WO2018119780A1 - Blocs structuraux faibles donneurs d'électrons, copolymères correspondants et dispositifs associés - Google Patents

Blocs structuraux faibles donneurs d'électrons, copolymères correspondants et dispositifs associés Download PDF

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WO2018119780A1
WO2018119780A1 PCT/CN2016/112715 CN2016112715W WO2018119780A1 WO 2018119780 A1 WO2018119780 A1 WO 2018119780A1 CN 2016112715 W CN2016112715 W CN 2016112715W WO 2018119780 A1 WO2018119780 A1 WO 2018119780A1
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polymer
btry
compound
film
pffbt
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Xugang GUO
Yulun Wang
Qiaogan LIAO
Han GUO
Shengbin SHI
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South University Of Science And Technology Of China
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Definitions

  • the present disclosure relates to a field of semiconductor technology, in particular to organic semiconductor compound, organic semiconductor polymer, organic semiconductor film, organic thin-film transistors, organic solar cells, and semiconductor devices.
  • Si-based amorphous semiconductors occupy the majority of the market presently due to the excellent workability thereof. However it is expected for the organic semiconductor to be applied to a wearable device because of such characteristics referred to as lightweight and flexibility.
  • OTFTs organic thin-film transistors
  • PSCs polymer solar cells
  • the performance improvement in OTFTs and PSCs are mainly driven by materials innovation in combination with device engineering.
  • the invention of new building blocks plays a critical role, which should afford the resulting semiconductors with improved solution processability and well tailored opto-electrical properties.
  • High-degree of polymer backbone coplanarity typically is a highly desired characteristics for achieving improved device performance in both OTFTs and PSCs.
  • the invention of new building blocks plays a critical role, which should afford the resulting semiconductors with improved solution processability and well tailored opto-electrical properties.
  • the present inventors surprisingly found a new building block, alkynyl-functionalized head-to-head linkage containing bithiophene, and the new building block may be a promising donor unit for high-performance polymer semiconductors.
  • Embodiments of the present disclosure seek to solve at least one of the problems existing in the related art to at least some extent.
  • a first object of the present disclosure is to provide a compound having a formula of in which each of A and B is independently and respectively one of and given that at least one of A and B comprise a alkynyl, each of R 1 and R 2 is independently and respectively a C 1-20 alkyl, a thienyl or a phenyl, and each of the thienyl and the phenyl is optionally and independently substituted with a C 1-20 alkyl.
  • the compound may be used as a promising donor unit for high-performance polymer semiconductors.
  • alkynyl is a versatile side chain for enabling semiconductors with good solublizing ability, high degree of backbone planarity, and optimized opto-electrical property.
  • a second object of the present disclosure is to provide a compound having a formula of , wherein A and B is defined previously, Me is methyl.
  • the compound may form a polymer with an electron acceptor, and the resulting polymer may exhibit excellent properties for use in semiconductor devices such as opo-electrical devices for example organic thin-film transistors and polymer solar cells.
  • a third object of the present disclosure is to provide an organic semiconductor polymer (copolymer) formed by an electron donor unit and an electron acceptor unit, wherein the electron donor is a compound described above, and the electron acceptor unit is at least one selected from a group comprising:
  • the organic semiconductor polymer may exhibit excellent properties for use in semiconductor devices such as opo-electrical devices for example organic thin-film transistors and polymer solar cells.
  • a fourth object of the present disclosure is to provide a semiconductor film formed by the organic semiconductor polymer described above.
  • the semiconductor film may exhibit excellent properties for use in semiconductor devices such as opo-electrical devices for example organic thin-film transistors and polymer solar cells.
  • a fifth object of the present disclosure is to provide a semiconductor device comprising the film described above or the polymer described above.
  • new building blocks having high degree of backbone planarity, good solublizing ability, and well-tailored physicochemical property are provided for constructing high-performance polymer semiconductors. Due to the detrimental steric hindrance created by the alkyl chains at the 3 and 3’ positions of bithiophene, the head-to-head linkage containing 3, 3’ -dialkyl-2, 2’ -bithiophene (BTR) is highly avoided in materials design. Replacing alkyl chains with less steric demanding alkynyl chains should greatly reduce the steric hindrance due to the elimination of two H atoms on the sp hybridized carbon.
  • a novel electron donor unit 3, 3’ -dialkynyl-2, 2’ -bithiophene (BTRy) , was invented and incorporated into polymer backbones.
  • the alkynyl-functionalized head-to-head linkage containing bithiophene enables the resulting polymers with good solubility without sacrificing backbone planarity, hence the BTRy-based polymers show high degree of conjugation with a narrow bandgap of ⁇ 1.6 eV.
  • the polymers When incorporated into organic thin-film transistors, the polymers show substantial hole mobility up to 0.13 cm 2 V -1 s -1 in top-gated devices.
  • the weak electron-withdrawing alkynyl chains lower the energy levels of frontier molecular orbitals, therefore the difluorobenzothiadiazole and difluorobenzoxadiazole copolymers show remarkable ambipolarity with electron mobility up to 0.06 cm 2 V -1 s -1 in bottom-gated transistors.
  • the BTRy-based polymers show promising PCEs approaching 8%with remarkable V oc s of 0.91-1.0 V, reflecting the weak electron withdrawing characteristics of the alkynyl chain.
  • the results demonstrate that alkynyl is versatile side chain for enabling semiconductors with good solublizing ability, high degree of backbone planarity, and optimized opto-electrical property.
  • the study offers a new approach for materials innovation in organic electronics.
  • Fig. 1 shows materials design strategies employed in developing polymer semiconductors with high degree of backbone coplanarity: (a) inserting non-alkylated ⁇ -spacers; (b) conformation locking through covalent bonds; (c) conformation locking through intramolecular non-covalent interaction; (d) introducing alkynyl side chains.
