CN113087875A - Water/alcohol soluble full furan polymer material, preparation method and application thereof - Google Patents

Water/alcohol soluble full furan polymer material, preparation method and application thereof Download PDF

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CN113087875A
CN113087875A CN202110318337.7A CN202110318337A CN113087875A CN 113087875 A CN113087875 A CN 113087875A CN 202110318337 A CN202110318337 A CN 202110318337A CN 113087875 A CN113087875 A CN 113087875A
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CN113087875B (en
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高跃岳
尚陆文
何盛华
黄军意
谭付瑞
岳根田
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Henan University
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Abstract

The application discloses a water/alcohol soluble all-furan polymer material, a preparation method and application thereof, wherein the structural formula of the target polymer is as follows:
Figure DEST_PATH_IMAGE002
n =10~30, wherein R1Is composed of
Figure DEST_PATH_IMAGE004
、
Figure DEST_PATH_IMAGE006
，x=2~8，R2Is composed of
Figure 161770DEST_PATH_IMAGE004
、
Figure 100004_DEST_PATH_IMAGE008
And y =3~ 8. In addition, the series of polymers PFF designed and synthesized by the invention has a better molecular conjugate plane, a higher HOMO energy level and a better light capture capability, and most importantly, the structural target polymer can be well dissolved in benign solvents (water/ethanol) with different proportions. Based on polymers PFF1 and PFF2 with receptor side chains of triethylene glycol monomethyl ether and tetraethylene glycol monomethyl ether as examples, the corresponding organic photovoltaic device can be prepared without depending on an expensive glove box by adopting a green solvent in the whole process, and particularly, the two polymers can obtain better photoelectric conversion efficiency under the condition of adding green degradable p-methoxybenzaldehyde.

Description

Water/alcohol soluble full furan polymer material, preparation method and application thereof
Technical Field
The invention belongs to the field of organic synthesis and organic photovoltaic cell application, and particularly relates to a water/alcohol soluble all-furan polymer material, and a preparation method and application thereof.
Background
Organic Photovoltaic (OPVs) cells are "sandwich" type energy conversion devices constructed by placing a photoactive layer between two electrodes, wherein the photoactive layer is generally a bulk heterojunction formed by blending a p-type Organic semiconductor material and an n-type Organic semiconductor material. The organic photovoltaic cell is concerned by scientific research personnel of universities and enterprises due to the advantages of wide material sources, strong molecular modifiability, light weight, capability of preparing large-area flexible devices, environmental protection and the like. More attractive, with the research and development of high-efficiency organic semiconductor materials, the modification of device interface layers and the improvement of device preparation processes, the maximum photoelectric conversion efficiency of a single organic photovoltaic cell in a laboratory at present exceeds 18 percent, reaches the commercialization threshold and shows great commercial prospects.
The premise of commercialization of the organic photovoltaic cell is that besides the photoelectric conversion efficiency of the device is continuously improved, the development of low-cost organic semiconductor materials and the development of green and environment-friendly device preparation processes are also of great significance. At present, the efficient p-type organic semiconductor material is mainly a condensed ring conjugated polymer constructed by thiophene. Thiophenes are mainly industrial petroleum derivatives and have limited reserves. In addition, although thiophene can also be prepared in large quantities by an industrial method, the related preparation method has the defects of high energy consumption, high pollution and high cost, and is contrary to the low-cost green environmental protection property of the organic photovoltaic cell. Furan, which is a family compound of thiophene, has various preparation methods, wherein the industrial preparation energy consumption is low, the pollution is small, and furan can be purified and prepared by fermenting biomass (straws, rotten vegetable leaves, hay and the like), so that furan and derivatives thereof have great development potential in the development of low-cost organic semiconductor materials. In addition, although the high-efficiency p-type organic semiconductor material is mainly a condensed ring conjugated polymer, the synthesis of the polymer is complex, the post-treatment is complex, and the cost is high, so that the preparation of the organic photovoltaic cell in a large area is limited. Therefore, the development of non-condensed ring high-efficiency conjugated polymers is also an urgent need for large-area industrialization of organic photovoltaic cells.
At present, the preparation of high-efficiency organic photovoltaic cells usually depends on the use of halogen-containing solvents and halogen-containing additives (chloroform, chlorobenzene, dichlorobenzene, 1, 8-diiodooctane, 1-chloronaphthalene and the like), and the halogen-containing reagents are not natural products, need to be prepared by an energy-consuming industrial method, and are relatively expensive. Meanwhile, the halogen-containing reagents have potential hazards to cell gene mutation, skin burn and vision damage of workers using the related organic photovoltaic cells, and the problems are more serious particularly in the large-area industrialization process of the organic photovoltaic cells. In addition, with the increasing awareness of environmental protection, many countries in the world have also made strict requirements and regulations on the use of halogen-containing reagents. Therefore, the development of green and environmentally friendly organic semiconductor materials and device fabrication industries thereof is extremely important for the commercialization of organic photovoltaic cells.
Disclosure of Invention
The invention aims to provide a water/alcohol soluble all-furan polymer material, a preparation method and application thereof.
