Method for preparing photosensitive polyion liquid photoelectric device through dispensing

Abstract

The invention belongs to the technical field of preparation of isocyanate polymerization products, and discloses a method for preparing a photosensitive polyion liquid photoelectric device through dispensing. The method comprises the following steps: firstly, preparing a photosensitive material and ionic liquid, and carrying out polymerization reaction on the photosensitive material and the ionic liquid to obtain a polyionic liquid photoelectric conversion material; and sequentially printing the first conductive layer, the polyion liquid photoelectric conversion material and the second conductive layer through a microelectronic printer to obtain the photosensitive polyion liquid photoelectric device. According to the invention, the preparation process is obviously simplified, and programmed control and batch production can be realized; and the consistency of photoelectric properties of the device is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of isocyanate polymer products, relates to a preparation technology of a photosensitive polyion liquid optoelectronic device, and specifically relates to a method for preparing a photosensitive polyion liquid optoelectronic device 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 using the methods reported in existing literature have the following main 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, which seriously affects the consistency of the device. The electrical performance test results of devices prepared from the same batch of samples are quite different. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing photosensitive polyionic liquid optoelectronic devices by dispensing to address the above-mentioned problems existing in the prior art, simplify the preparation steps of optoelectronic devices, and improve the consistency of the optoelectronic performance of the devices.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions to achieve it.

[0007] The present invention provides a method for preparing a photosensitive polyionic liquid optoelectronic device by dispensing, the steps of which are as follows: Preparing a photosensitive material; the photosensitive material is a spiropyran derivative, a spirooxazine derivative or an azobenzene derivative; Prepare an ionic liquid; the ionic liquid is an imidazolium ionic liquid or a quaternary ammonium salt ionic liquid; 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, the polyionic liquid photoelectric conversion material, and the second conductive layer are printed in sequence by a microelectronic printer to obtain the optoelectronic device.

[0008] The beneficial effect of adopting the above technical solution is that the present invention proposes for the first time to prepare a photosensitive polyionic liquid optoelectronic device by a dispensing method. The preparation method significantly simplifies the preparation process of the optoelectronic device, and can realize programmed control and batch production. Moreover, the performance consistency of the prepared device is greatly improved.

[0009] 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 pressure 50~120 MPa. For the polyionic liquid photoelectric conversion material, first prepare it into a 0.8~1.2g / mL solution; the solvent is ethanol or ethyl acetate; the dispensing setting parameters are: dispensing speed 1~2mm / s, dispensing pressure 5~30 MPa.

[0010] In one achievable manner, when the photosensitive material is spiropyran, the 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.

[0011] In step (1), the first solvent is one of methanol, anhydrous ethanol, ethyl acetate, etc.; the first solvent is measured 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 filtering the obtained reaction solution, the filtrate is evaporated to remove the first solvent, and then washed with water, the oil phase is collected, and the liquid is separated 2 to 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, thereby obtaining 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 step includes: first placing it in an 80°C forced air oven for 0.5 to 1 h, then placing it in an 85°C vacuum oven for 10 h, heating it to 103°C and then placing it for 10 h.

[0012] In step (2), the obtained reaction solution is first diluted with ice water (0-4°C), then neutralized with sodium bicarbonate to weak alkalinity (pH=7-8) or neutrality, 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 to dry and remove water. The amount of ice water used is measured by adding 30-50 mL of ice water per 1 g of intermediate 1.

[0013] In step (3), the second solvent is acetonitrile; the second solvent is measured 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 subjected to rotary evaporation to remove the second solvent, it can be further dried in a vacuum oven at 80 ° C to constant weight to obtain a brown solid 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-bromoindole.

[0014] In step (4), glacial acetic acid is measured according to the molar volume ratio of o-vanillin to glacial acetic acid of 0.25 mol:150 mL. After removing glacial acetic acid from the obtained reaction solution, deionized water is added and 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.

[0015] 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.

[0016] In step (6), the third solvent is one of methanol, anhydrous ethanol, ethyl acetate, etc., and the third solvent is measured 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.

[0017] In one achievable manner, 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.

[0018] The fourth solvent is dimethylacetamide (DMAc); the fourth solvent is measured according to a molar volume ratio of 4,5-dihydroxymethyl-2-phenyl-1H-imidazole, potassium carbonate, and the fourth solvent of 20 mmol:10 mmol:80 ml.

