An electron-transporting organic ion-electron hybrid conductor, preparation method thereof and applications thereof

Abstract

The electron-transporting organic ion-electron hybrid conductor of the present invention uses benzodifurandione as the device block material, has good solution processability and electrochemical cycling stability, and can be used as the material for electron-transporting electrochemical transistors. Compared with the existing n-type electrochemical transistor materials, it has a higher transconductance and a faster response speed. Due to the introduction of side chains containing small molecule structures or polymer structures, its alcohol solubility has been significantly improved, thus meeting the requirements of orthogonal solvent processing during the preparation of multilayer organic electronic devices. Since the material of the present invention has a high electron conductivity, it can significantly improve the electron transport efficiency of the electron transport layer in organic electronic devices, thereby improving the device performance and meeting the requirements of large-area device processing.

Description

Technical Field

[0001] The present invention belongs to the field of organic polymer materials, and particularly relates to an electron-transporting organic ion-electron hybrid conductor, a preparation method thereof, and an application thereof. Background Art

[0002] Organic polymers with a π-conjugated system are conducive to the transport of charge carriers in their conjugated main chains, thereby endowing the materials with properties such as semiconductors and conductors, and are widely used in fields such as organic solar cells (OPV), organic light-emitting diodes (OLED), and organic field-effect transistors (OFET). With the in-depth research, conjugated polymers that can simultaneously transport ionic charges and electronic charges (usually referred to as organic mixed ionic-electronic conductors (OMIEC)) have attracted attention. When OMIEC is combined with an electrolyte solution, the ion migration can be controlled by potential induction and a reversible doping and de-doping process within the OMIEC film can be achieved, thereby promoting electrochemical oxidation and reduction reactions. Based on this principle, through the addition of different electrolyte solutions and target substances in the solution / film, OMIEC has been used in fields such as sensors, biomedicine, and environmental monitoring. Its high sensitivity and selectivity make it an ideal material for preparing high-performance sensors, which can be used to detect parameters such as gases, humidity, and temperature in the environment. At the same time, OMIEC can also be used to prepare biosensors for analyzing specific molecules and biomarkers in biological samples. In addition, OMIEC has advantages such as flexibility and solution processability, which have promoted the development of various electronic devices including bioelectronics, neuromorphic computing, solar cells, and energy storage technologies.

[0003] Currently, the commercially available organic mixed ionic-electronic conductor material is mainly poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS). The conjugated main chain poly(3,4-ethylenedioxythiophene) in it carries a positive charge and forms an electrostatic interaction with polystyrene sulfonate to achieve aqueous solution processing. However, due to the certain acidity of polystyrene sulfonate, it may have an adverse impact on the device stability and physiological compatibility when preparing the corresponding electronic devices or for biological monitoring. In addition, the main chain of PEDOT:PSS mainly transports holes and is accompanied by the transport of anions between the chains and in the electrolyte solution, showing p-type transistor performance when preparing integrated circuits. In practical applications, the complete operation of a circuit usually requires the cooperation of n-type and p-type transistors. Therefore, a stable and efficient organic mixed ionic-electronic conductor material with a main chain that can transport electrons is needed.

[0004] Recently, the literature (A solution-processed n-type conducting polymer with ultrahigh conductivity. Nature, 2022, 611, 271.) and the patent (An n-type conjugated polymer and its preparation method and application. Application No.: 202110679959.2) have disclosed the n-type conducting polymer poly(benzodifurandione) (PBFDO) and its preparation method, which can achieve efficient electron transport in the polymer backbone and achieve an electron conductivity of more than 2000 S / cm. However, due to its high hydrophobicity, it is difficult to form good contact with the electrolyte solution; and the backbone spacing is too close, making it difficult for ions to move rapidly within the thin film, resulting in a slow response speed of the obtained device and making it difficult to combine with existing p-type transistors to fabricate logic circuits. Therefore, its structure needs to be improved to enhance its ionic conductivity and the response speed of the corresponding device. Summary of the Invention

[0005] Therefore, the object of the present invention is to provide an electron-transporting organic ion-electron hybrid conductor, which while maintaining high electron conductivity, effectively expands the chain spacing and improves the ion transport performance within the material.