  • the elimination of two hydrogen atoms on the sp hybridized C should reduce steric hindrance and promote backbone planarity (present disclosure) .
  • Fig. 2 shows chemical structures, optimized geometries, and energy levels of the frontier molecular orbitals of (a) 3, 3’ -dialkyl-2, 2’ -bithiophene (BTR) ; (b) 3, 3’ -dialkoxy-2, 2’ -bithiophene (BTOR) ; (c) 3-alkyl-3’ -alkoxy-2, 2’ -bithiophene (TRTOR) ; (d) 3, 3’ -dialkynyl-2, 2’ -bithiophene (BTRy) . Calculations were carried out at the DFT//B3LYP/6-31G*level. The alkyl substituents were truncated here to simplify the calculations.
  • Fig. 3 shows (a) UV-vis absorption spectra of polymers PffBT-BTRy and PffBX-BTRy in solution (1 ⁇ 10 -5 M in o-dichlorobenzene) and as thin film (spin coated from 1 mg mL -1 o-dichlorobenzene solution) ; (b) Cyclic voltammograms of polymer films measured in 0.1 M (n-Bu) 4 N .
  • Fig. 4 shows chemical structures and optimized geometries for the trimers of the repeating units of (a) PffBT-BTRy and (b) PffBX-BTRy. Calculations were carried out at the DFT//B3LYP/6-31G * level; dihedral angles between neighboring arenes are indicated by red circles. Alkyl substituents are truncated to simplify the calculation.
  • Fig. 5 shows electrical characteristics of bottom-gate/top-contact organic thin-film transistors containing PffBT-BTRy as the active layer.
  • Fig. 6 shows (a) J-V characteristics of the optimized polymer solar cells under simulated AM 1.5 G illumination (100 mW cm -2 ) ; (b) external quantum efficiency spectra of the corresponding PSCs.
  • Fig. 7 shows tapping-mode AFM height images of (a) PffBT-BTRy: PC 71 BM and (b) PffBX-BTRy: PC 71 BM blend films; TEM images of (c) PffBT-BTRy: PC 71 BM and (d) PffBX-BTRy: PC 71 BM blend films.
  • the films are prepared with the processing additive DPE under the same conditions for the optimal PSC fabrication.
  • Fig. 8 shows PL spectra obtained from the films of (a) PffBT-BTRy neat film; (b) PffBT-BTRy: PC71BM (1: 1.5, w: w) blend; (c) PffBX-BTRy neat film; (d) PffBX-BTRy: PC71BM (1: 1.5, w: w) blend.
  • Fig. 9 shows (a) Thermogravimetric analysis (heating ramp: 10 °C min -1 ) of polymers PffBT-BTRy and PffBX-BTRy; (b) DSC thermograms of polymers PffBT-BTRy and PffBX-BTRy for the second heating and cooling scans (heating ramp: 10 °C min -1 ) . Nitrogen was used as the purge gas for TGA and DSC measurements.
  • Fig. 10 shows electrical characteristics of bottom-gate/top-contact organic thin-film transistors containing PffBX-BTRy as the active layer.
  • the device dimension is 90 ⁇ m ⁇ 1.8mm.
  • Fig. 11 shows electrical characteristics of top-gate/bottom-contact organic thin-film transistors containing PffBT-BTRy and PffBX-BTRy as the active layer in p-type regime.
  • the device dimension is 100 ⁇ m ⁇ 5 mm.
  • Fig. 12 shows the corresponding J 1/2 –V curves for the hole-only (left) and electron-only (right) devices based on the polymer: PC 71 BM blend films with or without 3%DPE (in dark) .
  • Fig. 13 shows tapping-mode AFM height (a, b, e, and f) and phase images (c, d, g, and h) of polymer: PC 71 BM blend films prepared without processing additive diphenyl ether (DPE) (a, b, c and d) and with DPE (e, f , g and h) under the same conditions for the optimal PSC fabrication.
  • DPE diphenyl ether
  • Fig. 14 shows TEM images of polymer: PC 71 BM blend films prepared without processing additive diphenyl ether (DPE) and with DPE under the same conditions for the optimal PSC fabrication.
  • DPE diphenyl ether
  • High-degree of polymer backbone coplanarity typically is a highly desired characteristics for achieving improved device performance in both OTFTs and PSCs.
  • the planar backbone can result in highly delocalized intramolecular charge carrier transport due to the substantially overlapped ⁇ -orbitails.
  • the planar backbone can facilitate three-dimensional lamellar packing of polymer chains and assist in achieving long-range of materials ordering and film crystallinity, thus intermolecular charge carrier hopping can be greatly enhanced versus the amorphous polymer semiconductors.
  • polymer semiconductors with highly planar backbone conformation typically result in greatly improved charge carrier mobility in OTFTs.
  • high degree of backbone planarity enables polymer semiconductors with narrowed bandgaps and results in enhanced harvesting of solar spectrum, which is essential for maximizing the short-circuit currents (J sc s) .
  • the backbone planarity is beneficial to charge carrier transport and extraction, hence charge carrier recombination can be greatly suppressed, resulting in improved J sc s and fill factors (FFs) in PSCs.
  • solubilizing alkyl chains are essential for enabling materials solution processability.
  • introducing such chains typically generates undesired steric hindrance, which is detrimental to backbone planarity, polymer chain packing, and film crystallinity.
  • Fig. 1a non-alkylated ⁇ -spacers
  • PQT and PBTTT high mobility polymer semiconductors
  • the locking atom-containing building blocks are axisymmetric, which are not ideal for polymer chain packing versus centrosymmetric ones.
