WO2018035695A1 - Semi-conducteurs polymères et leurs procédés de préparation ainsi que leurs utilisations - Google Patents

Semi-conducteurs polymères et leurs procédés de préparation ainsi que leurs utilisations Download PDF

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WO2018035695A1
WO2018035695A1 PCT/CN2016/096290 CN2016096290W WO2018035695A1 WO 2018035695 A1 WO2018035695 A1 WO 2018035695A1 CN 2016096290 W CN2016096290 W CN 2016096290W WO 2018035695 A1 WO2018035695 A1 WO 2018035695A1
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boph
polymer
conducted
heating
dfbt
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Xugang GUO
Shengbin SHI
Qiaogan LIAO
Han GUO
Yumin TANG
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South University Of Science And Technology Of China
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Definitions

  • the present invention belongs to the field of organic semiconductor materials and device applications, in particular to polymeric semiconductors and their preparation methods, as well as their uses in organic thin-film transistors, polymer solar cells (both bulk heterojunction and layer-by-layer) .
  • organic and polymeric semiconductors offer new functionalities and features over traditional semiconducting materials, such as silicon and III-IV semiconductors.
  • organic semiconductor As the active layer, organic thin-film transistors have shown great potentials for enabling large-area, low-cost circuitries via solution-based high throughput fabrication fashion.
  • PSCs polymer solar cells
  • the solution-based processing techniques enable device fabrication in a cost-effective fashion and afford solar cells with new features, such as light-weight and mechanical flexibility.
  • the power conversion efficiencies (PCEs) of PSCs are driven by materials development in combination with device engineering now the highest PCEs of bulk heterojunction PSCs have surpassed 11%.
  • PCEs power conversion efficiencies
  • oligothiophenes are widely employed as the donor units to construct high mobility polymers due to the tendency to self-assemble into ordered microstructure in film state.
  • nTs As emerging building blocks for PSC polymers, nTs have also attracted substantial attention in photovoltaic field recently, in fact the PSCs with extremely large fill factors (FFs > 75%) are almost exclusively constructed from nTs as the electron donating building blocks, which is mainly attributed to the high mobility of the resulting polymers and favorable bulk heterojunction (BHJ) film morphologies.
  • FFs extremely large fill factors
  • oligothiophenes have demonstrated great success in the development of high-performance semiconductors for PSCs, the alkylation pattern and the number of thiophene must be carefully optimized for performance improvement. nT catenation and alkylation patterns show a remarkable consequence on the cell performance of the resulting polymers. As the thiophene number in nTs increases, the PSCs typically show reduced open-circuit voltages (V oc s) due to the gradually elevated HOMOs. However, if nTs contain minimal thiophene number, such as monothiophene (1T) and bithiophene (2T) , the resulting polymers typically suffer from limited solubility and low molecular weight or low degree of conjugation and ordering. Therefore, among various nTs, terthiophene (3T) is a highly promising one for high-performance semiconductors.
  • TRTOR 3-alkoxy-3’-alkyl-bithiophene
  • the analysis of the device performance indicates that the PCEs are limited by the wide bandgaps of the phthalimide-based polymers ( ⁇ 1.80 eV) , which result in insufficient absorption of solar spectrum.
  • the bandgaps should be substantially narrowed for TRTOR-based polymers.
  • Benzothiadiazole and its fluorinated derivatives have shown great success to construct donor-acceptor copolymers with narrow bandgaps via intramolecular electron transfer and quinoidal structure formation.
  • solubilizing chain on benzothiadiazole one large branched chain is installed on one thiophene in 2T to achieve enough solubility without sacrificing backbone planarity for difluorinated benzothiadiazole-2T copolymers.
  • polymer semiconductors are typically functionalized with solubilizing alkyl side chain substituents.
  • alkylation patterns must be strategically manipulated to minimize steric hindrance, hence head-to-head (HH) linkages should be avoided in semiconducting polymer design to minimize accompanying backbone torsion, which reduces conjugation along the polymer chain, compromises film crystallinity/order, and diminishes charge carrier mobility.
  • HH head-to-head
  • the present invention provides a strategy to employ strategically alkylated 3T or 4T containing unsubstituted thiophene or bithiophene as spacer (or bridge) to achieve good solubility and film crystallinity simultaneously.
  • R 1 is selected from the group consisting of O, S, Se and N-2-ethylhexyl
  • R 2 is selected from the group consisting of H, F, Cl, CN and CF 3 ;
  • R 3 is selected from the group consisting of H, F, Cl, CN and CF 3 ;
  • R 4 is selected from the group consisting of ethylhexyl, Butyl-1-octyloxy, propylheptan-1-oloxy and undecanol, nonanol.
  • TRTOR 3-alkoxy-3’-alkyl-bithiophene
  • the intramolecular noncovalent conformational locking enables the resulting polymers with high degree of backbone planarity and enhanced solubility since two solubilizing chains are attached to TRTOR.
  • TRTOR is copolymerized with benzothiadiazole having different number of fluorine atoms to afford a series of polymers (Scheme 1-3 with largely reduced bandgaps ( ⁇ 1.4 eV) and variable frontier molecular orbitals (FMOs) .
  • the polymeric semiconductor is selected from the following group:
  • the present invention provides a preparation method of the polymeric semiconductor described above comprising:
  • step (4) drying the solid precipitate obtained in step (4) to give the crude product, and then extracting the crude product using a series of solvents depending on the polymer molecular weight and polymer solubility;
  • the acceptor monomer is of the formula II:
  • R 1 O, S, Se, N-2-ethylhexyl
  • R 2 H, F, Cl, CN, CF 3
  • R 3 H, F, Cl, CN or CF 3
  • R 1 is selected from the group consisting of alkyl, alkylthio and alkyloxy
  • R 2 is selected from the group consisting of alkyl, alkylthio and alkyloxy,
  • R 3 is selected from the group consisting of H, F, Cl and CN,
  • R 4 is selected from the group consisting of O, S and Se,
  • R 5 is selected from the group consisting of O, S and Se.
  • the acceptor monomer is selected from the following group:
  • the donor monomer is selected from the following group:
  • the mole ratio of the acceptor monomer to the donor monomer is 1: 0.8-1.3, for example, 1: 0.9, 1: 1.2 and so on, preferably 1: 0.9-1.1, more preferably 1: 1.