[0006] The present invention discloses an electron-transporting organic ion-electron hybrid conductor (PBFDO-PEGx), and the electron-transporting organic ion-electron hybrid conductor is selected from the following structures:

[0007]

[0008] wherein, Y is selected from O, S, N, Se, Te or N-R2;

[0009] n is a positive integer from 1 to 2000, and n is not 1;

[0010] m and k are positive integers;

[0011] The linking unit is a conjugated unit that can form π-electron delocalization with adjacent copolymerization units;

[0012] The R1 is selected from alkyl derivatives or aryl derivatives, or a combination of the above optional objects;

[0013] wherein, all carbon atoms on the alkyl derivative are unsubstituted, or one or more carbon atoms are substituted by one or more of oxygen atom, nitrogen atom, amino group, sulfone group, carbonyl group, aryl group, alkenyl group, alkynyl group, ester group, cyano group, nitro group;

[0014] All hydrogen atoms on the alkyl derivative are unsubstituted, or one or more hydrogen atoms are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkenyl, and alkynyl;

[0015] The aryl derivative is selected from groups containing one or more benzene ring structures, and all hydrogen atoms on all benzene rings are unsubstituted,

[0016] or

[0017] one or more hydrogen atoms at any position on one or more benzene rings are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkenyl, alkynyl, carboxyl, ester group, cyano, or nitro;

[0018] The alkyl derivative or aryl derivative is selected from small molecule structures or polymer structures.

[0019] Specifically, the polymer structure includes but is not limited to polyethylene glycol, polypropylene glycol, and polybutylene glycol.

[0020] R2 is selected from one or more of alkyl derivatives, alkylene derivatives, and aryl derivatives.

[0021] The Ar is the conjugated part in the n-type conjugated polymer or n-type conjugated polymer structure containing counter ions, and the structure of M is selected from one of aromatic rings, heteroaromatic rings, fused aromatic rings, and fused heteroaromatic rings;

[0022] Further, the R1 includes a polymer structure containing polyol units.

[0023] Furthermore, the R1 is a polymer structure containing oligomeric polyol units.

[0024] Further, the R2 is selected from straight-chain alkyls with 1 to 20 carbon atoms or branched-chain alkyls with 1 to 20 carbon atoms;

[0025] Among them, all hydrogen atoms on the straight-chain alkyl with 1 to 20 carbon atoms or the branched-chain alkyl with 1 to 20 carbon atoms are unsubstituted,

[0026] or, one or more hydrogen atoms on the straight-chain alkyl with 1 to 20 carbon atoms or the branched-chain alkyl with 1 to 20 carbon atoms are substituted by other elements.

[0027] Preferably, the R2 is selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0028] Preferably, the number of carbon atoms of R2 includes but is not limited to 1, 2, 3, 4, 5, 6, 7, 8.

[0029] Further, Ar is selected from phenyl, biphenyl, indanyl, naphthyl, thienyl, furyl, pyrrolyl, pyridyl, imidazolyl, acridinyl, azetidinyl, azocinyl, benzimidazolyl, benzofuryl, benzothienyl, benzoxazolyl, benzoxazolinyl, benzothiazolyl, benzotriazolyl, benzotetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2-pyrrolidone, 2H-pyrrole, quinazolinyl, quinolinyl, 4H-quinolizine, quinoxalinyl, quinuclidinyl, tetrazolyl, tetrahydrofuryl, tetrahydroisoquinoline, tetrahydroquinoline, 6H-1,2,5-thiadiazine, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, thianthrenyl, thiazolyl, thienyl, thiazolopyridine, thienothiazole, thienoxazole, thienimidazole, thienyl, triazinyl, 1,2,3-triazole, 1,2,4-triazole, 1,2,5-triazole, 1,3,4-triazole and xanthenyl, quinolinyl, isoquinolinyl, phthalazinyl, quinazolinyl, and derivatives of the above optional objects, and one or more of the above any one or more optional objects combined in any form.

[0030] Further, Ar includes but is not limited to the following structures:

[0031]

[0032] Among them, the dashed line --- in the aromatic ring indicates that it is fused with the adjacent five-membered ring here, that is, sharing a ring edge;

[0033] R8 - R 13 independently are independently selected from one or more of a hydrogen atom, an aryl derivative, and an alkyl derivative;

[0034] All carbon atoms on the alkyl derivative or alkylene derivative are unsubstituted, or one or more carbon atoms are substituted by one or more of an oxygen atom, an amino group, a sulfone group, a carbonyl group, an aryl group, an alkenyl group, an alkynyl group, an ester group, a cyano group, and a nitro group;

[0035] All hydrogen atoms on the alkyl derivative or alkylene derivative are unsubstituted, or one or more hydrogen atoms are substituted by one or more of a halogen, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group;

[0036] The aryl derivative is selected from groups containing one or more benzene ring structures, where all hydrogen atoms on all benzene rings are unsubstituted,

[0037] or

[0038] One or more hydrogen atoms at any position on one or more benzene rings are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkenyl, alkynyl, carboxyl, ester group, cyano or nitro.

