CN109749058B - Anthracene bithiophene imide polymer and preparation method and application thereof - Google Patents
Anthracene bithiophene imide polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an anthradithiophene imide polymer and a preparation method and application thereof. The structural formula of the anthradithiophene imide polymer is shown as a formula I, wherein R is C1～C60Linear or branched alkyl. The compound shown in the formula I can be used as a semiconductor layer for preparing a polymer field effect transistor. The mobility (mu) and the on-off ratio of the organic field effect transistor prepared by taking the anthradithiophene imide polymer as the semiconductor layer are both very high (mu is more than 4cm at most)2V‑1s‑1On-off ratio of greater than 104) And the method has good application prospect in organic field effect transistors.
Description
Technical Field
The invention relates to an anthradithiophene imide polymer and a preparation method and application thereof, belonging to the field of materials.
Background
Organic semiconductor materials have been rapidly developed in recent years. Devices such as organic field effect transistors, organic solar cells, organic light emitting diodes and the like, which are prepared from organic semiconductor layer materials, are receiving wide attention. Compared with the traditional inorganic material, the organic material has the advantages of adjustable and controllable structure, low cost, easy preparation of flexible devices and the like, has great advantages in the aspects of ink-jet printing, roll-to-roll processing and the like, and becomes one of the latest research hotspots.
Imide-like molecules are the current focus of research. The modified polyester has a controllable energy level structure, and alkyl chains can be introduced to improve the solubility and improve the processability. By introducing different alkyl chains, the self-assembly performance of molecules and the stacking structure of the film can be effectively adjusted, so that the purpose of adjusting and controlling the electrical performance of the film is achieved. In addition, the highly condensed ring structure has good planarity and pi-pi interaction, is favorable for arrangement and accumulation among molecules, and improves the performance of a device.
Disclosure of Invention
The invention aims to provide an anthradithiophene imide compound and researches the application of the anthradithiophene imide compound in a field effect transistor.
The structural general formula of the anthradithiophene imide polymer provided by the invention is shown as the formula I:
in the formula I, R is C1～C60Is straight-chain or branched alkyl and may be C1～C24The straight-chain or branched alkyl group of (1) may be specifically n-octyl, 4-decyltetradecyl or 2-decyltetradecyl;
the group pi is a common copolymerization unit, and can be specifically selected from any one of the following groups:
In the copolymerization unit,
represents a substitution bit;
n is 5 to 100, specifically, n can be 5 to 60 or 10 to 13, more specifically, n is 10 or 13.
The polymer shown in the formula I provided by the invention can be polymer PADTDI-BT or PADTDI-FBT;
wherein the structural formula of the polymer PADTDI-BT is as follows:
the structural formula of the polymer PADTDI-FBT is as follows:
the invention further provides a preparation method of the polymer shown in the formula I, which comprises the following steps:
under the action of a catalyst and a ligand, a compound (2, 8-dibromo anthraceno [1,2-b:5,6-b' ] dithiophene-4, 5,10, 11-diimide) shown in a formula IV and a bis-methyl tin compound are subjected to polymerization reaction, and a polymer shown in the formula I is obtained after the reaction is finished;
r is as defined for R in formula I above.
In the above method, the bis-methyl tin compound is selected from any one of the following compounds:
The catalyst is at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, tris (dibenzylideneacetone) dipalladium and bis (dibenzylideneacetone) palladium;
the ligand is selected from at least one of triphenylphosphine, tri (o-tolyl) phosphine, tri (furyl) phosphine and triphenylarsine.
The molar ratio of the compound of formula IV, the bis-methyl tin compound, the catalyst, and the ligand may be 1: 0.95-1.05: 0.01-0.10: 0.04 to 0.40.
