Method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing glue

Abstract

The present invention belongs to the technical field of the preparation of isocyanate polymer products, and discloses a method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing; firstly, a photosensitive material and an ionic liquid are prepared, and the photosensitive material and the ionic liquid are subjected to a polymerization reaction to obtain a polyionic liquid optoelectronic conversion material; then, according to the order of the first conductive layer, the polyionic liquid optoelectronic conversion material, and the second conductive layer, a photosensitive polyionic liquid optoelectronic device is printed in sequence by a microelectronic printer. The present invention significantly simplifies the preparation process, can realize programmed control and batch production; and improves the consistency of the optoelectronic performance of the device.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of isocyanate polymer products, relates to the preparation technology of photosensitive polyion liquid optoelectronic devices, and specifically relates to a method for preparing photosensitive polyion liquid optoelectronic devices by dispensing. Background Art

[0002] The design idea and working principle of "photosensitive polyionic liquid ultraviolet photoelectric conversion material" are: azobenzene, spirooxazine and other photoisomer compounds are used as "photosensitive units" and ionic liquids are used as "piezoelectric units" and introduced into the same polymer main chain through polymerization reaction. Under ultraviolet light irradiation, the photosensitive unit undergoes isomerization reaction (such as cis-trans isomerization and ring-opening isomerization), inducing endogenous force. The rigid chain segment in the polymer acts as a "lever" to amplify and transmit this force, prying the cation movement of the ionic liquid on the same main chain, while the larger anion lags behind the cation movement, and the anion and cation are relatively displaced, thereby generating a potential difference and converting light energy into electrical energy.

[0003] The preparation method of "photosensitive polyionic liquid ultraviolet photoelectric devices" reported in existing literature is "manual coating" (see Zhao J, Zhang YH, Jia YF, Bao LX, Yang LJ, Xiao SY, et al. Photomechaelectricnanogenerator. Matter. 2022;5:3977-3996 and Sui JF, Liu PP, Jia YF, Guo RL, BaoLX, Zhao J, et al. Photomechaelectric Nanogenerators with DifferentPhotoisomers and Dipole Units for Harvesting UV Light Energy. Small. 2023:2307786). First, the synthesized photosensitive polyionic liquid material is dissolved in a good solvent (such as DMAc) to prepare a polymer solution of a certain concentration (such as 0.05 g / mol); then, the solution is sprayed on a PET transparent electrode with Ni-Cu alloy deposited on the surface (model: 190116-1.46), and placed in an oven for vacuum drying to constant weight; then, a layer of PET transparent electrode of the same material is attached to the other side of the material, and pressed at a pressure of 10 kN for 5 minutes at room temperature to ensure sufficient contact between the polyionic liquid and the electrode; finally, the wires are led out and encapsulated with dimethylsiloxane (PDMS) to obtain a photosensitive polyionic liquid ultraviolet photoelectric device. The actual device picture and the structural schematic diagram are shown in Figure 1 (a) and 1(b).

[0004] The optoelectronic devices prepared by the methods reported in the existing literature mainly have the following problems: (1) The steps are cumbersome and not suitable for mass production; (2) It is difficult to control the thickness and area of the polyionic liquid sample spraying, seriously affecting the consistency of the devices. There are large differences in the electrical performance test results of the devices prepared from the samples of the same batch. Summary of the Invention

[0005] The purpose of the present invention aims at the above problems existing in the prior art, and provides a method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing, which simplifies the preparation steps of the optoelectronic device and improves the consistency of the optoelectronic performance of the device.

[0006] To achieve the above object, the present invention takes the following technical solutions to implement.

[0007] The present invention provides a method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing, and the steps are as follows:

[0008] Prepare a photosensitive material; the photosensitive material is a spiropyran derivative, a spirooxazine derivative or an azobenzene derivative;

[0009] Prepare an ionic liquid; the ionic liquid is an imidazole ionic liquid or a quaternary ammonium salt ionic liquid;

[0010] Prepare a polyionic liquid optoelectronic conversion material: polymerize the photosensitive material and the ionic liquid to obtain a polyionic liquid optoelectronic conversion material;

[0011] Prepare the optoelectronic device by the dispensing method: print in sequence according to the first conductive layer, the polyionic liquid optoelectronic conversion material, and the second conductive layer through a microelectronic printer to obtain the optoelectronic device.

