows the IV curves of the CM-Si / PE3 thin film before and after immersion in water for 1 hour. [Figure 18] FIG. 18 shows the normalized UV-Vis absorption spectra of the CM-Si / PE3 / PE3 composite thin film before and after water or chloroform treatment. [Figure 19] Figure 19 shows images of a glass substrate and a thin film formed on its surface, with the lower half of each substrate immersed in a chloroform bath. Figure 19(A) shows an image of a CM-Si / PE3 composite thin film formed on a glass substrate, Figure 19(B) shows an image of a pure polymer PE3 thin film formed on a glass substrate, and Figure 19(C) shows an image of the glass substrate. DETAILED DESCRIPTION OF THE INVENTION

[0042] In the following description, certain specific details are set forth to provide a thorough understanding of various embodiments of the present invention. However, it will be understood by those skilled in the art that the present invention may be practiced without these details. Furthermore, while various embodiments of the present invention are disclosed herein, various changes and modifications can be made within the scope of the present invention in accordance with the general knowledge of those skilled in the art. Such modifications include the substitution of known equivalents for any aspect of the present invention in order to achieve the same result in substantially the same way.

[0043] Unless the context requires otherwise, throughout this specification and claims, the word "comprise" and variations thereof (e.g., "comprises," "comprising") should be interpreted in an open and inclusive sense, i.e., "including, but not limited to." Throughout this specification, the recitation of ranges of values ​​is intended to serve as a shorthand notation for individually referring to each value falling within the range, inclusive of the values ​​defining the range, each value being incorporated herein as if set forth individually herein. In this disclosure, the term "about" can allow for variation of a given numerical value or range (e.g., within 10%, 5%, or 1% of the specified numerical value, or other specified range). Additionally, the singular forms "a," "an," and "the" also include the plural of their referent unless the context clearly dictates otherwise.

[0044] Throughout this specification, the terms "one embodiment," "an embodiment," and the like mean that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrases "one embodiment," "an embodiment," and the like in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0045] The present disclosure provides thermally stable and solvent-resistant conductive polymer composites comprising a doped electron-rich host thiophene conjugated polymer and a crosslinked siloxane network.

[0046] Throughout this specification, testing of a "conductive polymer composite" or "composite" refers to testing of a composite thin film formed by depositing the composite on a glass substrate.

[0047] Various embodiments disclosed herein relate to various forms of crosslinkable silane precursors and various electron-rich host thiophene conjugated polymers for forming thermally stable and solvent-resistant conductive polymer composite thin films. The host thiophene conjugated polymers have a low oxidation potential and can be easily doped. The crosslinkable silane precursor requires at least three functional groups to form a crosslinkable siloxane network through a condensation reaction, and also has at least one dopant for the doping reaction. When a solution of the crosslinkable silane precursor is mixed with a solution of the host thiophene conjugated polymer, the crosslinkable silane precursor forms a crosslinked siloxane network within the host thiophene conjugated polymer, and simultaneously, a doping reaction occurs between the crosslinkable silane precursor and the host thiophene conjugated polymer (see Figures 1(A)-(C)). The crosslinked siloxane network is formed by mixing the crosslinkable silane precursor with the host thiophene conjugated polymer. During mixing, the functional groups capable of undergoing a condensation reaction are replaced with hydroxides from the small amount of water in chloroform, thereby generating silanol groups in the solution. As shown in Figure 1(A), a crosslinked siloxane network is formed by the condensation reaction of two adjacent silanol groups in adjacent precursors in solution. In addition, the host thiophene conjugated polymer shown in Figure 1(C) has a low oxidation potential, making it easy to dope. When a crosslinked network is formed within the host thiophene conjugated polymer by mixing a crosslinkable silane precursor with the host thiophene conjugated polymer, the dopant contained in the crosslinkable silane precursor undergoes a doping reaction with the host thiophene conjugated polymer, resulting in the production of a conductive polymer composite material as shown in Figure 1(D). The crosslinked siloxane network constrains the doped polymer, preventing rearrangement of the doped polymer chains and dopant diffusion. Furthermore, since dedoping involves changes in the three-dimensional structure and morphology, the crosslinked siloxane network also contributes to the stability of the dope. Thus, the introduction of a crosslinked siloxane network not only significantly improves the conductivity of conjugated polymers (CPs), but also improves their thermal stability and solvent resistance.

[0048] In some embodiments, the crosslinked siloxane network is formed from a crosslinkable silane precursor having the following chemical formula:

[0049] [ka]

[0050] During the ceremony, n is an integer greater than 0, X is a monomer unit and can be oxygen, a urea group (N2H2CO-), C1-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl; R1, R2, R3, R4, R5, and R6 are each independently hydrogen, a halide group, a hydroxyl group, a carboxyl group, a C1-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30heteroarylalkyl; At least three of R1, R2, R3, R4, R5, and R6 are selected from the group consisting of chloride groups, bromine groups, hydroxyl groups, and alkyloxyl groups; At least one of R1, R2, R3, R4, R5, and R6 comprises a dopant.

[0051] The crosslinkable silane precursors described above require at least three functional groups capable of condensation reactions to form a crosslinked siloxane network. In contrast, silane precursors with two functional groups capable of condensation reactions can form linear siloxane bridges that can bend and twist within the host thiophene conjugated polymer to form a siloxane matrix. While such siloxane matrices are not crosslinked but still constrain the polymer chains to some degree, they can significantly improve the electrical conductivity of the conjugated polymer (CP) (in some embodiments, by four to five orders of magnitude, compared with six orders of magnitude for silane precursors with at least three functional groups). However, their thermal stability is not as good as that of silane precursors with at least three functional groups.

[0052] In some embodiments, the crosslinked siloxane network is formed from a crosslinkable silane precursor having the following chemical formula: [ka]

[0053] During the ceremony, R7, R8, R9, and R 10 Each of these is a hydrogen, halide group, hydroxyl group, carboxyl group, C1-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl; R7, R8, R9, and R 10 at least three of are selected from the group consisting of chloride groups, bromine groups, hydroxyl groups, and alkyloxyl groups; R7, R8, R9, and R 10 At least one of the layers contains a dopant.

