Benzotriazole and benzothiadiazole containing conjugated copolymers for organic solar cell applications

2-Dodecyl benzotriazole (BTz) and benzothiadiazole (BTd) containing copolymers poly(4-(2-dodecyl-2H-benzo[d][1,2,3]triazol-4-yl)benzo[c][1,2,5]thiadiazole (P1), poly(4-(5-(2-dodecyl-7-(thiophen-2yl)-2H-benzo[d][1,2,3]triazol-4-yl)thiophen-2-yl)benzo[c][1,2,5] thiadiazole (P2) and poly(4-(5-(2-dodecyl-7-(4-hexylthiophen-2-yl)-2H-benzo[d] [1,2,3]triazol-4-yl)-3-hexylthiophen-2-yl) benzo[c][1,2,5] thiadiazole (P3) were synthesized via Suzuki polycondensation. We report the application of conjugated copolymers in bulk heterojunction photovoltaic devices. When the copolymers were blended with [6,6]phenyl-C₆₁-butyric acid methyl ester (PCBM), P2 showed the best performance with an open circuit voltage (V_oc), a short-circuit current density (J_sc) and a power conversion efficiency (PCE) of 0.45 V, 3.48 mA cm^?2 and 0.45%, respectively, under AM 1.5G illumination conditions (100 mW cm^?2). The hole mobilities of the devices were calculated from J–V curves using Space Charge Limited Current (SCLC) method and the maximum mobility value was found to be 3.15 × 10^?5 cm² V^?1 s^?1 for the P2:PCBM blend.     

Effects of thiophene units on substituted benzothiadiazole and benzodithiophene copolymers for photovoltaic applications

Two conjugated copolymers, poly{4,7-[5,6-bis(octyloxy)]benzo(c)(1,2,5)thiadiazole-alt-4,8-di(2-ethylhexyloxyl)benzo[1,2-b:3,4-b]dithiophene} ( P1 ) and poly(2-{5-[5,6-bis(octyloxy)-4-(thiophen-2-yl)benzo(c)(1,2,5)thiadiazol-7-yl] thiophen-2-yl}-4,8-di(2-ethylhexyloxyl)benzo(1,2-b:3,4-b)dithiophene) ( P2 ), composed of benzodithiophene and 5,6-dioctyloxybenzothiadiazole derivatives with or without thiophene units were synthesized via a Stille cross-coupling polymerization reaction. These copolymers are promising for applications in bulk heterojunction solar cells because of their good solubility, proper thermal stability, moderate hole mobility, and low band gap. The photovoltaic properties of these copolymers were investigated on the basis of blends of the different polymer/(6,6)-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) weight ratios under AM1.5G illumination at 100 mW/cm². The device with indium tin oxide/poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate)/ P2: PC₇₁BM (1 : 2 w/w)/Ca/Al gave a relatively better photovoltaic performance with a power conversion efficiency of 1.55%. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of a terpolymer containing fluorene,side chain conjugated thiophene and benzothiadiazole and its applications in photovoltaic devices

A terpolymer (POTVTh‐8FO‐DBT) containing fluorene, side chain conjugated thiophene and 4,7‐dithieny‐2,1,3‐benzothiadiazole was synthesized by palladium‐catalyzed Suzuki coupling method. The polymer is soluble in common organic solvents. The thermal, absorption, and electrochemical properties of the polymer were examined. Photovoltaic properties of POTVTh‐8FO‐DBT were studied by fabricating the polymer solar cells (PSCs) based on POTVTh‐8FO‐DBT as donor and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) as acceptor. With the weight ratio of POTVTh‐8FO‐DBT : PC₆₁BM of 1 : 1 and the active layer thickness of 80 nm, the power conversion efficiency (PCE) of the device reached 0.47% with V_oc = 0.61 V, J_sc = 1.61 mA/cm², and filled factor (FF) = 0.49 under the illumination of AM 1.5, 100 mW/cm². The results indicated that this polymer was promising donor candidates in the application of PSCs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Photophysical and photovoltaic properties of a PPV type copolymer containing alternated fluorene and thiophene units

The synthesis and photophysical characterization of a PPV-type copolymer containing a fluorene derivative alternated with thiophene units is presented: poly(9,9’-dioctylfluorene-thiophene) (LAPPS29). Photophysical studies demonstrated that in the solid state only preformed ground state aggregates are responsible for exciton formation. These aggregates are formed with a wide range of size distribution. The emission from isolated segments is quenched either by resonant energy transfer, or by migration processes. Also, the main photovoltaic parameters are discussed in connection with the photophysical behavior.     