[0012] The beneficial effects of adopting the above technical solutions are: The present invention first proposes to prepare a photosensitive polyionic liquid optoelectronic device by the dispensing method. By adopting this preparation method, the preparation process of the optoelectronic device is significantly simplified, and programmed control and mass production can be realized. Moreover, the performance consistency of the prepared devices has been greatly improved.

[0013] In the process of preparing the optoelectronic device by the dispensing method, for the first conductive layer and the second conductive layer, conductive silver paste is used, with a viscosity of 15000 - 25000 mPa·S, a particle size ≤ 10 μm, a solid content of 62 ± 5%, and a sheet resistance < 60 mΩ / cm 2 ; The dispensing setting parameters are: dispensing speed 1 - 2 mm / s, dispensing air pressure 50 - 120 MPa. For the polyionic liquid optoelectronic conversion material, first configure it into a solution with a concentration of 0.8 - 1.2 g / mL; the solvent is ethanol or ethyl acetate; the dispensing setting parameters are: dispensing speed 1 - 2 mm / s, dispensing air pressure 5 - 30 MPa.

[0014] In one implementable manner, when the photosensitive material is spiropyran, the preparation steps are as follows:

[0015] (1) Prepare 2,3,3-trimethyl-5-methoxy-3H-indole

[0016] Dissolve 4-methoxyphenylhydrazine hydrochloride and 3-methyl-2-butanone in a first solvent, and then heat and reflux at 100 - 110 °C for 8 - 10 h; the obtained reaction solution is filtered, washed, and dried to obtain 2,3,3-trimethyl-5-methoxy-3H-indole, denoted as intermediate 1; the molar ratio of 4-methoxyphenylhydrazine hydrochloride to 3-methyl-2-butanone is 1:1.5;

[0017] (2) Prepare 2,3,3-trimethyl-5-hydroxy-3H-indole

[0018] Add intermediate 1 and hydrogen bromide, and heat and reflux at 110 - 130 °C for 8 - 10 h; the obtained reaction solution is precipitated, filtered, washed, and dried to obtain 2,3,3-trimethyl-5-hydroxy-3H-indole, denoted as intermediate 2; the molar ratio of intermediate 1 to hydrogen bromide is 1:5 - 6;

[0019] (3) Prepare 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-indole bromide

[0020] Add intermediate 2 to a reaction vessel, then dropwise add 1,4-dibromobutane, add a second solvent to dissolve, and then heat and reflux at 60 - 80 °C for 12 - 14 h; the obtained reaction solution is rotary evaporated to remove the second solvent to obtain 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-indole bromide, denoted as intermediate 3; the molar ratio of intermediate 2 to 1,4-dibromobutane is 1:1.5;

[0021] (4)Prepare 2-hydroxy-3-methoxy-5-nitrobenzaldehyde

[0022] Dissolve o-vanillin in glacial acetic acid, and then dropwise add a nitric acid solution to the obtained solution; then stir and react under ice-water bath conditions for 4 - 5 h, and then rotary evaporate the obtained reaction solution to remove glacial acetic acid, and then precipitate, filter, and wash to obtain 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, denoted as intermediate 4; the molar ratio of o-vanillin to nitric acid is 10:9;

[0023] (5)Prepare 2,3-dihydroxy-5-nitrobenzaldehyde

[0024] Add intermediate 4 and hydrogen bromide, and heat and reflux at 110 - 130 °C for 5 - 7 h; the obtained reaction solution is precipitated and filtered to obtain 2,3-dihydroxy-5-nitrobenzaldehyde, denoted as intermediate 5; the molar ratio of intermediate 4 to hydrogen bromide is 2:5;

[0025] (6) Preparation of spiropyran

[0026] Mix intermediate 3, intermediate 5 and piperidine in a third solvent, and under a nitrogen atmosphere, heat and reflux at 80 - 85 °C for 5 - 6 h; Rotate and remove the third solvent from the obtained reaction solution; The obtained reaction product is freeze-dried to obtain 1-bromobutyl-3,3-dimethyl-5,8'-dihydroxy-6'-nitro-3H-indolinospiropyran, that is, spiropyran; The molar ratio of intermediate 3, intermediate 5 and piperidine is 1:1:1.