  • the mole ratio of the tris (dibenzylideneacetone) dipalladium (0) (Pd 2 (dba) 3 ) to tris (o-tolyl) phosphine (P (o-tolyl) 3 ) is 1: 4-15, for example, 1: 6, 1: 9, 1: 13 and so on, preferably 1: 6-10, more preferably 1: 8; the Pd loading is 0.005-0.1 equiv, preferably 0.01-0.06 equiv.
  • reaction vessel and the mixture are subjected to 1-5 pump/purge cycles with Ar.
  • the inert gas is selected from any one of Ar, N 2 , He, Ne, or a mixture of at least two of them.
  • the organic solvent is selected from any one of anhydrous toluene, benzene, chlorobenzene, DMF, or a mixture of at least two of them, preferably anhydrous toluene.
  • the inert gas is selected from any one of Ar, N 2 , He, Ne, or a mixture of at least two of them.
  • the ratio of the organic solvent to the acceptor monomer is 10-50 mL/mmol, preferably 15-30 mL/mmol.
  • the heating is conducted at 50-170 °C for 1-72h, preferably at 80-150 °C for 3-50h.
  • the heating is conducted using oil bath or microwave.
  • the heating is conducted by 80 °C for 10 minutes, 100 °C for 10 minutes, and 140 °C for 3 h under microwave irradiation.
  • step (3) the heating is conducted at 80-170 °C for more than 0.2 h, preferably at 100-160 °C for more than 0.4 h.
  • the heating is conducted using oil bath or microwave.
  • the heating is conducted under microwave irradiation at 140 °C for 0.5 h.
  • the heating after adding 2-bromothiophene is conducted at 140 °C for another 0.5 h.
  • step (3) the 2- (tributylstanny) thiophene may be added or not added, which does not have much impact on the results. If added, the amount thereof is preferably sufficient such that the bromine groups in the product obtained in the step prior to it can be replaced completely.
  • the 2-bromothiophene may be added or not added, which does not have much impact on the results. If added, the amount there of is preferably sufficient such that the Sn-in the product obtained in the step prior to it can be replaced completely.
  • the amount of the methanol is adjusted according to the amount of the reaction mixture.
  • the volume ratio of the methanol to the reaction mixture is about 20-200: 1, preferably 40-150: 1.
  • the amount of the methanol may be about 200-300mL.
  • the methanol contains 12 mol/L hydrochloric acid, preferably contains 1 mL HCl/100 mL methanol.
  • the dripping is conducted under vigorous stirring, preferably the strirring is continued for at least 0.5 h, preferably at least 1 h.
  • the extracting is conducted by Soxhlet extraction with the solvent combinations depending on the solubility and molecular weight of the particular polymer.
  • the solvent sequence for Soxhlet extraction is methanol, acetone, hexane, dichloromethane, and chloroform.
  • the solvent sequence for Soxhlet extraction is methanol, acetone, hexane, dichloromethane, chloroform, and chlorobenzene.
  • the solvent sequence for Soxhlet extraction is methanol, acetone, hexane, dichloromethane, chloroform, chlorobenzene, and dichlorobenzene.
  • the solvent sequence for Soxhlet extraction may be refereed to the above sequence for BT-BOPH, FBT-BOPH and DFBT-BOPH according to the molecular weight and solubility of the polymers.
  • the polymer solution is concentrated to less than 10 ml, preferably 4-8 mL.
  • the dripping is conducted under vigorous stirring.
  • the collecting is conducted by filtration.
  • the drying is conducted under reduced pressure.
  • the present invention provides an use of the polymeric semiconductor according to the present invention in thin-film transistor or polymer solar cell.
  • a series of narrow bandgap (1.37-1.46 eV) polymer semiconductors incorporating a head-to-head linkage containing bithiophene, 3-alkoxy-3’-alkyl-bithiophene (TRTOR) , as the electron donor unit and the benzothiadiazole with varied number of fluorine atoms as the electron acceptor counit are synthesized.
  • the head-to-head linkage enables the bithiophene-based polymers with sufficient solubility and substantial molecular weight even though the acceptor counit does not possess any solubilizing chain.
  • the intramolecular noncovalent sulfur-oxygen interaction leads to polymers with high degree of backbone planarity and film ordering.
  • the TRTOR-based polymeric semiconductors show broad absorption and narrow bandgaps with tunable HOMOs.
  • the difluorinated benzothiadiazole-TRTOR copolymer shows a substantial short-circuit current (21.46 mA/cm 2 ) and a high fill factor (70.9%) simultaneously, which result in a promising PCE about 10.1%.
  • the performance is the highest among polymers containing a head-to-head linkage and among bithiophene-based polymers reported to date.
  • the PCE (10.1%) is also the highest for polymer semiconductors with bandgaps smaller than 1.50 eV, which indicates that the TRTOR-based polymer could be an excellent candidate for the rear cell in tandem/multijunction device.
  • the head-to-head linkage containing bithiophene (2T) is also a highly promising donor unit for constructing polymer semiconductors with the state-of-the-art solar cell performance.
  • the raw material used in above preparation method can be prepared by known method in the art or by the following method described below or buying on the market.
  • Figure 1 are UV-vis absorption spectras of polymers DFBT-BOPH, FBT-BOPH, BT-BOPH, DFBT-BO, FBT-PH and BT-PH in solution (1 ⁇ 10 -5 M in o-DCB) .
  • Figure 2 are UV-vis absorption spectras of polymers DFBT-BOPH, FBT-BOPH, BT-BOPH, DFBT-BO, FBT-PH and BT-PH in film.
  • Figure 3 are UV-vis absorption spectras of polymer DFSeBT-BOPH in solution (1 ⁇ 10 -5 M in o-DCB) and film state (spin-coated from 1 mg mL -1 o-DCB solution) .
  • Figure 4 are UV-vis absorption spectras of polymer FTAZ-PH in solution (1 ⁇ 10 -5 M in o-DCB) and film state (spin-coated from 1 mg mL -1 o-DCB solution) .
  • Figure 5 are cyclic voltammograms of polymer thin films measured in 0.1 M (n-Bu) 4 N . PF 6 acetonitrile solution at scan rate of 50 mV s -1 .