[0039] Furthermore, the linking unit is selected from aromatic ring derivatives or conjugated units having intermolecular double bonds or intermolecular triple bonds.

[0040] Furthermore, the linking unit is selected from units containing the following conjugated structures:

[0041]

[0042] X is independently selected from S, O, Se or N-R7;

[0043] A is a carbon atom or a silicon atom;

[0044] R3-R7 are independently selected from one or more of aryl derivatives, alkyl derivatives, alkylene derivatives;

[0045] Wherein,

[0046] All carbon atoms on the alkyl derivative or alkylene derivative are unsubstituted, or one or more carbon atoms are substituted by one or more of oxygen atom, nitrogen atom, amino group, sulfone group, carbonyl group, aryl group, alkenyl group, alkynyl group, ester group, cyano group, nitro group;

[0047] All hydrogen atoms on the alkyl derivative or alkylene derivative are unsubstituted, or one or more hydrogen atoms are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkenyl, alkynyl;

[0048] The aryl derivative is selected from groups containing one or more benzene ring structures, wherein all hydrogen atoms on the benzene rings are unsubstituted,

[0049] or

[0050] One or more hydrogen atoms at any position on one or more benzene rings are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkenyl, alkynyl, carboxyl, ester group, cyano or nitro.

[0051] Specifically, the linking unit is a conjugated unit that can form π-electron delocalization with adjacent copolymer units, that is, the unit contains one or several π bonds, and these π bonds can form electron delocalization with π bonds in other adjacent units, so that π electrons can freely transfer and disperse in the main chain. The π bond can be a double bond or a triple bond.

[0052] The present invention also provides a preparation method of an electron-transporting organic ion-electron hybrid conductor, comprising the following steps:

[0053] S1. Graft a structure containing the R1 unit onto the halo-1H-indole-2,3-dione to obtain compound S1;

[0054] S2. Carry out a Stille coupling reaction between compound S1 and the trimethylstannylated linking unit, and purify to obtain compound S2;

[0055] S3. Blend the compound S2 with a DMSO solution of poly(benzodifurandione), heat for reaction, and purify to obtain the electron-transporting organic ion-electron hybrid conductor.

[0056] Further, in step S1, one or more hydrogens on the benzene ring of the halo-1H-indole-2,3-dione are substituted by halogens;

[0057] Among them, when one hydrogen atom on the benzene ring of the halo-1H-indole-2,3-dione is substituted by a halogen, the halogen is selected from one of chlorine, bromine, and iodine;

[0058] Or,

[0059] when multiple hydrogen atoms on the benzene ring of the halo-1H-indole-2,3-dione are substituted by halogens, one of the halogens is selected from one of chlorine, bromine, and iodine, and the remaining halogens are fluorine.

[0060] Specifically, the halogens on the benzene ring of the halo-1H-indole-2,3-dione are active and can undergo a Stille coupling with the trimethyltin compound on the linking unit to form a product; the active halogen is one of chlorine, bromine, and iodine, while fluorine does not have this reaction activity and will not participate in the Stille coupling.

[0061] Further, in step S2, the molar ratio of compound S2 to the trimethylstannylated linking unit is ≥2.

[0062] Further, in step S1, the R1 unit contains a polyol structure.

[0063] Further, the solvent is selected from one or more of water, aromatic solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, ketone solvents, and amide solvents.

[0064] Specifically, the above solvents are preferably common polar solvents in the art, and can be but are not limited to: tetrahydrofuran, methyltetrahydrofuran, dichloromethane, chloroform, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, trichlorobenzene, methanol, ethanol, propanol, ethylene glycol, isobutanol, propylene glycol, acetonitrile, formic acid, acetic acid, propionic acid, trifluoroacetic acid, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dimethylacetamide, acetone, butanone, cyclohexanone, methyl butanone, methyl ether, ethyl ether, propyl ether, pyridine, phenol, N-methylpyrrolidone, ethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylamine, tetramethylethylenediamine, trioctylamine, aniline, hexamethylphosphoric triamide; and a mixture of two or more of the above substances in any proportion.

[0065] Another object of the present invention is to provide an organic electrochemical transistor, comprising an electron-transporting organic ion-electron hybrid conductor.