[0027] In step (1), the first solvent is one of methanol, absolute ethanol, ethyl acetate, etc.; The first solvent is metered according to the molar volume ratio of 4-methoxyphenylhydrazine hydrochloride, 3-methyl-2-butanone, and the first solvent of 0.1 mol: 0.15 mol: 150 mL. After the obtained reaction solution is filtered, the filtrate is rotary evaporated to remove the first solvent, then washed with water, the oil phase is collected, and liquid separation is carried out 2 - 3 times until the color of the waste liquid becomes light yellow or nearly colorless and there are no obvious solid particles in the product, to obtain a black viscous product (2,3,3-trimethyl-5-methoxy-3H-indole); The obtained black viscous product is further dried to obtain intermediate 1, and the drying steps include: first placing it in a forced-air oven at 80 °C for 0.5 - 1 h, then placing it in a vacuum oven at 85 °C for 10 h, raising the temperature to 103 °C and then placing it for another 10 h.

[0028] In step (2), the obtained reaction solution is first diluted with ice water (0 - 4 °C), then neutralized to weakly alkaline (pH = 7 - 8) or neutral with sodium bicarbonate, then filtered and washed with deionized water until it is neutral to obtain a brown solid (2,3,3-trimethyl-5-hydroxy-3H-indole); It can also be placed in a vacuum oven at 105 °C for drying to remove water. The amount of ice water used is metered according to 30 - 50 mL of ice water added per 1 g of intermediate 1.

[0029] In step (3), the second solvent is acetonitrile; The second solvent is metered according to the molar volume ratio of intermediate 2, 1,4-dibromobutane, and the second solvent of 0.1 mol: 0.15 mol: 200 - 250 ml. After the obtained reaction solution is rotary evaporated to remove the second solvent, it can be further dried to constant weight in a vacuum oven at 80 °C to obtain a yellowish-brown solid 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-indole bromide.

[0030] In step (4), the glacial acetic acid is metered according to the molar volume ratio of o-vanillin and glacial acetic acid of 0.25 mol: 150 mL. After the glacial acetic acid in the obtained reaction solution is removed, deionized water is added, and it is cooled to 0 - 4 °C; The formed precipitate is filtered and washed with water to obtain a pale yellow solid 2-hydroxy-3-methoxy-5-nitrobenzaldehyde.

[0031] In step (5), deionized water is added to the obtained reaction solution and cooled to 0 - 4 °C; the formed precipitate is filtered to obtain the yellow solid 2,3-dihydroxy-5-nitrobenzaldehyde.

[0032] In step (6), the third solvent is one of methanol, absolute ethanol, ethyl acetate, etc., and the third solvent is metered according to the molar volume ratio of intermediate 3, intermediate 5, piperidine, and the third solvent of 0.025 mol : 0.025 mol : 0.025 mol : 150 ml.

[0033] In an implementable manner, when the ionic liquid is an imidazole ionic liquid, the preparation steps are as follows: 4,5-bis(hydroxymethyl)-2-phenyl-1H-imidazole and potassium carbonate are mixed in a fourth solvent, and then heated to reflux with stirring at 75 - 80 °C until evenly mixed; then n-butyl bromide is added, and the temperature is raised to 110 - 120 °C for reflux reaction for 24 - 30 h; the obtained reaction solution is filtered and the fourth solvent is removed by rotary evaporation to obtain the imidazole ionic liquid; the molar ratio of 4,5-bis(hydroxymethyl)-2-phenyl-1H-imidazole, potassium carbonate, and n-butyl bromide is 2:1:5.

[0034] The above-mentioned fourth solvent is dimethylacetamide (DMAc); the fourth solvent is metered according to the molar volume ratio of 4,5-bis(hydroxymethyl)-2-phenyl-1H-imidazole, potassium carbonate, and the fourth solvent of 20 mmol : 10 mmol : 80 ml.

[0035] In an implementable manner, the polymerization reaction of spiropyran and the imidazole ionic liquid to obtain the polyionic liquid photovoltaic conversion material includes:

[0036] After vacuum dehydrating polytetrahydrofuran ether glycol (PTMG-1000), diphenylmethane diisocyanate (MDI) and a catalyst are added successively, and the reaction is carried out at 40 - 60 °C for 0.5 - 2 h, then the temperature is raised to 80 - 100 °C for reaction for 0.2 - 2 h; then spiropyran is added, and the reaction is carried out at 100 - 140 °C for 2 - 4 h; then the imidazole ionic liquid is added, and the reaction is carried out at 100 - 140 °C for 1 - 3 h to complete the polymerization reaction; the molar ratio of polytetrahydrofuran ether glycol, diphenylmethane diisocyanate, spiropyran, and the imidazole ionic liquid is 2:4:1:1. The catalyst is dibutyltin dilaurate (DBTDL), and its dosage can be added according to the dosage of the reaction raw materials as long as it can satisfy the reaction. In a preferred implementation manner, the dosage of the catalyst is 0.01 - 0.03% of the total mass of polytetrahydrofuran ether glycol, diphenylmethane diisocyanate, spiropyran, and the imidazole ionic liquid.

