CN108947927B - Alcohol/water-soluble organic small molecule cathode interface material with side chain containing aromatic heterocycle with high electron mobility - Google Patents
Alcohol/water-soluble organic small molecule cathode interface material with side chain containing aromatic heterocycle with high electron mobility Download PDFInfo
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Abstract
The invention provides a preparation method of an organic micromolecule cathode interface material with side chains containing aromatic heterocycles with high electron mobility and application of the organic micromolecule cathode interface material as a cathode interface layer in an organic solar cell. According to the invention, the aromatic heterocycle with high electron mobility is introduced on the side chain of the organic micromolecule, so that the electron transmission performance of the organic micromolecule interface material is improved, the thickness insensitivity of the organic micromolecule interface material is enhanced, the efficiency of the organic solar cell is improved, and the wet large-scale industrial production of the organic solar cell solar energy is facilitated. The material can be used as an interface layer to effectively prevent the performance reduction of devices caused by moisture, oxygen, light and the like, thereby obviously improving the stability of the organic solar cell. Meanwhile, the alcohol/water-soluble organic small molecular material has simple synthesis steps and low raw material price, and has great advantages in commercial application. The organic solar cell applying the interface material sequentially comprises the following structures from bottom to top: transparent glass, indium tin oxide anode, hole transport layer, active layer, cathode interface layer and metallic aluminum cathode.
Description
Technical Field
The invention relates to the technical field of organic solar cell materials, in particular to a preparation method of an alcohol/water-soluble organic micromolecule cathode interface material with a side chain containing aromatic heterocycle with high electron mobility and application of the alcohol/water-soluble organic micromolecule cathode interface material in an organic solar cell.
Technical Field
Since the industrial revolution, the use of energy has been increasing at a geometric level, and the most important energy currently for the development of human society is the traditional coal, oil and natural gas resources, but the sustainable development of human society is seriously threatened due to the non-renewable nature of the traditional energy. Meanwhile, the use of the traditional energy also brings great harm to human living environment, and influences the health and survival of human beings. Solar energy is an inexhaustible renewable energy source which is a necessary choice for the sustainable development of human society. Solar cells have received great attention in recent years as a means for directly converting solar energy into electric energy. Especially organic solar cells are considered as a representative of the next generation solar cells due to their advantages of light weight, flexibility, roll-to-roll mass production, etc. With the continuing efforts of researchers, the efficiency of current single-layer organic solar cells has exceeded 14%. However, since active metal calcium is generally used as a cathode interlayer in the preparation process of the conventional organic solar cell, great challenges are provided for the encapsulation of the device. With the development of a cathode interface and the use of an alcohol/water-soluble cathode interface layer, the stability and efficiency of the organic solar cell are greatly improved. However, the conductivity of the currently used alcohol/water-soluble cathode interface material is poor, so that strict requirements are imposed on the thickness of the interface layer in the preparation process, the thickness is generally controlled to be about 5 nanometers, and the precision is not favorable for the subsequent large-scale industrial production. The invention provides a preparation method of a cathode interface layer material insensitive to film thickness, namely, aromatic heterocyclic units with high electron mobility, such as thiadiazole, oxadiazole and the like, are introduced into side chains of an organic small molecular interface material, so that the conductivity of the material is improved, the cathode interface modification capability of the material is improved, and a technical guarantee is provided for preparing a high-efficiency cathode interface layer insensitive to film thickness.
According to the invention, monomers containing 2, 5-diphenyl-1, 3, 4-thiadiazole and 2, 5-diphenyl-1, 3, 4-oxadiazole flexible side chains are respectively prepared into an alcohol/water-soluble organic micromolecule cathode interface layer material by a Suzuki coupling method, and through the introduction of the high electron mobility structural units, the conductivity of the material is effectively improved, the cathode interface layer material insensitive to the film thickness is prepared, and the problem that the organic solar cell is not suitable for large-scale production is solved.