  • the polymers typically show limited charge carrier mobilities in OTFTs and sub-optimal FFs in PSCs. While in the strategy using non-covalent bond-based conformational locking, highly polarizable heteroatoms, sush as oxygen (Fig.
  • the head-to-head linkage containing 3, 3’ -dialkyl bithiophene (BTR, Fig. 2a) is highly avoided in polymer semiconductors due to the substantial backbone torsion induced by the steric hindrance. Thanks to the smaller van der waals radius of oxygen versus that of the methylene group, the oxygen insertion beteween thiophene backbone and alkyl chain should greatly mitigate the steric hindrance, which in combination with the non-covalent interaction-based conformation locking affords a new materials design strategy (Fig. 1c) . In spite of the great success of this strategy, the alkoxy-functionalized bithiophenes, BTOR and TRTOR (Fig.
  • the present inventors surprisingly found a new building block, 3, 3’ -dialkynyl-2, 2’ -bithiophene unit (BTRy, Fig. 2d) .
  • the sp hybridized carbon on the alkynyl should lead to greatly decreased steric hindrance due to the elimination of two H atoms.
  • the van der waals radius of the sp hybridized C is comparable to that of O atom, which can result in greatly reduced steric hindrance in the head-to-head linkage containing 3, 3’ -dialkynyl-2, 2’ -bithiophene.
  • Density functional theory (DFT) computation reveals a highly coplanar BTRy backbone (Fig. 2d) with a dihedral angle of 0.01° between the two thiophene planes.
  • the alkynyl substituents should afford good materials solubility.
  • ethynylene or acetylene moieties have been widely used in polymeric semiconductors, typically incorporated into backbone, which results in a class of polymers, poly (phenylene ethynylene) s (PPEs) .
  • PPEs poly (phenylene ethynylene) s
  • the sp hybridized C can stablize the frontier molecualr orbitals (FMOs) of PPEs due to its weak electron withdrawing ability.
  • the resulting semiconductor shows a 0.3 eV lower-lying HOMO than the parent polymer P3HT.
  • the new building block BTRy contains two solubilizing alkynyl chains on the 3 and 3’ positions of bithiophene, which should enable the resulting polymers with good solubility.
  • the weak electron-withdrawing alkynyl group affords BTRy unit with a low-lying HOMO (-5.16 eV, Fig.
  • a first object of the present disclosure is to provide a compound having a formula of in which each of A and B is independently and respectively one of and given that at least one of A and B comprise a alkynyl, each of R 1 and R 2 is independently and respectively a C 1-20 alkyl, a thienyl or a phenyl, and each of the thienyl and the phenyl is optionally and independently substituted with a C 1-20 alkyl.
  • the compound may be used as a promising donor unit for high-performance polymer semiconductors.
  • alkynyl is a versatile side chain for enabling semiconductors with good solublizing ability, high degree of backbone planarity, and optimized opto-electrical property.
  • the compound is represented by the following formula:
  • each R is C1 ⁇ 20 alkyl independently.
  • the compound may act as an electron donor and form polymer with an electron receptor at the sites shown in the following formulas:
  • each R is C10 alkyl independently.
  • each R is C10 branched alkyl.
  • each R is
  • the compound is represented by the following formula:
  • a second object of the present disclosure is to provide a compound having a formula of wherein A and B is defined previously, Me is methyl.
  • the compound may form a polymer with an electron acceptor, and the resulting polymer may exhibit excellent properties for use in semiconductor devices such as opo-electrical devices for example organic thin-film transistors and polymer solar cells.
  • the compound is represented by the following formula:
  • a third object of the present disclosure is to provide an organic semiconductor polymer formed by an electron donor unit and an electron acceptor unit, wherein the electron donor is a compound described above, and the electron acceptor unit is at least one selected from a group comprising:
  • the electron accpetor may form the organic semiconductor polymer at the sites shown in the following formulas:
  • the organic semiconductor polymer may exhibit excellent properties for use in semiconductor devices such as opo-electrical devices for example organic thin-film transistors and polymer solar cells.
  • organic semiconductor polymer according to embodiments of the present disclosure may further have at least one of the following additional technical features:
  • the organic semiconductor polymer is represented by the following formula:
  • n is an integer ranging from 1 to10, and x is S or O.
  • n is an integer ranging from 1 to 5, for example, 1, 2, 3, 4, and 5. In some embodiments, n is an integer sufficient to afford an polymer dispersity index (PDI) of 4.7 and 2.8 respectively.
  • PDI polymer dispersity index
  • the organic semiconductor polymer shows a band gap of about 1.6eV.
  • the organic semiconductor polymer shows a substantial hole mobility up to 0.13 cm 2 V -1 s -1 in a top-gated organic thin-film transistor.
  • the organic semiconductor polymer shows an electron mobility up to 0.06 cm 2 V -1 s -1 in a bottom-gated organic thin-film transistor.
  • the organic semiconductor polymer shows a maximum Power Conversion Efficiency approaching 8%and/or a V oc s of 0.91-1.0 V in a polymer solar cell.
  • the organic semiconductor polymer is represented by the following formula: wherein n is suitable to achieve a number average molecular weight of 43.8 kDa.
  • the organic semiconductor polymer is represented by the following formula: wherein n is suitable to achieve a number average molecular weight of 33.0 kDa.
  • a fourth object of the present disclosure is to provide a semiconductor film formed by the organic semiconductor polymer described above.
  • the semiconductor film may exhibit excellent properties for use in semiconductor devices such as opo-electrical devices for example organic thin-film transistors and polymer solar cells.
  • a fifth object of the present disclosure is to provide a semiconductor device comprising the film described above or the polymer described above.