[0037] In the preparation of the above-mentioned polyionic liquid optoelectronic conversion material, spiropyran is used as the photosensitive material, and imidazole ionic liquid is used as the piezoelectric material. The polyionic liquid optoelectronic conversion material is prepared by polymerization. Since the molecular structure of spiropyran consists of two parts, an indoline ring and a benzopyran ring, which are connected by a spiro carbon atom, the two parts in its closed-ring structure are perpendicular and orthogonal to each other, and the open-ring form is a coplanar structure. Under ultraviolet light irradiation, the C-O bond in the spiropyran structure is broken, and it is isomerized from the closed-ring form to the open-ring form. Due to the weak charge interaction between the anion and cation in the imidazole ionic liquid, it is easily separated under external stimuli or internal molecular stimuli, and a potential difference is generated. In the prepared photosensitive polyionic liquid ultraviolet optoelectronic conversion material, the cation of the spiropyran unit and the imidazole ionic liquid unit are introduced into the same polymer main chain, while the anion pairs with the cation by a weak charge interaction. Under ultraviolet light stimulation, the spiropyran unit undergoes ring-opening isomerization, resulting in a change in the microscopic shape and size of the molecule, generating an internal force. The polymer chain transfers this force to the imidazole ionic liquid unit, driving the cation of the ionic liquid unit on the same main chain to move, and the movement of the anion lags behind relatively, causing the separation of the anion and cation, thereby generating a potential difference.

[0038] The advantages of this optoelectronic conversion material are as follows: (1) It can effectively utilize ultraviolet light, making up for the insufficient utilization of ultraviolet light by current commercial photovoltaic materials (currently, commercial solar cells mainly utilize near-infrared light and visible light), and achieving a more comprehensive utilization of the solar spectrum; (2) Since both spiropyran and ionic liquid are easily subjected to structural modification, this optoelectronic conversion material is also easy to be structurally modified, so that its light response rate, absorbance, maximum absorption wavelength, etc. can be effectively adjusted; (3) It avoids the use of substances with relatively high toxicity such as azobenzene in the "photosensitive polyionic liquid material based on azobenzene" reported in the existing literature; (4) It avoids the disadvantages of the manual "spin coating method" reported in the existing literature for preparing polyionic liquid optoelectronic devices, such as cumbersome steps, unsuitability for mass production, and poor performance consistency.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0040] (1) The present invention provides a novel polyionic liquid optoelectronic conversion material, using spiropyran as the photosensitive material and imidazole ionic liquid as the piezoelectric material, and the two are polymerized to obtain the polyionic liquid optoelectronic conversion material;

[0041] (2) The present invention prepares a photosensitive polyionic liquid optoelectronic device by the dispensing method for the first time;

[0042] (3) The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing proposed by the present invention significantly simplifies the preparation process, and can achieve programmed control and mass production;

[0043] (4)The photosensitive polyionic liquid optoelectronic device prepared by the present invention is obtained by sequentially printing the first conductive layer, the polyionic liquid optoelectronic conversion material, and the second conductive layer through a microelectronic printer, and the sizes of the three layers can be precisely controlled;

[0044] (5)For the photosensitive polyionic liquid optoelectronic device prepared by the dispensing method of the present invention, the consistency of the voltage output performance has been greatly improved. Description of the Drawings

[0045] Figure 1 Schematic diagram of an optoelectronic conversion device prepared by the existing coating method; among them, (a) is a physical diagram, and (b) is a schematic diagram of the internal structure of the optoelectronic conversion device;

[0046] Figure 2 The photosensitive polyionic liquid optoelectronic device prepared by the method of the embodiment of the present invention; among them, (a) is a physical diagram, (b) is a schematic diagram of the lower layer structure; (c) is a schematic diagram of the middle layer structure; (d) is a schematic diagram of the upper layer structure;

[0047] Figure 3A Output open circuit voltage obtained in the test of the photosensitive polyionic liquid optoelectronic device prepared by the coating method;

[0048] Figure 3B Output open circuit voltage obtained in the test of the photosensitive polyionic liquid optoelectronic device prepared in Example 4 of the present invention. Detailed Embodiments

[0049] The principles and features of the present invention are described below. The examples given are only used to explain the present invention and are not intended to limit the scope of the present invention.