Disclosure of Invention
Based on the above, the present invention aims to provide a class of alcohol/water-soluble organic small molecule cathode interface materials with high electron mobility, and the materials are applied to organic solar cells as cathode interface layers. Importantly, functional groups with excellent electron transmission performance such as thiadiazole/oxadiazole and the like are introduced, so that the insensitivity of the film thickness is improved, and the wet large-scale industrial production of the organic solar cell is facilitated.
The technical scheme of the invention is as follows:
the invention provides an alcohol/water-soluble organic micromolecule cathode interface material with high electron mobility, which has the following general formula:
wherein R is C with terminal trimethyl ammonium bromide1-C12Alkyl groups of (a); a is an aromatic heterocyclic functional group with high electron mobility shown in a formula II, wherein R1Is C1-C12Alkyl or alkoxy of (a); x is a heteroatom such as O, S, Se or Te.
Preferred embodiment, R1Is C2-C8Alkoxy group of (a); x is O or S atom, A adopts group structures shown in formulas III and IV:
2. the organic small molecule cathode interface material as claimed in claim 1, wherein R is preferably C2-C8Linear alkyl or alkoxy groups of (a).
3. The small organic molecule cathode interface material according to claim 1, wherein X is preferably selected from O and S heteroatoms.
4. The organic small molecule cathode interface material according to claim 1, wherein a preferably has the following structure:
wherein R is1Is C2-C8Alkoxy group of (2).
The most preferred organic small molecule based cathode interface material has the following molecular structure:
the main advantages of the invention are:
1. the organic micromolecule cathode interface material has good alcohol/water solubility, can be dissolved in strong polar solvents such as methanol and the like, has limited solubility in dichloromethane, and is suitable for preparing devices by an orthogonal solvent method.
2. The organic micromolecule cathode interface material has good cathode modification capacity, can effectively reduce the work function of a metal cathode, improves ohmic contact with an active layer, and reduces contact resistance.
3. The organic micromolecule cathode interface material has higher conductivity, and can still obtain higher energy conversion efficiency when the prepared device film thickness reaches 50 nanometers when being applied to an organic solar cell.
Drawings
FIG. 1 is an ultraviolet-visible light absorption spectrum of an organic small molecule cathode interface material of the present invention;
FIG. 2 is a graph of the photoelectric conversion efficiency of the organic small molecule cathode interface material of the present invention;
FIG. 3 is a J-V curve of the organic small molecule cathode interface material O-TFBr of the present invention under different film thicknesses;
FIG. 4 is a J-V curve of the organic small molecule cathode interface material S-TFBr of the present invention under different film thicknesses;
fig. 5 is a structure of an organic solar cell applying the interface material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings.
The synthetic route of the alcohol/water-soluble organic micromolecule cathode interface material is as follows:
(i) sodium hydroxide (50%), tetrabutylammonium bromide, alkyl bromide; (ii)2-4,4,5, 5-tetramethyl- [1,3,2] -dioxaborane-9, 9-bis (3' -bromopropyl) fluorene, tetrakistriphenylphosphine palladium, anhydrous potassium carbonate, toluene; (3) tetrahydrofuran, trimethylamine
Example 1
Preparation of compound O-TFBr
The method comprises the following specific steps:
(1) synthesis of Compound 1a
2, 7-dibromo-9H-fluorene (0.31g, 0.97mmol) and a catalytic amount of tetrabutylammonium bromide were added to degassed dimethyl sulfoxide (60 mL). Then 4 ml of sodium hydroxide solution (50%) were added. At this time, the reaction solution turned deep red. Then, a solution of the compound 2- (4-bromomethylphenyl) -5- [ 4-hexyloxyphenyl ] - [1,3,4] oxadiazole (1.0 g, 2.41 mmol) in dimethyl sulfoxide (40 ml) was added dropwise. The reaction solution gradually became purple during the dropping process. Stirring was continued for 24 hours after the addition was complete. After the reaction, the reaction mixture was poured into 400mL of water to precipitate a solid. Filtering and drying the filter cake. Then purifying by column chromatography. 0.46 g of product is obtained, yield 48.0%.