[0019] In one achievable manner, the step of polymerizing spiropyran and imidazolium ionic liquid to obtain a polyionic liquid photoelectric conversion material comprises: After vacuum dehydration of polytetramethylene glycol (PTMG-1000), diphenylmethane diisocyanate (MDI) and a catalyst are added in sequence, and the reaction is carried out at 40-60°C for 0.5-2 h, and then the temperature is raised to 80-100°C for 0.2-2 h; then spiropyran is added, and the reaction is carried out at 100-140°C for 2-4 h; then imidazolium 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 the polytetramethylene glycol, diphenylmethane diisocyanate, spiropyran and imidazolium ionic liquid is 2:4:1:1. The catalyst is dibutyltin dilaurate (DBTDL), and its amount can be added according to the amount of reaction raw materials, as long as it can satisfy the reaction. In a preferred implementation, the amount of the catalyst is 0.01-0.03% of the total mass of polytetramethylene glycol, diphenylmethane diisocyanate, spiropyran, and imidazolium ionic liquid.

[0020] In the preparation of the polyionic liquid photoelectric conversion material, spiropyran is used as a photosensitive material, imidazolium ionic liquid is used as a piezoelectric material, and the polyionic liquid photoelectric conversion material is prepared by polymerization; since the molecular structure of spiropyran is composed of two parts, an indoline ring and a benzopyran ring, which are connected by a spiro carbon atom, the two parts are perpendicular to each other in the closed-loop structure, and the open-loop structure is a coplanar structure. Under ultraviolet light irradiation, the CO bond in the spiropyran structure breaks, and the closed-loop structure is isomerized to the open-loop structure. Since the anions and cations of the imidazolium ionic liquid are attracted by a weak charge force, they are easily separated under external stimulation or internal stimulation of the molecule, and a potential difference is generated. The prepared photosensitive polyionic liquid ultraviolet photoelectric conversion material introduces the cations of the spiropyran unit and the imidazolium ionic liquid unit into the same polymer main chain, and the anions and cations are paired with the cations by a weak charge force. Under ultraviolet light stimulation, the spiropyran unit undergoes open-loop isomerization, which brings about changes in the microscopic shape and size of the molecule and generates an endogenous force. The polymer chain transmits this force to the imidazolium ionic liquid unit, driving the movement of the cations of the ionic liquid unit on the same main chain, and lagging behind the movement of the anions, causing separation of anions and cations, thereby generating a potential difference.

[0021] The advantages of this photoelectric conversion material are: (1) It can effectively utilize ultraviolet light, making up for the problem of insufficient utilization of ultraviolet light by current commercial photovoltaic materials (currently commercial solar cells mainly utilize near-infrared light and visible light), and realize more comprehensive utilization of the solar spectrum; (2) Since spiropyran and ionic liquids are easy to be structurally modified, this photoelectric 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 azobenzene-based highly toxic substances in the "azobenzene-based photosensitive polyionic liquid materials" reported in existing literature; (4) It avoids the shortcomings of the manual "rotary spraying method" reported in existing literature for preparing polyionic liquid photoelectric devices, which has cumbersome steps, is not suitable for mass production, and has poor performance consistency.

[0022] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention provides a novel polyionic liquid photoelectric conversion material, which uses spiropyran as a photosensitive material and imidazolium ionic liquid as a piezoelectric material, and the two are polymerized to prepare the polyionic liquid photoelectric conversion material; (2) The present invention is the first to prepare a photosensitive polyionic liquid optoelectronic device by dispensing method; (3) The method for preparing photosensitive polyionic liquid optoelectronic devices by dispensing proposed in the present invention significantly simplifies the preparation process and can realize programmed control and batch production; (4) The photosensitive polyionic liquid optoelectronic device prepared by the present invention is obtained by printing the first conductive layer, the polyionic liquid photoelectric conversion material, and the second conductive layer in sequence by a microelectronic printer, and the sizes of the three layers can be precisely controlled; (5) The photosensitive polyionic liquid optoelectronic device prepared by the dispensing method of the present invention has greatly improved the consistency of voltage output performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Schematic diagram of a photoelectric conversion device prepared by an existing coating method; wherein (a) is a physical diagram, and (b) is a schematic diagram of the internal structure of the photoelectric conversion device; Figure 2 The photosensitive polyionic liquid optoelectronic device prepared by the method of the embodiment of the present invention; wherein (a) is a real picture, (b) is a schematic diagram of the lower structure; (c) is a schematic diagram of the middle structure; (d) is a schematic diagram of the upper structure; Figure 3A The output open circuit voltage obtained in the test of the photosensitive polyionic liquid optoelectronic device prepared by the coating method; Figure 3B This is the output open circuit voltage obtained in the test of the photosensitive polyionic liquid optoelectronic device prepared in Example 4 of the present invention. DETAILED DESCRIPTION

[0024] 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 used to limit the scope of the present invention.

[0025] Example 1 Synthesis of Spiropyran (SP) This embodiment provides the following steps for preparing spiropyran: (1) Preparation of 2,3,3-trimethyl-5-methoxy-3H-indole

[0026] Dissolve 4-methoxyphenylhydrazine hydrochloride (17.5 g, 0.1 mol) and 3-methyl-2-butanone (12.9 g, 0.15 mol) in 150 ml of anhydrous ethanol and heat under reflux at 110 °C for 8 h to obtain a black solution.