  • the semiconductor device is an opto-electrical device comprising at least one of organic thin-film transistor and polymer solar cell.
  • the organic thin-film transistor is a top-gated organic thin-film transistor or a bottom-gated organic thin-film transistor.
  • the film or the polymer shows: a substantial hole mobility up to 0.13 cm 2 V -1 s -1 in a top-gated organic thin-film transistor, an electron mobility up to 0.06 cm 2 V -1 s -1 in a bottom-gated organic thin-film transistor, or a maximum Power Conversion Efficiency approaching 8%and/or a V oc s of 0.91-1.0 V in a polymer solar cell.
  • new building blocks having high degree of backbone planarity, good solubilizing ability, and well-tailored physicochemical property are provided for constructing high-performance polymer semiconductors. Due to the detrimental steric hindrance created by the alkyl chains at the 3 and 3’ positions of bithiophene, the head-to-head linkage containing 3, 3’ -dialkyl-2, 2’ -bithiophene (BTR) is highly avoided in materials design. Replacing alkyl chains with less steric demanding alkynyl chains should greatly reduce the steric hindrance due to the elimination of two H atoms on the sp hybridized carbon.
  • a novel electron donor unit 3, 3’ -dialkynyl-2, 2’ -bithiophene (BTRy) , was invented and incorporated into polymer backbones.
  • the alkynyl-functionalized head-to-head linkage containing bithiophene enables the resulting polymers with good solubility without sacrificing backbone planarity, hence the BTRy-based polymers show high degree of conjugation with a narrow bandgap of ⁇ 1.6 eV.
  • the polymers When incorporated into organic thin-film transistors, the polymers show substantial hole mobility up to 0.13 cm 2 V -1 s -1 in top-gated devices.
  • the weak electron-withdrawing alkynyl chains lower the energy levels of frontier molecular orbitals, therefore the difluorobenzothiadiazole and difluorobenzoxadiazole copolymers show remarkable ambipolarity with electron mobility up to 0.06 cm 2 V -1 s -1 in bottom-gated transistors.
  • the BTRy-based polymers show promising PCEs >7%with remarkable V oc s of 0.91-1.0 V, reflecting the weak electron withdrawing characteristics of the alkynyl chain.
  • the results demonstrate that alkynyl is versatile side chain for enabling semiconductors with good solubilizing ability, high degree of backbone planarity, and optimized opto-electrical property.
  • the study offers a new approach for materials innovation in organic electronics.
  • the cathode interfacial layer PFN for solar cells was purchased from Solarmer Materials Inc..
  • PC 71 BM was bought from American Dye Source, Inc..
  • the P (VDF-TrFE) ( 300) dielectrics for the top-gate transistors was purchased from Solvay S.A..
  • 1 H and 13 C NMR spectra of monomers and their precursors were measured on Bruker Ascend 400 and 500 MHz spectrometers, respectively.
  • 1 H NMR of the polymers were recorded on Bruker Ascend 400 MHz spectrometer at 80 °C. Chemical shifts were referenced to residual protio-solvent signals.
  • TGA curves were collected on a TA Instrument (Mettler, STARe) .
  • UV-vis absorption spectra of polymer solution and film at room temperature were collected on a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer.
  • Temperature dependent UV-vis absorption spectra of polymer solutions at various temperatures were collected on Perkin Elmer Lambda 950 UV/VIS/NIR Spectrometer.
  • Steady-state photoluminescence (PL) spectra were conducted using a Horiba iHR320 spectrometer with the Andor Newton EMCCD detector.
  • PL spectra were excited using a Coherent 532 CW laser.
  • Cyclic voltammetry measurements of polymer films were carried out under argon atmosphere using a CHI760 Evoltammetric analyzer with 0.1 M tetra-n-butylammoniumhexafluorophosphate in acetonitrile as the supporting electrolyte.
  • a platinum disk working electrode, a platinum wire counter electrode, and a silver wire reference electrode were employed, and Fc/Fc + redox couple was used as the internal reference for all measurements.
  • the scanning rate was 50 mV S -1 .
  • PCBM blend films were conducted 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. After drying, substrates were transferred to deionized water and the floated films were transferred to TEM grids.
  • TEM images were obtained on Tecnai Spirit (20 kV) TEM.
  • Scheme 1 depicts the synthetic route to BTRy (6) .
  • 5-ethynylundecane 4 was synthesized following the published procedures starting from the commecial alcohol.
  • 4-butyloctanol is oxidized using pyridinium chlorochromate (PCC) to form 2-butyloctanal 2, then the Corey-Fuchs sequence is carried out to provide the terminal alkyne 4.
  • Sonogashira coupling between 4 and the dibromobithiophene 5 affords the key compound 6, which is subjected to column chromatography on silica and then careful purification using C18 reversed-phase chromatography. High purity 6 is lithiated and then quenched with Me 3 SnCl to afford the monomer 7.
  • the product polymers are collected by precipitation into methanol and then are purified by Soxhlet extraction.
  • Polymers PffBT-BTRy and PffBX-BTRy exhibit good solubility in common organic solvents for device fabrication.
  • Molecular weights are measured by high-temperature (140 °C) gel permeation chromatography (GPC) versus polystyrene standards.
  • M n number average molecular weight
  • PDI polydispersity index
  • Reagents and conditions (i) PCC, dichloromethane; (ii) PPh 3 , CBr 4 , dichloromethane; (iii) n-BuLi, THF, H 2 O; (iv) CuI, Pd (PPh 3 ) 4 , DIPA, toluene, 135 °C; (v) n-BuLi, Me 3 SnCl, THF; (vi) Pd 2 (dba) 3 , P (o-tolyl) 3 , toluene, microwave, 140 °C.