The invention designs and synthesizes a water/alcohol soluble type all-furan polymer material, which has the following structural formula:
Figure DEST_PATH_IMAGE001
n=10~30，
wherein R is1Is composed of
Figure 456814DEST_PATH_IMAGE002
、
Figure DEST_PATH_IMAGE003
，x=2~8，R2Is composed of
Figure 373954DEST_PATH_IMAGE002
、
Figure 966741DEST_PATH_IMAGE004
，y=3~8。
The preparation method of the water/alcohol soluble all-furan polymer material has the following synthetic route:
Figure DEST_PATH_IMAGE005
the synthesis steps of the target polymer are as follows:
(1) adding liquid bromine (Br)2) Dropwise adding the acetic acid (HAc) solution into the acetic acid solution of the compound 1, stirring at 85-95 ℃ under an inert atmosphere until the reaction is complete, and carrying out post-treatment to obtain a compound 2;
(2) dissolving compound 2, Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in anhydrous dichloromethane according to a proportion, and dropwise adding R in an inert atmosphere at room temperature1Stirring and reacting at 35-45 ℃ to complete reaction, and performing post treatment to obtain a compound 3;
(3) the compound R2adding-OH, potassium tert-butoxide (t-BuOK) and cuprous iodide (CuI) into a reaction bottle, and stirring at room temperature for 1.0-3.0 h to obtain a solution; dropwise adding the compound 4 into the solution, stirring at 95-105 ℃ until the reaction is complete, and carrying out post-treatment to obtain a compound 5;
(4) dissolving the compound 5 in anhydrous tetrahydrofuran, dropwise adding n-hexane solution of n-butyllithium (n-BuLi) at low temperature, and continuously stirring at low temperature for 1.0-3.0 h; uniformly and dropwise adding 2-trimethyltin chloride n-hexane solution into the solution, continuously stirring at low temperature for 1.0-2.0 h, naturally returning to room temperature, stirring for 6.0-12.0 h, and performing post-treatment to obtain a compound 6;
(5) dissolving the compound 3 and the compound 6 in a mixed solvent of toluene and N, N-dimethylformamide, and adding a catalyst of tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) Ligand tris (o-tolyl) phosphine (P (o-tol)3) And refluxing until the reaction is complete, and performing post-treatment to obtain the target polymer PFF.
Further, the compound 1 of step (1) is reacted with Br2The molar ratio of (1.0) - (4.0-10.0), the compound 2, DCC, DMAP and R in the step (2)1The molar ratio of-OH to-OH is 1.0 (1.0-3.0): 0.2-1.0): 1.0-10.0, and the compound 2, t-BuOK, CuI and R in the step (3)2The molar ratio of-OH is 1.0 (1.0-3.0): 0.2-1.0): 1.0-10.0, the molar ratio of the compound 5, n-BuLi and trimethylstannic chloride in the step (4) is 1.0 (2.0-3.0): 2.0-3.0), the compound 3, the compound 6, Pd in the step (5)2(dba)3And P (o-tol)3The molar ratio of (1.0) - (1.5) to (0.03) - (0.05) to (0.1-0.2) is 1.0.
Preferably, the compound 1 of step (1) is reacted with Br2The molar ratio of (A) to (B) is 1.0, (5.0-6.0); compounds 2, DCC, DMAP and R described in step (2)1The molar ratio of-OH to-OH is 1.0 (1.2-1.5): (0.3-0.5): 5.0-7.0); the compounds 2, t-BuOK, CuI and R in the step (3)2The molar ratio of-OH is 1.0 (1.5-2.0): (0.2-0.5): 2.0-3.0); the molar ratio of the compound 5, n-BuLi and trimethyl tin chloride in the step (4) is 1.0 (2.2-2.5) to (2.1-2.4).
Further, the reaction low temperature in the step (4) is-100 to-80 oC, optimum temperature is-78oC。
Furthermore, the volume ratio of the toluene to the N, N-dimethylformamide in the step (5) is 10.0 (1.0-3.0), and the optimal ratio is 10.0: 1.0. Particularly, the post-treatment of the target polymer in the step (5) is to cool the mixed solution to room temperature, add the mixed solution into n-hexane and stir for 1.0h to 3.0h, then filter and collect the solid, place the solid in a soxhlet extractor, sequentially extract the solid with petroleum ether, n-hexane and chloroform for 10.0h to 24.0h respectively, finally remove most of the solvent from the chloroform solution under reduced pressure, add the remaining viscous mixture into n-hexane again for precipitation, filter and dry to obtain the target polymer PFF.
The method for preparing the organic photovoltaic device based on the water/alcohol soluble all-furan polymer material comprises the following steps:
(1) cleaning the ITO conductive glass;
(2) drying the ITO conductive glass by using high-purity nitrogen flow, and then placing the ITO conductive glass in an ozone atmosphere for treatment;
(3) preparing a ZnO electron transport layer;
(4) taking a target polymer PFF as a donor material, and co-dissolving the target polymer PFF and an acceptor material PBCO-12 in a mixed solvent of high-purity water/absolute ethyl alcohol to obtain a photosensitive layer precursor solution; preheating ZnO to a certain temperature, and spin-coating a photosensitive layer precursor solution on the ZnO to prepare a photosensitive layer;
(5) vacuum evaporation of MoO on photosensitive layer3A hole transport layer;
(6) in MoO3And (4) performing vacuum evaporation on the metal Ag on the hole transport layer to prepare the photo-anode.
