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1.
2.
A new donor‐acceptor conjugated copolymer (PDTPyDPP), comprising 2,7‐di‐2‐thienyl‐4,5,9,10‐tetrakis(hexyloxy)pyrene as a donor and diketopyrrolopyrrole (DPP) as an acceptor, was synthesized. PDTPyDPP showed good solubility in common organic solvents, broad visible absorption from 300 to 900 nm, and a moderate hole mobility up to 6.3 × 10?3 cm2 V?1 s?1. The power conversion efficiency of the photovoltaic device based on the PDTPyDPP/PC71BM photoactive layer reached 4.43% with 0.66 V of open‐circuit voltage (Voc), 10.52 mA cm?2 of short‐circuit current (Jsc) and 64.11% of fill factor. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3198–3204  相似文献   

3.
Two conjugated copolymers PADT‐DPP and PADT‐FDPP based on anthradithiophene and diketopyrrolopyrrole, with thiophene and furan as the π‐conjugated bridge, respectively, were successfully synthesized and characterized. The number‐averaged molecular weights of the two polymers are 38.7 and 30.2 kg/mol, respectively. Polymers PADT‐DPP and PADT‐FDPP exhibit broad absorption bands and their optical band gaps are 1.44 and 1.50 eV, respectively. The highest occupied molecular orbital energy level of PADT‐DPP is located at ?5.03 eV while that of PADT‐FDPP is at ?5.16 eV. In field‐effect transistors, PADT‐DPP and PADT‐FDPP displayed hole mobilities of 4.7 × 10?3 and 2.7 × 10?3 cm2/(V s), respectively. In polymer solar cells, PADT‐DPP and PADT‐FDPP showed power conversion efficiency (PCE) of 3.44% and 0.29%, respectively. Atomic force microscopy revealed that the poor efficiency of PADT‐FDPP should be related to the large two‐phase separation in its active layer. If 1,8‐diiodooctane (DIO) was used as the solvent additive, the PCE of PADT‐DPP remained almost unchanged due to very limited morphology variation. However, the addition of DIO could remarkably elevate the PCE of PADT‐FDPP to 2.62% because of the greatly improved morphology. Our results suggest that the anthradithiophene as an electron‐donating polycyclic system is useful to construct new D–A alternating copolymers for efficient polymer solar cells. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1652–1661  相似文献   

4.
We synthesized a novel low‐band‐gap, conjugated polymer, poly[4,7‐bis(3′,3′‐diheptyl‐3,4‐propylenedioxythienyl)‐2,1,3‐benzothiadiazole] [poly(heptyl4‐PTBT)], consisting of alternating electron‐rich, diheptyl‐substituted propylene dioxythiophene and electron‐deficient 2,1,3‐benzothiadiazole units, and its photovoltaic properties were investigated. A thin film of poly(heptyl4‐PTBT) exhibited an optical band gap of 1.55 eV. A bulk‐heterojunction solar cell with indium tin oxide/poly(3,4‐ethylenedioxythiophene)/poly(heptyl4‐PTBT): methanofullerene [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) (1:4)/LiF/Al was fabricated with poly(heptyl4‐PTBT) as an electron donor and PCBM as an electron acceptor and showed an open‐circuit voltage, short‐circuit current density, and power conversion efficiency of 0.37 V, 3.15 mA/cm2, and 0.35% under air mass 1.5 (AM1.5G) illumination (100 mW/cm2), respectively. A solid‐state, dye‐sensitized solar cell with a SnO2:F/TiO2/N3 dye/poly(heptyl4‐PTBT)/Pt device was fabricated with poly(heptyl4‐PTBT) as a hole‐transport material. This device exhibited a high power conversion efficiency of 3.1%, which is the highest power conversion efficiency value with hole‐transport materials in dye‐sensitized solar cells to date. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1394–1402, 2007  相似文献   