[0066] Another object of the present invention is to provide an organic solar cell, comprising an electron-transporting organic ion-electron hybrid conductor and its blend with other substances.

[0067] Compared with the prior art, the main advantages of the present invention are as follows:

[0068] 1. The electron-transporting organic ion-electron hybrid conductor of the present invention has good solution processability and electrochemical cycling stability, and can be used as an electron-transporting electrochemical transistor material. Compared with the existing n-type electrochemical transistor materials, it has a higher transconductance and a faster response speed. Thus, it can be matched with transistors prepared using p-type materials to realize the preparation of integrated circuits, and has broad application potential in biological signal detection, physiological signal-electrical signal conversion, and logic calculation.

[0069] 2. Due to the introduction of side chains with small molecule structures or polymer structures in the electron-transporting organic ion-electron hybrid conductor of the present invention, its alcohol solubility has been significantly improved, thus meeting the requirements of orthogonal solvent processing during the preparation of multi-layer organic electronic devices. Since the material of the present invention has a high electron conductivity, it can significantly improve the electron transport efficiency of the electron transport layer in organic electronic devices, thereby improving device performance and meeting the requirements of large-area device processing. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 1H NMR spectrum of compound S1-1 prepared in Example 1 1 1H NMR spectrum;

[0071] Figure 21H NMR spectrum of compound S1 prepared in Example 2 1 ;

[0072] Figure 3 1H NMR spectrum of compound S2 prepared in Example 3 1 ;

[0073] Figure 4 Schematic diagram of the organic electrochemical transistor device prepared in Application Example 1;

[0074] Figure 5 Schematic diagram of the integrated circuit prepared in Application Example 2;

[0075] Figure 6 Schematic diagram of the structure of the organic solar cell device prepared in Application Example 3;

[0076] Figure 7 (a) Structure of PM6 used in the organic solar cell prepared in Application Example 3;

[0077] Figure 7 (b) Structure of Y6 used in the organic solar cell prepared in Application Example 3;

[0078] Figure 7 (c) Structure of PEDOT:PSS used in the organic solar cell prepared in Application Example 3;

[0079] Figure 7 (d) Structure of PFN-Br used in the organic solar cell prepared in Application Example 3;

[0080] Figure 8 J-V curve of the organic solar cell prepared in Application Example 3;

[0081] Figure 9 Water contact angles of different electron-transporting organic ion-electron hybrid conductors tested in Test Example 1;

[0082] Figure 10 (a) Output curve of the organic electrochemical transistor device in Test Example 2;

[0083] Figure 10 (b) Transfer and transconductance curves of the organic electrochemical transistor device in Test Example 3;

[0084] Figure 11 (a) Response time diagram of the organic electrochemical transistor device prepared using poly(benzodifurandione) as a raw material;

[0085] Figure 11 (b) Response time diagram of the organic electrochemical transistor device prepared using the electron-transporting organic ion-electron hybrid conductor of Example 4 as a raw material;

[0086] Figure 11 (c) is the response time diagram of an organic electrochemical transistor device prepared using the electron-transporting organic ion-electron hybrid conductor of Example 5 as a raw material;

[0087] In the figure: 1. Substrate; 2. Hole transport layer; 3. Active layer; 4. Electron transport layer; 5. Electrode; 6. Source electrode; 7. Drain electrode; 8. Substrate; 9. Electron-transporting organic ion-electron hybrid conductor; 10. Electrolyte; 11. Gate electrode. Detailed implementation manners

[0088] To more clearly illustrate the technical solutions of the present invention, the following examples are listed. Unless otherwise specified, the raw materials, reactions, and post-treatment means in the examples are common raw materials on the market and technical means well-known to those skilled in the art.

[0089] In the embodiments of the present invention, unless otherwise mentioned, the preparation steps related to organic solar cells all adopt conventional means well-known to those skilled in the art.

[0090] Poly(benzodifurandione) (PBFDO) was purchased from Dongguan Fuan Optoelectronic Co., Ltd.