The photosensitive layer donor material is a water/alcohol soluble all-furan polymer material with different side chains, wherein a representative target polymer molecular structure is as follows:
Figure 361950DEST_PATH_IMAGE006
，n=18，
Figure DEST_PATH_IMAGE007
， n=14。
further, the photosensitive layer is prepared as follows:
PFF and PBCO-12 are dissolved in a mixed solvent of high-purity water/absolute ethyl alcohol according to a mass ratio of 1.0 to 1.25, stirring is carried out for 2.0h to 4.0h at 60 to 90 ℃ to obtain a photosensitive layer precursor liquid, a ZnO electron transport layer is preheated for 5mins to 10mins at 75 to 80 ℃, the photosensitive layer precursor liquid is spin-coated on the electron transport layer at a rotating speed of 2000 to 4000rpm, the volume ratio of the high-purity water to the absolute ethyl alcohol is 9:91, and the concentration of the PFF in the high-purity water/absolute ethyl alcohol is 4 to 7 mg/mL.
Further, the preparation process of the ZnO electron transport layer of the device is as follows: the precursor solution is zinc acetate dihydrate (C)4H10O6Zn) in 2-methoxyethanol and adding an ethanolamine stabilizer, wherein C4H10O6The mol ratio of Zn, 2-methoxyethanol to ethanolamine is 1.0 (0.5-1.0): (20.0-30.0), ZnO precursor liquid is spin-coated at the spin-coating speed of 3000-5000 rpm, pre-annealed at 120-150 ℃ for 1-10 mins, and annealed at 200-250 ℃ for 20-60 mins, and the ZnO precursor liquid is obtained.
Furthermore, p-methoxybenzaldehyde is added into the photosensitive layer precursor liquid, and the addition amount of the p-methoxybenzaldehyde is 1-3% of the volume of the photosensitive layer precursor liquid.
According to the organic photovoltaic device prepared by the preparation method, the thickness of the ZnO electron transmission layer is 35-40 nm, the thickness of the photosensitive layer is 90-100nm, and MoO3The thickness of the hole transport layer is 8-10 nm, and the thickness of the photo-anode is 90-100 nm.
The water/alcohol soluble all-furan polymer material is applied to the field of organic photovoltaic devices.
The technical scheme of the invention at least has the following beneficial effects:
(1) the invention designs and synthesizes a series of polymer materials which can be dissolved in environment-friendly solvents (water and ethanol);
(2) the prepared full furan polymer is a non-condensed ring polymer, and has the advantages of cheap synthetic raw materials, simple synthesis and low cost;
(3) the all-furan polymer prepared by the invention has excellent photophysical property and photovoltaic property;
(4) the organic photovoltaic device prepared by the invention completely avoids the use of halogen-containing solvents or additives, and greatly reduces the safety and expandability of the preparation of the organic photovoltaic device.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of a water/alcohol soluble all-furan polymer according to the present invention;
FIG. 2 is a schematic structural view of an organic photovoltaic device made according to the present invention;
FIG. 3 is a graph showing UV-VIS absorption spectra of solutions and films of PFF1 and PFF2 in example 3 of the present invention;
FIG. 4 is a molecular structural formula of an organic photovoltaic device receptor material in accordance with the present invention;
FIG. 5 is a schematic diagram showing electron orbital levels of PFF1, PFF2 and PBCO-12 in example 4 of the present invention;
FIG. 6 shows PFF1: PBCO-12 (1: 1.15, mass ratio) based device and PFF2: PBCO-12 (1: 1.20, mass ratio) based device in example 6 of the present invention J-a V curve;
FIG. 7 shows PFF1: PBCO-12 (1: 1.15 mass ratio; 2.5% by volume p-methoxybenzaldehyde added) and PFF2: PBCO-12 (1: 1.20 mass ratio; 1.0% by volume p-methoxybenzaldehyde added) devices in example 7 of the present inventionJ-a V curve;
FIG. 8 is AFM and TEM pictures of PFF1: PBCO-12 (1: 1.15, mass ratio) blended film and PFF2: PBCO-12 (1: 1.20, mass ratio) blended film in example 6 of the present invention, wherein a, d are TEM pictures; b and e are AFM height maps; and c and f are AFM phase diagrams.
Figure 9 is an AFM and TEM picture of PFF1: PBCO-12 (1: 1.15, mass ratio; 2.5% v p-methoxybenzaldehyde added) blended film and PFF2: PBCO-12 (1: 1.20, mass ratio; 1.0% v p-methoxybenzaldehyde added) blended film in example 7 of the present invention, wherein a, d are TEM pictures; b and e are AFM height maps; and c and f are AFM phase diagrams.
Detailed Description
To make the purpose, technology and advantages of the present invention clearer and more complete description of the technical solutions related to the present invention will be given below with reference to specific embodiments of the present invention, and it will be apparent to those skilled in the art that various modifications may be made without departing from the principles of the embodiments of the present invention, and these modifications are also considered as the scope of the embodiments of the present invention.