  • Figure 6 are DSC thermograms of polymers BT-BOPH, FBT-BOPH and DFBT-BOPH for the second heating and cooling scans (heating ramp: 10 °C min -1 ) .
  • Figure 7 are thermogravimetric analysises (heating ramp: 10 °C min -1 ) of polymers BT-BOPH, FBT-BOPH and DFBT-BOPH. Nitrogen was used as the purge gas for TGA measurement.
  • Figure 8 are J-V characteristics of the optimized polymers solar cells under simulated AM 1.5 G illumination (100 mW cm -2 ) .
  • Figure 9 are J-V and EQE curves of Device performance parameters of conventional layer-by-layer fabricated PSCs with a device architecture of ITO/PEDOT: PSS/DFBT-BOPH/PC 71 BM/Ca/Al.
  • Figure 10 are Linear I-V characteristics of top-gate/bottom-contatc organic thin-film transistors with the polymer films annealed at 220 °C for 15 minutes.
  • the channel length is 20 ⁇ m and the channel width is 5 mm.
  • Figure 11 are Linear I-V characteristics of top-gate/bottom-contatc organic thin-film transistors with the polymer DCNBT-BOPH films annealed at 100 °C for 10 minutes.
  • the channel length is 20 ⁇ m and the channel width is 5 mm.
  • Figure 12 are Linear I-V characteristics of top-gate/bottom-contatc organic thin-film transistors with the polymer DCNBSe-EH films annealed at 100 °C for 10 minutes.
  • the channel length is 20 ⁇ m and the channel width is 5 mm.
  • THF and toluene were distilled from Na/benzophenone.
  • the reagents 4, 7-dibromobenzo [c] [1, 2, 5] thiadiazole, 4, 7-dibromo-5-fluorobenzo [c] [1, 2, 5] thiadiazole, and 4, 7-dibromo-5, 6-difluorobenzo [c] [1, 2, 5] thiadiazole were purchased from Derthon Optoelectronic Materials Science Technology Co., Ltd. (Shenzhen, Guangdong, China) .
  • TGA curves were collected on a TA Instrument (Mettler, STAR e ) .
  • UV-Vis data were collected on a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer. Cyclic voltammetry measurements of polymers were carried out under argon atmosphere using a CHI760 Evoltammetric analyzer with 0.1 M tetra-n-butylammoniumhexafluorophosphate in acetonitrile as supporting electrolyte.
  • a platinum disk working electrode, a platinum wire counter electrode, and a silver wire reference electrode were employed, and Fc/Fc + was used as internal reference for all measurements.
  • the scanning rate was 100 mV/S.
  • the external quantum efficiency (EQE) was measured by a QE-R3011 measurement system (Enli Technology, Inc. ) .
  • the light intensity at each wavelength was calibrated with a standard single crystal Si photodiode.
  • AFM measurements of polymer: PC 71 BM blend films were performed by using a Dimension Icon Scanning Probe Microscope (Asylum Research, MFP-3D-Stand Alone) in tapping mode.
  • TEM specimens were prepared following identical conditions as the actual devices, but were drop-cast onto 40 nm PEDOT: PSS covered substrate.
  • TEM images were obtained on Tecnai Spirit (20 kV) TEM.
  • Grazing incidence X-ray diffraction (GIXD) characterization was performed at beamline 7.3.3, Advanced Light Source (ALS) , Lawrence Berkeley National Lab (LBNL) .
  • ALS Advanced Light Source
  • LBNL Lawrence Berkeley National Lab
  • X-ray energy was 10 keV and operated in top off mode.
  • the scattering intensity was recorded on a 2D detector (Pilatus 2M) with a pixel size of 172 m (1475 ⁇ 1679 pixels) .
  • the samples were ⁇ 10 mm long in the direction of the beam path, and the detector was located at a distance of 300 mm from the sample center (distance calibrated by AgB reference) .
  • the incidence angle was chosen to be 0.16° (above critical angle) for the entire film structure measurement.
  • Step 1 Synthesis of 2-Butyl-1-octylbromide (BOBr) : 2-butyl-1-octanol (18.64 g, 100 mmol) and triphenylphosphine (26.18 g, 100 mmol) were dissolved in 250 mL DCM and the solution was purged with argon for 10 min. N-Bromosuccinimide (24.91 g, 140 mmol) was added in several portions at 0 °C and stirred at this temperature for 0.5 h and then at room temperature for 12 h. Finally to the reaction was added a small amount of Na 2 SO 3 , after the removal of solvent, the residue was washed with hexane and then filtrated. The filtrate was concentrated and purified using column chromatography with petroleum ether as the eluent to give a colorless oil (22.0 g, 88.1%) .
  • Step 2 Synthesis of 3- (2-Butyl-1-octyl) thiophene (T-BO) : Magnesium turnings (1.15 g, 47.17 mmol) and iodine (76.60 mg, 0.30 mmol) were added to 50 mL THF under an argon atmosphere, and the mixture was stirred for 2 h. 2-Butyl-1-octylbromide (9.50 g, 38.10 mmol) in 25 mL THF was added over 10 min and the mixture was refluxed for 2 h to afford the Grignard reagent.
  • Step 3 Synthesis of 2-Bromo-3- (Butyl-1-octyl) thiophene (T-BOBr) : 3- (2-Butyl-1-octyl) thiophene (6.0 g, 23.77 mmol) and N-bromosuccinimide (4.23 g, 23.77 mmol) were dissolved in 100 mL1: 1 mixture of acetic acid and chloroform solution and the mixture was stirred at room temperature overnight. Water was added to the reaction and the organic layer was washed with water, saturated sodium bicarbonate aqueous solution, and water, sequentially. After the removal of solvent with rotary evaporator, the crude product was purified through a plug of silica gel with petroleum ether. The product was obtained as a colorless oil (6.36 g, 81.3%) .
  • Step 4 Synthesis of 2- (3- (2-Butyl-1-octyl) ) -4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane (T-BOB) : A solution of bromide 3 (5.0 g, 15.09 mmol) in 35 mL THF was cooled to -78 °C, and to the solution was added a 2.4 M solution of n-BuLi in hexane (6.92 mL, 16.6 mmol) .