The nmr spectrum of compound 1a was:1H NMR(400MHz,CDCl3,δ/ppm):7.99-7.94(m,4H,-ArH),7.70-7.64(m,1H,ArH),7.55-7.47(s,4H,-ArH),7.46-7.42(m,1H,ArH),7.39-7.36(m,2H,-ArH),7.22-7.19(m,2H,-ArH),7.01-6.74(m,8H,-ArH),4.12-3.99(m,4H,-CH2-),3.49-3.45(m,4H,-CH2-),1.83-1.75(m,4H,-CH2-),1.50-1.31(m,12H,-CH2-),0.94-0.86(m,6H,-CH3).13C NMR(100MHz,CDCl3,δ/ppm):164.4,163.9,161.9,149.0,139.7,138.9,131.0,130.6,128.6,127.6,125.9,122.2,121.5,120.9,116.1,114.9,68.2,57.2,45.3,31.6,29.1,25.7,22.6,14.0.
(2) synthesis of Compound 2a
Compound 1a (0.61 g, 0.62 mmol), 9-bis (3-bromopropylyl) -9H-fluorene-2-boronic acid pinacol ester (0.83 g, 1.56 mmol) were dissolved in 15 ml of degassed toluene, then 5 ml of degassed saturated potassium carbonate solution was added, and tetratriphenylphosphine palladium catalyst was added under argon. The reaction was refluxed for 24 hours. After the reaction was completed, 10 ml of water and 20 ml of dichloromethane were added. The organic layer was separated, and the organic layer was dried over anhydrous magnesium sulfate. Filtering, and concentrating the filtrate by using a rotary evaporator to obtain a crude product. Column chromatography of the crude product gave 0.92 g of a pale yellow solid in 49% yield.
The nmr spectrum of compound 2a was:1H NMR(400MHz,CDCl3,δ/ppm):7.90-7.59(m,22H,ArH),7.39-7.36(m,6H,ArH),6.99-6.93(s,8H,ArH),4.04-3.96(s,4H,-CH2-),3.62-3.55(s,4H,-CH2-),3.19-3.11(m,6H,-CH2-),2.45-2.18(m,6H,-CH2-),1.83-1.75(m,4H,-CH2-),1.56-1.21(m,20H,-CH2-),0.93-0.86(m,6H,-CH3).13C NMR(100MHz,CDCl3,δ/ppm):164.4,164.0,161.9,150.3,150.0,149.6,149.4,148.5,140.9,140.5,140.4,140.3,139.9,139.7,133.8,133.5,131.0,128.6,127.4,127.4,127.3,127.0,126.6,126.4,125.8,123.8,123.4,123.2,122.2,121.8,120.5,120.4,120.2,120.1,119.9,117.9,68.2,56.8,54.3,54.2,45.6,43.5,37.2,34.7,31.5,29.1,27.4,25.7,22.6,14.1.
(3) synthesis of Compound O-TFBr
Compound 2a (0.62 g, 0.38 mmol) was dissolved in 20 ml of tetrahydrofuran at 0 ℃, and an aqueous trimethylamine solution (33%, 5 ml) was added dropwise to the reaction system at room temperature, followed by heating to reflux and continuing the reaction for 3 hours. After the reaction is finished, the reaction solution is concentrated to 2 ml by rotary evaporation, and then is dropwise added into 300 ml of acetone, a large amount of solid is separated out, and a crude product is obtained by filtration. The crude product was isolated by column chromatography to give 0.34 g of product in 48.2% yield.
The nuclear magnetic spectrum of the compound O-TFBr is as follows:1H NMR(400MHz,CDCl3,δ/ppm):8.27-8.09(m,4H,ArH),8.05-7.83(m,10H,ArH),7.65-7.50(m,8H,ArH),7.49-7.40(m,6H,ArH),7.12-6.90(m,6H,ArH),4.10-3.90(s,8H,-CH2-),3.25-3.11(m,4H,-CH2-),2.92-2.84(s,36H,-CH3-Br),2.43-2.15(m,8H,-CH2-),1.86-1.65(m,4H,-CH2-),1.56-1.14(m,20H,-CH2-),0.94-0.86(m,6H,-CH3).13C NMR(100MHz,CDCl3,δ/ppm):164.6,164.2,162.4,149.3,148.5,142.7,140.8,140.7,140.2,139.2,131.0,128.4,127.8,127.7,126.8,126.5,125.2,123.4,121.6,120.9,120.5,120.2,114.9,69.2,66.3,58.6,57.5,54.7,54.2,52.0,35.6,31.4,30.8,29.4,28.8,25.4,22.3,18.0,13.0.