[0054] The crosslinkable silane precursors described above require at least three functional groups capable of condensation reactions to form a crosslinked siloxane network. In contrast, silane precursors with two functional groups capable of condensation reactions can form linear siloxane bridges that can bend and twist within the host thiophene conjugated polymer to form a siloxane matrix. While such siloxane matrices are not crosslinked but still constrain the polymer chains to some degree, they can significantly improve the electrical conductivity of the conjugated polymer (CP) (in some embodiments, by four to five orders of magnitude, compared with six orders of magnitude for silane precursors with at least three functional groups). However, their thermal stability is not as good as that of silane precursors with at least three functional groups.

[0055] In some embodiments, the crosslinked siloxane network is formed from a combination of silane precursors, including at least one of the two crosslinkable silane precursors represented by Formula (1) and Formula (2) above. In addition to either of the crosslinkable silane precursors represented by Formula (1) and Formula (2) above, the system may also include a non-crosslinkable silane precursor (e.g., a silane precursor having only one or two functional groups) that is incapable of forming a crosslinked siloxane network.

[0056] In some embodiments, the crosslinked siloxane network is formed from a crosslinkable chlorosilane precursor having the formula:

[0057] [ka]

[0058] During the ceremony, n is the number of spacer carbons, n is an integer greater than 0 and ranging from 1 to 13. The chlorine group can function not only in condensation reactions but also as a doping agent, and can undergo doping reactions with host conjugated polymers (CPs).

[0059] In some embodiments, the crosslinked siloxane network is formed from a crosslinkable chlorosilane precursor having the formula:

[0060] [ka]

[0061] During the ceremony, R 11 is hydrogen, halide group, hydroxyl group, carboxyl group, C1-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl.

[0062] In some embodiments, the crosslinkable chlorosilane precursor is 1,6-bis(trichlorosilyl)hexane (C6-Si) with 6 spacers, 1,10-bis(trichlorosilyl)decane (C6-Si) with 10 spacers, and the like, represented by the following formula: 10 -Si), or monotrichlorosilyl (C M -Si).

[0063] [ka]

[0064] These crosslinkable chlorosilane precursors are hereinafter collectively referred to as C-Si.

[0065] In some embodiments, the doped electron-rich host thiophene-conjugated polymer comprises a p-type thiophene-conjugated polymer with an oxidation potential 0.4 V lower than Ag / AgCl.

[0066] Various embodiments disclosed herein relate to a variety of electron-rich host thiophene conjugated polymers that can be combined with crosslinkable siloxane networks to form the thermally stable and solvent-resistant conductive polymer composites of the present disclosure. Such host thiophene conjugated polymers include those represented by the following chemical formula:

[0067] [ka]

[0068] During the ceremony, a and b are integers of 0 or greater, The values ​​of a and b indicate the ratio of the two monomer units (but do not necessarily indicate the exact sequence of monomers in the polymer), n is an integer greater than 0, R 12 , R 13 , R 14 , and R 15 Each of the groups may be independently selected from the group consisting of, but not limited to, hydrogen, C-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl; R 12 , R 13 , R 14 , and R15 At least one of the atoms is electron rich and has an excess of donating electrons. An example of such a polymer is represented by the following chemical formula:

[0069] [ka]

[0070] In some embodiments, the host thiophene-conjugated polymer comprises a polymer represented by the following formula:

[0071] [ka]

[0072] During the ceremony, a and b are integers of 0 or greater, The values ​​of a and b indicate the ratio of the two monomer units (but do not necessarily indicate the exact sequence of monomers in the polymer), n is an integer greater than 0, R 16 , R 17 , R 18 , and R 19 Each of the groups may be independently selected from the group consisting of, but not limited to, hydrogen, C-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl. An example of such a polymer is represented by the following chemical formula:

[0073] [ka]

[0074] In some embodiments, the host thiophene-conjugated polymer comprises a polymer represented by the following formula:

[0075] [ka]

[0076] During the ceremony, a and b are integers of 0 or greater, The values ​​of a and b indicate the ratio of the two monomer units (but do not necessarily indicate the exact sequence of monomers in the polymer), n is an integer greater than 0, R 20 , R 21 , R22 , and R 23 Each of the groups may be independently selected from the group consisting of, but not limited to, hydrogen, C-C 30 Alkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C2-C 30 Alkylcarbonyl, C1-C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4-C 30 Alkoxycarbonylalkyl, C1-C 30 Aminyl carbonyl, C4-C 30 Aminyl alkyl, C1-C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkyloxy, C1-C 12 Heterocyclyl C1-C 12 Heterocyclyloxy, C3-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl and C3-C 30 heteroarylalkyl.

[0077] In some embodiments, the host thiophene conjugated polymer comprises a dioxythiophene copolymer containing soluble 3,4-propylenedioxythiophene (ProDOT) units and electron-rich 3,4-ethylenedioxythiophene (EDOT) units, represented by the following chemical formula:

[0078] [ka] where x is an integer greater than 0, y is an integer equal to or greater than 0, and n is an integer greater than 0. The values ​​of x and y indicate the ratio of two monomer units. However, the values ​​of x and y do not necessarily indicate the exact monomer sequence in the polymer. This means that the reaction may be regular or random polymerization. In some embodiments, the host thiophene-conjugated polymer is ProDOTx-EDOTy (P) with an average ratio of y:x ranging from 0 to 10. x E y An example of a PxEy polymer is PE3, whose sequence is, for example, PE-PEEEE-PEE-PEEEEE-PEEE... in the case of random polymerization, with an average y:x ratio of 3, and PEEE-PEEE-PEEE-PEEE-PEEE... in the case of regular polymerization.

[0079] In some embodiments, the host thiophene conjugated polymer is a dioxythiophene copolymer P where x=1 and y=1, 2, or 3, corresponding to PE1, PE2, and PE3, respectively. x E y An example of such a polymer is represented by the following chemical formula:

[0080] [ka]

[0081] Example

[0082] 1. Ability to form cross-linked siloxane networks

[0083] The following various embodiments relate to a crosslinkable silane precursor having at least three chlorine groups, namely, crosslinkable 1,6-bis(trichlorosilyl)hexane (hereinafter referred to as "C6-Si"), and a dioxothiophene random copolymer containing one soluble 3,4-propylenedioxythiophene (ProDOT) unit and three electron-rich 3,4-ethylenedioxythiophene (EDOT) units, namely, a host conjugated polymer (host CP). The dioxothiophene random copolymer has the chemical formula ProDOT1-EDOT3 (PE3). For comparison, two non-crosslinkable silane precursors with one or two chlorine groups, which cannot form a crosslinked siloxane network, were also evaluated. The two non-crosslinkable silane precursors with one or two chlorine groups are referred to as the linear crosslinkable silane precursor (L6-Si) and the flowable silane precursor (F-Si), respectively. The chemical formulas of L6-Si and F-Si are shown below.