Molecular structure-property engineering for photovoltaic applications: Fluorene-acceptor alternating conjugated copolymers with varied bridged moieties

A series of novel soluble conjugated copolymers consisting of electron-accepting 2-pyran-4-ylidenemalononitrile (PM) and electron-donating fluorene connected by different electron-donating ability conjugated moieties were synthesized by Suzuki coupling polymerization. The structures of the copolymers were characterized and their physical properties were investigated. High molecular weight (M_n up to 43.8 kg/mol) and thermostable copolymers were obtained. The conjugated bridge between PM and fluorene building block with gradually increased electron-donating ability moieties results in enhanced intramolecular charge transfer (ICT) transition bands, which lead to an extension of their absorption spectral range. Cyclic voltammetry measurement displayed that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the copolymers can be fine-tuned. The resulting copolymers possessed relatively low HOMO energy levels, promising good air stability and high open circuit voltage (V_oc) for photovoltaic application. Bulk heterojunction photovoltaic devices were fabricated by using the copolymers as donors and (6,6)-phenyl C₆₁-butyric acid methyl ester (PCBM) as acceptor. The power conversion efficiencies (PCE) of the devices were in the range of 0.02-0.52% under simulated AM 1.5 solar irradiation of 100 mW/cm², and the highest V_oc reached 0.82 V. The significant improvement of PCE indicates a novel concept for developing donor-acceptor (D-A) conjugated copolymers with high photovoltaic performance by adjusting electron-donating ability of conjugated bridge.     

Synthesis and characterization of new fluorene-acceptor alternating and random copolymers for light-emitting applications

A series of novel light-emitting copolymers consisted of 9,9-dihexylfluorene (F) and different acceptor segments, including quinoxaline (Q), 2,1,3-benzothiadiazole (BT) and thieno[3,4-b]-pyrazine (TP), were synthesized by the palladium-catalyzed Suzuki coupling reaction. Three fluorene-acceptor alternating copolymers (PFQ, PFBT, PFTP) and six F-TP (PFTP0.5-PFTP35) random copolymers were investigated and compared with the parent polyfluorene (PF). The experimental results suggest that the acceptor strength or content significantly affect the electronic and optoelectronic properties. The optical absorption maxima of the PF, PFQ, PFBT, and PFTP are 368, 416, 470, and 578 nm, respectively, which indicates the significance of intramolecular charge transfer. The electrochemical band gap also shows a similar trend. The incorporation of the acceptor into the PF lowers the LUMO level and thus could improve the electron-accepting ability of the PF. The emission maxima on the photoluminescence (PL) spectra of the PF, PFQ, PFBT, and PFTP films are 424, 493, 540, and 674 nm, which correspond to the color of blue, green, yellow, and red, respectively. It suggests that the full color of emission can be achieved by different acceptors. The significant positive solvatochromism on the PL spectra in different polar solvents suggests the efficient intramolecular charge transfer in PFTP. However, such charge transfer or heavy-atom effect results in fluorescence quenching and thus reduces the PL efficiencies. By random copolymerizing the TP into the PF, the PL efficiency could be improved. A significantly reduction on the PF emission peak with increasing the TP content suggests the energy transfer between the PF and TP segments. Besides, the characteristics on the electroluminescence (EL) devices of ITO/PEDOT:PSS/emissive layer/Ca/Ag suggest that such energy transfer results in the complete quenching of the PF emission at only 1% TP content in the PFTP01. The maximum external quantum efficiency (EQE) of the EL device based on the PFTP01 is superior to that of the PF due to the reduced LUMO level in matching with the Ca. The CIE 1931 coordinates of the PFTP01 based EL device under the condition of maximum EQE is (0.66, 0.31), which is close to the standard red of (0.66, 0.34) demanded by the National Television System Committee (NTSC). The luminescence characteristics based on the prepared polymers depend on the Förster energy transfer or the intramolecular charge transfer, or heavy-atom fluorescence quenching. The present study suggests that the tuning of the electronic and optoelectronic properties could be achieved by incorporating various acceptors or content into the polyfluorenes.     