5.
A new liquid crystalline (LC) acceptor monomer 2,5‐bis[4‐(4′‐cyanobiphenyloxy)dodecyl]‐3,6‐dithiophen‐2‐yl‐pyrrolo[3,4‐c]pyrrole‐1,4‐dione (TDPPcbp) was synthesized by incorporating cyanobiphenyl mesogens into diketopyrrolopyrrole (DPP). The monomer was copolymerized with bis(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′] dithiophene (BDT) and N‐9′‐heptadecanylcarbazole (CB) donors to obtain donor–acceptor alternating copolymers poly[4,8‐bis(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐3,6‐bis(thiophen‐5‐yl)‐2,5‐bis[4‐(4′‐cyanobiphenyloxy)dodecyl]‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione] (PBDTDPPcbp) and poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐3,6‐bis(thiophen‐5‐yl)‐2,5‐bis[4‐(4′‐cyano‐biphenyloxy)dodecyl]‐2,5‐dihydropyrrolo[3, 4‐c]pyrrole‐1,4‐dione] (PCBTDPPcpb) with reduced band gap, respectively. The LC properties of the copolymers, the effects of main chain variation on molecular packing, optical properties, and energy levels were analyzed. Incorporating the mesogen cyanobiphenyl units not only help polymer donors to pack well through mesogen self‐organization but also push the fullerene acceptor to form optimized phase separation. The bulk heterojunction photovoltaicdevicesshow enhanced performance of 1.3% for PBDTDPPcbp and 1.2% for PCBTDPPcbp after thermal annealing. The results indicate that mesogen‐controlled self‐organization is an efficient approach to develop well‐defined morphology and to improve the device performance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

6.
A new donor–acceptor (D‐A) conjugated copolymer (PBDTT(ff)‐ttTPD) based on fluorine‐substituted benzodithiophene (BDT) and 6‐alkylthienothienyl thieno[3,4‐c]pyrrole‐4,6‐dione (ttTPD) has been synthesized via a Stille cross‐coupling reaction. As a control, the nonfluorinated BDT‐based ttTPD copolymer (PBDTT‐ttTPD) was also synthesized by using the same polymerization method. The number‐average molecular weights (M n) of PBDTT(ff)‐ttTPD and PBDTT‐ttTPD were found to be 48,000 g/mol (? = 2.2) and 43,000 g/mol (? = 2.1), respectively. The HOMO levels of PBDTT(ff)‐ttTPD and PBDTT‐ttTPD were calculated to be ?5.65 and ?5.45 eV, respectively. The inclusion of fluorinated BDT units is a very effective approach to lowering the polymer's HOMO level. The SCLC mobilities of PBDTT(ff)‐ttTPD and PBDTT‐ttTPD were determined to be 5.9 × 10?4 and 3.0 × 10?4 cm2/Vs, respectively. Polymer solar cell devices prepared with PBDTT(ff)‐ttTPD and PBDTT‐ttTPD as their active layers were found to exhibit power conversion efficiencies of 7.45 and 6.79% with open circuit voltages of 0.98 and 0.84 V, respectively. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2506–2512  相似文献   

7.
A low-band-gap alternating copolymer, poly{5,6-bis(octyloxy)-4-(thiophen-2-yl)benzo[c]-1,2,5-thiadiazole} (PTBT), was synthesized and investigated for photovoltaic applications. PTBT showed a minimized torsion angle in its main backbone owing to the introduction of solubilizing octyloxy groups on the electron-poor benzothiadiazole unit, thereby resulting in pronounced intermolecular ordering and a deep level of the HOMO (-5.41 eV). By blending PTBT with [6,6]phenyl-C61-butyric acid methyl ester (PC(61)BM), highly promising performance was achieved with power-conversion efficiencies (PCEs) of 5.9 and 5.3% for the conventional and inverted devices, respectively, under air mass 1.5 global (AM 1.5G, 100 mW cm(-2)) illumination. The open-circuit voltage (V(OC) ≈ 0.85-0.87 V) is one of the highest values reported thus far for thiophene-based polymers (e.g., poly(3-hexylthiophene) V(OC) ≈ 0.6 V). The inverted device also achieved a remarkable PCE compared to other devices based on low-band-gap polymers. Ideal film morphology with bicontinuous percolation pathways was expected from the atomic force microscopy (AFM) images, space-charge-limited current (SCLC) mobility, and selected-area electron-diffraction (SAED) measurements. This molecular design strategy is useful for achieving simple, processable, and planar donor-acceptor (D-A)-type low-band-gap polymers with a deep HOMO for applications in photovoltaic cells.  相似文献   

8.
An original strategy to construct a new donor–acceptor (D–A)‐integrated structure by directly imposing “pull” unit on the “push” moiety to form fused ring architecture has been developed, and poly{N‐alkyl‐carbazole[3,4‐c:5,6‐c]bis[1,2,5]thiadiazole‐alt‐thiophene} (PCBTT) with D–A‐integrated structure, in which two 1,2,5‐thiadiazole rings are fixed on carbazole in 3‐, 4‐ and 5‐, 6‐position symmetrically and thiophene is used as bridge, has been synthesized. The interaction between pull and push units has fine tuned the HOMO/LUMO energy levels, and the resulting copolymer covers the solar flux from 300 to 750 nm. The interaction between pull and push units is worth noting that due to the fused five rings inducing strong intermolecular interaction, an extremely short π–π stacking distance of 0.32 nm has been achieved for PCBTT both in powder and solid states. This is the shortest π–π stacking distance reported for conjugated polymers. Additionally, an obvious intramolecular charge transfer and energy transfer from donor units to acceptor units have been detected in this D–A integration. A moderate‐to‐high open‐circuit voltage of ~0.7 V in PCBTT:[6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM) (w/w = 1/2) solar cells is achieved due to the low‐lying HOMO energy level of PCBTT. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