[0091] Example 1

[0092] Preparation of Compound S1-1 (6-bromo-1-(but-3-yn-1-yl)-7-fluoroindoline-2,3-dione)

[0093] The preparation method of the compound S1-1 is as follows:

[0094]

[0095] 6-bromo-7-fluoro-2,3-dihydro-1H-indole-2,3-dione (500 mg, 2.05 mmol) and anhydrous potassium carbonate (311.5 mg, 2.255 mmol) were added to a 100 mL two-necked flask; subsequently, anhydrous N,N-dimethylformamide (35 mL) was added, and the mixture was evacuated and filled with argon three times to maintain an inert atmosphere; the reaction mixture was initially stirred at 80 °C for 30 min, then 4-bromo-1-butyne (408.9 mg, 8.2 mmol) was injected with a syringe, and the mixture was heated at 80 °C overnight. After cooling to room temperature, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography to obtain compound S1-1 (414 mg, yield: 68%). The 1 1H NMR spectrum of compound S1-1 is as Figure 1 shown.

[0096] Example 2

[0097] Preparation of Compound S1

[0098] The preparation method of the said Compound S1 is as follows:

[0099]

[0100] Add Compound S1-1 (365.7 mg, 1.235 mmol), azide-terminated polyethylene glycol (molecular weight 2000) (2.5 g, 1.25 mmol), copper sulfate (12 mg, 0.07 mmol) and sodium L-ascorbate (25 mg, 0.12 mmol) into a 250 mL two-necked flask; under argon protection, dissolve the reactants in tetrahydrofuran (100 mL) and water (10 mL). The obtained reaction mixture is stirred overnight at room temperature, then extracted with water and dichloromethane. Collect the organic phase, remove the solvent by rotary evaporation, and purify the crude product by silica gel column chromatography to obtain Compound S1 as an orange solid (2.67 g, yield: 94%). The 1 1H NMR spectrum of Compound S1 is as Figure 2 shown.

[0101] Example 3

[0102] Preparation of Compound S2

[0103] The preparation method of the said Compound S2 is as follows:

[0104]

[0105] Introduce Compound S1 (1000 mg, 0.434 mmol), 2,5-bis(trimethylstannyl)thiophene (89 mg, 0.217 mmol) and tris(o-tolyl)phosphine (80 mg) into a Schlenk reaction tube; then add 2,4-dioxane (67 mL) to dissolve the reactants; evacuate the mixture and refill with argon three times; subsequently, add tris(dibenzylideneacetone)dipalladium (40 mg, 0.043 mmol) to the reaction mixture under argon protection; the reaction is carried out at 100 °C for 24 h; after the reaction is completed, remove the solvent by rotary evaporation, purify the product by column chromatography, then wash the product with n-hexane and dry it under vacuum to obtain Compound S2 as a red solid (810 mg, yield: 83%). The 1 1H NMR spectrum of Compound 3 is as Figure 3 shown.

[0106] Example 4

[0107] Preparation of M1 (PBFDO-PEG 50 wt% Polymer)

[0108] The preparation method of the said M1 is as follows:

[0109]

[0110] Under argon protection, 20 mL of a DMSO solution of poly(benzodifurandione) (polymer solid content is 10 mg / mL) was taken, and 100 mg of the compound S2 of Example 3 was added thereto; the mixed solution was heated to 85 °C and reacted for 8 h, and then returned to room temperature; the obtained solution was dialyzed for three days using a dialysis bag with a cut-off molecular weight of 10 kDa, and the electron-transporting organic ion-electron mixed conductor in the dialysis bag was collected to obtain M1, and its solid content was measured to be 10 mg / mL.

[0111] Example 5

[0112] Preparation of M2 (PBFDO-PEG 100 wt% polymer)

[0113] The preparation method of the said M2 is as follows:

[0114] Under argon protection, 20 mL of a DMSO solution of poly(benzodifurandione) (polymer solid content is 10 mg / mL) was taken, 200 mg of the compound S2 of Example 3 was dissolved in 10 mL of DMSO, the above two solutions were mixed and heated to 85 °C, reacted for 8 h, then returned to room temperature, the obtained solution was dialyzed for three days using a dialysis bag with a cut-off molecular weight of 10 kDa, and the electron-transporting organic ion-electron mixed conductor in the dialysis bag was collected to obtain M2, and its solid content was measured to be 12 mg / mL.

[0115] Example 6

[0116] Preparation of M3 (PBFDO-PEG 250 wt% polymer)

[0117] The preparation method of the said M3 is as follows:

[0118]

[0119] Under argon protection, 200 mg of benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (cas: 30272-74-3) and 285 mg of tetramethyl-p-benzoquinone (cas: 527-17-3) were dissolved in 20 mL of DMSO solution, reacted at 80 °C for 6 h, then 500 mg of the compound S2 of Example 3 was dissolved in 25 mL of DMSO, the above two solutions were mixed and heated to 85 °C, reacted for 8 h, then returned to room temperature; the obtained solution was dialyzed for three days using a dialysis bag with a cut-off molecular weight of 10 kDa, and the electron-transporting organic ion-electron mixed conductor in the dialysis bag was collected to obtain M3, and its solid content was measured to be 14 mg / mL.