[0084] [ka]

[0085] Atomic force microscopy (AFM) phase images of the pure thiophene-conjugated polymer PE3 and conductive polymer composite thin films prepared using various silane precursors, C6-Si, L6-Si, and F-Si, are shown in Figures 2 and 3. As shown in Figure 2(B), the conductive polymer composite thin film prepared from C6-Si and PE3 exhibited clear phase separation between the thiophene-conjugated polymers, whereas this phase separation was not observed in the pure PE3 thin film, as shown in Figure 2(A). On the other hand, as shown in Figure 3, the conductive polymer composite thin films prepared from L6-Si and PE3 (Figure 3(A)) and F-Si and PE3 (Figure 3(B)) both exhibited no clear phase separation. This indicates that L6-Si can form a linear matrix that can bend and twist within the host during thin film processing, and F-Si can form a flowable matrix, but they are unable to form a crosslinked network through condensation reactions within the entire composite. The formation of a cross-linked siloxane network in the C6-Si / PE3 composite is indicated by the characteristic Si-O-Si stretching vibration at approximately 1050 cm, as indicated by the arrow in Figure 4. -1 and 1150cm -1 This is further confirmed by monitoring the presence of IR bands. Due to the lack of trichlorosilyl groups that form a crosslinked network during the condensation reaction, the L6-Si and F-Si composites form linear and fluid matrices, resulting in fewer Si-O-Si stretching vibration bands in their IR spectra. When the host CP solution was mixed with the silane precursor solution, a conductive polymer composite immediately and spontaneously formed in the solution. The solution was coated onto a substrate to form a thin film, followed by thermal annealing at 393 K. Interestingly, the temperature-dependent in situ IR spectra of the C6-Si / PE3 composite were well overlapped before and after thermal annealing at 393 K, as shown in Figure 5, indicating the simultaneous formation of a crosslinked siloxane network at room temperature.

[0086] 2. Effect of silane precursor concentration on electrical performance

[0087] The concentration of silane precursor significantly affects the electrical performance of conductive polymer composites. However, conductive polymer composites containing various silane precursors and thiophene conjugated polymers may have different optimal concentrations. Here, we investigated the effect of the concentration of specific silane precursors (C6-Si, L6-Si, and F-Si) on the electrical performance of conductive polymer composites containing a specific conjugated polymer (PE3). Figure 6 shows the electrical conductivities of three conductive polymer composites containing different concentrations of silane precursor: C6-Si / PE3, L6-Si / PE3, and F-Si / PE3. To better visualize the concentration differences, the conductivities are plotted on a logarithmic scale. Among the various silane precursor contents, all three conductive polymer composites exhibited the highest conductivity when containing approximately 56 wt% silane precursor. The conductivity of PE3 was only 10 -6While the conductivity of the three conductive polymer composites was 0.1 S / cm, most of them were above 0.1 S / cm. This significant improvement in conductivity is attributed to the presence of chlorine (a p-type dopant) and silanol (a well-known electron trap). This can be confirmed by the fact that the most phase separation was observed in C6-Si / PE3, which contained approximately 56 wt% silane precursor, as shown in the AFM phase image in Figure 7(B). Excessive silane precursor resulted in a lack of conductive domains in the composite, which resulted in decreased conductivity in all three composites containing approximately 72 wt% silane precursor in Figure 6. This is likely due to insufficient and isolated conductive domains in the composite, as shown in Figure 7(A). In addition, among the three silane precursors (crosslinked C6-Si, non-crosslinked L6-Si, and non-crosslinked F-Si), the highest conductivity increase (up to six orders of magnitude) was achieved with C6-Si / PE3 containing approximately 56 wt% silane precursor. On the other hand, the conductivity increase was low for both L6-Si / P and F-Si / PE3. When containing 56 wt% silane precursor, the C6-Si / PE3 composite with a crosslinked network had the highest chlorine species incorporated among the three composites, resulting in the highest conductivity. Because approximately 56 wt% silane precursor was found to provide the best electrical performance for the conductive polymer composites, we will use approximately 56 wt% silane precursor in all subsequent experiments unless another concentration is specified.

[0088] 3. Doping process

[0089] As shown in Figure 8, the doping process was monitored using UV-vis absorption spectra of pure PE3 and three conductive polymer composites containing approximately 56 wt% of the silane precursor: C6-Si / PE3, L6-Si / PE3, and F-Si / PE3. Each spectrum was normalized by the absorbance at 400 nm. Upon mixing the host CP with the silane precursor, a doping process simultaneously occurs between the dopant contained in the silane precursor and the host CP, resulting in the formation of a crosslinked siloxane network. The chlorine groups contained in the silane precursor act as dopants. As shown in the shaded wavelength region of Figure 8, three critical peaks (a neutral absorption band at approximately 550 nm, a polaron peak at approximately 850 nm, and a λ peak) are observed. max The neutral absorption band at about 550 nm is usually related to the band gap energy required to excite an electron from the valence band to the conduction band. The decrease in the neutral absorption peak indicates that the doping process has increased the conductivity of the polymer. The polaron peak (about 850 nm) and the bipolaron peak (about λ max ) is typically used to indicate the generation of various charge carriers along the polymer backbone upon doping. The neutral absorption peak at approximately 550 nm decreased for all three silane / PE3 composites compared to the PE3 polymer, indicating the doping process occurred in all three composites. The increase in both the polaron and bipolaron peaks further indicates the formation of the doping process in all three composites. Figure 8 also shows that both the polaron and bipolaron peaks increased most significantly for the C6-Si / PE3 composite, followed by the L6-Si / PE3 and F-Si / PE3 composites. This increase corresponds to the abundance of chlorine groups in the silane precursors. The more chlorine groups present, the greater the doping effect, resulting in an increase in both the polaron and bipolaron peaks.