Example 1
Synthesis of water/alcohol-soluble all-furan polymer material PFF1:
Figure DEST_PATH_IMAGE009
Figure DEST_PATH_IMAGE010
(1) preparation of Compound 2
3-Furanecarboxylic acid (compound 1, 1.12 g, 10.0 mmol) and 80mL of acetic acid were charged into a 250mL two-necked flask equipped with a tail gas absorber (which was a saturated aqueous solution of sodium hydroxide), a coiled reflux condenser and a constant pressure dropping funnel, and stirred at room temperature for 0.5h under an inert atmosphere. A solution of liquid bromine in acetic acid (1 mol/L, 52 mmol) was added dropwise to a two-necked flask via a constant pressure dropping funnel, and after the addition, the temperature was slowly raised to 90 ℃ and stirred overnight. After the reaction was cooled to room temperature, the mixture was slowly added to 250mL of ice water and stirring was continued at room temperature for 0.5 h. Saturated aqueous sodium sulfite solution was slowly added to the above solution until the mixture became light in color. The mixture was filtered and the filter cake was recrystallized from hot water to give compound 2 in a mass of 1.82g with a yield of 68%.1H-NMR(400MHz, DMSO, TMS):δ 6.95 (s, H)。
(2) Preparation of Compound 3a
Placing the compound 2 (0.94 g, 3.5 mmol), DCC (0.91 g, 4.4 mmol) and DMAP (0.16 g, 1.3 mmol) in a 50mL double-neck flask provided with a reflux condenser tube and a constant-pressure dropping funnel, vacuumizing and filling nitrogen for 3-4 times in a circulating way, adding 20 mL of anhydrous dichloromethane under the protection of nitrogen, and stirring at room temperature for 0.5 h. Tetraethylene glycol monomethyl ether (4.16 g, 20 mmol) was added to the mixture via a constant pressure dropping funnel and slowly warmed to 40 ℃ with stirring for 10.0 h. And cooling the reaction to room temperature, pouring the mixture into deionized water, extracting the water phase by using 3X 30mL of dichloromethane, combining the dichloromethane phases, washing the dichloromethane phases for 3-4 times by using the deionized water, and drying the dichloromethane organic phase by using anhydrous sodium sulfate. Separating the crude product by silica gel column chromatography, loading with n-hexane/ethyl acetate (volume ratio 6: 5) as eluent, collecting target solution,and the solvent was spun off under reduced pressure to give compound 3a in a mass of 0.83g with a yield of 52%.1H-NMR(400MHz, CDCl3, TMS):δ 6.91 (s, H)，4.17 (t, J = 5.6 Hz, 2H)，3.83 (t, J = 5.2 Hz, 2H)，3.69 (q, J = 4.7 Hz, 2H)，3.72 (q, J = 4.8 Hz, 2H)，3.55 (m, 8H)，3.31 (s, 3H)。
(3) Preparation of Compound 5
Cuprous iodide (2.86 g, 15 mmol) and potassium tert-butoxide (2.58 g, 23 mmol) were placed in a 100mL two-necked flask equipped with a reflux condenser and an isobaric dropping funnel, evacuated and nitrogen-filled for 3-4 cycles, and diethylene glycol monomethyl ether (18.02 g, 150 mmol) was added via the isobaric dropping funnel. The mixture was stirred at room temperature for 1.0h, then 3-bromofuran (11.02 g, 75 mmol) was added via a constant pressure dropping funnel, and after the addition was completed, the temperature was slowly raised to 100 ℃ for reaction for 24.0 h. After the reaction was cooled to room temperature, the mixture was poured into deionized water, the aqueous phase was extracted with 3X 30mL of dichloromethane, and the dichloromethane phases were combined and dried over anhydrous sodium sulfate. And (3) separating the crude product by silica gel column chromatography, loading the crude product by a wet method, taking n-hexane/ethyl acetate (volume ratio is 3: 2) as eluent, collecting a target solution, and performing decompression to spin out the solvent to obtain a compound 5 with the mass of 8.37g and the yield of 60%.1H-NMR(400MHz, CDCl3, TMS):δ 7.01 (s, H)，δ 6.89 (d, J = 5.2 Hz，H)，δ 6.03 (d, J = 5.4 Hz，H)，4.31 (t, J = 4.8 Hz, 2H)，3.79 (t, J = 4.7 Hz, 2H)，3.54 (m, 4H)，3.30 (s, 3H)。
(4) Preparation of Compound 6
The compound 5 (1.86 g, 10.0 mmol) is placed in a 50mL single-neck flask, the flask is vacuumized and filled with nitrogen for 3-4 times in a circulating mode, and 20 mL of anhydrous tetrahydrofuran is added under the protection of nitrogen. The reaction flask was placed in a liquid nitrogen/ethanol bath (-78 ℃) and stirred for 0.5 h. 8.4mL of n-butyllithium in n-hexane (2.5mol/L, 21mmol) were slowly added dropwise, and stirring was continued for 0.5h in a liquid nitrogen/ethanol bath. An n-hexane solution of trimethyltin chloride (1.0 mol/L, 21mL, 21mmol) was slowly added dropwise, and stirring was continued for 0.5h in a liquid nitrogen/ethanol bath after the addition was complete. Then, naturally return toAnd continuously stirring for 4.0-6.0 h when the temperature is raised to the room temperature until the reaction is complete. The mixture was poured into deionized water and extracted with dichloromethane. The organic phases were combined and washed with saturated brine, the organic phase was dried over anhydrous sodium sulfate, filtered and the organic solvent was decanted. The crude product is firstly quickly pretreated by a neutral silica gel column, then partial impurities are removed by reduced pressure distillation to obtain a target compound 6 with the mass of 3.44g and the yield of 67 percent,1H-NMR(400MHz, CDCl3, TMS):δ 6.01 (s, H)，4.33 (t, J = 4.8 Hz, 2H)，3.81 (t, J = 4.7 Hz, 2H)，3.55 (m, 4H)，3.31 (s, 3H)，0.65-0.31 (m, 18H)。