The feeding molar ratio of the compound shown in the formula IV, the dimethyl tin compound, the catalyst and the ligand is specifically 1.0: 1.0: 0.035: 0.27, 1.0: 1.0: 0.028: 0.226 or 1.0: 1.0: 0.034: 0.28.
in the step of polymerization reaction, the temperature is 100-130 ℃, specifically 110 ℃;
the time is 6 to 24 hours;
the polymerization reaction is carried out in a solvent;
the solvent is specifically selected from at least one of toluene, chlorobenzene, and tetrahydrofuran.
In addition, the compound shown in the formula IV as the starting material in the above method also belongs to the protection scope of the invention.
In the formula IV, R is the same as the definition of R in the formula I; specifically, it may be 2-decyltetradecyl.
The compound shown in the formula IV can be prepared according to the following steps: 2-oxo-2- (thien-3-yl) acetic acid was synthesized according to the literature (Hatanaka, M.; Ishimaru, T.J.Med.chem.1973,16,978.). Other starting materials were all commercial:
1) reacting 2, 5-dibromo-1, 4-p-phenylenediacetic acid in a methanol solution under the catalysis of sulfuric acid to obtain dimethyl 2,2' - (2, 5-dibromo-1, 4-phenyl) diacetate shown in a formula V after the reaction is finished;
2) reacting 2-oxo- (thiophene-3-yl) acetic acid with thionyl chloride, and dropwise adding the obtained product into concentrated ammonia water after the reaction to obtain 2-oxo- (thiophene-3-yl) acetamide shown in the formula VI;
3) reacting 2,2'- (2, 5-dibromo-1, 4-phenyl) diacetic acid dimethyl ester shown in the formula V obtained in the step 1) with 2-oxo- (thiophene-3-yl) acetamide shown in the formula VI obtained in the step 2) in the presence of alkali to obtain 4,4' - (2, 5-dibromo-1, 4-phenyl) bis (3- (thiophene-3-yl) -1H-pyrrole-2, 5-dione shown in the formula VII after the reaction is finished;
4) reacting 4,4'- (2, 5-dibromo-1, 4-phenyl) bis (3- (thiophene-3-yl) -1H-pyrrole-2, 5-dione) shown in formula VII obtained in the step 3) with potassium carbonate and alkyl halide to obtain 4,4' - (2, 5-dibromo-1, 4-phenyl) bis (1-alkyl-3- (thiophene-3-yl) -1H-pyrrole-2, 5-dione) shown in formula VIII after the reaction is finished;
in the formula VIII, R is the same as the definition of R in the formula I; specifically, it may be 2-decyltetradecyl.
5) Reacting 4,4'- (2, 5-dibromo-1, 4-phenyl) bis (1-alkyl-3- (thiophene-3-yl) -1H-pyrrole-2, 5-diketone) shown in the formula VIII obtained in the step 4) with alkali under the action of a catalyst to obtain anthra [1,2-b:5,6-b' ] dithiophene-4, 5,10, 11-diimide shown in the formula IX after the reaction is finished;
in the formula IX, R is as defined for R in the formula I. Specifically, it may be 2-decyltetradecyl.
6) Reacting the anthra [1,2-b:5,6-b '] dithiophene-4, 5,10, 11-diimide shown in the formula IX obtained in the step 5) with N-bromosuccinimide to obtain 2, 8-dibromo anthra [1,2-b:5,6-b' ] dithiophene-4, 5,10, 11-diimide shown in the formula IV after the reaction is finished.