[0050] Example 1 Synthesis of Spiropyran (SP)

[0051] The preparation steps of spiropyran provided in this example are as follows:

[0052] (1)Preparation of 2,3,3-trimethyl-5-methoxy-3H-indole

[0053]

[0054] 4-Methoxyphenylhydrazine hydrochloride (17.5 g, 0.1 mol) and 3-methyl-2-butanone (12.9 g, 0.15 mol) were dissolved in 150 ml of absolute ethanol and heated under reflux at 110 °C for 8 h to obtain a black solution.

[0055] The black solution was filtered through a fritted funnel, and the filtrate was taken and the ethanol was removed by rotary evaporation at 80 °C. It was washed with water. The aqueous phase was on top and the oil phase (black in color) was at the bottom. The oil phase was retained and separated three times to obtain the black viscous product 2,3,3-trimethyl-5-methoxy-3H-indole, denoted as Intermediate 1.

[0056] During drying, first place the black viscous product in a forced-air oven at 80 °C for 1 h, then place it in a vacuum oven at 85 °C for 10 h, raise the temperature to 103 °C and place it for another 10 h.

[0057] (2)Preparation of 2,3,3-trimethyl-5-hydroxy-3H-indole

[0058]

[0059] Take Intermediate 1 (10 g, 0.053 mol), add HBr (30 ml, 0.27 mol), heat to 130 °C, and reflux for 8 h.

[0060] After the reaction, dilute the obtained reaction solution with 500 ml of ice water, then neutralize it to weak alkalinity (pH = 8) with sodium bicarbonate, and then filter it with a Buchner funnel and wash it with deionized water until it is neutral (pH = 7) to obtain the brown solid 2,3,3-trimethyl-5-hydroxy-3H-indole, denoted as Intermediate 2. Then place Intermediate 2 in a vacuum oven at 105 °C to dry and remove water.

[0061] (3)Preparation of 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-indolium bromide

[0062]

[0063] Place Intermediate 2 (17.5 g, 0.1 mol) in a 500 ml single-necked flask, add 1,4-dibromobutane (32.4 g, 0.15 mol) dropwise, then add 250 ml of acetonitrile solution to dissolve it, react at 80 °C and reflux for 12 h. After completion, rotary evaporate the obtained reaction solution at 80 °C to remove acetonitrile to obtain the yellowish-brown solid 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-indolium bromide, denoted as Intermediate 3. Then, dry Intermediate 3 in a vacuum oven at 80 °C to constant weight.

[0064] (4)Preparation of 2-hydroxy-3-methoxy-5-nitrobenzaldehyde

[0065]

[0066] Weigh vanillin (yellow solid) (38.0 g, 0.25 mol) and dissolve it in 150 mL of glacial acetic acid. Dropwise add a nitric acid solution with a concentration of 65% - 68% (22.5 g, 0.225 mol) to the mixture. After stirring for 5 hours under the condition of 0 °C (ice - water bath), rotary evaporate the glacial acetic acid from the resulting reaction solution at 110 °C.

[0067] Add 300 ml of deionized water to the mixture obtained after removing the glacial acetic acid and cool it to 0 °C. The formed precipitate is filtered and washed with deionized water to obtain the pale - yellow solid 2 - hydroxy - 3 - methoxy - 5 - nitrobenzaldehyde, denoted as intermediate 4.

[0068] (5)Preparation of 2,3 - dihydroxy - 5 - nitrobenzaldehyde

[0069] Weigh intermediate 4 (39.4 g, 0.2 mol), add HBr (85 g, 0.5 mol), and reflux the reaction at 130 °C for 5 h. Dilute the resulting reaction solution with 200 mL of water and cool it to 0 °C. The formed precipitate is filtered to obtain the yellow solid 2,3 - dihydroxy - 5 - nitrobenzaldehyde, denoted as intermediate 5.