(5) preparation of target Polymer PFF1
Compound 3a (0.3 mmol, 137 mg), compound 6 (0.3 mmol, 154 mg) was added to the charge N2In a 25.0 mL single neck flask with a protective device. Then, vacuumizing and filling nitrogen for 3-4 times in a circulating way, and rapidly adding Pd under the protection of nitrogen2(dba)3（0.012mmol，11mg），P(o-tol)3(0.04 mmol, 12 mg) and 10mL of anhydrous toluene, 1mL of anhydrous N, N-dimethylformamide were injected with a syringe. After the addition, the single-neck flask was again evacuated and charged with nitrogen. The mixture was then heated rapidly to 100 ℃ and observed for changes in viscosity. When the rotor speed in the reaction flask slowed and the mixture was tacky, 0.1 mL of 2-tributylstannane furan end-capping agent was injected with a syringe and stirring was continued for 2.0 h. 0.1 mL of the 2-bromofuran blocking agent was then injected with a syringe and stirring was continued for 2.0 h. After the mixture was cooled to room temperature, it was slowly added to 100mL of n-hexane and stirred for 2.0 h. Filtering and collecting solid, placing the solid in a Soxhlet extractor, and sequentially extracting with 80mL petroleum ether, 80mL n-hexane and 80mL chloroform for 8.0h-12.0 h. Finally, the chloroform solution was rotary evaporated under reduced pressure to remove most of the solvent, and the remaining viscous mixture was added dropwise to 100mL of n-hexane to precipitate again, filtered, and dried under vacuum at 50 ℃ to obtain PFF1 (57.2 mg, 61%), GPC (chlorobenzene) as a dark blue solid, Mn =8.6 kDa, Mw =18.3 kDa, n =18, and PDI = 2.13.
Example 2
Figure 238639DEST_PATH_IMAGE011
(6) Preparation of Compound 3b
Placing the compound 2 (0.94 g, 3.5 mmol), DCC (0.91 g, 4.4 mmol) and DMAP (0.16 g, 1.3 mmol) in a 50mL double-neck flask provided with a reflux condenser tube and a constant-pressure dropping funnel, vacuumizing and filling nitrogen for 3-4 times in a circulating way, adding 20 mL of anhydrous dichloromethane under the protection of nitrogen, and stirring at room temperature for 0.5 h. Pentaethylene glycol monomethyl ether (5.04 g, 20 mmol) was added to the mixture via a constant pressure dropping funnel and slowly warmed to 50 ℃ with stirring for 12.0 h. And cooling the reaction to room temperature, pouring the mixture into deionized water, extracting the water phase by using 3X 30mL of dichloromethane, combining the dichloromethane phases, washing the dichloromethane phases for 3-4 times by using the deionized water, and drying the dichloromethane organic phase by using anhydrous sodium sulfate. And (3) separating the crude product by silica gel column chromatography, loading the crude product by a wet method, taking n-hexane/ethyl acetate (volume ratio is 6: 5) as eluent, collecting a target solution, and performing decompression to remove the solvent to obtain a compound 3 with the mass of 1.18g and the yield of 67%.1H-NMR(400MHz, CDCl3, TMS):δ 6.64 (s, H)，4.35 (t, J = 4.8 Hz, 2H)，3.81 (t, J = 4.6 Hz, 2H)，3.72 (q, J = 5.0 Hz, 2H)，3.66 (q, J = 5.2 Hz, 2H)，3.54 (m, 12H)，3.30 (s, 3H)。
(7) Preparation of target Polymer PFF2
Compound 6 (0.25 mmol, 128.5 mg), compound 3b (0.25 mmol, 125.5 mg) was added to the charge N2In a 25.0 mL single neck flask with a protective device. Then, vacuumizing and filling nitrogen for 3-4 times in a circulating way, and rapidly adding Pd under the protection of nitrogen2(dba)3（0.011mmol，10mg），P(o-tol)3(0.043 mmol, 13 mg) and 10mL of dry toluene, 1mL of dry N, N-dimethylformamide were injected with a syringe. After the addition, the single-neck flask was again evacuated and charged with nitrogen. The mixture was then heated rapidly to 100 ℃ and observed for changes in viscosity. When the rotor speed in the reaction flask slowed and the mixture was tacky, 0.1 mL of 2-tributylstannane furan end-capping agent was injected with a syringe and stirring was continued for 2.0 h. Followed by injection of 0.1 by syringemL of end-capping reagent on 2-bromofuran and stirring was continued for 2.0 h. After the mixture was cooled to room temperature, it was slowly added to 100mL of n-hexane and stirred for 2.0 h. Filtering and collecting solid, placing the solid in a Soxhlet extractor, and sequentially extracting with 80mL petroleum ether, 80mL n-hexane and 80mL chloroform for 8.0h-12.0 h. Finally, the chloroform solution was rotary evaporated under reduced pressure to remove most of the solvent, and the remaining viscous mixture was added dropwise to 100mL of n-hexane to precipitate again, filtered, and dried under vacuum at 50 ℃ to obtain PFF2 (64.4 mg, 55%), GPC (chlorobenzene) Mn =7.4 kDa, Mw =16.5 kDa, n =14, and PDI =2.22 as a dark blue solid.