  • Triphenylphosphine 32.83 g, 125.2 mmol was added slowly to a solution of tetrabromomethane (20.69 g, 62.4 mmol) in dichloromethane (170 mL) at 0 °C. 2 (5.75 g, 31.2 mmol) was then added dropwise over a period of 30 min. The reaction mixture was stirred at room temperature for 2 h and was then poured into stirring brine (200 mL) followed by extraction with dichloromethane several times.
  • the tube and its contents were subjected to 3 pump/purge cycles with argon, followed by the addition of anhydrous toluene (3-4 mL) via syringe.
  • 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.
  • 0.05 mL of 2- (tributylstanny) thiophene was added and the reaction mixture was stirred under microwave irradiation at 140 °C for 0.5 h.
  • 0.10 mL of 2-bromothiophene was added and the reaction mixture was stirred at 140 °C for another 0.5 h.
  • the reaction mixture was slowly dripped into 100 mL of methanol (containing 2 mL 12 N hydrochloric acid) under vigorous stirring. After stirring for 1h, the solid precipitate was transferred to a Soxhlet thimble. After drying, the crude product was subjected to sequential Soxhlet extraction. After final extraction, the polymer solution was concentrated to approximately 10 mL, and then dripped into 100 mL of methanol under vigorous stirring. The polymer was collected by filtration and dried under reduced pressure to afford a deep colored solid as the product.
  • methanol containing 2 mL 12 N hydrochloric acid
  • the solvent sequence for Soxhlet extraction was methanol, acetone, hexane, dichloromethane, and chloroform.
  • the chloroform 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 deep colored solid (63.8%) .
  • the solvent sequence for Soxhlet extraction was methanol, acetone, hexane, dichloromethane, and chloroform.
  • the chloroform 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 deep colored solid (56.3%) .
  • the solvent sequence for Soxhlet extraction was methanol, acetone, hexane, dichloromethane, and chloroform.
  • the chloroform 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 deep colored solid (48.3%) .
  • the solvent sequence for Soxhlet extraction was methanol, acetone, hexane, dichloromethane, and chloroform.
  • the chloroform 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 deep colored solid (59.4%) .
  • the solvent sequence for Soxhlet extraction was methanol, acetone, hexane, dichloromethane, and chloroform.
  • the chloroform 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 deep colored solid (48.1%) .
  • Example 2 Thermal Properties and GIWAXS Measurements of Polymers prepared in Example 1
  • Example 1 The thermal properties of polymers synthesized in Example 1 were tested in this example, and the results were shown in Fig. 9, (a) Thermogravimetric analysis (heating ramp: 10 °C min -1 ) of polymers PffBT-BTRy and PffBX-BTRy; (b) DSC thermograms of polymers PffBT-BTRy and PffBX-BTRy for the second heating and cooling scans (heating ramp: 10 °C min -1 ) . Nitrogen was used as the purge gas for TGA and DSC measurements.
  • Grazing incidence wide-angle x-ray scattering (GIWAXS) measurements were performed at Beamline 8-ID-E of the Advanced Photon Source at Argonne National Laboratory. Polymer samples were prepared on Si substrate using identical spin speeds, solvents, concentrations and annealing temperature and times to the relevant OTFT and PSC devices. All spectra were collected in air. The photon energy is 7.35 keV and data were collected on a Pilatus 1M pixel array detector at a sample-detector distance of 204 mm. Spectra were collected at an incidence angle of 0.2°; the films were exposure for 20 seconds. To account for the gaps in the detector array, two images were taken per sample, one with the detector in the standard position and the other translated 23 mm down to fill the gap, the two images are then merged.
  • GIWAXS Grazing incidence wide-angle x-ray scattering
  • 1D line cuts were taken from the 2D scattering spectra in the in-plane and out-of-plane directions using the GIXSGUI software package developed by the beamline scientists. To account for air scatter, the line cuts were background subtracted utilizing an exponential fit. The background-subtracted peaks were fit using the multipeak fit function in igor pro. Scherrer analysis was performed utilizing the method by Smiglies to account for instrumental broadening and detection limits in the 2d detector. The values presented represent a lower limit for correlation length, as the Scherrer analysis does not account for broadening due to defects in the crystallites.
  • the benzoxadiazole-based polymer PffBX-BTRy exhibits a stronger aggregation than the benzothiadiazole-based polymer PffBT-BTRy since PffBX-BTRy shows sharper and more structured absorption at elevated temperatures.
  • the stronger PffBX-BTRy aggregation is likely attributed to the more electron-deficient nature of difluorobenzoxadiazole versus that of difluorobenzothiadiazole, resulting in more intense inter-polymer chain interactions.
  • both polymers show distinct absorption shoulder, an indicative of a high degree of polymer backbone coplanarity and ordering, in good accord with the DFT computation.
  • the DFT results show complete planar backbone formation for the trimmers of the repeating units of the BTRy-based polymers (Fig. 4) .
  • the optical bandgaps derived from the absorption onsets of PffBT-BTRy and PffBX-BTRy films are 1.66 and 1.62 eV, respectively.
  • the slightly smaller bandgap of PffBX-BTRy is a reflection of the stronger electron-withdrawing ability of difluorobenzoxadiazole (versus difluorobenzothiadiazole) .
  • the bandgap (1.66 eV) of PffBT-BTRy is comparable to those (1.60-1.65 eV) of the difluorobenzothiadiazole-oligothiophene copolymers, which show high degree of polymer backbone coplanarity and film crystallinity.
  • the head-to-head linkage containing BTRy-based polymers should maintain a high-degree of polymer backbone planarity, which is attributed to the reduced steric hindrance due to the elimination of two hydrogen atoms on the sp hybridized carbon.