In step 1) of the above method, the ratio of the charged amounts of the 2,2' - (2, 5-dibromo-1, 4-phenyl) diacetic acid, the sulfuric acid and the methanol is 20 mmol: 1-2 mL: 20-50 mL, preferably 20 mmol: 2mL of: 30 mL; in the reaction step, the temperature is 65-70 ℃, and the time is 3-12 hours;
in the step 2), the feeding molar ratio of the 2-oxo- (thiophene-3-yl) acetic acid to the thionyl chloride to the concentrated ammonia water is 1: 1.2-2.0: 10-20, preferably 1:1.7: 14; in the reaction step, the reaction temperature of the 2-oxo- (thiophene-3-yl) acetic acid and thionyl chloride is 65-75 ℃, and the reaction time is 3-6 hours; then reacting with ammonia water at room temperature for 0.5 hour;
in the step 3), the alkali is at least one of sodium ethoxide, potassium tert-butoxide and sodium tert-butoxide; the feeding molar ratio of the 2,2' - (2, 5-dibromo-1, 4-phenyl) diacetic acid dimethyl ester to the 2-oxo- (thiophene-3-yl) acetamide to the alkali is 1: 2-3: 5-10, preferably 1:2.1: 6; in the reaction step, the temperature is 25-60 ℃, and the time is 3-12 hours;
in the step 4), the alkyl halide is C1～C60The alkyl bromide or the alkyl iodide can be at least one of linear chain or branched chain alkyl bromide or alkyl iodide, and specifically can be 1-iodo-2-decyltetradecane or 1-iodo-4-decyltetradecane; the feeding molar ratio of the 4,4' - (2, 5-dibromo-1, 4-phenyl) bis (3- (thiophene-3-yl) -1H-pyrrole-2, 5-diketone), the potassium carbonate and the alkyl halide is 1: 2-5: 2.0-3.0, preferably 1:3: 2.5; in the reaction step, the temperature is 25-60 ℃, and the time is 3-12 hours;
in the step 5), the catalyst is selected from at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, tris (dibenzylideneacetone) dipalladium and bis (dibenzylideneacetone) palladium; the alkali is at least one of potassium acetate, potassium carbonate and cesium carbonate; the feeding molar ratio of the 4,4' - (2, 5-dibromo-1, 4-phenyl) bis (1-alkyl-3- (thiophene-3-yl) -1H-pyrrole-2, 5-dione), the catalyst and the alkali is 1: 0.01-0.20: 2-10, preferably 1:0.05: 3; in the reaction step, the temperature is 100-140 ℃, and the time is 3-12 hours;
in the step 6), the feeding molar ratio of the anthra [1,2-b:5,6-b' ] dithiophene-4, 5,10, 11-diimide to the N-bromosuccinimide is 1: 2.0-5.0, preferably 1: 2.3; in the reaction step, the temperature is 25-65 ℃ and the time is 3-12 hours;
the reactions in the steps 1) to 6) are all carried out in a solvent. In the step 1), the solvent is methanol; in the step 2), the solvent is at least one selected from 1, 2-dichloroethane, dichloromethane, chloroform and acetonitrile; in the step 3), the solvent is at least one selected from methanol and ethanol; in the step 4), the solvent is at least one selected from the group consisting of N, N '-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone and N, N' -dimethylacetamide; in the step 5), the solvent is at least one selected from the group consisting of N, N '-dimethylformamide, N-methylpyrrolidone and N, N' -dimethylacetamide; in the step 6), the solvent is at least one selected from the group consisting of N, N' -dimethylformamide, tetrahydrofuran, acetic acid, trifluoroacetic acid and chloroform.
The synthetic routes (formula I and formula IV) of the above process are shown in fig. 6.
The application of the compound shown in the formula I in the preparation of the polymer field effect transistor and the polymer field effect transistor using the compound as a semiconductor layer also belong to the protection scope of the invention.
The invention has the advantages that:
1. the raw material is a commercial product and can be popularized to the synthesis of anthradithiophene imide polymers containing substituents with different lengths;
2. the anthradithiophene imide monomer has central symmetry and high planarity, and is beneficial to the self-assembly of polymer molecules;
3. the anthradithiophene imide polymer molecule has proper energy level and band gap, and is expected to be applied to other photoelectric devices such as organic photovoltaic devices;
4. the mobility (mu) and the on-off ratio of the organic field effect transistor prepared by taking the anthradithiophene imide polymer as the semiconductor layer are both very high (mu is more than 4cm at most)2V-1s-1On-off ratio of greater than 104) And the method has good application prospect in organic field effect transistors.