example 2
Preparation of Compound S-TFBr
The method comprises the following specific steps:
(1) synthesis of Compound 1b
2, 7-dibromo-9H-fluorene (0.31g, 0.97mmol) and a catalytic amount of tetrabutylammonium bromide were added to degassed dimethyl sulfoxide (60 mL). Then 4 ml of sodium hydroxide solution (50%) were added. At this time, the reaction solution turned deep red. Then, a solution of the compound 2- (4-bromomethylphenyl) -5- [ 4-hexyloxyphenyl ] - [1,3,4] thiadiazole (1.0 g, 2.41 mmol) in dimethyl sulfoxide (40 ml) was added dropwise thereto. The reaction solution gradually became purple during the dropping process. Stirring was continued for 24 hours after the addition was complete. After the reaction, the reaction mixture was poured into 400ml of water to precipitate a solid. Filtering and drying the filter cake. Then purifying by column chromatography. 0.46 g of product is obtained, yield 48.0%.
The nmr spectrum of compound 1b was:1H NMR(400MHz,CDCl3,δ/ppm):7.98-7.87(m,14H,ArH),7.84-7.78(m,2H,ArH),7.92-7.89(m,3H,ArH),7.76-7.74(m,3H,ArH),7.50-7.44(m,10H,ArH),7.02-6.96(m,6H,ArH),4.04-4.00(t,4H,-CH2-),2.06-2.03(s,4H,-CH2-),1.49-1.46(m,4H,-CH2-),1.37-1.34(m,6H,-CH2-),1.27-1.24(m,6H,-CH2-),0.93-0.91(t,6H,-CH3)13C NMR(100MHz,CDCl3,δ/ppm):167.0,161.6,161.5,149.3,146.5,141.3,139.1,138.9,138.5,138.3,132.7,131.7,130.9,130.8,129.4,128.8,128.4,127.9,127.8,120.1,127.6,126.9,122.5,121.6,120.8,115.0,68.2,65.9,57.2,53.5,46.1,45.1,31.6,29.4,29.1,25.7,22.6,14.1.
(2) synthesis of Compound 2b
Compound 1b (0.63 g, 0.62 mmol), 9-bis (3-bromopropylyl) -9H-fluorene-2-boronic acid pinacol ester (0.83 g, 1.56 mmol) was dissolved in 15 ml of degassed toluene, then 5 ml of degassed saturated potassium carbonate solution was added, and tetratriphenylphosphine palladium catalyst was added under argon. The reaction was refluxed for 24 hours. After the reaction was completed, 10 ml of water and 20 ml of dichloromethane were added. The organic layer was separated, and the organic layer was dried over anhydrous magnesium sulfate. Filtering, and concentrating the filtrate by using a rotary evaporator to obtain a crude product. Column chromatography of the crude product gave 0.47 g of a pale yellow solid in 46.3% yield.
The nmr spectrum of compound 2b was:1H NMR(400MHz,CDCl3,δ/ppm):7.90-7.59(m,22H,ArH),7.39-7.36(m,6H,ArH),6.97-6.95(s,8H,ArH),4.02-3.99(s,4H,-CH2-),3.62-3.58(s,4H,-CH2-),3.18-3.11(m,6H,-CH2-),2.45-2.18(m,6H,-CH2-),1.83-1.75(m,4H,-CH2-),1.55-1.16(m,20H,-CH2-),0.94-0.86(m,6H,-CH3).13C NMR(100MHz,CDCl3,δ/ppm):149.8,149.4,148.7,140.8,140.5,140.4,140.2,139.9,133.6,131.2,129.4,128.3,127.6,127.4,126.9,126.8,126.6,123.3,122.6,121.8,121.4,120.5,120.4,120.2,120.1,117.9,115.0,66.3,56.6,54.3,54.2,45.4,44.9,38.6,34.7,31.5,29.1,27.4,27.2,25.7,22.6,14.1.