The following examples are the photophysical properties, electron orbital energy levels, and applications of water/alcohol soluble all-furan polymer materials in organic photovoltaic devices.
Example 3
The water/alcohol-soluble all-furan polymer materials (PFF 1 and PFF 2) prepared in examples 1-2 were dissolved with water/ethanol (V: V, 9: 91) to prepare 10-4mg/mL solution, and 60. mu.L of water/ethanol solution was spin-coated on the pretreated quartz glass using a pipette, air-dried, and the UV-visible absorption spectrum of the polymer film was tested as shown in FIG. 3. According to the UV-Vis absorption spectrum of the film by formula Egap=1240/λonsetThe optical energy gaps of PFF1 and PFF2 under the spectrum are calculated to be 1.90eV and 1.89eV respectively, and the material belongs to a wide-band-gap polymer material.
Example 4
The water/alcohol-soluble all-furan polymer materials (PFF 1 and PFF 2) prepared in examples 1-2 were dissolved with water/ethanol (V: V, 9: 91) to prepare 10-4mg/mL solution, 60 μ L water/ethanol solution is measured by a pipette and spin-coated on the pretreated quartz glass, the solution is naturally air-dried, the electron orbital level of the film of the polymer is tested by using ultraviolet electron spectroscopy, and as shown in FIG. 5, the HOMO energy levels of PFF1 and PFF2 are-5.27 eV and-5.22 eV. Combining the optical bandgaps of the two polymers, using the equation | < E >LUMO│=│EHOMO│−EgapThe LUMO energy levels of PFF1 and PFF2 are calculated to be-3.37 eV and-3.33 eV, and are well matched with the PBCO-12 energy levels (HOMO-5.71 eV and LUMO-3.86 eV) of the water/alcohol-soluble fullerene derivative acceptor material.
Example 5
According to the absorption spectrum and the electron orbital level of the water/alcohol-soluble all-furan polymer materials (PFF 1 and PFF 2) prepared by the invention, the water/alcohol-soluble all-furan polymer materials (PFF 1 and PFF 2) and PBCO-12 are blended to prepare the organic solar cell, and the specific process is as follows:
1) cleaning an ITO conductive glass substrate: the ITO conductive glass substrate (12 omega/square) is sequentially subjected to ultrasonic cleaning for 20mins by using a detergent, deionized water, ultrapure water, ethanol, acetone and isopropanol.
2) ITO pretreatment: the ITO was blown dry with a stream of nitrogen and then treated in an ozone atmosphere for 30 mins.
3) Preparing an electron transport layer: 0.2807g of zinc acetate dihydrate (C) were taken4H10O6Zn) dissolved in 2.56ml of 2-methoxyethanol and added with 78. mu.l of an ethanolamine stabilizer, wherein C4H10O6The mol ratio of Zn, 2-methoxyethanol and ethanolamine is 1.0:0.78:26.0, stirring is carried out for 2 hours at room temperature to prepare zinc oxide precursor solution, then the zinc oxide precursor solution is filtered by a 0.22 mu m organic microporous filter membrane filter, then spin coating is carried out on the treated ITO substrate by a spin coater at the speed of 5000rpm for 30 seconds, and then pre-annealing is carried out for 5mins at 120 ℃ and annealing is carried out for 30mins at 220 ℃, and the thickness of the layer film is about 40 nm.
4) Preparing a photosensitive layer: PFF1 or PFF2 and PBCO-12 are dissolved in water/ethanol (V: V, 9: 91) at 75oStirring for at least 2.0h under C, and spin-coating the photosensitive layer film on the ZnO layer at 3000rpm for 40s by a spin coater.
5) Preparing a hole transport layer: MoO thermal evaporation by utilizing vacuum coating equipment3The thickness of the display can be regulated and controlled by controlling the display through the crystal oscillator.
6) Preparing a photo-anode: at 3X 10-4Preparing a photo-anode by thermally evaporating Ag under Pa vacuum degree, wherein the effective area of the cell is 3.114 mm2。
7) And testing the photovoltaic performance of the device. Tests show that the device prepared based on the water/alcohol soluble all-furan polymer material obtains more than poor efficiency without any post-treatment, and the device can obtain nearly 2% of photoelectric conversion efficiency after p-methoxybenzaldehyde is added, so that the device belongs to one of high-efficiency all-water/alcohol soluble photosensitive devices.