[0070] (6)Preparation of spiropyran

[0071]

[0072] Weigh intermediate 3 (9.775 g, 0.025 mol) into a 250 - ml two - necked flask. Then weigh intermediate 5 (4.575 g, 0.025 mol), add about 150 ml of ethanol as a solvent, and add piperidine (2.125 g, 0.025 mol). Under nitrogen, heat and reflux the reaction at 85 °C for 5 h to obtain a black solution.

[0073] Rotary evaporate the ethanol from the black solution at 80 °C to obtain a black viscous product 1 - bromobutyl - 3,3 - dimethyl - 5,8’ - dihydroxy - 6’ - nitro - 3H - indolinospiropyran. After freezing it in the freezer for 24 h, it can be scraped to obtain the spiropyran unit SP.

[0074] Example 2 Synthesis of imidazole ionic liquid (IL)

[0075]

[0076] Weigh 4,5-dihydroxymethyl-2-phenyl-1H-imidazole (pink solid powder) (4.081 g, 20 mmol) into a 250 ml round-bottom flask, and then weigh potassium carbonate (white solid particles) (1.3821 g, 10 mmol) into the round-bottom flask. Then add 80 ml of DMAc solvent, reflux at 80 °C, stir evenly until the solution turns orange-red.

[0077] Add n-butyl bromide (colorless liquid) (6.7995 g, 50 mmol), raise the temperature to 120 °C and reflux for 24 h. After the reaction, a black solution is obtained.

[0078] Filter the black solution with a Buchner funnel, and rotary evaporate the filtrate at 120 °C to remove the solvent DMAc to obtain a black viscous product, imidazolium ionic liquid (IL).

[0079] Example 3 Synthesis of spiropyran-based photosensitive polyionic liquid (SP-IL)

[0080] Dehydrate polytetrahydrofuran ether diol (PTMG-1000) under vacuum at 103 °C for 1 h, add diphenylmethane diisocyanate (MDI), start the reaction and add the catalyst dibutyltin dilaurate (DBTDL), then react at 60 °C for 1 h, and then raise the temperature to 80 °C and react for 1 h; then add SP for chain extension, and then raise the temperature to 120 °C and react for 3 h; then add IL and continue to react at 120 °C for 2 h, and discharge; the dosage of the catalyst DBTDL is 0.02% of the total mass of PTMG, MDI, SP and IL.

[0081] The specific material ratios are shown in Table 1 below:

[0082] Table 1 Addition amounts of each raw material of SP-IL

[0083]

[0084] Example 4 Use the dispensing method to prepare optoelectronic devices from the synthesized SP-IL material:

[0085] In this example, for the first time, the "dispensing module" of the MP1100 type microelectronic printer produced by Shanghai Mifang Electronic Technology Co., Ltd. is used to prepare photosensitive polyionic liquid ultraviolet optoelectronic devices, and the software is DB1.6.6. The device is divided into three layers in total and printed in the order of "bottom, middle, top" in sequence. After printing each layer, it is left to dry naturally in the air. The physical diagram is as Figure 2 (a).

[0086] Both the upper and lower layers (i.e., the first conductive layer and the second conductive layer) are Elec-L705 conductive silver paste produced by Shenzhen Yilai Technology Co., Ltd. (appearance: silver-gray paste, viscosity: 15000 - 25000 mPa·S, particle size ≤ 10 μm, solid content 62 ± 5%, sheet resistance < 60 mΩ / cm 2 , adhesion: 5 B, hardness: 80 D, solvent: DBE). The dispensing parameters are set as follows: dispensing speed: 1.5 mm / s, dispensing air pressure: 80 MPa.

[0087] The middle layer is a synthesized SP-IL sample (first, dissolve the SP-IL sample with the solvent ethyl acetate, 1 mL of solvent for every 1 g of sample; then print using the "dispensing module"). The dispensing parameters are set as follows: dispensing speed: 1.5 mm / s, dispensing air pressure: 20 MPa.

[0088] The shape and size of each layer are as shown in Figure 2 (b)-(d).