[0090] 4. Thermal stability provided by cross-linked siloxane network and abundant doping

[0091] As mentioned above, all three different techniques (AFM, IR, and UV-vis absorption) revealed that the conductive polymer composite with a crosslinkable silane precursor (C6-Si / PE3) exhibited both a crosslinked siloxane network and a more extensive doping process compared to the other composites (L6-Si / PE3 and F-Si / PE3) constructed with a non-crosslinkable silane precursor and less chlorine dopant. Correspondingly, the thermal stability of these three composites was tested to investigate the influence of the crosslinked siloxane network and the extensive doping process on thermal stability. - Anions readily diffuse from non-thermally stable systems upon thermal annealing at 100°C (373K), resulting in a decrease in conductivity. If the thermal stability of a composite is good, its conductivity will not change significantly upon heating. Therefore, we investigated the change in conductivity of C6-Si / PE3, L6-Si / PE3, and F-Si / PE3 composites containing approximately 56 wt% silane precursor before and after 1 hour of thermal annealing at 373K. As shown in Figure 9, after 1 hour of thermal annealing at 373K, only the C6-Si / PE3 composite still maintained more than 90% of its original conductivity, demonstrating stable high conductivity. Meanwhile, the other composites with linear and flowable matrices showed little conductive behavior. These results indicate that the crosslinked siloxane network and doping process significantly improved thermal stability, while the linear or flowable silane matrix achieved little improvement in thermal stability. Because the dopant is contained in the silane precursor, the doping process occurs simultaneously with the crosslinking process. Herein, both the processes of doping and crosslinked siloxane network formation can be simplified as the process of crosslinked network formation.

[0092] The electrical thermal stability was further investigated by monitoring the dedoping process of the composites at high temperatures through in situ temperature-dependent UV-vis absorption spectra of the three composites (C6-Si / PE3, L6-Si / PE3, and F-Si / PE3) at various temperatures ranging from 293 K to 453 K, as shown in Figures 10(A)-(C). For each conductive polymer composite thin film, all absorbance values ​​at various temperatures were normalized to the absorbance at 400 nm at 293 K. As shown in Figure 10(A), the C6-Si / PE3 composite exhibited a λ attributed to bipolaron absorption at room temperature. max (approximately 1600 nm) shows a broad signal. maxThe bipolaron absorption peak at λ = ≈1600 nm decreased with increasing temperature. The polaron peak at λ = ≈850 nm increased with increasing temperature to 373, 393, and 413 K, then decreased slightly with increasing temperature to 433 and 453 K (although still higher than the peak at 373 K). The neutral peak at λ = ≈550 nm increased with increasing temperature. The increase in the polaron peak below 413 K is attributed to the formation of polarons from bipolarons exceeding the dedoping process. With increasing temperature to 433 K, the dedoping process dominates over the dedoping process, resulting in a slight decrease in the polaron peak. In the undoped state of conjugated polymers, the neutral peak at ≈550 nm typically dominates. The decrease in the bipolaron peak at approximately 1600 nm and the increase in the neutral peak at approximately 550 nm indicate the effectiveness of the dedoping process. Comparing Figures 10(A)–(C), it is observed that at all test temperatures, C6-Si / PE3 exhibits much higher bipolaron and polaron peaks and a much lower neutral peak than the L6-Si / PE3 and F-Si / PE3 composites. This indicates that C6-Si / PE3 has higher conductivity at the test temperatures. Meanwhile, C6-Si / PE3 exhibits a smaller decrease in the polaron and bipolaron peaks and a smaller increase in the neutral peak than the L6-Si / PE3 and F-Si / PE3 composites. The small changes in the polaron, bipolaron, and neutral peak intensities demonstrate the thermal stability of the C6-Si / PE3 composite.

[0093] Since the intensity of the bipolaron peak and the neutral peak more directly reflects the conductivity of the composite, the optical density ratio between the neutral peak (approximately 550 nm) and the bipolaron peak (approximately 1600 nm) was used to indicate the electrical conductivity and thermal stability of the composite. The smaller the optical density ratio of a composite, the higher the conductivity of the composite. The higher the temperature, the smaller the change in the optical density ratio of the composite, indicating higher thermal stability of the composite. Furthermore, the change in the optical density ratio at various elevated temperatures was evaluated for three silane / PE3 composites (C6-Si / PE3, L6-Si / PE3, and F-Si / PE3). As shown in Figure 11, the C6-Si / PE3 composite had the smallest optical density ratio among the three composites, and also the smallest change in the optical density ratio with increasing temperature. This indicates that the C6-Si / PE3 composite has the highest thermal stability among the three composites. As mentioned above, only the C6-Si / PE3 composite forms a crosslinked siloxane network. The crosslinked siloxane network in the composite effectively confines (confines) the doped polymer, restricting the movement of the doped polymer chains, thereby significantly reducing the morphological changes and dopant diffusion at high temperatures, resulting in improved thermal stability of the conductive polymer composite.

[0094] 5. Effect of the number of spacer carbon atoms in the crosslinkable silane precursor on the thermal stability of the composite

[0095] The number of spacer carbon atoms in the crosslinkable silane precursor can increase the rigidity of the crosslinked network, which can further improve the thermal stability of the composite. To investigate the effect of the number of spacer carbon atoms in the crosslinkable silane precursor on the thermal stability of the composite, two other crosslinkable chlorosilanes, namely, monotrichlorosilyl (C M Hexyltrichlorosilane having 10 spacers (C 101,10-bis(triphorosilyl)decane with a siloxane-containing siloxane (C6-Si) was compared with C6-Si. As shown in Figure 12, the conductivity of the three composites was investigated in situ at 353 K for 6 hours. All data were normalized to the corresponding conductivity at time zero. For ease of visualization, the normalized conductivity is shown on a logarithmic scale. The non-crosslinked silane precursor, L6-Si, was shown as a control. As shown in Figure 12, the conductivity of L6-Si / PE3 dropped sharply by almost two orders of magnitude in the first hour and remained at about 5% of its as-spun conductivity under prolonged thermal stress. In contrast, all three C-Si / PE3 composites showed little change in conductivity. C6-Si / PE3 and C6-Si / PE3, which have flexible spacers in the siloxane network, exhibited almost no conductivity change. 10 The conductivity of the / PE3 composite material decreased to about 60% of that of the spin-coated material, while the C M The -Si / PE3 composite maintains its electrical conductivity as spin-coated. M The excellent thermal stability of the L6-Si composite is attributed to the stiffest cross-linked network without flexible spacers in the silane precursor. The large decrease in conductivity of the L6-Si / PE3 composite indicates poor thermal stability due to the lack of a cross-linked siloxane network.