Synthesis and photovoltaic properties of two-dimensional conjugated polythiophene derivatives presenting conjugated triphenylamine/thiophene moieties

In this study we synthesized three two-dimensional (2-D) polythiophene derivatives (PTs), namely PTBPTPA, PTStTPA, and PTCNStTPA, featuring three different conjugated units—biphenyl (BP), stilbene (St), and cyanostilbene (CNSt), respectively—in the polymer backbones and presenting conjugated triphenylamine/thiophene (TPATh) moieties on the side chains. In addition, we also synthesized three conjugated BP-, St-, and CNSt-based main-chain-type conjugated polymers (PTBP, PTSt, and PTCNSt, respectively). Incorporating the St and CNSt moieties into the polymer backbones and appending TPATh units induced high degrees of intramolecular charge transfer within the conjugated frameworks of the polymers, thereby resulting in lower band gap energies and red-shifting of the maximal UV–Vis absorption wavelengths. Moreover, the energy levels of the highest occupied molecular orbitals of the BP-, St-, and CNSt-based main-chain-type and 2-D PTs were lower than that of P3HT, implying that they would be applicable for the preparation of polymer solar cells (PSC) with greater open-circuit voltages. The photovoltaic performances of PSCs fabricated from blends of the 2-D PTs and the fullerene derivative PC₆₁BM were superior to those of PSCs based on the main-chain-type polymer/PC₆₁BM blends.     

Synthesis and properties of conjugated copolymers having a tricarbonyl(arene)chromium and thiophene units in the main chain

Summary Palladium-catalyzed polymerization of η ⁶-(1,4-diethynylbenzene)tricarbonyl chromium (1) with 3-alkyl-2,5-dibromothiophene (2a-c) was carried out to give the corresponding alternating conjugated copolymers (5a-c) in good yields. The structures of the polymers were supported by ¹H NMR and IR spectra. The polymers obtained were soluble in common solvents such as THF, CH₂Cl₂, CHCl₃ and toluene. The molecular weights of the polymers were determined by GPC. Their thermal, optical and electrical properties were investigated in detail. Received: 18 March 2002 /Accepted: 1 April 2002     

A study of light‐emitting diodes constructed with copolymers having cyclohexyl thiophene and hexyl thiophene units

We report visible light emission from a diode made from copolymers of 3‐alkylthiophenes. These chemically synthesized copolymers exhibit improved electroluminescence and quantum efficiencies compared to poly (3‐cyclohexylthiophene). Good solubility of copolymers allows the fabrication of the light emitting diodes by spin‐cast polymer film. The devices emit greenish‐blue light in wavelength region of 550–580 nm, which is easily visible in poorly lighted room. The quantum efficiencies are in the range of 0.002 to 0.01% (photons per electron) at room temperature; which are significantly higher than corresponding values for poly(3‐cyclohexylthiophene) based light emitting diodes. The charge carrier mobility in the device is found to be 5.6 × 10⁻⁴ cm²/Vs. ©2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1051–1055, 2000     

喹喔啉类衍生物与甲基噻吩共聚物的合成及性质

在二价镍配合物催化下,2,5-二溴-3-甲基噻吩格氏试剂与5,8-二溴-萘基喹喔啉和5,8-二溴-菲基喹喔啉共聚,得到相应的喹喔啉类共轭共聚物,收率分别为65%和68%。通过FT IR、1H-NM R对聚合物及中间体的结构进行了表征。聚合物的循环伏安图中,分别在0.66 V(Epa)/0.37 V(Epc)(Copo ly-m er I),0.78 V(Epa)/-0.06V(Epc)和1.26(Epa)/0.46(Epc)(Copo lym erⅡ)处观察到氧化还原峰,表明该类聚合物有电化学活性。在紫外-可见光谱中,分别在263 nm,323 nm处(Copo lym erⅠ)和299 nm,402 nm处(Copo lym erⅡ)出现吸收峰。所得聚合物分别在504 nm和513 nm处出现荧光最大发射峰。     