  • Step 5 Synthesis of 3- (2-propylheptan-1-oloxy) thiophene (T-OPH) : To an dry around bottom flask was charged with 3-methoxythiophene (3.0 g, 26.28 mmol) , 2-propylheptan-1-ol (4.16 g, 26.28 mmol) , and anhydrous sodium hydrogen sulfate (0.5 g, 4.16 mmol) . Toluene (100 mL) was then added, and the reaction was purged with argon for 30 min and the mixture was heated to 130 °C and stirred for 19 h under argon protection.
  • 3-methoxythiophene 3.0 g, 26.28 mmol
  • 2-propylheptan-1-ol 4.16 g, 26.28 mmol
  • anhydrous sodium hydrogen sulfate 0.5 g, 4.16 mmol
  • Step 6 Synthesis of 2-bromo-3- (2-propylheptan-1-oloxy) thiophene (T-OPHBr) : Compound T-OPH (3.5 g, 14.56 mmol) was dissolved in anhydrous CHCl 3 (50 mL) and cooled down to 0-4°C using an ice bath. NBS (2.46 g, 13.85 mmol) was then dissolved in anhydrous DMF and added into the solution dropwise via a dropping funnel. The mixture was stirred for 1 h with exclusion from light. After the removal of the ice bath, the reaction was warmed to room temperature and stirred for 12 h with protection from light. Finally to the reaction was added water and then extracted with CHCl 3 . The combined organic layer was dried over anhydrous MgSO 4 , filtered, and concentrated for purification via column chromatography (silica gel, petroleum ether) to afford the pure compound T-OPHBr (3.6 g, 77.4%) .
  • Step 7 Synthesis of 3- (2-Butyl-1-octyl) -3′- (2-propylheptan-1-oloxy) -2, 2′-bithiophene (T-BO-OPH) : To a 150 mL 3-necked reaction flask was added compound 4 (2.58 g, 6.82 mmol) , compound 6 (2.72 g, 8.52 mmol) , and 80 mL anhydrous toluene.
  • Step 8 Synthesis of 3- (2-Butyl-1-octyl) -3′- (2-propylheptan-1-oloxy) -5, 5’ -bis (trimethylstannyl) 2, 2′-bithiophene (D4) : To a flask was added compound 7 (1.32 g, 2.68 mmol) and 15 mL dry THF. The resulting clear solution was cooled to -78 °C using dry ice/acetone bath. Then 2.68 mL n-BuLi solution in hexane (6.44 mmol, 2.4 M) was added dropwise.
  • Step 1 Synthesis of 3- (2-Butyl-1-octyloxy) thiophene (S-OBO) : This compound was prepared with the same procedure according to T-OPH.
  • T-BO-OBO bithiophene
  • Step 4 Synthesis of 3- (2-propylheptan) -3′- (2-propylheptan-1-oloxy) -2, 2′-bithiophene (S-PH-OPH) : This compound was prepared with the same procedure according to S-BO-OPH:
  • Step 1 Synthesis of 3- (2-ethylhexyl) -3′- (2-ethylhexyl -1-oloxy) -2, 2′-bithiophene (S-EH-OEH) : This compound was prepared with the same procedure according to S-BO-OPH.
  • Step 1 Synthesis of 3, 6-dibromobenzene-1, 2-diamine (BT-NH) .
  • the sodium borohydride 14, 370mmol, 18.5eq
  • a suspension of dibromobenzo [c] [1, 2, 5] thiadizole 5.88g, 20.0mmol, 1.0eq
  • ethanol 180mL
  • 1 H NMR 400 MHz, CDCl 3 ) ⁇ 6.84 (s, 2H) , 3.90 (s, 4H) .
  • Step 2 Synthesis of 4, 7-dibromobenzo [c] [1, 2, 5] selenadiazole (M4) .
  • the 3, 6-dibromobenzene-1, 2-diamine (3.96g, 14.89mmol, 1.00eq) is desolved in 85 mL of ethanol, then heated to refluxed and stirred. Afterwards, a solution of SeO 2 (1.74g, 15.64mmol, 1.05eq) in 34 mL hot water was added dropwise. The resulting reaction mixture was refluxed for 3 h to obtain a yellow precipitate in a pale brown solution.
  • Step 1 Synthesis of 6-Difluoro-2, 1, 3-benzoxadiazole 1-oxide (FBX-O) :
  • Step 2 Synthesis of 6-Difluoro-2, 1, 3-benzoxadiazole (FBXH) .
  • Compound FBXH (13.0g, 84.4mmol) and triethylphosphite (18.92g, 113.9mmol) were dissolved in tetrahydrofuran (200mL) .
  • the mixture was refluxed for 4 h.
  • the mixture is cooled to room temperature, and concentrated under vacuum.
  • the product was obtained as a colourless liquid (7.4g, 63.5%) .
  • FBXT benzoxadiazole
  • Compound FBXH (6.2g, 44.9mmol, 1.0eq) and trimethysilyl chloride (15.61g, 143.66mmol, 3.2eq) were dissolved in anhydrous tetrahydrofuran (120 mL) under nitrogen atmosphere. The solution was cooled to -78°C and a new prepare lithium diisopropylamide solution (107.76mmol, 2.4eq) was added dropwise. The mixture was reaction at -78°C for 2h and then warm to roomtemperature for 4 h. The reaction was quenched by a saturated solution of ammonium chloride and extracted with diethyl ether for several times.
  • Step 4 Synthesis of 4, 7-Dibromo-5-Difluoro-2, 1, 3-benzoxadiazole (M7) .
  • Compound FBXT (10.8g, 38.23mmol, 1.0eq) and N-bromosuccinimide (16.3g, 91.76mmol, 2.4eq) were dissolved in sulfuric acid (160mL) .
  • the mixture was heated at 60°C for 3.5 h, cooled to roomperture, then dropwise into ice water.
  • the product was obtained as a white solid (8.3g, 73.5%) .
  • Step 1 Synthesis of 4-chloro-5-fluoro-2, 1, 3-benzothiadiazole (FClBH) .
  • 1, 2-Diamino-4-chloro-5-fluorobenzene (8.7g, 54.2mmol) was dissolved in 65 mL of dichloromethane. Then, triethylamine (29.5 mL, 210 mmol) was added. Then cooled to 0°C. Thionylchloride (14 mL) was added dropwise. Then the mixture was heated to 70°C for 4 h. The mixture was poured into ice-water and extracted with ethyl acetate. The organic layer was evaporated in vacuo.