Drawings
FIG. 1 is a diagram of the UV-VIS absorption spectrum of an anthradithiophene imide polymer provided by the present invention.
FIG. 2 is a cyclic voltammogram of an anthradithiophene imide polymer provided by the present invention.
Fig. 3 is a schematic structural diagram of an anthradithiophene imide polymer field effect transistor provided by the present invention.
FIG. 4 is a graph showing the output characteristics and transfer characteristics of a polymer field effect transistor using an anthradithiophene imide polymer as a semiconductor layer according to the present invention (upper graph is PADTDI-BT, and lower graph is PADTDI-FBT).
FIG. 5 is an atomic force microscope (upper panel is PADTDI-BT, lower panel is PADTDI-FBT, and from left to right, annealing is performed at room temperature, 60 deg.C, 100 deg.C, and 140 deg.C) of the anthraquinonedithiophene imide polymer as a semiconductor layer.
FIG. 6 is a synthetic route provided by the present invention for preparing compounds of formula I.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The synthetic procedures used in the examples below for 2, 5-dibromo-1, 4-p-phenylenediacetic acid and 2-oxo- (thiophen-3-yl) acetic acid were synthesized according to literature procedures (chem.Commun.2013,49,7552; J.Med.chem.1973,16,978.).
Example 1 preparation of the Polymer PADTDI-BT
The synthetic route shown in FIG. 1.
1) Synthesis of dimethyl 2,2' - (2, 5-dibromo-1, 4-phenyl) diacetate
2, 5-dibromo-1, 4-p-phenylenediacetic acid (7.223g,20.5mmol) was added to 30mL of methanol, and 2mL of sulfuric acid was added as a catalyst. After the reaction was boiled for 6 hours, it was poured into water and filtered. Recrystallization from methanol/tetrahydrofuran gave the product as a white solid (7.42g, yield: 95.2%). The structural characterization data is as follows:
mass spectrum: EI: [ M]+calcd for C12H12Br2O4:380,found:380.
Nuclear magnetic hydrogen and carbon spectra:1H NMR(300MHz,CDCl3)7.50(s,2H),3.74(s,4H),3.72(s,6H).13C NMR(75MHz,CDCl3)170.28,135.15,135.02,123.82,52.36,40.79.
2) synthesis of 2-oxo- (thiophen-3-yl) acetamide
2-oxo- (thiophen-3-yl) acetic acid (15.0g,96.0mmol) and excess thionyl chloride (12mL) were dissolved in chloroform (50mL) the solution was boiled with heat for 6 hours to prepare the corresponding 2-oxo- (thiophen-3-yl) acetyl chloride in situ. After the solvent was removed by spinning, the mixture was diluted with anhydrous tetrahydrofuran. The solution was slowly dropped into an excess of cold saturated aqueous ammonia (100mL), and after stirring the reaction for 0.5 hour, a large amount of a brownish white solid was precipitated. After washing with water, drying gives the crude product. The crude product was chromatographed on a silica gel column (eluent ethyl acetate: petroleum ether: 1: 2) to give a white solid (8.2g, yield: 55.0%).
The structural characterization data is as follows:
mass spectrum: EI: [ M]+calcd for C6H5NO2S:155,found:155。
Nuclear magnetic hydrogen and carbon spectra:1H NMR(300MHz,DMSO-d6)8.74(dd,J＝2.8,1.3Hz,1H),8.20(s,1H),7.87(s,1H),7.66(dd,J＝5.1,2.8Hz,1H),7.59(dd,J＝5.1,1.3Hz,1H).13C NMR(75MHz,DMSO-d6)183.67,166.15,138.90,137.75,128.19,127.81.