Synthesis and characterizations of conjugated copolymers containing benzo[f]isoindole-1,3-dione and diketopyrrolopyrrole units

A weak electron acceptor, 4,9-bis(5-bromothiophen-2-yl)-2-(2-ethylhexyl)-benzo[f]isoindole-1,3-dione (BIDO) was designed and synthesized. Polymer P1 derived from BIDO and 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester by Suzuki cross-coupling reaction has a band gap of 2.41 eV. To expand the absorption range, a different amount of BIDO was copolymerized with a diketopyrrolopyrrole monomer to produce a series of copolymers P_a–c. The optical properties, electrochemical behavior, and energy levels of these four copolymers were investigated. The photovoltaic properties copolymers P_a–c were studied. A photovoltaic device containing P_c and [70]PCBM with a ratio of 1:2 had a power conversion efficiency of 1.17%.     

Synthesis and characterization of thieno[3,4-c]pyrrole-4,6-dione and pyrrolo[3,4-c]pyrrole-1,4-dione-based random polymers for photovoltaic applications

New random poly{benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione-pyrrolo[3,4-c]pyrrole-1,4-dione} (PBDT-TPD-DPP) based on benzo[1,2-b:4,5-b']dithiophene (BDT) as donor and thieno[3,4-c]pyrrole-4,6-dione (TPD, 60–90%), pyrrolo[3,4-c]pyrrole-1,4-dione (DPP, 10–40%) as acceptors were synthesized through Stille coupling reaction. The photophysical, electrochemical and photovoltaic properties of random polymers were investigated. The random polymers with high molecular weight (M_n = 33.5–41.7 kDa) exhibited broad and strong absorption covering the spectra range from 350 nm up to 922 nm with absorption maxima at around 700 nm, the relatively deep highest occupied molecular orbital (HOMO) energy levels vary between ?5.25 and ?5.42 eV and suitable lowest unoccupied molecular orbital (LUMO) energy levels ranging from ?3.85 to ?3.91 eV. Polymer solar cells (PSC) based on these new random polymers were fabricated with device structures of ITO/PEDOT: PSS/random polymers: PC₇₁BM (1:2, w/w)/Ca/Al. The photovoltaic properties of random polymers were evaluated under AM 1.5G illumination (100 mW/cm²). Devices based on the random polymers showed open circuit voltage (V_oc) of 0.71–0.83 V, and power conversion efficiency (PCE) of 0.82–1.80%.     

Acetophenone and thiophene side‐arm polyaryleneethynylene conjugated polymers for enrichment of electronic applications

In the present work, a new type of semiconducting acetophenone and thiophene side‐arm based polyaryleneethynylene (PAE) conjugated polymers (CPs) were synthesized using the Heck–Sonogashira cross‐coupling reaction. The new type of monomers and APAEC₈, APAEC₁₂, APAEF₈, TPAEC₈, TPAEC₁₂, and TPAEF₈ (PAE CPs) were synthesized and characterized using Fourier transform IR, NMR and high resolution mass spectrometry studies. The average molecular weight of the CPs was determined using gel permeation chromatography. The data obtained from optical properties in the UV–visible and photoluminescence spectral studies were used to calculate the values of the Stokes shift. Among the six CPs studied, TPAEC₈ was found to possess a lower optical band gap (E_g = 2.112 eV) than those of the other CPs. The data obtained from different studies, it was found that TPAEC₈ exhibits better properties than the other CPs and can be used in the field of organic based photonic, electronic and other sensor applications. © 2020 Society of Chemical Industry     

Synthesis, characterization, and reactivity ratio studies on new sulfide copolymers containing ethylbenzene units