[0120] Example 7

[0121] Preparation of M4 (PBFDO-PEG 500wt% polymer)

[0122] The preparation method of the said M4 is as follows:

[0123] Under argon protection, take 200 mg of benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (cas: 30272-74-3) and 285 mg of tetramethylbenzoquinone (cas: 527-17-3), dissolve them in 20 mL of DMSO solution, react at 80 °C for 6 h, then dissolve 1000 mg of the compound S2 in Example 3 in 50 mL of DMSO; after mixing the above two solutions, heat to 85 °C and react for 8 h, then cool back to room temperature; dialyze the obtained solution using a dialysis bag with a cut-off molecular weight of 10 kDa with DMSO solution for three days, and then dialyze with a sufficient amount of methanol solution for six days (change the solvent outside the dialysis bag every two days); collect the electron transport type organic ion electron mixed conductor in the dialysis bag to obtain M4, and measure its solid content to be 15 mg / mL.

[0124] Application Example 1

[0125] Prepare an organic electrochemical transistor (OECT) with the electron transport type organic ion electron mixed conductor prepared in Examples 4-5. The process is as follows:

[0126] An organic electrochemical transistor, the specific device structure is as Figure 4 shown, including a substrate 8, an electron transport type organic ion electron mixed conductor 9, an electrolyte 10, a gate 11, a source 6 and a drain 7. The source 6 and the drain 7 are respectively located at both ends of the upper surface of the substrate 8. There is a channel between the source 6 and the drain 7. The electron transport type organic ion electron mixed conductor 9 is distributed on the upper surface of the channel. An insulating protective material is provided outside the source 6 and the drain 7;

[0127] The substrate 8, the electron transport type organic ion electron mixed conductor 9, the source 6 and the drain 7 are all immersed in the electrolyte 10, and the gate 11 is inserted into the electrolyte 10;

[0128] Among them, the material of the substrate 8 is glass, the insulating protective material is polydimethylsiloxane (PDMS), the material of the electron transport type organic ion electron mixed conductor is the electron transport type organic ion electron mixed conductor prepared in Examples 4-5, the source 6 and the drain 7 are gold electrodes, and the material of the electrolyte 7 is 0.1 M NaCl solution.

[0129] The preparation method of the said organic electrochemical transistor is as follows:

[0130] The preparation process of the organic electrochemical transistor (OECT) is fabricated according to the method described in the literature (Adv. Funct. Mater. 2019, 29, 1902085.).

[0131] Before preparing the organic film, the substrate is surface-treated with plasma to improve surface wettability. Subsequently, in a nitrogen atmosphere, the substrate is first preheated to 80 °C, and then the electron-transporting organic ion-electron hybrid conductor of Examples 4-5 is spin-coated onto the substrate at a speed of 3000 rpm to obtain an organic channel with a thickness of about 40 nm. Then, the obtained film is transferred to a vacuum oven and dried overnight at 45 °C to remove the residual solvent, obtaining an electron-transporting OECT.

[0132] The prepared OECT device is placed in a 0.1 M NaCl solution, and an Ag / AgCl electrode is used as the gate.

[0133] Application Example 2

[0134] The organic electrochemical transistor prepared based on the electron-transporting organic ion-electron hybrid conductor of Example 4 is applied to the preparation of a logic integrated circuit, and the process is as follows:

[0135] Before preparing the organic film, the glass substrate is surface-treated with plasma. 5 vol% of DMSO and 5 vol% of ethylene glycol are added to the commercially purchased aqueous PEDOT:PSS (Clevios PH1000) solution to obtain a PEDOT:PSS mixed solution.

[0136] Subsequently, the prepared PEDOT:PSS mixed solution is spin-coated onto the glass substrate at a speed of 3000 rpm to obtain an organic channel with a thickness of about 40 nm; then the obtained film is heated and dried at 140 °C for 15 min to remove the residual solvent, obtaining a hole-transporting OECT.

[0137] The electron-transporting OECT is prepared according to Application Example 1, and the obtained electron-transporting OECT and hole-transporting OECT are combined to construct an integrated circuit according to Figure 5 for combination to construct an integrated circuit.