[0096] The effect of the number of spacer carbons on the thermal stability of the conductive polymer composite thin film of the present disclosure was investigated using the 1050 cm stretching vibration, which corresponds to the Si-O-Si stretching vibration. -1 and 1150cm -1 As shown in Figures 13(A) to 13(C), the C6-Si / PE3, C 10 -Si / PE3, C M The IR spectra of the three conductive polymer composites of -Si / PE3 were compared before and after thermal annealing at 393 K for 30 and 60 minutes. As indicated by the arrows in the figure, all three composites exhibited a peak at approximately 1050 cm -1 and approximately 1150 cm -1 It shows a clear IR band. M -Si / PE3 composite material has a peak at 1050-1150 cm-1 The broadest Si-O-Si band is observed between C and C, which indicates the most abundant siloxane network. M The IR spectra of the -Si / PE3 composite overlap each other, which indicates that the composite has the highest thermal stability. M The composites were prepared using the C-Si silane precursor, which has the highest thermal stability. M Due to the introduction of the -Si silane precursor, in all the following experiments, C M -Si silane precursor is used.

[0097] 6. Effect of host CP on electrical performance and thermal stability

[0098] C-Si / P x E y The electrical performance of the composite also depends on the oxidation potential of the CP. To investigate the effect of different host CPs on the electrical performance of the conductive polymer composite thin films of this disclosure, we compared composites made from three different host CPs. These three CPs are similar dioxythiophene copolymers containing soluble 3,4-propylenedioxythiophene (ProDOT) units and electron-rich 3,4-ethylenedioxythiophene (EDOT) units. x -EDOT y , P x E y (x=1; y=1, 2, 3 (separate for the three host CPs)). As shown in Figure 14, M The conductivity of the composites made from the -Si silane precursor and each CP (PE1, PE2, PE3) was compared to that of the pure polymer. After doping with the chlorosilane precursor, the conductivity of all three CPs increased significantly. For ease of visualization, the conductivity is shown on a logarithmic scale. With the pure host CP, the conductivity of PE1, PE2, and PE3 is 10 -7 , 10 -6 , 10 -6 S / cm. By mixing the polymer solution with the chlorosilane precursor, MWhen doped with -Si, the conductivity of PE1, PE2, and PE3 increased by 10 -6 , 10 -1 , and increased to 6 S / cm. The magnitude of the increase in conductivity for PE1, PE2, and PE3 was 10 3 , 10 5 , 10 6 The highest conductivity and the largest increase in conductivity were observed for PE3, which indicates that PE3 is the most susceptible to doping among the three PCs. x E y This is thought to be due to the fact that the increase in the EDOT content in the repeating units of the copolymer reduces the oxidation onset potential and electron gap (Eg) of the polymer.

[0099] 3 Cs with the same variety of CPs as above M -Si / P x E y The thermal stability of the composites was compared by the conductivity change under thermal stress shown in Figure 15 and the in situ temperature-dependent UV-vis absorption spectra shown in Figures 16(A)-(C). Figure 15 shows the in situ normalized conductivity change measured over 24 hours at 353 K. All data are from the zero C M The conductivity was normalized to that of -Si / PE3. For ease of visualization, the normalized conductivity is shown on a logarithmic scale. After baking at 353 K for 24 hours, C M -Si / PE2 and C M The conductivity of -Si / PE3 was almost unchanged (more than 80% of the original conductivity), but M The conductivity of -Si / PE1 increased slightly during the first few hours and then decreased dramatically after prolonged baking (approximately 19 hours), losing more than 90% of its original conductivity. M -Si / PE2 and C M CM-Si / PE3 shows higher thermal stability than CM-Si / PE1. Figure 16(A)-(C) shows the thermal stability of the three C M -Si / P x E yThe in situ temperature-dependent UV-vis absorption spectra of the composites are shown. For each conductive polymer composite thin film, the spectra at various temperatures were normalized to the absorbance at 400 nm at 293 K. At 293 K, C M The -Si / PE3 composites exhibited very high bipolaron absorption and very low spontaneous absorption, which is due to the C M The polaron absorption peak increased from 293 K to 393 K and decreased slightly from 413 K to 453 K. However, the final polaron absorption peak at 453 K still showed a clearly higher peak and higher intensity than the initial peak at 293 K, which is indicative of the C M This shows that the thermal stability of -Si / PE3 is high. M -Si / PE2 is C M As with -Si / PE3, the absorption peaks tend to change with increasing temperature, and the bipolaron and polaron peaks decrease. M -Si / PE1 shows even lower bipolaron and polaron band absorption and a more reduced polaron band absorption, which indicates a lower electrical conductivity and a lower thermal stability. M -Si / PE3 showed the best thermal stability.

[0100] 7. Solvent resistance of the composite thin film of the present disclosure

[0101] The conductive polymer composite material of the present disclosure not only has excellent thermal stability, but also has excellent water resistance and organic solvent resistance due to the entanglement of polymers within the crosslinked siloxane network. The solvent resistance of the C-Si / PE3 composite material of the present disclosure was confirmed by monitoring the changes in conductivity and UV-vis absorption spectrum before and after immersion in water or organic solvents commonly used in the processing of conductive polymer composites. M As shown in Figure 17, the C MThe IV curve of the -Si / PE3 composite after immersion in water for 1 hour (gray line) is only slightly deviated from the original IV curve (black line) before immersion in water. M The UV-vis absorption spectra of the -Si / PE3 composite before and after water treatment and after 1 minute of chloroform treatment are shown. For each treatment, the entire spectrum was normalized to the absorbance at 400 nm. The spectrum after 1 hour of water treatment showed a decrease of less than 10% compared to the spectrum before water treatment. In addition, the C M The -Si / PE3 composite also showed excellent robustness against organic solvents. After immersion in chloroform, the absorption peak intensity only slightly decreased, which is due to the C M -Si / PE3 composite exhibits excellent solvent resistance.

[0102] C M The excellent organic solvent resistance of the -Si / PE3 composite thin film can be visualized as shown in Figure 19(A)-(C). M The bottom halves of each of the C-Si / PE3 composite thin films were immersed in a chloroform bath for 1 minute. A clear color change was observed with the naked eye between the top and bottom halves of the pure PE3 thin film. However, the C M No significant color change was observed between the upper and lower halves of either the -Si / PE3 composite thin film or the glass substrate. M This indicates that the -Si / PE3 composite thin film has high organic solvent resistance. Similar results were observed in acetone, another commonly used organic solvent. M The excellent solvent resistance of the -Si / PE3 composite thin film was reconfirmed.

[0103] In another aspect, the present disclosure provides a method for producing a conductive polymer composite that is thermally stable and solvent resistant.