[0027] The black solution was filtered through a sand core funnel, and the filtrate was evaporated at 80°C to remove ethanol. The filtrate was washed with water, with the aqueous phase on top and the oil phase (black) on the bottom. The oil phase was retained and separated three times to obtain a black viscous product 2,3,3-trimethyl-5-methoxy-3H-indole, which was recorded as intermediate 1.

[0028] During drying, the black viscous product was first placed in an 80 °C forced air oven for 1 h, then placed in an 85 °C vacuum oven for 10 h, and then heated to 103 °C and left for another 10 h.

[0029] (2) Preparation of 2,3,3-trimethyl-5-hydroxy-3H-indole

[0030] Take intermediate 1 (10 g, 0.053 mol), add HBr (30 ml, 0.27 mol), heat to 130 °C, and reflux for 8 h.

[0031] After the reaction, the reaction solution was diluted with 500 ml of ice water, neutralized with sodium bicarbonate to weak alkalinity (pH = 8), filtered with a Buchner funnel and washed with deionized water until it was neutral (pH = 7), to obtain a brown solid 2,3,3-trimethyl-5-hydroxy-3H-indole, recorded as intermediate 2. Intermediate 2 was then placed in a vacuum oven at 105 °C to dry and remove water.

[0032] (3) Preparation of 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-indole bromide

[0033] The intermediate 2 (17.5 g, 0.1 mol) was added to a 500 ml single-necked flask, and 1,4-dibromobutane (32.4 g, 0.15 mol) was added, and then 250 ml of acetonitrile solution was added to dissolve, and the mixture was reacted at 80 °C and refluxed for 12 h. After the reaction, the acetonitrile was removed by rotary evaporation at 80 °C to obtain a brown solid 1-bromobutyl-2,3,3-trimethyl-5-hydroxy-3H-bromoindole, which was recorded as the intermediate 3. Then, the intermediate 3 was dried in a vacuum oven at 80 °C to a constant weight.

[0034] (4) Preparation of 2-hydroxy-3-methoxy-5-nitrobenzaldehyde

[0035] Weigh o-vanillin (yellow solid) (38.0 g, 0.25 mol) and dissolve it in 150 mL of glacial acetic acid. Add 65% to 68% nitric acid solution (22.5 g, 0.225 mol) dropwise to the mixture. After stirring at 0°C (ice-water bath) for 5 hours, the resulting reaction solution was evaporated at 110°C to remove the glacial acetic acid.

[0036] 300 ml of deionized water was added to the mixture obtained after removing the glacial acetic acid, and the mixture was cooled to 0° C. The formed precipitate was filtered and washed with deionized water to obtain light yellow solid 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, which was recorded as intermediate 4.

[0037] (5) Preparation of 2,3-dihydroxy-5-nitrobenzaldehyde Intermediate 4 (39.4 g, 0.2 mol) was weighed, HBr (85 g, 0.5 mol) was added, and the mixture was refluxed at 130 °C for 5 h. The resulting reaction solution was diluted with 200 mL of water and cooled to 0 °C. The formed precipitate was filtered to obtain yellow solid 2,3-dihydroxy-5-nitrobenzaldehyde, which was recorded as intermediate 5.

[0038] (6) Preparation of spiropyran

[0039] Weigh intermediate 3 (9.775 g, 0.025 mol) into a 250 ml two-necked bottle, then weigh intermediate 5 (4.575 g, 0.025 mol), add about 150 ml of ethanol as solvent, then add piperidine (2.125 g, 0.025 mol), heat under nitrogen at 85 °C for reflux reaction for 5 h to obtain a black solution.

[0040] The black solution was rotary evaporated at 80 °C to remove ethanol, and a black viscous product, 1-bromobutyl-3,3-dimethyl-5,8'-dihydroxy-6'-nitro-3H-indoline spirobenzopyran, was obtained. After being placed in a freezer for 24 h, the product could be scraped off to obtain the spiropyran unit SP.

[0041] Example 2 Synthesis of Imidazolium Ionic Liquid (IL)

[0042] Weigh 4,5-dihydroxymethyl-2-phenyl-1H-imidazole (pink solid powder) (4.081 g, 20 mmol) into a 250 ml round-bottom flask, then weigh potassium carbonate (white solid particles) (1.3821 g, 10 mmol) into the round-bottom flask, then add 80 ml DMAc solvent, reflux at 80 °C, and stir evenly until the solution turns orange-red.

[0043] 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 is completed, a black solution is obtained.

[0044] The black solution was filtered with a Buchner funnel, and the filtrate was rotary evaporated at 120 °C to remove the solvent DMAc to obtain a black viscous product imidazolium ionic liquid (IL).