  • the electrochemical properties of the BTRy-based polymers are investigated using cyclic voltammetry and the ferrocene/ferrocium (Fc/Fc + ) redox couple is used as the internal standard. Both polymers show distinct reduction and oxidation peaks (Fig. 3b) , and the derived HOMO/LUMOs are-5.54/-3.88 and-5.71/-4.09 eV for PffBT-BTRy and PffBX-BTRy, respectively.
  • the HOMO of the difluorobenzothiadiazole-BTRy copolymer PffBT-BTRy is further decreased, which reflects the weak electron withdrawing capability of alkynyl chains.
  • the low-lying HOMOs should be beneficial to the V oc s of the PSCs.
  • PffBX-BTR shows suppressed HOMO and LUMO, which are attributed to the higher electron negativity of oxygen in benzoxadiazole versus sulfur in benzothiadiazole.
  • the low-lying LUMOs in combination with the substantial reduction peaks indicate that the BTRy-based polymers can function as n-type semiconductors, which is in good accord with the OTFT performance (vide infra) .
  • BGTC Bottom-Gate/Top-Contact
  • Top-gate/bottom-contact (TGBC) thin-film transistors Source–drain electrodes (3 nm Cr and 30 nm Au) were patterned on borosilicate glass by photolithography. The substrates were cleaned by sonication in acetone and isopropanol followed by UV-ozone treatment. The polymer active layers were spin coated from 5 mg mL -1 chlorobenzene solutions, and then they were thermally annealed at various temperatures for 20 min. The P(VDF-TrFE) ( 300) dielectric layers were spin-coated from 60 mg mL -1 2-butanone (MEK) solutions, then they were annealed at 60 °C for 30 min. Finally, 50 nm Al was evaporated on top as the gate electrode.
  • Source–drain electrodes (3 nm Cr and 30 nm Au) were patterned on borosilicate glass by photolithography. The substrates were cleaned by sonication in acetone and isopropanol followed by UV-ozone treatment.
  • ITO indium tin oxide
  • PSS Creatibility P VP A1 4083
  • ⁇ 30 nm was spin coated onto ultraviolet ozone-treated ITO substrates. After annealing at 140 °C for 15 min. in air, the substrates were transferred into a N 2 glove-box.
  • the ODCB blend solution stirred at 110 °C overnight (4 mg/mL for PffBT-BTRy and 8 mg/mL for PffBX-BTRy) was spin coated on top of the PEDOT: PSS layer.
  • the blend film thickness was controlled at ⁇ 60-130 nm (KLA-TENCOR Alpha-Step Surface Profiler) .
  • ⁇ 6 nm PFN 0.2 mg/ml ethanol solution
  • 100 nm Al cathode was deposited (area 4.5 mm 2 defined by metal shadow mask) on the active layer under high vacuum (1 ⁇ 10 -4 Pa) using a thermal evaporator.
  • All current-voltage (I-V) characteristics of the devices were measured under simulated AM1.5G irradiation (100 mW/cm 2 ) using a Xe lamp-based Newport 91160 300-W Solar Simulator.
  • a Xe lamp equipped with an AM1.5G filter was used as the white light source.
  • the light intensity was controlled with an NREL-calibrated Si solar cell with a KG-5 filter.
  • the external quantum efficiency (EQE) was measured by a QE-R3011 measurement system (Enli Technology, Inc. ) .
  • Table S Device performance of bottom-gate/top-contact organic thin-film transistors containing PffBT-BTRy as the active layer under various annealing temperature.
  • Fig. 10 shows electrical characteristics of bottom-gate/top-contact organic thin-film transistors containing PffBX-BTRy as the active layer.
  • the device dimension is 90 ⁇ m ⁇ 1.8 mm.
  • Table S3 Device performance of top-gate/bottom-contact organic thin-film transistors containing PffBT-BTRy and PffBX-BTRy as the active layers.
  • Fig. 11 shows lectrical characteristics of top-gate/bottom-contact organic thin-film transistors containing PffBT-BTRy and PffBX-BTRy as the active layer in p-type regime.
  • the device dimension is 100 ⁇ m ⁇ 5 mm.
  • the additive is 3vol%DPE; b thermal annealing is under 80 °C for 5 min.
  • Fig. 12 shows the corresponding J 1/2 –V curves for the hole-only (left) and electron-only (right) devices based on the polymer: PC 71 BM blend films with or without 3%DPE (in dark) .
  • Fig. 13 shows tapping-mode AFM height (a, b, e, and f) and phase images (c, d, g, and h) of polymer: PC 71 BM blend films prepared without processing additive diphenyl ether (DPE) (a, b, c and d) and with DPE (e, f , g and h) under the same conditions for the optimal PSC fabrication.
  • DPE diphenyl ether
  • Fig. 14 shows TEM images of polymer: PC 71 BM blend films prepared without processing additive diphenyl ether (DPE) and with DPE under the same conditions for the optimal PSC fabrication.
  • DPE diphenyl ether
  • PL blend and PL polymer are the PL intensity of the blend films and neat polymer films, respectively.
  • Blend film ⁇ PL (%) PffBT-BTRy: PC 71 BM 94.52
  • PffBX-BTRy PC 71 BM 85.59
  • OTFTs organic thin-film transistors in two different architectures of bottom-gate/top-contact (BGTC) and top-gate/bottom-contact (TGBC) are fabricated to investigate the charge carrier transport properties of the BTRy-based polymers and the relevant device performance parameters are compiled in Table 2 and Table S1-S3.
  • BGTC architectures both polymers show ambipolar transport (Fig. 5) .