[0089] Four SP-IL optoelectronic devices were prepared by the coating method of existing literature and the dispensing method of Example 4 of the present invention respectively, and the open-circuit voltage was tested. The operation of the coating method is as follows: First, dissolve the sample SP-IL with the solvent ethyl acetate (1 mL of solvent for every 1 g of sample); then, spin-spray the solution onto the PET transparent electrode with Ni-Cu alloy deposited on the surface (model: 190116 - 1.46), and place it in an oven for vacuum drying to constant weight; then, attach another layer of PET transparent electrode of the same material on the other side of the material; press at a pressure of 10 kN for 5 min at room temperature to ensure sufficient contact between the polyionic liquid and the electrode. Finally, after leading out the wires, encapsulate and process with dimethyl silicone (PDMS) to obtain a photosensitive polyionic liquid ultraviolet optoelectronic device. The open-circuit voltage test process is as follows: Connect the two electrodes of the optoelectronic device to an oscilloscope respectively; irradiate the surface of the optoelectronic device with an ultraviolet lamp (power: 4 W, light intensity: 3100 μW / cm 2 ), and record the real-time open-circuit voltage data of the optoelectronic device under ultraviolet light irradiation. The test results are shown in Figure 3A 、 Figure 3B and Table 2.

[0090] Table 2 Open-circuit voltage of SP-IL devices prepared by coating method and dispensing method

[0091]

[0092] The results show that: the open-circuit voltage output by the devices prepared by the dispensing method remains consistent within the error range, while there are significant differences in the open-circuit voltage of the devices prepared by the coating method.

[0093] There is no similar report at home and abroad. The present invention provides a new method for the preparation of photosensitive polyionic liquid ultraviolet optoelectronic devices, and other similar optoelectronic devices, piezoelectric devices, thermoelectric devices, etc. made of polymer materials can also be used for reference.

[0094] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing, characterized in that: Here are the steps: Prepare a photosensitive material; the photosensitive material is spiropyran; the spiropyran structural formula is: ； Prepare an ionic liquid; the ionic liquid is an imidazolium ionic liquid; the structural formula of the imidazolium ionic liquid is: ； Preparation of polyionic liquid photoelectric conversion material: polymerization reaction of photosensitive material and ionic liquid to obtain polyionic liquid photoelectric conversion material; Preparation of optoelectronic devices by dispensing method: the first conductive layer, polyionic liquid photoelectric conversion material, and the second conductive layer are printed in sequence by a microelectronic printer.

2. The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing according to claim 1, characterized in that: In the process of preparing optoelectronic devices by the dispensing method, for the polyionic liquid photoelectric conversion material, it is first configured into a 0.8~1.2g / mL solution; the solvent is ethanol or ethyl acetate; the dispensing setting parameters are: the dispensing speed is 1~2 mm / s, and the dispensing gas pressure is 5~30MPa.

3. The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing according to claim 1, characterized in that: In the process of preparing optoelectronic devices by dispensing method, for the first conductive layer and the second conductive layer, conductive silver glue is used, with a viscosity of 15000~25000 mPa·S, a particle size of ≤10 μm, a solid content of 62±5%, and a square resistance of <60 mΩ / cm 2 ; The dispensing setting parameters are: dispensing speed 1~2 mm / s, dispensing air pressure 50~120 MPa.

4. The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing according to claim 1, characterized in that: The spiropyran preparation steps are as follows: (1) Preparation of 2,3,3-trimethyl-5-methoxy-3H-indole Dissolving 4-methoxyphenylhydrazine hydrochloride and 3-methyl-2-butanone in a first solvent, and then heating under reflux at 100-110° C. for 8-10 hours; filtering, washing, and drying the resulting reaction solution to obtain 2,3,3-trimethyl-5-methoxy-3H-indole, recorded as intermediate 1; the molar ratio of 4-methoxyphenylhydrazine hydrochloride to 3-methyl-2-butanone is 1:1.5; (2) Preparation of 2,3,3-trimethyl-5-hydroxy-3H-indole The intermediate 1 and hydrogen bromide are heated to reflux at 110-130° C. for 8-10 hours; the resulting reaction solution is precipitated, filtered, washed, and dried to obtain 2,3,3-trimethyl-5-hydroxy-3H-indole, which is recorded as intermediate 2; the molar ratio of the intermediate 1 to hydrogen bromide is 1:5-6; (3) Preparation of 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-indole bromide The intermediate 2 is added to a reaction container, and then 1,4-dibromobutane is added dropwise, and then a second solvent is added to dissolve, and then heated to reflux at 60-80° C. for 12-14 hours; the obtained reaction solution is subjected to rotary evaporation to remove the second solvent to obtain 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-bromoindole, which is recorded as intermediate 3; the molar ratio of the intermediate 2 to 1,4-dibromobutane is 1:1.5; (4) Preparation of 2-hydroxy-3-methoxy-5-nitrobenzaldehyde o-Vanillin is dissolved in glacial acetic acid, and a nitric acid solution is added dropwise to the resulting solution; the reaction is then stirred in an ice-water bath for 4-5 hours, and the resulting reaction solution is then subjected to rotary evaporation to remove the glacial acetic acid, followed by precipitation, filtration, and washing to obtain 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, which is recorded as intermediate 4; the molar ratio of o-vanillin to nitric acid is 10:9; (5) Preparation of 2,3-dihydroxy-5-nitrobenzaldehyde The intermediate 4 and hydrogen bromide are heated to reflux at 110-130° C. for 5-7 hours; the resulting reaction solution is precipitated and filtered to obtain 2,3-dihydroxy-5-nitrobenzaldehyde, which is recorded as intermediate 5; the molar ratio of the intermediate 4 to hydrogen bromide is 2:5; (6) Preparation of spiropyran The intermediate 3, the intermediate 5 and the piperidine are mixed in a third solvent, and heated under reflux at 80-85° C. for 5-6 hours in a nitrogen atmosphere; the obtained reaction solution is rotated to remove the third solvent; the obtained reaction product is freeze-dried to obtain 1-bromobutyl-3,3-dimethyl-5,8'-dihydroxy-6'-nitro-3H-indoline spirobenzopyran, i.e., spiropyran; the molar ratio of the intermediate 3, the intermediate 5 and the piperidine is 1:1:

1.

5. The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing according to claim 4, characterized in that: In step (1), the first solvent is one of methanol, anhydrous ethanol, and ethyl acetate; in step (3), the second solvent is acetonitrile; in step (6), the third solvent is one of methanol, anhydrous ethanol, and ethyl acetate.

6. The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing according to claim 4, characterized in that: In step (2), the obtained reaction solution is first diluted with ice water, then neutralized with sodium bicarbonate to weak alkalinity or neutrality, and then filtered and washed with deionized water until it is neutral to obtain a brown solid 2,3,3-trimethyl-5-hydroxy-3H-indole; the amount of ice water used is measured by adding 30-50 mL of ice water per 1 g of intermediate 1; In step (4), after removing glacial acetic acid from the obtained reaction solution, deionized water is added and the solution is cooled to 0-4°C; the formed precipitate is filtered and washed with water to obtain a light yellow solid 2-hydroxy-3-methoxy-5-nitrobenzaldehyde; In step (5), deionized water is added to the obtained reaction solution, and the solution is cooled to 0-4° C.; the formed precipitate is filtered to obtain yellow solid 2,3-dihydroxy-5-nitrobenzaldehyde.

7. The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing according to claim 1, characterized in that: When the ionic liquid is an imidazolium ionic liquid, the preparation steps are as follows: 4,5-dihydroxymethyl-2-phenyl-1H-imidazole and potassium carbonate are mixed in a fourth solvent, and then heated to reflux at 75-80° C. and stirred evenly; then n-butyl bromide is added, and then the temperature is raised to 110-120° C. and refluxed for reaction for 24-30 hours; the obtained reaction solution is filtered and the fourth solvent is removed by rotary evaporation to obtain an imidazolium ionic liquid; the molar ratio of the 4,5-dihydroxymethyl-2-phenyl-1H-imidazole, potassium carbonate and n-butyl bromide is 2:1:

5.

8. The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing according to claim 7, characterized in that: The fourth solvent is dimethylacetamide.

9. The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing according to any one of claims 1 to 8, characterized in that: The spiropyran is polymerized with an imidazolium ionic liquid to obtain a polyionic liquid photoelectric conversion material; comprising: After dehydrating polytetramethylene glycol in vacuo, diphenylmethane diisocyanate and a catalyst are added in sequence, reacting at 40-60°C for 0.5-2 h, and then heating to 80-100°C for 0.2-2 h; then spiropyran is added, reacting at 100-140°C for 2-4 h; then imidazolium ionic liquid is added, reacting at 100-140°C for 1-3 h to complete the polymerization reaction; the molar ratio of the polytetramethylene glycol, diphenylmethane diisocyanate, spiropyran and imidazolium ionic liquid is 2:4:1:

1.

10. The method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing according to claim 9, characterized in that: The catalyst is dibutyltin dilaurate; the amount of the catalyst is 0.01-0.03% of the total mass of polytetramethylene glycol, diphenylmethane diisocyanate, spiropyran and imidazolium ionic liquid.

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