[0104] Doping is considered a promising approach to achieving robust electrical conductivity of conjugated polymers at high temperatures and in various solvent environments. However, designing and synthesizing simple and efficient doping methods to achieve thermally stable and solvent-resistant systems remains a significant challenge. The disclosed method for fabricating thermally stable and solvent-resistant conductive polymer composite thin films involves simply mixing a conjugated polymer with a crosslinkable silane precursor in air at room temperature. During mixing, crosslinking and doping occur simultaneously, resulting in a sol-gel solution of the disclosed thermally stable and solvent-resistant conductive polymer composite. The disclosed thermally stable and solvent-resistant conductive polymer composite thin films can be easily fabricated using conventional film coating techniques.

[0105] The present disclosure provides a method for producing a thermally stable, solvent-resistant conductive polymer composite material, comprising the steps of: preparing a crosslinkable silane precursor solution containing a crosslinkable silane precursor and a solvent; preparing an electron-rich host thiophene conjugated polymer solution containing an electron-rich host thiophene conjugated polymer and a solvent; and mixing the crosslinkable silane precursor solution with the electron-rich host thiophene conjugated polymer solution in a crosslinkable silane precursor ratio ranging from 0.1 to 90 wt % and reacting for a reaction time of up to 168 hours to produce a solution containing a conductive polymer composite material. The present disclosure also optionally includes, after the step of preparing the solution containing the conductive polymer composite material, adding a hydrogen-bond blocking solvent to break hydrogen bonds and improve solution consistency. The resulting solution containing the conductive polymer composite material (composite sol-gel solution) can then be coated onto a substrate using conventional film coating techniques to form a thin film of the present disclosure's thermally stable, solvent-resistant conductive polymer composite material. The above preparation method can be used to fabricate conductive polymer composites from doped electron-rich thiophene conjugated polymers and crosslinked siloxane networks as described in the first embodiment.

[0106] In some embodiments, the solvent for preparing the solution of the crosslinkable silane precursor and the solvent for preparing the solution of the electron-rich host thiophene conjugated polymer are selected from one or more aprotic solvents, such as chloroform, dichloromethane, nitromethane, or toluene.

[0107] In some embodiments, a hydrogen bond blocking solvent is a solvent that can be used to break hydrogen bonds. Examples of hydrogen bond blocking solvents include alcohols and acetone.

[0108] In some embodiments, the thin film can be formed using methods known in the art, such as spin coating, slot die coating, spray coating, bar coating, and the like.

[0109] In some embodiments, the annealing methods used in the coating process include thermal annealing and IR radiation annealing.

[0110] In one embodiment, a method for forming a C6-Si / PE3 composite thin film is provided. First, a PE3 solution is prepared in dichloromethane at a concentration of 25 mg / mL, and a C6-Si solution is prepared in dichloromethane at a concentration of 80 mg / mL. The two solutions are mixed together, with approximately 56 wt% C6-Si. After mixing for 48 hours or more, the mixture transforms into a sol-gel solution. To form the thin film, 5-20 μl (preferably 10 μl) of ethanol is added to the sol-gel solution to break the hydrogen bonds and return the mixture to a solution state. The silane / PE3 composite is deposited on a glass substrate by spin-coating at 1500 rpm for 60 seconds. After spin-coating, the thin film is dried in an oven at 353 K for 10 minutes.

[0111] In another embodiment, C M A method for forming a thin film of Si / PE1 composite is provided. First, a solution of PE1 is prepared in chloroform at a concentration of 25 mg / mL. MThe -Si solution is prepared in dichloromethane, preferably at a concentration of 80 mg / mL. M -Si. After mixing for 24 hours, the mixture turns into a sol-gel solution. The sol-gel solution is deposited on a glass substrate by spin-coating at 1500 rpm for 60 seconds. After spin-coating, the thin film is dried in an oven at 353 K for 10 minutes.

[0112] In another embodiment, a method for forming a C6-Si / PE2 composite thin film is provided. First, a PE3 solution is prepared in chloroform at a concentration of 25 mg / mL, and a C6-Si solution is prepared in chloroform, preferably at a concentration of 80 mg / mL. The two solutions are mixed with 24 wt% C6-Si. After mixing for 24 hours, the mixture transforms into a sol-gel solution. The sol-gel solution is deposited on a glass substrate by spin-coating at a speed of 1500 rpm for 60 seconds. After spin-coating, the thin film is dried in an oven at 353 K for 10 minutes.

[0113] In another embodiment, a method for forming a C6-Si / ProDOT composite thin film is provided. First, a ProDOT solution is prepared in chloroform at a concentration of 25 mg / mL, and a heptyltrichlorosilane (C6-Si) solution is prepared in chloroform at a concentration of 80 mg / mL. These two solutions are mixed with 56 wt% C6-Si. After mixing for 90 hours, the mixture transforms into a sol-gel solution. For the thin film formation process, 5-20 μl (preferably 10 μl) of ethanol is added to the sol-gel solution to break the hydrogen bonds and return the mixture to a solution state. The C6-Si / ProDOT composite is deposited on a glass substrate by spin-coating at 1500 rpm for 60 seconds. After spin-coating, the composite thin film is dried in an oven at 353 K for 10 minutes. Overall, this disclosure describes a thermally stable and solvent-resistant conductive polymer composite material comprising a host thiophene conjugated polymer and a crosslinked siloxane network. The present disclosure also provides a manufacturing-friendly method for producing the disclosed composite material. To improve the stability of the doped system, we disclose an approach to simultaneously introduce both a dopant and a rigid, crosslinked siloxane network into the polymer system by simply mixing a host thiophene-conjugated polymer with a crosslinkable silane precursor. Thin films formed by the disclosed thermally stable and solvent-resistant conductive polymer composite can be applied to the fabrication of various devices, such as OLEDs and OECDs.