(3) synthesis of Compound S-TFBr
Compound 2b (0.47 g, 0.28 mmol) was dissolved in 20 ml of tetrahydrofuran at 0 ℃, and an aqueous trimethylamine solution (33%, 5 ml) was added dropwise to the reaction system at room temperature, followed by heating to reflux and continuing the reaction for 3 hours. After the reaction is finished, the reaction solution is concentrated to 2 ml by rotary evaporation, and then is dropwise added into 300 ml of acetone, a large amount of solid is separated out, and a crude product is obtained by filtration. The crude product was isolated by column chromatography to give 0.26 g of product in 49.2% yield.
The nuclear magnetic spectrum of the compound S-TFBr is as follows:1H NMR(400MHz,CDCl3,δ/ppm):8.21-8.09(m,4H,ArH),7.85-7.63(m,14H,ArH),7.55-7.40(m,10H,ArH),7.02-6.90(m,8H,ArH),4.00-3.80(s,8H,-CH2-),3.35-3.11(m,4H,-CH2-),2.92-2.84(s,36H,-CH3-Br),2.13-2.45(m,8H,-CH2-),1.65-1.86(m,4H,-CH2-),1.14-1.56(m,20H,-CH2-),0.94-0.86(m,6H,-CH3).13C NMR(100MHz,CDCl3,δ/ppm):168.2,167.7,161.9,149.4,148.5,141.8,140.8,140.7,140.2,139.1,131.2,129.1,127.9,127.7,127.4,126.7,126.5,126.2,123.4,121.8,121.5,120.6,120.2,114.9,68.0,66.3,58.8,57.4,54.3,54.2,52.0,35.6,31.4,29.4,28.9,25.5,22.3,18.0,13.1.
example 3
Preparation of organic solar cell device
The method comprises the following specific steps:
4 mg PTBT and 6 mg PC71BM mixed and dissolved in 0.5 ml of chlorobenzene to obtain an active layer solution for later use. A layer of PEDOT PSS transparent film with the diameter of about 40 nanometers is prepared on indium tin oxide conductive glass in a spin coating mode and is annealed for 15 minutes at the temperature of 140 ℃. The annealed conductive glass was then transferred to a glove box, and the active layer solution prepared above was spin coated and then deposited on the active layer by spin coating in a methanol solution of the cathode interface layer of 0.5 mg/l of O-TFBr. And finally, evaporating a layer of metal aluminum electrode with the thickness of 100 nanometers on the cathode interface layer in a vacuum evaporation mode. The performance of the solar cell device is as follows: short circuit current is 17.64 milliampere/square centimeter; open circuit voltage is 0.78 volts; the fill factor was 73.4%; the energy conversion efficiency under simulated sunlight (a.m. 1.5100 milliwatts per square centimeter) is 10.10%.
Example 4
Preparation of organic solar cell device
The method comprises the following specific steps:
4 mg PTBT and 6 mg PC71BM mixed and dissolved in 0.5 ml of chlorobenzene to obtain an active layer solution for later use. A transparent film of PEDOT: PSS of about 40nm was prepared by spin coating on ITO conductive glass and annealed at 140 ℃ for 15 minutes. The annealed conductive glass was then transferred to a glove box, spin coated with the active layer solution, and then deposited on the active layer by spin coating on the prepared cathode interface layer material of 0.5 mg/l S-TFBr. And finally, evaporating a layer of metal aluminum electrode with the thickness of 100 nanometers on the cathode interface layer in a vacuum evaporation mode. The performance of the solar cell device is as follows: short circuit current is 17.22 milliampere/square centimeter; open circuit voltage is 0.78 volts; the filling factor is 70.4%; the energy conversion efficiency under simulated sunlight (AM 1.5; 100 mw/cm) was 9.45%.