  • benzothiadiazole (M9) Compound FClBH (7.0g, 37.1mmol) and HBr (160mL) were taken in a round bottom flask. 50.0mL of bromine was added slowly. The reaction mixture was refluxed for 3 days. Then, it was cooled down to room temperature. The excess of bromine was quenched with saturated Na 2 SO 3 solution. The precipitate formed was filtered off and purified by column chromatography on silica gel using petroleum ether/dichloromethane (10 ⁇ 1) to obtain the title compound (9.0g , 70%) .
  • Step 1 Synthesis of 4, 5-Diamino-3, 6-dibromphthalonitrile (CN-Br) 4, 5-Diaminophthalonitrile (3.0g, 18.97mmol) was dissolved in methanol (330mL) under argon atmosphere, 10 g potassium bromide were added and the mixture was cooled down to 0°C. Hydrobromic acid (48%, 4.34mL) was added dropwise, followed by dropwise addition of tert-butylhydroperoxide 70% (1.8mL) . Then warmed to room temperature and stired for 8 hours, completion of the reaction was confirmed by TLC analysis, the addition of the peroxide was repeated several time using the same amount if the reaction is not complete.
  • Step 2 Synthesis of 4, 7-Dibromo-5, 6-Dicyano-2, 1, 3-benzothiadiazole (M19) :
  • Example 11 Synthesis of 4, 7-Dibromo-5, 6-Dicyano-2, 1, 3-selenadiazole (M20) : 0.2g (0.633mmol) of CN-Br in 20 mL of tetrahydrofuran in a round-bottomed single-necked flask was heated to reflux, and then 77.3mg (0.696mmol) of SeO 2 in hot water was added. The reaction mixture was allowed to reflux for several hours, and completion of the reaction was confirmed by TLC analysis, the addition of the SeO 2 was added several time using the same amount if the reaction is not complete. After that, The reaction was diluted with water and extracted with ethyl acetate for several times. The organic extract was evaporated in vacuo.
  • the tube was sealed under argon flow and then stirred at 80 °C for 10 minutes, 100 °C for 10 minutes, and 140 °C for 3 h under microwave irradiation. Then, 0.05 mL 2- (tributylstanny) thiophene was added and the reaction mixture was stirred under microwave irradiation at 140 °C for 0.5 h. Finally, 0.10 mL 2-bromothiophene was added and the reaction mixture was stirred at 140 °C for another 0.5 h. After cooling to room temperature, the reaction mixture was dripped into 100 mL methanol containing 1 mL 12 N HCl under vigorous stirring.
  • the polymer precipitate was transferred to a Soxhlet thimble. After drying, the crude product was subjected to sequential Soxhlet extraction with the solvent combinations depending on the solubility of the particular polymer. After the extraction with the final solvent, the polymer solution was concentrated to ⁇ 6 mL, and then dripped into 100 mL methanol under vigorous stirring. The polymer was collected by filtration and dried under reduced pressure to afford a deep colored solid as the product.
  • the solvent sequence for Soxhlet extraction was methanol, acetone, hexane, dichloromethane, and chloroform.
  • the chloroform solution was concentrated by removing most of solvent and precipitated into methanol.
  • the solid was collected by filtration and dried in vacuum to afford the polymer as black solid (95.0 mg, 72.1%) .
  • the solvent sequence for Soxhlet extraction was methanol, acetone, hexane, dichloromethane, chloroform, and chlorobenzene.
  • the chlorobenzene fraction was concentrated by removing most of solvent, and precipitated into methanol.
  • the solid was collected by filtration and dried in vacuum to afford the polymer as a black solid (109.10 mg, 59.6%) .
  • the solvent sequence for Soxhlet extraction was methanol, acetone, hexane, dichloromethane, chloroform, chlorobenzene, and dichlorobenzene.
  • the dichlorobenzene solution was concentrated by removing most of solvent, and precipitated into methanol.
  • the solid was collected by filtration and dried in vacuum to get the polymer as a black solid (136.0mg, 73.3%) .
  • TRTOR containing branched chains is essential.
  • High purity trimethylstannyl monomer can be readily synthesized using conventional lithiation followed by quenching with trimethyltin chloride, which is used for polymerization without further purification.
  • Polymers are synthesized via Pd-mediated Stille coupling using microwave irradiation (Scheme 3) . After polymerization, polymers are subjected to end-capping with mono-functionalized thiophene and the polymer purification is carried out using Soxhlet extraction with different solvent combination depending on polymer solubility, and the final fraction is collected for device fabrication.
  • the reduced solubility indicates a stronger intermolecular interaction in DFBT-BOPH, which should be beneficial to charge transport and PSC performance.
  • PSCs are fabricated employing both conventional and inverted architectures, specifically ITO/PEDOT: PSS/polymer: PC 71 BM/Ca/Al and ITO/ZnO/polymer: PC 71 BM/MoO 3 /Ag, respectively.
  • PC 71 BM was selected as the acceptor layer material since it shows better absorption than PC 61 BM, which compensates the deficient absorption in the short wavelength region (400-600 nm) of BT-BOPH, FBT-BOPH and DFBT-BOPH.
  • inverted cells typically show enhanced performance than conventional ones, and inserting a thin interlayer PEIE or PFN between the ZnO layer and the active layer can further enhance the PSC performance.
  • the cathode interfacial layer PFN or PEIE can greatly lower the work functions of ZnO and ITO due to the strong dipole moment at the interface; and the modified ZnO and ITO can lead to ohmic contact with the active layer, which should result in improved charge collection.
  • the inverted device architecture of ITO/ZnO/PEIE (or PFN) /polymer: PC 71 BM/MoO 3 /Ag was adopted to optimize the PSC performance of BT-BOPH, FBT-BOPH and DFBT-BOPH.
  • the optimized polymer/PC 71 BM (w/w) ratios for BT-BOPH, FBT-BOPH and DFBT-BOPH solar cells are 1:1.2, 1:1.2, and 1:1.5, respectively.