Example 6
The bulk heterojunction photovoltaic device prepared by adopting PFF1 as a donor material and PBCO-12 as an acceptor material has the structure of ITO/ZnO (40nm)/PFF1: PBCO-12 (90nm)/MoO3(8nm)/Ag (90 nm). The device performance was best when PFF1 was 5mg/mL in water/ethanol (V: V, 9: 91) and the mass ratio of PFF1 to PBCO-12 was 1:1.15, as shown in FIG. 6, with Voc=0.71 V，J sc =3.18mA/cm2，FF=34.7%，PCE=0.78%。
The bulk heterojunction photovoltaic device prepared by using PFF2 as a donor material and PBCO-12 as an acceptor material has the structure of ITO/ZnO (40nm)/PFF2: PBCO-12 (98nm)/MoO3(8nm)/Ag (90 nm). The device performance was best when PFF2 was 6mg/mL in water/ethanol (V: V, 9: 91) and the mass ratio of PFF1 to PBCO-12 was 1:1.20, as shown in FIG. 6, with Voc=0.66 V，J sc =2.87mA/cm2，FF=30.9%，PCE=0.56%。
The higher open circuit voltage of PFF 1-based devices compared to PFF 2-based devices stems from the higher HOMO level of PFF 1; the higher short-circuit current of the PFF 1-based device is derived from the higher molecular conjugate plane, wider absorption and stronger crystallinity of the PFF 1-based device; the poor fill factors of PFF1 and PFF2 devices resulted from the rougher surface topography of both, and furthermore PFF1: PBCO-12 bulk morphology observed large numbers of aggregates, while PFF1: PBCO-12 bulk morphology phase separated less significantly, as shown in fig. 8.
Example 7
The bulk heterojunction photovoltaic device prepared by adopting PFF1 as a donor material and PBCO-12 as an acceptor material has the structure of ITO/ZnO (40nm)/PFF1: PBCO-12 (90nm)/MoO3(8nm)/Ag (90 nm). When PFF1 was 5mg/mL in water/ethanol (V: V, 9: 91) and the mass ratio of PFF1 to PBCO-12 was 1:1.15, the device performance was best when p-methoxybenzaldehyde was added at 2.5% by volume of the photosensitive layer precursor solution, as shown in FIG. 7, where V isoc=0.71 V，J sc =4.67mA/cm2，FF=55.6%，PCE=1.84%。
The bulk heterojunction photovoltaic device prepared by using PFF2 as a donor material and PBCO-12 as an acceptor material has the structure of ITO/ZnO (40nm)/PFF2: PBCO-12 (98nm)/MoO3(8nm)/Ag (90 nm). When PFF2 was present at a concentration of 6mg/mL in water/ethanol (V: V, 9: 91) and the mass ratio of PFF1 to PBCO-12 was 1:1.20, the best device performance was obtained when p-methoxybenzaldehyde was added at 1.0% by volume of the photosensitive layer precursor solution, as shown in FIG. 7, where V isoc=0.66 V，J sc =4.87mA/cm2FF =44.2%, PCE = 1.42%. After the p-methoxybenzaldehyde is added, the device performance is mainly due to the reduction of the surface morphology roughness of the photosensitive layer and the slight improvement of the phase separation, as shown in fig. 9.
The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention are considered to be within the scope of the present invention.

Claims (10)

1. A water/alcohol soluble all-furan polymer material is characterized in that: the molecular structural formula of the water/alcohol-soluble all-furan polymer material is as follows:
Figure 181668DEST_PATH_IMAGE001
n =10~30, wherein R1Is composed of
Figure 36491DEST_PATH_IMAGE002
、
Figure 816228DEST_PATH_IMAGE003
，x=2~8，R2Is composed of
Figure 401318DEST_PATH_IMAGE002
、
Figure 215690DEST_PATH_IMAGE004
，y=3~8。
2. The method for preparing the water/alcohol-soluble all-furan polymer material of claim 1, wherein the synthetic route is as follows:
Figure 975836DEST_PATH_IMAGE005
the specific synthesis steps are as follows:
(1) adding liquid bromine (Br)2) Dropwise adding the acetic acid (HAc) solution into the acetic acid solution of the compound 1, stirring at 85-95 ℃ under an inert atmosphere until the reaction is complete, and carrying out post-treatment to obtain a compound 2;
(2) dissolving compound 2, Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in anhydrous dichloromethane according to a proportion, and dropwise adding R in an inert atmosphere at room temperature1OH, stirring and reacting at 35-45 ℃ until the reaction is complete, and carrying out post-treatment to obtain a compound 3;
(3) the compound R2adding-OH, potassium tert-butoxide (t-BuOK) and cuprous iodide (CuI) into a reaction bottle, and stirring at room temperature for 1.0-3.0 h to obtain a solution; dropwise adding the compound 4 into the solution, stirring at 95-105 ℃ until the reaction is complete, and carrying out post-treatment to obtain a compound 5;
(4) dissolving the compound 5 in anhydrous tetrahydrofuran, dropwise adding n-hexane solution of n-butyllithium (n-BuLi) at low temperature, and continuously stirring at low temperature for 1.0-3.0 h; uniformly and dropwise adding 2-trimethyltin chloride n-hexane solution into the solution, continuously stirring at low temperature for 1.0-2.0 h, naturally returning to room temperature, stirring for 6.0-12.0 h, and performing post-treatment to obtain a compound 6;
(5) dissolving the compound 3 and the compound 6 in a mixed solvent of toluene and N, N-dimethylformamide, and adding a catalyst of tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) Ligand tris (o-tolyl) phosphine (P (o-tol)3) And refluxing until the reaction is complete, and performing post-treatment to obtain the target polymer PFF.