[0138] Application Example 3

[0139] Since M4 prepared in Example 7 is alcohol-soluble, M4 of Example 7 is respectively used as an additive for the electron transport layer in an organic solar cell to fabricate electron transport layers with different thicknesses, and PFN-Br (purchased from Dongguan Fuan Optoelectronic Co., Ltd.) is used as an additive for the electron transport layer in an organic solar cell to fabricate electron transport layers with different thicknesses as a comparison;

[0140] Taking this as an example, it shows that the electron-transporting organic ion-electron hybrid conductor proposed by the present invention can significantly improve the electron-transporting performance of existing materials and meet the requirements of their thick-film processing.

[0141] An organic solar cell device includes the following structures in sequence from bottom to top: substrate 1 (ITO) / hole-transporting layer 2 (PEDOT:PSS, 40 nm) / active layer 3 (PM6:Y6 = 1:1:5, m / m, 100 nm) / electron-transporting layer 4) / electrode 5 (silver, 80 nm), and the structure is as Figure 6 shown, and the structures of the compounds involved are as Figure 7 (a)-(d) shown;

[0142] Among them, the thicknesses of M4 in Example 7 as the raw material of the electron-transporting layer 4 are 5 nm, 10 nm, 20 nm, and 50 nm respectively;

[0143] The thicknesses of PFN-Br as the raw material of the electron-transporting layer 4 are 5 nm, 10 nm, and 20 nm respectively;

[0144] The preparation process of the organic solar cell device is as follows:

[0145] The glass substrate coated with indium tin oxide (ITO) was cleaned with deionized water, acetone, and isopropanol for 15 min at room temperature respectively, and then dried in an oven at 60 °C for 12 h; then 40 nm of PEDOT:PSS (CLEVIOS PVPAl 4083) was spin-coated on the cleaned ITO glass substrate and heated on a hot plate at 140 °C in air for 15 min; the active layer donor material conjugated polymer PM6 and acceptor material Y6 (1:1:5, m / m) were weighed in a clean bottle, transferred into a glove box dedicated for film formation under nitrogen protection (purchased from VAC company), dissolved in chloroform solvent containing 1 wt% of 1,8-diiodooctane, and then a 100 nm thick active layer film was spin-coated on the PEDOT:PSS film through a spin coater and a surface profiler;

[0146] The methanol solution of the electron-transporting organic ion-electron hybrid conductor synthesized in Example 7 was blended with commercially purchased PFN-Br (the addition amount of PFN-Br was 50 wt% of the mass of the electron-transporting organic ion-electron hybrid conductor in Example 7), spin-coated on the active layer film as the electron-transporting layer of the solar cell device, and then transferred to a vacuum evaporation chamber connected to the glove box, and then silver electrodes were evaporated under the condition of about 10 -7 Pa to obtain the organic solar cell device;

[0147] Among them, all processes of the preparation of the solar cell device were carried out in a glove box with the oxygen and water content lower than 1 ppm.

[0148] Test method:

[0149] Before the test, the energy of simulated sunlight was corrected to 100 mW / cm² using a silicon photodiode calibrated by the National Renewable Energy Laboratory (NREL) of the United States and a KG5 filter. 2 The energy conversion efficiency of the device was measured under a standard solar spectrum AM1.5 solar simulator, and the photon and dark current density-voltage (J-V) characteristics of the solar cell device were recorded using a Keithley 2410 and a Keithley 236 digital source meter, respectively.

[0150] The test results are shown in Table 2 and Figure 8 as shown below.

[0151] Table 2 Performance results of organic solar cells based on different electron transport layers

[0152]

[0153]

[0154] Note: In the above sample column, the percentage represents the mass fraction of Example 7. For example, 50 wt% PFN-Br means 50 wt% of PFN-Br in Example 7.

[0155] The relationship between the current density and voltage of the device under illumination is as Figure 8 shown below, and the specific device efficiency is shown in Table 2. After using the electron-transporting organic ion-electron hybrid conductor of the present invention as an additive, the efficiency of the original electron transport layer can be significantly improved and exhibits the characteristic of being insensitive to thickness.

[0156] Test Example 1

[0157] The electron-transporting organic ion-electron hybrid conductors of Examples 4-6 were spin-coated on a glass substrate to form a film (thickness: 50 nm), and unmodified poly(benzodifurandione) (PBFDO) was used as a comparison; pure water was dropped on the film, and its water contact angle was measured.