Claims

1. A conductive polymer composite material, comprising: a doped electron-rich host thiophene conjugated polymer; a crosslinked siloxane network; The conductive polymer composite material is characterized in that the crosslinked siloxane network is produced from a crosslinkable silane precursor represented by the following chemical formula: 【Chemical 1】 During the ceremony, n is an integer greater than 0, X is a monomer unit, and is an oxygen, a urea group (N ２ H ２ CO-), C １ -C ３０ Alkyl, C ２ -C ３０ Alkenyl, C ２ -C ３０ Alkynyl, C ２ -C ３０ Alkylcarbonyl, C １ -C ３０ Alkoxy, C ３ -C ３０ Alkoxyalkyl, C ２ -C ３０ Alkoxycarbonyl, C ４ -C ３０ Alkoxycarbonylalkyl, C １ -C ３０ Aminyl carbonyl, C ４ -C ３０ Aminyl alkyl, C １ -C ３０ Alkylaminyl, C １ -C ３０ Alkylsulfonyl, C ３ -C ３０ Alkylsulfonylalkyl, C ６ -C １８ Aryl, C ３ -C １５ Cycloalkyl, C ３ -C ３０ Cycloalkylaminyl, C ５ -C ３０ Cycloalkylalkylaminyl, C ５ -C ３０ Cycloalkylalkyl, C ５ -C ３０ Cycloalkyloxy, C １ -C １２ Heterocyclyl C １ -C １２ Heterocyclyloxy, C ３ -C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl and C ３ ~C ３０ heteroarylalkyl; R １ , R ２ , R ３ , R ４ , R ５ , and R ６ are each independently selected from hydrogen, a halide group, a hydroxyl group, a carboxyl group, C １ -C ３０ Alkyl, C ２ -C ３０ Alkenyl, C ２ -C ３０ Alkynyl, C ２ -C ３０ Alkylcarbonyl, C １ -C ３０ Alkoxy, C ３ -C ３０ Alkoxyalkyl, C ２ -C ３０ Alkoxycarbonyl, C ４ -C ３０ Alkoxycarbonylalkyl, C １ -C ３０ Aminyl carbonyl, C ４ -C ３０ Aminyl alkyl, C １ -C ３０ Alkylaminyl, C １ -C ３０ Alkylsulfonyl, C ３ -C ３０ Alkylsulfonylalkyl, C ６ -C １８ Aryl, C ３ -C １５ Cycloalkyl, C ３ -C ３０ Cycloalkylaminyl, C ５ -C ３０ Cycloalkylalkylaminyl, C ５ -C ３０ Cycloalkylalkyl, C ５ -C ３０ Cycloalkyloxy, C １ -C １２ Heterocyclyl C １ -C １２ Heterocyclyloxy, C ３ -C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl and C ３ ~C ３０ heteroarylalkyl; R １ , R ２ , R ３ , R ４ , R ５ , and R ６ at least three of are selected from the group consisting of chloride groups, bromine groups, hydroxyl groups, and alkyloxyl groups; R １ , R ２ , R ３ , R ４ , R ５ , and R ６ At least one of the first and second electrodes comprises a dopant.

2. A conductive polymer composite material, comprising: a doped electron-rich host thiophene conjugated polymer; a crosslinked siloxane network; The conductive polymer composite material is characterized in that the crosslinked siloxane network is produced from a crosslinkable silane precursor represented by the following chemical formula: 【Chemistry 2】 During the ceremony, R ７ , R ８ , R ９ , and R １０ Each of the groups may be selected from the group consisting of hydrogen, halide, hydroxyl, carboxyl, C １ -C ３０ Alkyl, C ２ -C ３０ Alkenyl, C ２ -C ３０ Alkynyl, C ２ -C ３０ Alkylcarbonyl, C １ -C ３０ Alkoxy, C ３ -C ３０ Alkoxyalkyl, C ２ -C ３０ Alkoxycarbonyl, C ４ -C ３０ Alkoxycarbonylalkyl, C １ -C ３０ Aminyl carbonyl, C ４ -C ３０ Aminyl alkyl, C １ -C ３０ Alkylaminyl, C １ -C ３０ Alkylsulfonyl, C ３ -C ３０ Alkylsulfonylalkyl, C ６ -C １８ Aryl, C ３ -C １５ Cycloalkyl, C ３ -C ３０ Cycloalkylaminyl, C ５ -C ３０ Cycloalkylalkylaminyl, C ５ -C ３０ Cycloalkylalkyl, C ５ -C ３０ Cycloalkyloxy, C １ -C １２ Heterocyclyl C １ -C １２ Heterocyclyloxy, C ３ -C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl and C ３ ~C ３０ heteroarylalkyl; R ７ , R ８ , R ９ , and R １０ at least three of are selected from the group consisting of chloride groups, bromine groups, hydroxyl groups, and alkyloxyl groups; R ７ , R ８ , R ９ , and R １０ At least one of the first and second electrodes comprises a dopant.

3. The conductive polymer composite material according to claim 1, The conductive polymer composite material is characterized in that the crosslinkable silane precursor contains a crosslinkable chlorosilane precursor represented by the following chemical formula: 【Chemistry 3】 During the ceremony, n is an integer greater than 0 and less than or equal to 13.

4. The conductive polymer composite material according to claim 3, The conductive polymer composite material is characterized in that the crosslinkable chlorosilane precursor contains a crosslinkable chlorosilane precursor having 6 or 10 spacer carbons, which is represented by the following chemical formula: 【Chemistry 4】

5. The conductive polymer composite material according to claim 2, The conductive polymer composite material is characterized in that the crosslinkable silane precursor contains a crosslinkable chlorosilane precursor represented by the following chemical formula: 【Chemistry 5】 During the ceremony, R １１ is a hydrogen, halide group, hydroxyl group, carboxyl group, C １ -C ３０ Alkyl, C ２ -C ３０ Alkenyl, C ２ -C ３０ Alkynyl, C ２ -C ３０ Alkylcarbonyl, C １ -C ３０ Alkoxy, C ３ -C ３０ Alkoxyalkyl, C ２ -C ３０ Alkoxycarbonyl, C ４ -C ３０ Alkoxycarbonylalkyl, C １ -C ３０ Aminyl carbonyl, C ４ -C ３０ Aminyl alkyl, C １ -C ３０ Alkylaminyl, C １ -C ３０ Alkylsulfonyl, C ３ -C ３０ Alkylsulfonylalkyl, C ６ -C １８ Aryl, C ３ -C １５ Cycloalkyl, C ３ -C ３０ Cycloalkylaminyl, C ５ -C ３０ Cycloalkylalkylaminyl, C ５ -C ３０ Cycloalkylalkyl, C ５ -C ３０ Cycloalkyloxy, C １ -C １２ Heterocyclyl C １ -C １２ Heterocyclyloxy, C ３ -C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl and C ３ ~C ３０ heteroarylalkyl.