3. The method for preparing a water/alcohol-soluble all-furan polymeric material as claimed in claim 2, wherein the step (1) is performedCompound 1 with Br2The molar ratio of (1.0) - (4.0-10.0), the compound 2, DCC, DMAP and R in the step (2)1The molar ratio of-OH to-OH is 1.0 (1.0-3.0): 0.2-1.0): 1.0-10.0, and the compound 2, t-BuOK, CuI and R in the step (3)2The molar ratio of-OH is 1.0 (1.0-3.0): 0.2-1.0): 1.0-10.0, the molar ratio of the compound 5, n-BuLi and trimethylstannic chloride in the step (4) is 1.0 (2.0-3.0): 2.0-3.0), the compound 3, the compound 6, Pd in the step (5)2(dba)3And P (o-tol)3The molar ratio of (1.0) - (1.5) to (0.03) - (0.05) to (0.1-0.2) is 1.0.
4. The method for preparing a water/alcohol-soluble all-furan polymeric material as claimed in claim 3, wherein the compound 1 and Br in step (1)2The molar ratio of (A) to (B) is 1.0, (5.0-6.0); compounds 2, DCC, DMAP and R described in step (2)1The molar ratio of-OH to-OH is 1.0 (1.2-1.5): (0.3-0.5): 5.0-7.0); the compounds 2, t-BuOK, CuI and R in the step (3)2The molar ratio of-OH is 1.0 (1.5-2.0): (0.2-0.5): 2.0-3.0); the molar ratio of the compound 5, n-BuLi and trimethyl tin chloride in the step (4) is 1.0 (2.2-2.5) to (2.1-2.4).
5. The method for preparing an organic photovoltaic device by using the water/alcohol-soluble all-furan-based polymer material as claimed in claim 1, wherein the steps are as follows:
(1) cleaning the ITO conductive glass;
(2) drying the ITO conductive glass by using high-purity nitrogen flow, and then placing the ITO conductive glass in an ozone atmosphere for treatment;
(3) preparing a ZnO electron transport layer;
(4) taking a target polymer PFF as a donor material, and co-dissolving the target polymer PFF and an acceptor material PBCO-12 in a mixed solvent of high-purity water/absolute ethyl alcohol to obtain a photosensitive layer precursor solution; preheating ZnO to a certain temperature, and spin-coating a photosensitive layer precursor solution on the ZnO to prepare a photosensitive layer;
(5) vacuum evaporating on the photosensitive layerMoO plating3A hole transport layer;
(6) in MoO3And (4) performing vacuum evaporation on the metal Ag on the hole transport layer to prepare the photo-anode.
6. The method for the preparation of an organic photovoltaic device according to claim 5, characterized in that the target polymer PFF is in particular a compound of the following structure:
Figure 242869DEST_PATH_IMAGE006
，n=18，
Figure DEST_PATH_IMAGE008
， n=14。
7. the method of claim 5, wherein the photosensitive layer is prepared by the following steps:
PFF and PBCO-12 are dissolved in a mixed solvent of high-purity water/absolute ethyl alcohol according to the mass ratio of 1.0 (1.0-1.25), stirring is carried out for 2.0h-4.0h at the temperature of 60-90 ℃ to obtain a photosensitive layer precursor solution, a ZnO electron transport layer is preheated for 5 min-10 min at the temperature of 75-80 ℃, the photosensitive layer precursor solution is spin-coated on the electron transport layer, the volume ratio of the high-purity water to the absolute ethyl alcohol is 9:91, and the concentration of the PFF in the high-purity water/absolute ethyl alcohol is 4-7 mg/mL.
8. The method of making an organic photovoltaic device according to claim 5, wherein the ZnO electron transport layer of the device is made by: the precursor solution is zinc acetate dihydrate (C)4H10O6Zn) in 2-methoxyethanol and adding an ethanolamine stabilizer, wherein C4H10O6The mol ratio of Zn, 2-methoxyethanol to ethanolamine is 1.0 (0.5-1.0) to 20.0-30.0, the ZnO precursor solution is spin-coated, pre-annealed at 120-150 ℃ for 1-10 mins, and annealed at 200-250 ℃ for 20-60 mins, and the ZnO/2-ethanolamine/ZnO composite material is obtained.
9. The method for preparing an organic photovoltaic device according to claim 5 or 7, wherein the green degradable p-methoxybenzaldehyde is added into the photosensitive layer precursor solution in an amount of 1% to 3% by volume of the photosensitive layer precursor solution.
10. The organic photovoltaic device prepared by the preparation method of any one of claims 5 to 9, wherein the thickness of the ZnO electron transport layer is 35-40 nm, the thickness of the photosensitive layer is 90-100nm, and MoO is3The thickness of the hole transport layer is 8-10 nm, and the thickness of the photo-anode is 90-100 nm.
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