  • the ambipolarity is in good accord with the electrochemical property, showing both oxidation and reduction peaks (Fig. 3) .
  • the PffBT-BTRy OTFTs exhibit low off-currents of 10 -11 –10 -10 A in both p- and n-channels, which are remarkable for ambipolar OTFTs.
  • the suppressed off-currents are likely attributed to the low-lying HOMO of the BTRy-based polymers.
  • Fig. 5 shows Electrical characteristics of bottom-gate/top-contact organic thin-film transistors containing PffBT-BTRy as the active layer.
  • the PffBX-BTRy OTFTs exhibit further decreased off-currents (10 -12 –10 -11 A) and one order of magnitude higher I on /I off ratios (Fig. 10) due to its lower HOMO versus that of PffBT-BTRy.
  • the PffBT-BTRy OTFTs typically show large threshold voltages (V T : ⁇ 65 V) , which are likely attributed to the large electron inject barrier ( ⁇ 1.2 eV) between the fermi level of Au electrode and the LUMO lvele of PffBT-BTRy.
  • the benzoxadiazole-based polymer PffBX-BTRy exhibits smaller V T ( ⁇ 45 V) for the n-channel operation and slightly larger V T ( ⁇ -45 V) for the p-channel operation, consistent with the FMO evolution, which results in reduced electron injection barrier and enlarged hole injection barrier, respectively.
  • Top-gate/bottom-contact (TGBC) OTFTs with the fluorinated dielectrics, poly (vinylidenefluoride-trifluoroethylene) P (VDF-TrFE) , are also fabricated, which exhibit hole dominating transport with negligible electron mobility.
  • TGBC OTFTs the ⁇ h, OTFT s are greatly enhanced to 0.13 and 0.097 cm 2 V -1 s -1 for PffBT-BTRy and PffBX-BTRy, respectively.
  • the representative transfer and output curves are given in Fig. 11 and the device performance parameters are summerized in Table 2.
  • the carrier mobility of polymer semiconductors generally increases with carrier concentrations, but this is not the case here since the dielectric capacitance of the TG/BC and BG/TC devices are highly comparable (1.5 ⁇ 10 -8 F cm -2 for TG/BC and 1.7 ⁇ 10 -8 F cm -2 for BG/TC) and the mobility values are extracted at the same voltages.
  • the mobility increase could be linked to the improved molecule packing and polymer chain orientation at the top surface of the semiconductor film in the TG/BC OTFTs versus that at the burried bottom surface in the BG/TC OTFTs, as the result of the different liquid-air and liquid-solid interfaces during the spin-coating process.
  • the directional interface state modulation by the C-F dipole in P (VDF-TrFE) can decrease the hole injection barrier, but increase the electron injection barrier.
  • the hole mobility is improved and the electron mobility is greatly suppressed in the top-gated OTFTs containing the P (VDF-TrFE) dielectrics.
  • the hole mobility increase could be attributed to the improved semiconductor/dielectrics interfacial properties in the top-gate OTFTs.
  • the electron transport in the P (VDF-TrFE) -containing devices is substantially suppressed, which could be attributed to the presence of electron trapping groups at the semiconductor/P (VDF-TrFE) interface, similar to the earlier observation in ambipolar P (NDI2OD-T2) transistors.
  • both polymers show substantial hole mobilities in the optimized OTFTs, which reflect the high degree of backbone planarity and good film crystallinity of the BTRy-based polymer semiconductors (vide infra) .
  • a BGTC bottom-gate/top-contact
  • TGBC top-gate/bottom-contact.
  • b Data represent device with the best mobilities and the average mobilities from more than 5 devices are shown in parentheses.
  • the PffBT-BTRy PSCs show a PCE of 7.69%with a J sc of 14.13 mA cm -2 and a FF of 59.8%and the PffBX-BTRy PSCs show a PCE of 3.35%with a J sc of 6.56 mA cm -2 and a FF of 49.0%.
  • the J sc s integrated from the external quantum efficiency spectra (Fig. 6b) of the optimized PSCs are 13.51 and 5.86 mA cm -2 for the PffBT-BTRy and PffBX-BTRy, respectively, showing good internal consistency.
  • the BTRy-based polymers exhibit remarkable V oc s of 0.91 and 1.04 V for the PffBT-BTRy and PffBX-BTRy PSCs, respectively.
  • the V oc (0.91 V) of PffBT-BTRy is 0.03 V larger than that (0.88 V) of difluorobenzothiadiazole-bithiophene copolymer.
  • the attachment of alkynyl side chain results in a larger V oc , which is attributed to the suppressed HOMO of PffBT-BTRy.
  • V oc of PffBX-BTRy is in good accord with its HOMO due to the higher electronegativity of O on benzoxathiazole versus that of S in benzothiadiazole.
  • Both the BTRy-based polymers exhibit sub-optimal FFs ( ⁇ 60%) in PSCs.
  • the PffBX-BTRy shows greatly smaller J sc (6.56 mA cm -2 ) and lower FF (49.0%) compared to those of PffBT-BTRy, which could be related to its very low-lying LUMO and hence substantial monomolecular recombination due to the small energetic driving force for charge separation across the polymer: fullerenen heterojunction.
  • the polymer molecular weight may also play a role considering their M n difference is not negligible.
  • Fig. 6. Shows (a) J-V characteristics of the optimized polymer solar cells under simulated AM 1.5 G illumination (100 mW cm -2 ) ; (b) external quantum efficiency spectra of the corresponding PSCs.
  • the blend film morphology was also characterized using atomic force microscopy (AFM) and transmission electron microscopy (TEM) .