3) synthesis of 4,4' - (2, 5-dibromo-1, 4-phenyl) bis (3- (thiophen-3-yl) -1H-pyrrole-2, 5-dione)
2-oxo- (thien-3-yl) acetic acid (1.63g,10.5mmol) and dimethyl 2,2' - (2, 5-dibromo-1, 4-phenyl) diacetate (1.90g,5.0mmol) were added to ethanol (50mL), and after stirring, sodium tert-butoxide (2.88g,30.0mmol) was added. The reaction suspension was stirred at room temperature overnight and then allowed to warm to 60 ℃ for 6 hours. After cooling, the reaction was quenched with saturated ammonium chloride solution, filtered, and the product was washed with water, ethanol, methanol, and cold acetone to give a yellow solid (1.89g, yield: 64.0%). The product was used directly in the next step without further purification.
Nuclear magnetism:1H NMR(300MHz,DMSO-d6)11.34(s,2H),8.32–8.18(m,2H),7.97(d,J＝1.2Hz,2H),7.77–7.56(m,2H),6.80(m,2H).
4) synthesis of 4,4' - (2, 5-dibromo-1, 4-phenyl) bis (1- (2-decyltetradecyl) -3- (thiophen-3-yl) -1H-pyrrole-2, 5-dione)
4,4' - (2, 5-dibromo-1, 4-phenyl) bis (3- (thiophen-3-yl) -1H-pyrrole-2, 5-dione) (1.20g,2.03mmol) was dissolved in N, N-dimethylformamide (30mL), potassium carbonate (0.843g,6.10mmol) was added under argon protection, the temperature was raised to 70 ℃ and the reaction was carried out for 0.5 hour, and then 1-iodo-2-decyltetradecane (2.36g,5.08mmol) was added dropwise and the reaction was carried out for 6 hours. The reaction mixture was extracted with ethyl acetate after adding water, and the organic phase was washed with saturated brine, separated, and dried over sodium sulfate. After the solvent was removed by rotary evaporation, the column was passed through petroleum ether/toluene to obtain a yellow amorphous solid (2.30g, yield: 71.6%).
Mass spectrum: HR-MALDI-TOF: [ M + Na ]]+calcd for C70H106Br2NaN2O4S2:1283.58380,found:1283.58358.
Nuclear magnetism:1H NMR(300MHz,CDCl3)8.33–8.27(m,2H),7.63–7.62(m,2H),7.33–7.28(m,2H),7.03–6.97(m,2H),3.56(d,J＝7.2Hz,4H),1.88(m,2H),1.23(m,80H),0.87(m,12H).
5) synthesis of N, N' -di (2-decyltetradecyl) -anthracenedithiophene diimide
4,4' - (2, 5-dibromo-1, 4-phenyl) bis (1- (2-decyltetradecyl) -3- (thiophen-3-yl) -1H-pyrrole-2, 5-dione) (2.36g,1.87mmol), potassium acetate (0.552g,5.62mmol) were dissolved in N, N-dimethylacetamide (110mL) under argon protection, stirred to dissolve, palladium tetratriphenylphosphine (115mg,0.1mmol) was added, reacted for 4 hours, cooled, poured into methanol, and filtered. The crude product was subjected to a petroleum ether/tetrahydrofuran column to give an orange solid (1.70g, yield: 82.6%).
Mass spectrum: HR-MALDI-TOF: [ M + H ]]+calcd for C70H105N2O4S2:1101.75103,found:1101.75096.
Nuclear magnetism:1H NMR(300MHz,CDCl3)9.72(s,2H),8.15(d,J＝5.3Hz,2H),7.80(d,J＝5.3Hz,2H),3.66(d,J＝7.2Hz,4H),1.97(m,2H),1.37–1.23(m,80H),0.84(m,12H).13C NMR(75MHz,CDCl3)169.45,168.49,144.26,129.44,129.30,128.69,127.45,124.24,123.02,120.46,42.39,37.46,31.94,31.61,30.14,29.74,29.69,29.38,26.53,22.69,14.12.