  • the film thickness is optimized by varying the spin-coating rate, and the optimal thicknesses are 100, 160, and 210 nm for BT-BOPH, FBT-BOPH and DFBT-BOPH blends, respectively.
  • 1,8-octanedithiol (ODT) is found to be the most effective one for enhancing PSC performance, which is attributed to the improved nanoscale phase separation (vide infra) .
  • the DFBT-BOPH cell shows a J sc of 16.82 mA/cm 2 with a small FF of 48%.
  • the DFBT-BOPH cell achieves a greatly enhanced J sc of 20.69 mA/cm 2 and a promising FF of 71%, simultaneously.
  • PC 71 BM layer is reduced to 210 nm, the FF is increased to 71%, which results in an optimal PCE of 9.76%.
  • the PCE is the highest among bithiophene-based polymers and among polymers with bandgaps ⁇ 1.5 eV.
  • fluorine addition gradually increases the V oc s, which is in good agreement with the evolution of BT-BOPH, FBT-BOPH and DFBT-BOPH HOMO levels (Table 1, Figure 5) . Moreover, the fluorine addition simultaneously increases the J sc s and FFs, which is attributed to the increased charge carrier mobility of the blend films and improved film morphology.
  • DFBT-BOPH cell shows the highest FF (71%) even though it has the thickest active layer (210 nm) , which is benefitted from the highest mobilities ( ⁇ h : 2.68 ⁇ 10 -3 cm 2 /Vs; ⁇ e : 1.21 ⁇ 10 -3 cm 2 /V) among the series as revealed by the space charge limited current (SCLC) measurement. Therefore, fluorine addition leads to stronger inter-chain interaction, shorter ⁇ - ⁇ stacking distance, and favorable crystal orientation as revealed by X-ray scattering studies.
  • the LUMOs are calculated from the HOMOs and optical bandgaps of polymers, which are -3.56, -3.76, and -3.74 eV for BT-BOPH, FBT-BOPH, and DFBT-BOPH, respectively.
  • the low-lying LUMOs of FBT-BOPH and DFBT-BOPH are still in good match with that (-4.30 eV) of fullerene derivatives for efficient exciton dissociation without sacrificing the short-circuit currents (J sc ) , which is beneficial to the PCEs.
  • E HOMO - (E ox onset + 4.80) eV, and E ox onset determined electrochemically using Fc/Fc + internal standard.
  • E LUMO E HOMO + E g opt .
  • Polymer BT-BOPH shows featureless solution absorption profile and a large (138nm) blue-shifted absorption maxium ( ⁇ max ) from film to solution, indicating high degree of molecularly dissolved form in solution at room temperature. While FBT-BOPH and DFBT-BOPH exhibit strong aggregation in solution, as revealed by almost identical absorption profiles in both solution, as revealed by almost identical absorption profiles in both solution and film state.
  • polymers show more transition peaks (FBT-BOPH vs BT-BOPH) or the transition peaks at higher temperatures (DFBT-BOPH versus FBT-BOPH) , which reflects increased crystallinity from BT-BOPH to DFBT-BOPH.
  • the thermal properties of the polymers DFBT-BOPH, FBT-BOPH and BT-BOPH were investigated by thermogravimetric analysis (TGA) ( Figure 7) .
  • TGA thermogravimetric analysis
  • the three polymers exhibited good thermal stability with decomposition temperature more than 360 °C.
  • the thermal stabilities of polymer are good enough for their application in PSCs.
  • the absorption spectra of polymer DFSeBT-BOPH in solution and film are show in Figure 3, polymer DFSeBT-BOPH have a little red shift in the film compare with solution. The absorption could reach 940nm, which mean this polymer have low optical bandgap.
  • the absorption spectra of polymer FTAZ-PH in solution and film are show in Figure 4, Polymer FTAZ-PH shows featureless solution absorption profile and a large (100nm) blue-shifted absorption maxium ( ⁇ max ) from film to solution, indicating high degree of molecularly dissolved form in solution at room temperature.
  • PSCs are fabricated employing both conventional and inverted architectures, specifically ITO/PEDOT: PSS/polymer: PC 71 BM/Ca/Al and ITO/ZnO/polymer: PC 71 BM/MoO 3 /Ag, respectively.
  • PC 71 BM was selected as the acceptor layer material since it shows better absorption than PC 61 BM, which compensates the deficient absorption in the short wavelength region (400-600 nm) of polymers.
  • inverted cells typically show enhanced performance than conventional ones, and inserting a thin interlayer PEIE or PFN between the ZnO layer and the active layer can further enhance the PSC performance.
  • the cathode interfacial layer PFN or PEIE can greatly lower the work functions of ZnO and ITO due to the strong dipole moment at the interface; and the modified ZnO and ITO can lead to ohmic contact with the active layer, which should result in improved charge collection.
  • the inverted device architecture of ITO/ZnO/PEIE (or PFN) /polymer: PC 71 BM/MoO 3 /Ag was adopted to optimize the PSC performance.
  • the J-V curves of the best performing PSCs are shown in Figure 8, and the performance data are collected in Table 2.
  • all PSCs show substantial J sc s (>10mAcm -2 ) , which are mainly attributed to their narrow bandgaps and broad absorptions in the visible region.
  • the ODT addition substantially improves the PCEs from 3.27%to 4.90%for the BT-BOPH cells, from 5.32%to 6.88%for the FBT-BOPH cells, and from 5.08%to 10.12%for the DFBT-BOPH cells, respectively.
  • the PCE enhancement for PSCs fabricated with ODT is attributed to the substantial increment in J sc s and FFs, which is much more remarkable for the DFBT-BOPH cells.
  • the DFBT-BOPH cells Without ODT, the DFBT-BOPH cells hows a J sc of 16.82 mA cm -2 with a small FF of 48%.
  • the DFBT-BOPH cell Upon the addition of 3 vol%ODT, the DFBT-BOPH cell achieves a greatly enhanced J sc of 21.46 mA cm -2 and a promising FF of 70.9%, simultaneously.
  • the layer-by-layer (LBL) solution-processed method has received much attention to prepare highly efficient organic solar cells.
  • the bulk heterojunction OSC could be fabricated when solvents for the second layer could be diffused into the first layer, and if not, the planar heterojunction OSC could be fabricated.