Example 5
The performance of the compounds O-TFBr and S-TFBr was analyzed as follows:
(1) spectral analysis of Compounds O-TFBr and S-TFBr
The absorption spectra of the compounds O-TFBr and S-TFBr in methanol solution and film-forming state are shown in FIG. 1, the compounds have obvious absorption in the range of 200-400 nm, and do not compete with the active layer for absorption in the solar cell.
(2) Photovoltaic performance analysis of compounds O-TFBr and S-TFBr
The photovoltaic performance of the compounds O-TFBr and S-TFBr is shown in FIG. 2. The results show that devices based on both O-TFBr and S-TFBr have good photovoltaic performance. The device short circuit current based on the compound S-TFBr was 17.22 milliamperes per square centimeter; open circuit voltage is 0.78 volts; the fill factor was 70.4% and the energy conversion efficiency under simulated sunlight (AM 1.5; 100 mw/cm) was 9.45%. The short-circuit current of the device based on O-TFBr is 17.64 milliampere/square centimeter; open circuit voltage is 0.78 volts; the fill factor was 73.4% and the energy conversion efficiency under simulated sunlight (AM 1.5; 100 mw/cm) was 10.10%. See table 1 for detailed data.
Table 1 is based on PTB 7: PC (personal computer)71Device parameters when BM is an active layer and O-TF or S-TF is an interfacial layer
Photovoltaic data of O-TFBr and S-TFBr at different film thicknesses are shown in FIG. 3, and detailed data are shown in Table 2. The result shows that the electron mobility of the device is obviously enhanced by introducing the functional group with high electron transport property through the side chain, and the efficiency of the device is not sensitive to the thickness of the cathode interface material.
Table 2 cathode interfacial layer based on PTB7 at different film thicknesses: PC (personal computer)71Device parameters of BM active layer
In conclusion, the invention provides an alcohol/water-soluble organic small molecule cathode interface material with a side chain containing high electron mobility. The material has good solubility in methanol, and can be used for preparing organic solar cell devices by an orthogonal solvent method. Due to the introduction of the aromatic heterocyclic conjugated side chain with high electron transmission performance, the organic micromolecule interface material has better conductivity and insensitivity to film thickness, and is suitable for large-scale industrial preparation of organic solar cells. When the material provided by the invention is used as a cathode interface layer, the device efficiency of more than 10 percent is obtained.
The discussion of any embodiment above is meant to be exemplary only, and not limiting as to the scope of the disclosure (including the claims). For the sake of brevity and conciseness, combinations of features between different embodiments and other variations in different aspects are not provided in full detail under the inventive concept. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be within the scope of the invention.
Claims (2)
1. An alcohol/water-soluble organic small molecule cathode interface material with a side chain containing aromatic heterocycle with high electron mobility is characterized by having a molecular structure shown in a formula (I):
Ⅰ
wherein R is C with terminal trimethyl ammonium bromide1-C12Alkyl groups of (a); a is an aromatic heterocyclic functional group with high electron mobility shown in a formula II, wherein R1Is C1-C12Alkyl or C1-C12Alkoxy group of (a); x is a heteroatom of O or S;
Ⅱ。
2. the organic small molecule cathode interface material according to claim 1, wherein R is R1Is C2-C8Straight chain alkyl or C2-C8Linear alkoxy groups of (1).
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| Conjugated Oligoelectrolyte Electron Transport/Injection Layers for Organic Optoelectronic Devices;Renqiang Yang等;《J.AM.CHEM.SOC.》;20080227;第130卷;第3282页Scheme 1 * |
| Solvent Effects on the Architecture and Performance of Polymer White-Light-Emitting Diodes with Conjugated Oligoelectrolyte Electron-Transport Layers;Yunhua Xu等;《Advanced Materials》;20081125;第21卷;第585页Figure 1 * |
| Synthesis and Characterization of Conjugated Oligoelectrolytes Based on Fluorene and Carbazole Derivative and Application of Polymer Solar Cell as a Cathode Buffer Layer;Thu Trang Do等;《Macromolecular Research》;20151231;第23卷(第4期);第371页Scheme I * |
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