[0158] The results are as Figure 9 shown below. It can be seen that as the content of the polyethylene glycol side chain copolymerization increases, the water contact angle of the material significantly decreases, indicating that the hydrophilicity of the material is greatly improved; this is beneficial to the transport of ions in the electrolyte solution in the channels formed by the electron-transporting organic ion-electron hybrid conductor.

[0159] Test Example 2

[0160] Use a Keithley 4200 semiconductor analyzer to measure the source meter and test the transmission, output, and transient response characteristics of the organic electrochemical transistor prepared from the electron-transporting organic ion-electron hybrid conductor of Example 4 as the raw material in Application Example 1.

[0161] The results are as Figure 10 shown. It can be seen that the device can operate in the low voltage range of -0.6 to 0.6 V, which is suitable for detecting, simulating, and calculating physiological electrical signals.

[0162] At the same time, the prepared device has a maximum transconductance exceeding 7 ms, which is at the leading level among n-type electrochemical transistors, thus facilitating signal amplification.

[0163] Test Example 3

[0164] Perform performance testing on the OECT device prepared in Application Example 1.

[0165] Test method:

[0166] Use an arbitrary function generator AFG1062 to generate square wave pulses and apply them to the gate electrode to obtain the transient response speed of the OECT.

[0167] The response time is as Figure 11 shown. Compared with the original poly(benzodifurandione) (PBFDO), the electron-transporting organic ion-electron hybrid conductor (PBFDO-PEGx) prepared by graft modification with polyethylene glycol in the present invention has a faster response speed, thus being able to meet the requirements of fast integrated circuit operations.

[0168] Test Example 4

[0169] Test the signal amplification effect of the integrated circuit prepared in Application Example 2.

[0170] Test method:

[0171] By controlling the V dd voltage, apply a voltage at the input end using a source meter and read the voltage at the output end to obtain the signal amplification factor. The integrated circuit structure is as Figure 5 shown. When the V dd is controlled at 0.7 V and a voltage of 0.6 V is input, a voltage of 12.2 V is obtained at the output end, that is, the integrated circuit constructed based on the electron-transporting organic ion-electron hybrid conductor of the present invention can achieve a circuit signal gain effect of more than 20 times. In contrast, the integrated circuit prepared based on unmodified poly(benzodifurandione) is difficult to operate normally because the n-type OECT has a slow operation response speed and is difficult to match with the p-type.

[0172] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-described exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention. Therefore, in any regard, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be embraced within the present invention.

[0173] In addition, it should be understood that although this specification is described in terms of embodiments, not every embodiment only contains an independent technical solution. This narrative manner of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An electron transport type organic ion-electron mixed conductor, characterized in that: The electron transport type organic ion-electron mixed conductor is selected from the following structures: Wherein, Y1 is N; Y2 is O; n is a positive integer from 1 to 2000, and n is not 1; m, k are positive integers; The connecting unit is The R1 is a polymer structure including polyethylene glycol; The Ar is 2. The method for preparing the electron transport type organic ion-electron mixed conductor according to claim 1, characterized in that: The steps include: S1, grafting a structure containing an R1 unit onto a halogenated 1H-indole-2,3-dione to obtain a compound S1; S2, subjecting compound S1 to a trimethyltinated linker unit, subjecting the compound to a Stille coupling reaction, and purifying the reaction to obtain compound S2; S3, blending the compound S2 with a DMSO solution of poly(benzodifurandione), heating for reaction, and purifying to obtain the electron transport type organic ion-electron mixed conductor.

3. The method for preparing the electron transport type organic ion-electron mixed conductor according to claim 2, characterized in that: In step S1, one or more hydrogen atoms on the benzene ring of the halogenated 1H-indole-2,3-dione are replaced by halogen atoms; Wherein, when a hydrogen atom on the benzene ring of the halogenated 1H-indole-2,3-dione is replaced by a halogen, the halogen is selected from one of chlorine, bromine and iodine; or, When multiple hydrogen atoms on the benzene ring of the halogenated 1H-indole-2,3-dione are replaced by halogens, one of the halogens is selected from chlorine, bromine and iodine, and the remaining halogens are fluorine.

4. The method for preparing the electron transport type organic ion-electron mixed conductor according to claim 2, characterized in that: In step S1, the R1 unit contains a polyol structure.

5. The method for preparing the electron transport type organic ion-electron mixed conductor according to claim 2, characterized in that: In step S2, the molar ratio of the compound S2 to the trimethyltinated linking unit is ≥2.

6. Use of the electron transport type organic ion-electron mixed conductor according to claim 1 in organic electrochemical transistors and organic solar cells.

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