  • the LBL processed method was developed to fabricated efficient ternary blend OSCs based on polymer (DFBT-BOPH) as donors, and PC 71 BM as acceptor.
  • the solar cells were prepared with the structure ITO/PEDOT: PSS/DFBT-BOPH/PC 71 BM/Ca/Al.
  • the solution (orth-dichlorobenzene was used for solvent) of polymer DFBT-BOPH was first deposited on PEDOT: PSS by spin coating , and then the solution (orth-dichlorobenzene was used for solvent) of PC 71 BM was soin-coated on top of the polymer DFBT-BOPH layer. In this case, the PC 71 BM were penetrated into the polymer DFBT-BOPH layer.
  • a highly efficient ternary blend OSC with PCE of 8.76% was obtained without further optimizing the morphology of the active layer.
  • the device performance of the LBL ternary blend OSCs based on LBL method was investigated by changing the drying treatment, all the LBL ternary blend solar cells show better performance in the experimental range as shown in Table 3 and Figure 9 .
  • the typical current density-voltage (J-V) curves of LBL ternary blend solar cells under AM 1.5G illumination at 100mW/m 2 are shown in Figure 9a and the EQE curves is Figure 9b.
  • Top-gate/bottom-contact ogranic thin-film transistors with an amorphous fluoropolymer gate dielectric, CYTOP, are used to invesitigate the charge transport properties of polymers BT-BOPH, FBT-BOPH and DFBT-BOPH.
  • Device performance parameters under various fabrication conditions are compiled in Table 4 and the representative transfer curves of polymers are illustarted in Figure 10.
  • the as-cast films of BT-BOPH, FBT-BOPH and DFBT-BOPH show average hole mobilities of 0.13, 0.13, and 0.18 cm 2 V -1 s -1 , respectively, in the linear region (Supporting Information) .
  • the substantial mobilities are attributed to the high degree of polymer backbone planarity and the ordering film morphology.
  • Thermal annealing leads to improved charge transportation and the highest mobilities of 0.64, 0.56, and 0.83 cm 2 V -1 s -1 are obtained for BT-BOPH, FBT-BOPH, and DFBT-BOPH, respectively, under the optimal annealing temperature in saturated regime.
  • the difluorinated DFBT-BOPH shows the highest mobilities, which is attributed to its highest crystallinity and its shortest ⁇ - ⁇ stacking (vide infra) .
  • the substanial mobilities of the TRTOR polymers are benificial to the charge transport and collection in PSCs and the highest DFBT-BOPH mobility results in the largest short-circuit current in solar cells.
  • Data represent the best mobilities with average mobilities in parentheses.
  • the mobilities and threshold voltages are averaged from more than 5 devices.
  • Device structure glass/Cr-Au/polymer/CYTOP/Al.
  • Table 5 Top-gate/bottom-contact organic thin-film tarnsistor performance parameters of polymers DFBT-BO, DFBT-BONA, FFBX-BONA, DFSeBT-PHNA, DFSeBT-PHNA, FBT-PH, BSeT-BOPH, FseBT-BOPH, DFSeBT-BOPH, FBX-BONA and FBX-BOUD.
  • the pyran ring opening substantially improves the PCE for TRTOR-based polymer DFBT-BOPH, as seen from a larger FF (71%) and a higher J sc (20.69 mA/cm 2 ) versus those (FF: 63%; J sc : 18 mA/cm 2 ) in pyran-based polymer analogue.
  • the pyran ring opening leads to the elimination of out-of-plane side chains and more compact packing, contributing to enlarged FF and J sc .
  • PCE monoalkylated bithiophene-based polymer counterpart
  • the introduction of alkoxy chain on the 3-position of bithiophene leads to head-to-head linkage containing DFBT-BOPH with more than two times higher PCE.
  • the structure order of BT-BOPH, FBT-BOPH and DFBT-BOPH in pure films and BHJ blends is investigated by grazing incidence X-ray scattering (GIXD) .
  • the diffraction pattern indicates that the non-fluorinated polymer BT-BOPH in pure film takes an edge-on crystalline orientation, as seen from the orientation of (100) diffraction peak located at 0.38 A -1 .
  • the crystal coherence length (CCL) calculated from out-of-plane (OOP) direction is 10.0 nm.
  • a weak ⁇ - ⁇ stacking peak is seen in out-of-plane direction, indicating the co-existence of face-on crystalline content.
  • the ⁇ - ⁇ stacking located at 1.57 A -1 gives a stacking distance of 0.40 nm.
  • BT-BOPH in BHJ blends shows a similar diffraction as in pure film.
  • the OOP ⁇ - ⁇ stacking peak is not obvious in the blends.
  • the CCL of (100) plan in OOP direction in the blend film without using ODT is 12.7 nm; and this value in ODT processed film is 13.0 nm.
  • the FBT-BOPH polymer shows a different microstructure in comparison to BT-BOPH.
  • the diffraction of ⁇ - ⁇ stacking is prominent in OOP direction, which is located at 1.62 A -1 , corresponding to a distance of 0.39 nm.
  • the CCL of ⁇ - ⁇ stacking is estimated to be 2.6 nm.
  • the (100) stacking peak in in-plane (IP) direction is located at 0.36 A -1 , and the CCL is 17.0 nm.
  • polymer chains in FBT-BOPH take an improved packing, owning to the fluorination effect.
  • FBT-BOPH in the BHJ blends without using ODT maintains an OOP ⁇ - ⁇ stacking at the same position, indicating a face-on orientation.
  • the crystal size (CCL) is estimated to be 2.8 nm.
  • the CCL of (100) peak in IP direction is estimated to be 17.9 nm.
  • the (100) CCL is 17.6 nm, and the ⁇ - ⁇ stacking CCL is 2.9 nm.
  • DFBT-BOPH is quite similar to FBT-BOPH in both pure film and blends.
  • the (100) crystal size in IP direction is 14.4 nm; the ⁇ - ⁇ stacking peak located at 1.64 A -1 (corresponding to a stacking distance of 0.38 nm) gives a crystal size of 2.1 nm.
  • the (100) crystal size is 16.1 nm, and the ⁇ - ⁇ stacking crystal size is 2.6 nm.
  • the (100) crystal size is 16.5 nm, and the ⁇ - ⁇ stacking crystal size is 2.7 nm.