[0045] Example 3 Synthesis of Spiropyran-type Photosensitive Polyionic Liquid (SP-IL) Polytetramethylene glycol (PTMG-1000) was dehydrated at 103 °C in vacuum for 1 h, and diphenylmethane diisocyanate (MDI) was added. At the beginning of the reaction, the catalyst dibutyltin dilaurate (DBTDL) was added, and then the reaction was carried out at 60 °C for 1 h, and then the temperature was raised to 80 °C for 1 h; SP was then added to extend the chain, and the temperature was raised to 120 °C for 3 h; IL was then added, and the reaction was continued at 120 °C for 2 h, and the material was discharged; the amount of catalyst DBTDL was 0.02% of the total mass of PTMG, MDI, SP and IL.

[0046] The specific material ratio is shown in Table 1 below: Table 1 Addition amount of each raw material of SP-IL

[0047] Example 4: Synthesized SP-IL material is prepared into an optoelectronic device by using a dispensing method: This example uses the MP1100 microelectronic printer "dispensing module" produced by Shanghai Mifang Electronic Technology Co., Ltd. for the first time to prepare a photosensitive polyionic liquid ultraviolet photoelectric device. The software is DB1.6.6. The device is divided into three layers, which are printed in the order of "bottom, middle and top". After each layer is printed, it is placed in the air to dry naturally. The actual picture is as follows Figure 2 (a).

[0048] The upper and lower layers (i.e. the first conductive layer and the second conductive layer) are both Elec-L705 conductive silver paste produced by Shenzhen Yilai Technology Co., Ltd. (silver-gray paste, viscosity 15000~25000 mPa·S, particle size ≤10 μm, solid content 62±5%, square resistance <60 mΩ / cm 2 , adhesion is 5 B, hardness is 80 D, solvent is DBE). The dispensing parameters are set as: dispensing speed is 1.5 mm / s, and dispensing air pressure is 80 MPa.

[0049] The middle layer is the synthetic SP-IL sample (first use the solvent ethyl acetate to dissolve the SP-IL sample, and use 1 mL of solvent for every 1 g of sample; then use the "dispensing module" to print). The dispensing parameters are set as follows: dispensing speed is 1.5 mm / s, and dispensing pressure is 20 MPa.

[0050] The shape and size of each layer are as follows Figure 2 As shown in (b)-(d).

[0051] Four SP-IL optoelectronic devices were prepared by the coating method of the existing literature and the dispensing method of Example 4 of the present invention, and the open circuit voltage test was performed. The coating method is as follows: first, the sample SP-IL is dissolved in ethyl acetate (1 mL of solvent is used for every 1 g of sample); then, the solution is sprayed on a PET transparent electrode (model: 190116-1.46) with Ni-Cu alloy deposited on the surface, 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 a pressure of 10 kN is pressed for 5 min at room temperature to ensure sufficient contact between the polyionic liquid and the electrode. Finally, after the wires are led out, dimethylsiloxane (PDMS) is used for encapsulation to obtain a photosensitive polyionic liquid ultraviolet optoelectronic device. The open circuit voltage test process is as follows: the two electrodes of the optoelectronic device are connected to an oscilloscope respectively; a UV lamp (power of 4 W, light intensity of 3100 μW / cm 2 ) irradiate the surface of the photoelectric device and record the real-time open circuit voltage data of the photoelectric device under ultraviolet light. The test results are shown in Figure 3A , Figure 3B And as shown in Table 2.

[0052] Table 2 Open circuit voltage of SP-IL devices prepared by coating method and dispensing method

[0053] The results show that the output open-circuit voltage of the device prepared by the dispensing method remains consistent within the error range, while the open-circuit voltage of the device prepared by the coating method has a large difference.

[0054] There are no similar reports at home and abroad. The present invention provides a new method for the preparation of photosensitive polyionic liquid ultraviolet photoelectric devices, and other similar polymer material photoelectric devices, piezoelectric devices, thermoelectric devices, etc. can also be used for reference.

[0055] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary 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: Preparing a photosensitive material; the photosensitive material is a spiropyran derivative, a spirooxazine derivative or an azobenzene derivative; Prepare an ionic liquid; the ionic liquid is an imidazolium ionic liquid or a quaternary ammonium salt ionic liquid; 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, the polyionic liquid photoelectric conversion material, and the second conductive layer are printed in sequence by a microelectronic printer to obtain the optoelectronic device.

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: When the photosensitive material is spiropyran, the 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 the 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 photosensitive polyionic liquid optoelectronic devices by dispensing according to claims 1 to 7, characterized in that: The method comprises: polymerizing spiropyran and imidazolium ionic liquid to obtain a polyionic liquid photoelectric conversion material; 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 adding spiropyran and reacting at 100-140°C for 2-4 h; then adding imidazolium ionic liquid and 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 photosensitive polyionic liquid optoelectronic devices 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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