6. The conductive polymer composite material according to claim 5, A conductive polymer composite material, characterized in that the crosslinkable chlorosilane precursor contains a crosslinkable chlorosilane precursor having monotrichlorosilyl, represented by the following chemical formula: 【Chemistry 6】

7. The conductive polymer composite material according to claim 1 or 2, The doped electron-rich host thiophene conjugated polymer comprises a p-type thiophene conjugated polymer having an oxidation potential 0.4 V lower than that of Ag / AgCl.

8. The conductive polymer composite material according to claim 1 or 2, The doped electron-rich host thiophene conjugated polymer comprises a copolymer represented by the following chemical formula: 【Chemistry 7】 During the ceremony, a and b are integers of 0 or more, The values ​​of a and b indicate the ratio of the two monomer units (but do not necessarily indicate the exact sequence of the monomers in the polymer), n is an integer greater than 0, R １２ , R １３ , R １４ , and R １５ are each independently hydrogen, C １ -C ３０ Alkyl, C ２ -C ３０ Alkenyl, C ２ -C ３０ Alkynyl, C ２ -C ３０ Alkylcarbonyl, C １ -C ３０ Alkoxy, C ３ -C ３０ Alkoxyalkyl, C ２ -C ３０ Alkoxycarbonyl, C ４ -C ３０ Alkoxycarbonylalkyl, C １ -C ３０ Aminyl carbonyl, C ４ -C ３０ Aminyl alkyl, C １ -C ３０ Alkylaminyl, C １ -C ３０ Alkylsulfonyl, C ３ -C ３０ Alkylsulfonylalkyl, C ６ -C １８ Aryl, C ３ -C １５ Cycloalkyl, C ３ -C ３０ Cycloalkylaminyl, C ５ -C ３０ Cycloalkylalkylaminyl, C ５ -C ３０ Cycloalkylalkyl, C ５ -C ３０ Cycloalkyloxy, C １ -C １２ Heterocyclyl C １ -C １２ Heterocyclyloxy, C ３ -C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl and C ３ ~C ３０ heteroarylalkyl; R １２ , R １３ , R １４ , and R １５ At least one of the atoms is electron rich.

9. 9. The conductive polymer composite material according to claim 8, The doped electron-rich host thiophene conjugated polymer comprises a copolymer represented by the following chemical formula: 【Chemistry 8】 R １６ , R １７ , R １８ , and R １９ are each independently hydrogen, C １ -C ３０ Alkyl, C ２ -C ３０ Alkenyl, C ２ -C ３０ Alkynyl, C ２ -C ３０ Alkylcarbonyl, C １ -C ３０ Alkoxy, C ３ -C ３０ Alkoxyalkyl, C ２ -C ３０ Alkoxycarbonyl, C ４ -C ３０ Alkoxycarbonylalkyl, C １ -C ３０ Aminyl carbonyl, C ４ -C ３０ Aminyl alkyl, C １ -C ３０ Alkylaminyl, C １ -C ３０ Alkylsulfonyl, C ３ -C ３０ Alkylsulfonylalkyl, C ６ -C １８ Aryl, C ３ -C １５ Cycloalkyl, C ３ -C ３０ Cycloalkylaminyl, C ５ -C ３０ Cycloalkylalkylaminyl, C ５ -C ３０ Cycloalkylalkyl, C ５ -C ３０ Cycloalkyloxy, C １ -C １２ Heterocyclyl C １ -C １２ Heterocyclyloxy, C ３ -C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl and C ３ ~C ３０ heteroarylalkyl.

10. 10. The conductive polymer composite material according to claim 9, The doped electron-rich host thiophene conjugated polymer comprises a copolymer represented by the following chemical formula: 【Chemistry 9】 R ２０ , R ２１ , R ２２ , and R ２３ are each independently hydrogen, C １ -C ３０ Alkyl, C ２ -C ３０ Alkenyl, C ２ -C ３０ Alkynyl, C ２ -C ３０ Alkylcarbonyl, C １ -C ３０ Alkoxy, C ３ -C ３０ Alkoxyalkyl, C ２ -C ３０ Alkoxycarbonyl, C ４ -C ３０ Alkoxycarbonylalkyl, C １ -C ３０ Aminyl carbonyl, C ４ -C ３０ Aminyl alkyl, C １ -C ３０ Alkylaminyl, C １ -C ３０ Alkylsulfonyl, C ３ -C ３０ Alkylsulfonylalkyl, C ６ -C １８ Aryl, C ３ -C １５ Cycloalkyl, C ３ -C ３０ Cycloalkylaminyl, C ５ -C ３０ Cycloalkylalkylaminyl, C ５ -C ３０ Cycloalkylalkyl, C ５ -C ３０ Cycloalkyloxy, C １ -C １２ Heterocyclyl C １ -C １２ Heterocyclyloxy, C ３ -C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl and C ３ ~C ３０ heteroarylalkyl.

11. The conductive polymer composite material according to claim 10, The doped electron-rich host thiophene conjugated polymer comprises a polymer represented by the following chemical formula: 【Chemistry 10】 During the ceremony, x is an integer greater than 0, y is an integer equal to or greater than 0; The values ​​of x and y indicate the ratio of the two monomer units (but do not necessarily indicate the exact sequence of the monomers in the polymer), The average ratio of y:x ranges from 0-10.

12. 12. The conductive polymer composite material according to claim 11, x is 1, A conductive polymer composite material, wherein y is 1, 2 or 3.

13. 1. A method for making a conductive polymer composite, comprising: preparing a solution of the crosslinkable silane precursor comprising the crosslinkable silane precursor and a solvent; preparing a solution of the electron-rich host thiophene conjugated polymer comprising the electron-rich host thiophene conjugated polymer and a solvent; mixing the solution of the crosslinkable silane precursor with the solution of the electron-rich host thiophene conjugated polymer in a ratio of the crosslinkable silane precursor in the range of 0.1 to 90 wt % and reacting for a reaction time of up to 168 hours to produce a solution comprising a conductive polymer composite; Including, The method comprises: After the step of preparing the solution containing the conductive polymer composite, The method further comprising adding a hydrogen bond blocking solvent to break hydrogen bonds and improve the consistency of the solution.

14. 14. The method of claim 13, wherein the solvent for preparing the solution of the crosslinkable silane precursor and the solvent for preparing the solution of the electron-rich host thiophene conjugated polymer are selected from one or more aprotic solvents.

15. 14. The method of claim 13, The method, wherein the hydrogen bond blocking solvent comprises at least one of an alcohol or acetone.

16. A device incorporating a thin film made of the conductive polymer composite material of claim 1 or 2.

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