  • the fluorine addition on benzothiadiazole leads to more favored polymer orientation and at the meantime results in contracted ⁇ - ⁇ stacking from BT-BOPH, FBT-BOPH and DFBT-BOPH, likely due to the increased inter-chain interaction, which is beneficial to J sc and FF.
  • larger crystal coherence length is seen in blends than in pure films; and ODT addition could further promote the chain crystallization in both (100) and ⁇ - ⁇ stacking in blend films.
  • Such improved film crystalline quality in combination with phase separation at finer scale results in improved PCEs for the PSCs fabricated using the processing additive ODT.
  • the blend film morphology was also characterized using Atomic Force Microscopy (AFM) and Transmission Electron Microscopy (TEM) .
  • AFM Atomic Force Microscopy
  • TEM Transmission Electron Microscopy
  • the AFM images of DFBT-BOPH: PC 71 BM blend films reveal that the ODT addition leads to increased root mean square (RMS) roughness from 7.63 to 11.67 nm, which is reflection on increased film crystallinity, in accordance with the GIXD study.
  • RMS root mean square
  • the higher RMS roughness of the blend film surface also increases the contact area between the active layer and interfacial layer, which can lead to improved charge collections.
  • BT-BOPH and FBT-BOPH blend films show similar roughness increases after ODT addition.
  • TEM images show morphology evolution of DFBT-BOPH blend film.
  • Pre-patterned ITO-coated glass with a sheet resistance of ⁇ 10 ⁇ / ⁇ is used as the substrate, which is cleaned by sequential sonication in H 2 O containing detergent, deionized H 2 O, acetone and isopropanol followed by UV/ozone (BZS250GF-TC, HWOTECH, Shenzhen) treatment for 15 min.
  • ZnO precursor was prepared according to the published procedure.
  • the precursor solution was spin-coated (3000 rpm for 20 s) onto the pre-patterned ITO-coated glass.
  • the films ( ⁇ 30 nm) were annealed at 200 °C for 30 min in air, and then transferred into a N 2 -filled glovebox.
  • a 0.05 wt %PEIE in 2-methoxyethanol solution was spin-coated onto the ZnO layer and dried on a hot plate at 110 °C for 10 min right before use, the PEIE thickness is ⁇ 6 nm.
  • the PEIE thickness is ⁇ 6 nm.
  • 0.2 mg/mL PFN in methanol solution was spin-coated onto the ZnO without thermal annealing.
  • Polymer (12 mg/ml) PC 71 BM blend (varied w/w ratios) solutions were prepared in o-DCB with 3 vol%1, 8-octanedithiol (ODT) . To completely dissolve the polymer, the blend solutions should be stirred on a hot plate at 120 °C overnight.
  • both blend solutions and ITO substrates are preheated at 110 °C, and then the active layers were spin-coated onto the ZnO/PEIE (or PFN) interfacial layer.
  • the spin rate and the concentration of the blend were systematically varied.
  • MoO x ( ⁇ 10 nm) and Ag ( ⁇ 100 nm) were thermally evaporated using a shadow mask under vacuum (pressure ca. 10 -4 Pa) .
  • the effective area of the devices is 0.16 cm 2 .
  • Device characterization was performed in the N 2 -filled glovebox using a Xeno-lamp-based solar simulator (Newport, Oriel AM1.5G, 100 mW/cm 2 ) with a computerized Keithley 2400 source meter. The light intensity is calibrated using an NREL-certified monocrystalline Si diode coupled to a KG3 filter to bring spectral mismatch to unity.
  • SCLC Mobility Measurements Hole and electron mobilities were measured using the space charge limited current (SCLC) method. Device structures of ITO/PEDOT: PSS/Polymer: PC 71 BM/MoO 3 /Ag and ITO/ZnO/Polymer: PC 71 BM/Ca/Al were used for hole-only devices and electron-only devices, respectively.
  • the SCLC mobilities were calculated by MOTT-Gurney equation:
  • ⁇ r is the relative dielectric constant of active layer material usually 2-4 for organic semiconductors.
  • ⁇ 0 is the permittivity of empty space
  • ⁇ is the mobility of hole or electron
  • d is the thickness of the active layer
  • V is the internal voltage in the device
  • V V app -V bi , where V app is the voltage applied to the device, and V bi is the built-in voltage resulting from the relative work function difference between the two electrodes (in the hole-only and the electron-only devices, the V bi values can be neglected) .

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne des semi-conducteurs polymères et leurs procédés de préparation ainsi que leurs utilisations dans des transistors organiques à couches minces ou des cellules solaires polymères. Les semi-conducteurs polymères selon la présente invention sont de formule I. Les semi-conducteurs polymères obtenus par la présente invention peuvent être utilisés dans des transistors organiques à couches minces à mobilité élevée et présentent des rendements de conversion de puissance élevés à la fois dans des cellules solaires polymères à hétérojonction en volume et des cellules solaires polymères à couche par couche.
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CN112280008A (zh) * 2019-07-24 2021-01-29 华南协同创新研究院 一种桥联不对称的苯并二唑类和/或吡啶二唑类双受体的聚合物半导体及其制备方法与应用
WO2021041450A1 (fr) * 2019-08-27 2021-03-04 Phillips 66 Company Comonomère semi-conducteur organique
WO2021041458A3 (fr) * 2019-08-27 2021-03-25 Phillips 66 Company Comonomère semi-conducteur organique
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WO2019091995A1 (fr) * 2017-11-10 2019-05-16 Merck Patent Gmbh Composés semi-conducteurs organiques
US20230200202A1 (en) * 2017-11-10 2023-06-22 Raynergy Tek Incorporation Organic semiconducting compounds
US12101992B2 (en) 2017-11-10 2024-09-24 Raynergy Tek Incorporation Organic semiconducting compounds
CN112280008A (zh) * 2019-07-24 2021-01-29 华南协同创新研究院 一种桥联不对称的苯并二唑类和/或吡啶二唑类双受体的聚合物半导体及其制备方法与应用
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WO2021041450A1 (fr) * 2019-08-27 2021-03-04 Phillips 66 Company Comonomère semi-conducteur organique
WO2021041458A3 (fr) * 2019-08-27 2021-03-25 Phillips 66 Company Comonomère semi-conducteur organique

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