6) synthesis of N, N' -di (2-decyltetradecyl) -2, 8-dibromoanthracenedithiophene diimide
NBS (404mg, 2.27mmol) was added to a mixed solution of N, N' -bis (1-decyltetradecyl) -anthradithiophene diimide (1.00g, 0.907mmol) in acetic acid (10mL) and trifluoroacetic acid (10mL), and the reaction mixture was heated to 65 ℃ and stirred for 12 hours. The reaction mixture was poured into water, extracted with dichloromethane and dried over sodium sulfate. After removing the solvent, the crude product was subjected to column chromatography using toluene/petroleum ether to obtain a red solid (0.28g, yield: 24.5%).
Mass spectrum: HR-MALDI-TOF: [ M + H ]]+calcd for C70H103Br2N2O4S2:1257.57205,found:1257.57242.
Nuclear magnetism:1H NMR(300MHz,Chloroform-d)9.64(s,2H),8.17(s,2H),3.67(d,J＝7.2Hz,4H),1.95(s,2H),1.36(m,80H),0.85(m,12H).13C NMR(126MHz,373K,CDCl2CDCl2)169.49,168.22,145.76,130.33,129.05,127.46,126.39,125.59,124.23,121.72,118.64,42.94,37.44,32.09,31.81,29.93,29.58,29.54,29.49,29.19,26.56,22.52,13.87.
7) synthesis of Polymer PADTDI-BT
5,5' -bis (trimethylstannyl) -2,2' -bithiophene (49.2mg,0.1mmol), N ' -bis (2-decyltetradecyl) -2, 8-dibromoanthracenedithiophene diimide of the formula IV (126.0mg,0.1mmol), the catalyst tris (dibenzylideneacetone) dipalladium (4.5mg,0.0049mmol), the ligand tris (o-tolyl) phosphine (12.3mg,0.0404mmol) and chlorobenzene (5mL) were added to a reaction flask, oxygen was removed by three freeze-pump-thaw cycles under argon, and the reaction mixture was heated to 130 ℃ for 24h of polymerization. After cooling, the mixture was added to a mixture of 200mL of methanol/5 mL of hydrochloric acid, stirred at room temperature for 1 hour, and filtered. The polymer obtained was extracted with a soxhlet extractor. Firstly, methanol, acetone and normal hexane are used for extraction until the mixture is colorless, micromolecules and catalysts are removed, and then chloroform is used for extraction to obtain a final product of 110mg, wherein the yield is 87.0%.
The structural characterization data is as follows:
molecular weight: GPC Mn＝12.0kDa,PDI＝2.04，n＝10。
Nuclear magnetic hydrogen spectrum:1H NMR(300MHz,CDCl3,):9.22(br,2H),7.97(br,2H),7.20(br,4H),3.76(br,4H),1.90–0.80(m,94H).
as can be seen from the above, the compound has a correct structure and is a compound PADTDI-BT-C1 shown in the formula I, and the structural formula is shown as follows:
example 2 Synthesis of Polymer PADTDI-FBT
5,5 '-bis (trimethylstannyl) -3,3' -difluoro-2, 2 '-bithiophene (52.8mg,0.1mmol), N' -bis (2-decyltetradecyl) -6, 6-dibromo-7, 7-dianthranedithioeneimide (126.0mg,0.1mmol), the catalyst tris (dibenzylideneacetone) dipalladium (4.5mg,0.0049mmol), the ligand tris (o-tolyl) phosphine (12.3mg,0.0404mmol), and chlorobenzene (5mL) were added to a reaction flask, oxygen was removed by three freeze-thaw cycles under argon, and the reaction mixture was heated to 110 ℃ for polymerization for 24 h. After cooling, 200ml of methanol was added, stirred at room temperature for 1h and filtered. The obtained polymer was extracted by a Soxhlet extractor. Firstly, methanol, acetone and normal hexane are used for extraction until the mixture is colorless, micromolecules and catalysts are removed, and then chloroform is used for extraction to obtain a final product of 119mg, wherein the yield is 91.4%.