Soluble new sulfide copolymers were synthesized readily by the polycondensation of ethylene dibromide (EDB) (or methylene dibromide (MDB)) with styrene dibromide (SDB) and sodium sulfide (Na₂S) in the presence of phase transfer catalyst. The copolymers were characterized by using Fourier transform-infrared, ¹H NMR, ¹³C NMR, gel permeation chromatography, and thermogravimetric analysis (TGA) techniques. The copolymer composition obtained from the ¹H NMR spectra led to the determination of reactivity ratios. The analysis of reactivity ratios revealed that both EDB and MDB are more reactive than SDB towards Na₂S, and copolymers formed are random in nature. Furthermore, it also gave an insight on the microstructure of the copolymers that both poly (ethylene sulfide-co-styrene sulfide) (p(ES-co-SS)), and poly(methylene sulfide-co-styrene sulfide) (p(MS-co-SS)) copolymers have more of blocky structure with increase in the concentration of ethylene sulfide (ES) or methylene sulfide (MS) units in the respective copolymers. The TGA was used to find out the thermal stability of these polymers. The XRD data indicated an increase in the amorphous content of the copolymers with an increase in the concentration of styrene sulfide (SS) units and thereby resulting in most of these copolymers being soluble in common organic solvents. The solubility and molecular weight of the polymers formed were dependent on the concentration of SDB taken in the feed.     

Synthesis,characterization, and photovoltaic applications of dithienogermole-dithienylbenzothiadiazole and -dithienylthiazolothiazole copolymers

New dithienogermole-based conjugated polymers were synthesized by the Stille coupling reactions of distannyldithienogermole and dibromoarene, and their photovoltaic properties were studied. These polymers possess low band gaps with broad absorptions covering the 400–800 nm range, and exhibit good film forming properties. Bulk hetero-junction solar cells prepared from blends of these polymers with PC₇₀BM exhibit high power conversion efficiency up to 2.38%.     

Synthesis,spectroscopy, and electrochemical investigation of new conjugated polymers containing thiophene and 1,3,4-thiadiazole in the main chain

Novel photoluminescent donor–acceptor poly(p-phenylenevinylene)-type conjugated polymers containing thiophene and 1,3,4-thiadiazole units in the main chain were synthesized from 2,5-bis(5-bromomethyl-2-thienyl)-1,3,4-thiadiazole and 1,3/1,4-benzenedialdehyde by Wittig–Horner reaction. The synthesized polymers were characterized by the use of thermal analysis and spectroscopic (infrared, UV-visible absorption, and photoluminescence) measurement. The resultant material exhibited bluish green, green, and orange fluorescence in their solution and thin film and solid forms, respectively. The redox property of the polymers has also been studied by cyclic voltammetry. The optical and electrochemical studies reveal that these novel polymers are new promising materials for the development of efficient polymer light-emitting diodes. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electronic structure and properties of alternating donor-acceptor conjugated copolymers: 3,4-Ethylenedioxythiophene (EDOT) copolymers and model compounds

The electronic structure and properties of 3,4-ethylenedioxythiophene (EDOT) based alternating donor-acceptor conjugated copolymers and their model compounds were studied by the density functional theory (DFT) at the B3LYP level with 6-31G or 6-31G** basis set. The acceptors investigated include thiazole (Z), thiadiazole (D), thienopyrazine (TP), thienothiadiazole (TD), thiadiazolothienopyrazine (TPD), quinoxaline (BP), benzothiadiazole (BD), pyrazinoquinoxaline (BPP), benzobisthiadiazole (BDD), and thiadiazoloquinoxaline (BDP). The torsional angle, intramolecular charge transfer, bridge bond length, and bond length alternation were analyzed and correlated with the electronic properties. It was found that the geometries of the donor-acceptor materials were significantly affected by the ring size and intramolecular charge transfer. The HOMO level, LUMO level, and band gap of the model compounds were well correlated with the acceptor strength. However, the electronic properties of the copolymers did not vary systematically with the acceptor strength due to the change in geometry from model compound to polymer. The aromatic geometry of EDOT-TP model compound is transformed to quinoid in the corresponding copolymer and results in a small band gap (E_g) of 0.97 eV. Large intramolecular charge transfer and the small bond length alternation in the EDOT-BDP copolymer resulted in an E_g of 0.7 eV. Hence, these two polymers could have potential applications for transparent conductors or photovoltaic devices. The small effective masses and large HOMO and LUMO bandwidths of PEDOT-TP and PEDOT-BDP make them potential materials for ambipolar thin film transistors. The theoretical results suggest that both the acceptor strength and the stable geometry contribute significantly to the electronic properties of alternating donor-acceptor conjugated copolymers.     