  • AFM height images of PffBT-BTRy: PC 71 BM (Fig. 7a) and PffBX-BTRy: PC 71 BM (Fig. 7b) blend films reveal that the DPE addition leads to increased root mean square roughness (RMS) from 1.45 to 3.75 nm and from 2.87 to 5.94 nm (see Fig. 13 for the films without using DPE) , respectively, which is likely indicative of improved polymer chain packing and film crystallinity.
  • RMS root mean square roughness
  • Such large film roughness increases the contact area between the blend film and the interfacial layer/electrode, which can facilitate charge extraction.
  • Fig. 7c and Fig. 7d show the TEM images of the PffBT-BTRy: PC 71 BM and PffBX-BTRy: PC 71 BM blends under the optimized fabrication condition, respectively.
  • the phase separation at finer scale occurs and the interpenetrating bicontinuous network develops after DPE addition, which can contribute to more efficient exciton dissociation and charge carrier transportation/collection.
  • PC 71 BM blend shows distinct finer fibril structure after adding DPE.
  • DPE in the PffBX-BTRy: PC 71 BM blends results in the smearing of TEM image and the fibril structure is less obvious.
  • the charge carrier mobilities of the blend films are measured using space charge limited current (SCLC) method, and the derived ⁇ h, SCLC / ⁇ e, SCLC s are 9.61 ⁇ 10 -5 /1.10 ⁇ 10 -4 and 6.96 ⁇ 10 -5 /4.40 ⁇ 10 -4 cm 2 V -1 s -1 for the PffBT-BTRy and PffBX-BTRy blends (Table 3 and Fig. 12) , respectively.
  • SCLC space charge limited current
  • Fig. 7 shows tapping-mode AFM height images of (a) PffBT-BTRy: PC 71 BM and (b) PffBX-BTRy: PC 71 BM blend films; TEM images of (c) PffBT-BTRy: PC 71 BM and (d) PffBX-BTRy: PC 71 BM blend films.
  • the films are prepared with the processing additive DPE under the same conditions for the optimal PSC fabrication.
  • PL quenching efficiency is calculated using PL intensity of the blend films relative to those of neat polymer films, which to some extent can be employed to characterize the degree of exciton dissociation at the polymer: PC 71 BM interface in blend films.
  • the PL emission peaks of the neat polymers PffBT-BTRy and PffBX-BTRy are 774 and 791 nm, respectively.
  • Table S12 the optimized blend films in PSCs show different ⁇ PL.
  • the ⁇ PL of the PffBT-BTRy: PC 71 BM blend film reachs 94.52%, while that of PffBX-BTRy: PC 71 BM blend film is lower (85.49%) .
  • the higher ⁇ PL (94.52%) of PffBT-BTRy: PC 71 BM blend reflects more efficient exciton dissociation, which is consistent with its energy level and film morphology.
  • the lower ⁇ PL (85.49%) of PffBX-BTRy: PC 71 BM blend film indicates lower degree of exciton dissociation, in good accord with the PSC performance.
  • Fig. 8 shows PL spectra obtained from the films of (a) PffBT-BTRy neat film; (b) PffBT-BTRy: PC71BM (1: 1.5, w: w) blend; (c) PffBX-BTRy neat film; (d) PffBX-BTRy: PC71BM (1: 1.5, w: w) blend.
  • a novel building block 3, 3’ -dialkynyl-2, 2’ -bithiophene (BTRy) was invented and incorporated into polymer semiconductors.
  • the sp hybridized carbon on the alkynyl chain greatly reduces steric hindrance due to the elimination of two hydrogen atoms, hence the alkynyl-functionalized head-to-head linkage containing BTRy enables the resulting polymers with good solubility without sacrificing backbone planarity.
  • the weak electron withdrawing alkynyl chain enables the resulting polymer semiconductors with low-lying frontier molecular orbitals, hence the difluorobenzothiadiazole and difluorobenzoxadiazole copolymers show remarkable ambipolarity with electron mobility up to 0.06 cm 2 V -1 s -1 .
  • the BTRy-based polymers exhibit hole mobility up to 0.13 cm 2 V -1 s -1 .
  • the BTRy-based polymers show promising PCEs approaching 8%with remarkable V oc s of 0.91-1.0 V, which is attributed to the low-lying polymer HOMOs (-5.5 –-5.7 eV) .

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Abstract

L'invention concerne un composé représenté par la formule (I), dans laquelle chacun de A et B est indépendamment et respectivement l'un de la formule (II) et (III), étant donné qu'au moins l'un parmi A et B comprend un alcynyle, chacun de R1 et R2 étant indépendamment et respectivement un alkyle en C1-20, un thiényle ou un phényle, et chacun parmi le thiényle et le phényle est éventuellement et indépendamment substitué par un alkyle en C1-20. L'invention concerne également un polymère semi-conducteur organique formé par une unité donneuse d'électrons et une unité acceptrice d'électrons, un film formé par le polymère semi-conducteur organique et un dispositif semi-conducteur.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101971383A (zh) * 2008-03-12 2011-02-09 住友化学株式会社 有机光电转换元件
WO2012111811A1 (fr) * 2011-02-18 2012-08-23 コニカミノルタホールディングス株式会社 Élément de conversion photoélectrique organique et photopile

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CN101971383A (zh) * 2008-03-12 2011-02-09 住友化学株式会社 有机光电转换元件
WO2012111811A1 (fr) * 2011-02-18 2012-08-23 コニカミノルタホールディングス株式会社 Élément de conversion photoélectrique organique et photopile

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KESHTOV, M. L. ET AL.: "New Fused Thiophene Derivatives as Promising Building Blocks for Optoelectronic Devices", DOKLADY CHEMISTRY, vol. 460, no. Part 2, 28 February 2015 (2015-02-28), pages 50 - 56, XP055509496 *
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