The structural characterization data is as follows:
molecular weight: GPC Mn＝17.9kDa,PDI＝2.92，n＝13。
Nuclear magnetic hydrogen spectrum:1H NMR(300MHz,CDCl3,):9.20(br,2H),7.98(br,2H),7.10(br,2H),3.76(br,4H),1.90–0.80(m,94H).
as can be seen from the above, the compound has a correct structure and is a compound PADTDI-BT-C3 shown in the formula I, and the structural formula is shown as follows:
example 3 spectral and field Effect transistor Performance of polymers PADTDI-BT and PADTDI-FBT
1) Spectral and electrochemical Properties of the polymers PADTDI-BT and PADTDI-FBT
FIG. 1 shows the UV-VIS absorption spectra of the polymers PADTDI-BT and PADTDI-FBT3 in solution and in film.
As can be seen from FIG. 1, the optical band gaps of the polymers PADTDI-BT and PADTDI-FBT are 1.94eV and 2.41eV, respectively. The two polymer molecules both have stronger absorption peaks, which shows that the front-line orbit of the polymer main chain is better overlapped; the electron coupling peaks are stronger, which indicates that the molecules have stronger aggregation function.
FIG. 2 is a cyclic voltammogram of the polymers PADTDI-BT and PADTDI-FBT. Measured using the electrochemical workstation CHI660c and using a conventional three-electrode configuration. The test was performed in acetonitrile solution. Both polymers have a certain redox capacity. According to the cyclic voltammetry curve, the HOMO energy levels of the polymers PADTDI-BT and PADTDI-FBT are respectively-5.41 eV and-5.95 eV, and the LUMO energy levels are respectively-3.47 eV and-3.54 eV.
2) Field Effect transistor Performance of polymers PADTDI-BT and PADTDI-FBT
Fig. 3 is a schematic structural diagram of an organic field effect transistor, and as shown in the figure, polyethylene terephthalate is used as a substrate and a gate electrode, PVDF-TrFE with the thickness of 1100nm is used as an insulating layer, gold is used as a source electrode and a drain electrode, and aluminum is used as a gate electrode. The source and drain electrodes are prepared by evaporation, the substrate is ultrasonically cleaned in acetone, secondary water and ethanol, and then is vacuum-dried at 80 ℃, and is treated by plasma for 15 minutes. The surface of the silicon dioxide was modified with Octadecyl Trichlorosilane (OTS), and the polymers obtained in examples 1 to 2 were semiconductive layers. The polymer is dissolved in o-dichlorobenzene to form a thin film on an OTS modified substrate by a film spinning method, the thickness of the thin film is 40nm, and the thin film is annealed on a hot table for 5 minutes. The electrical properties of the prepared field effect devices were measured at room temperature with a Keithley 4200SCS semiconductor tester.
Two key parameters that determine the performance of OFETs are: carrier mobility (μ) and on-off ratio (I) of the deviceon/Ioff). The mobility means: average drift velocity of carriers in cm under a unit electric field2V-1s-1) Which reflects the mobility of holes or electrons in a semiconductor under an electric field. The on-off ratio is defined as: the ratio of the current in the "on" state and the "off" state of the transistor reflects the performance of the device switch. For a high performance field effect transistor, the mobility and switching ratio should be as high as possible.
Fig. 4 is a graph of the transfer and output characteristics of a field effect transistor prepared based on two anthradithiophene imide polymer molecules. The four polymer field effect transistors show good linear regions and saturation regions, which shows that the OFET device based on the anthradithiophene imide has good field effect regulation performance.
FIG. 5 is an atomic force microscope image of an anthradithiophene imide polymer molecule-based thin film. The figure shows that the film has good uniformity in morphology, the gaps of the grain boundary are filled after annealing, and the mobility of the film obtained by annealing at 100 ℃ is highest.