Infrared spectra and thermal reactivity of ethene copolymers containing 1,2-cyclopropane units

A comparison between ¹³C NMR spectra of polymer solutions and Fourier transform infrared spectra of polymer films for several ethene-butadiene copolymers, including most butadiene as 1,2-cyclopropane and 1,2-cyclopentane units, is presented. This spectral comparison, also with the help of a low-molecular-mass model compound specifically synthesized for this purpose, has allowed to locate infrared absorbances associated with the cyclic comonomer units. In particular, a satisfactory calibration curve for evaluation of the amount of the reactive cyclopropane units, from the absorbance of the 1020 cm⁻¹ band, has been achieved. An analysis of 1,2-cyclopropane unit reactivity in annealed films, has also pointed out that the presence of remnants of the polymerization catalyst can produce large increase in cyclopropane reactivity.     

Optical limiting materials: Synthesis,electrochemical and optical studies of new thiophene based conjugated polymers carrying 1,3,4‐oxadiazole units

In this communication we report synthesis of three new donor‐acceptor (D–A) type conjugated polymers carrying 1,3,4‐oxadiazole moiety and thiophene unit with different side groups at its 3,4 positions (4‐methoxybenzyl:P1, 3‐methylbenzyl:P2 and 4‐nitrobenzyl:P3) through polycondensation route using a series of newly synthesized monomers. The structures of new monomers and polymers were confirmed by NMR, FTIR spectroscopic methods followed by elemental analysis. Further, molecular weight and thermal stability were determined using gel permeation chromatography and thermogravimetric analysis. The linear optical and electrochemical properties of polymers were investigated by UV–vis absorption, fluorescence spectroscopic, and cyclic voltammetric studies. The polymers P1–P3 were found to be thermally stable and their electrochemical band gaps were determined to be 1.98, 2.14, and 2.18 eV respectively. Further their nonlinear optical properties were investigated by Z‐scan method using 532 nm, 7 ns laser pulses. The results reveal that they possess good optical limiting behavior due to effective three‐photon absorption (3PA) with absorption coefficient 2.5 × 10^?24 m^?3W², 1.6 × 10^?24 m^?3W², and 1.0 × 10^?24 m^?3W². POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Synthesis and characterization of alternating fluorene-based copolymers containing diaryl- and non-substituted bithiophene units

A series of soluble alternating fluorene-based copolymers containing diaryl- and non-substituted bithiophene units are synthesized by palladium-catalyzed Suzuki coupling reaction. All polymers demonstrate green colors of photoluminescence (PL) in chloroform, good thermal stability (with decomposition temperatures above 436 °C), and high glass transition temperatures (in the range of 120-144 °C). Owing to the large steric hindrance of diaryl substituents on bithiophenes in the polymers (P2-P4), the aggregation of solids is reduced as well as the solubility is improved, so the performance of their PLED devices are superior to that of the non-substituted polymer (P1). Compared with P1, the introduction of substitutents at 3,3′-position of bithiophene in P2-P4 has significant effects on the photophysical properties of resulting polymers in solution and solid states. Though the PL quantum yield of P1 is much higher than those of diaryl-substituted polymers (P2-P4), the PLED device of P1 has the worst electroluminescence (EL) properties due to the poor solubility of P1. Consequently, among these polymers, the device made of P3 as an emitter has the highest luminance of 2590 cd/m² at 9.5 V. For optimum device performance, a device of P3 blended with PVK can be further enhanced to a brighter luminance of 4284 cd/m² at 18 V.