The carrier mobility can be calculated from the equation:
IDS＝(W/2L)Ciμ(VG–VT)2(saturation region, V)DS＝VG–VT)
Wherein, IDSIs the drain current, μ is the carrier mobility, VGIs the gate voltage, VTFor threshold voltage, W is channel width (W1400 μm), L is channel length, CiIs an insulator capacitor (capacitance per unit area (SiO)2Relative dielectric constant 13, thickness 1100 nm). Utilizing (I)DS，sat)1/2To VGPlotting, and performing linear regression to obtain carrier mobility (μ) from the slope of the regression line, and determining V from the intercept of the regression line and the X-axisT。
The mobility can be calculated from the slope of the transfer curve according to the formula, and the device properties of the polymer field effect transistor prepared in each of the above examples are shown in table 1.
The experimental result shows that the anthradithiophene imide polymer is an excellent polymer semiconductor material.
TABLE 1 device Performance of Compound field Effect transistors
The invention is not limited to the reported materials, a series of polymers can be obtained by changing different substituents, and the synthesis method provided by the invention is simple and effective, is greatly helpful for researching the relationship between the structure and the performance of the polymer semiconductor material, and has guiding significance for further designing and preparing high-performance materials.
Claims (9)
1. A polymer of formula I:
in the formula I, R is C1～C60Linear or branched alkyl of (a);
the group pi is selected from any one of the following groups:
in the group of pi, the radical of pi,
represents a substitution bit;
n is 5 to 100.
2. A process for preparing a polymer of formula I according to claim 1, comprising the steps of:
under the action of a catalyst and a ligand, carrying out polymerization reaction on a compound shown as a formula IV and a bis-methyl tin compound to obtain a polymer shown as a formula I;
in the formula IV, R is C1～C60Linear or branched alkyl.
3. The method of claim 2, wherein: the bis-methyl tin compound is selected from any one of the following compounds:
the catalyst is at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, tris (dibenzylideneacetone) dipalladium and bis (dibenzylideneacetone) palladium;
the ligand is selected from at least one of triphenylphosphine, tri (o-tolyl) phosphine, tri (furyl) phosphine and triphenylarsine.
4. The production method according to claim 2 or 3, characterized in that: the molar ratio of the compound shown in the formula IV, the bis-methyl tin compound, the catalyst and the ligand is 1: 0.95-1.05: 0.01-0.10: 0.04 to 0.40.
5. The production method according to claim 2 or 3, characterized in that: the polymerization conditions were as follows:
the temperature is 100-130 ℃;
the time is 6 to 24 hours.
6. The production method according to claim 2 or 3, characterized in that: the polymerization reaction is carried out in a solvent;
the solvent is at least one selected from toluene and chlorobenzene.
7. Use of a polymer of the formula I as claimed in claim 1 for the production of organic effect transistors.
8. An organic field effect transistor, characterized by: in the organic field effect transistor, a material constituting a semiconductor layer is a polymer represented by formula I as defined in claim 1.
9. A compound of the formula IV,
in the formula IV, R is C1～C60Linear or branched alkyl.
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| GB776716A (en) * | 1954-08-06 | 1957-06-12 | Allied Chem & Dye Corp | Method of reducing aromatic nitrogen compounds |
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| CN106029678A (en) * | 2014-04-29 | 2016-10-12 | 沙特基础工业全球技术公司 | Synthesis of new small molecules/oligomers with high conductivity and absorption for optoelectronic application |
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| GB776716A (en) * | 1954-08-06 | 1957-06-12 | Allied Chem & Dye Corp | Method of reducing aromatic nitrogen compounds |
| JP2015533118A (en) * | 2012-09-29 | 2015-11-19 | 昆山維信諾顕示技術有限公司Ｋｕｎｓｈａｎ Ｖｉｓｉｏｎｏｘ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | Benzothiophene derivatives and their applications in the field of organic electroluminescence |
| CN106029678A (en) * | 2014-04-29 | 2016-10-12 | 沙特基础工业全球技术公司 | Synthesis of new small molecules/oligomers with high conductivity and absorption for optoelectronic application |
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