9.
Two donor–acceptor (D‐A) conjugated polymers, PQx and PphQx, composed of alkylthienyl‐substituted benzo[1,2‐b:4,5‐b']dithiophene (BDTT) as the electron donor and the new electron acceptors quinoxaline (Qx) or phenanthrenequinoxaline (phQx), were synthesized with Stille cross‐coupling reactions. The number‐averaged molecular weights (Mn) of PQx and PphQx were found to be 25.1 and 23.2 kDa, respectively, with a dispersity of 2.6. The band‐gap energies of PQx and PphQx are 1.82 and 1.75 eV, respectively. These results indicate that, because phQx units have highly planar structures, their inclusion in D‐A polymers will be a very effective method for increasing the polymers' effective conjugation lengths. The hole mobilities of PQx and PphQx were determined to be 5.0 × 10?5 and 2.2 × 10?4 cm2 V?1 s?1, respectively. A polymer solar cell device prepared with PphQx as the active layer was found to exhibit a power conversion efficiency (PCE) of 5.03%; thus, the introduction of phQx units enhanced both the short circuit current density and PCE of the device. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2804–2810  相似文献   

10.
Two poly(p‐phenylenevinylene) derivative alternating copolymers ( P1‐I and P2‐I ) have been prepared featuring iodo substituents and m‐phenylene units to periodically disrupt conjugation. P1‐I was derivatized with various chromophores to yield P1a‐f . In P1a‐f , the chromophores were positioned within a sterically protected pocket shielding them from interchain interactions so that intrachain interactions between polymer segments could be observed. Solution and film properties of polymers have been examined. Post‐polymerization chromophore modification leads to new photophysical properties such as intramolecular charge transfer and fluorescent resonance energy transfer processes in some cases.

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11.
New conjugated oligomers, oligo(9,9‐didodecylfluorene‐bis‐sulphurdiimide), consisting of 9,9‐didodecylfluorene separated by ? N?S?N? moieties, are reported. These oligomers are stable purple solids under ambient conditions with absorption covering a broad spectral window in the UV‐vis range and a main broad peak centered at 555 nm with onset extending to 700 nm. These oligomers show an obviously longer conjugation length than its dimeric analogue, bis‐9,9‐didodecyl‐fluorene‐2‐sulfurdiimide that shows a band‐edge absorption centered at 484 nm with onset at 590 nm. The dimer and oligomers are soluble in a variety of organic solvents. Moreover, we found that the oligomer with an average repeating‐unit number of six could significantly quench the photoluminescence (PL) of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenylene vinylene] (MEH‐PPV) or poly(3‐hexylthiophene) (P3HT) in the solid state. More importantly, the composites of this oligomer with P3HT showed a nearly 10‐fold enhancement of the photocurrent, compared with that of P3HT itself. In addition, the PL of this oligomer could be quenched by the presence of phenyl‐C61‐butyric acid methyl ester (PCBM) in toluene. These results suggest the presence of photoinduced charge transfer in composites of these oligomers blended with an electronic partner that either donates or accepts electrons. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

12.
Novel anthracene‐layered polymers containing fluorescence quenchers such as ferrocene and nitrobenzene units at the polymer termini were designed and synthesized. Their optical properties were investigated in detail. The photoluminescence spectra of the polymers were featureless without vibrational structures, indicating that the anthracenes are effectively interacting each other in a single polymer chain in the excited state. Fluorescence emission from the layered anthracene units was effectively quenched by the aromatic units at the polymer termini owing to energy and electron transfer through a single polymer chain. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2815–2821  相似文献   

13.
Two novel porphyrin‐based D‐A conjugated copolymers, PFTTQP and PBDTTTQP , consisting of accepting quinoxalino[2,3‐b′]porphyrin unit and donating fluorene or benzo[1,2‐b:4,5‐b′]dithiophene unit, were synthesized, respectively via a Pd‐catalyzed Stille‐coupling method. The quinoxalino[2,3‐b′]porphyrin, an edge‐fused porphyrin monomer, was used as a building block of D‐A copolymers, rather than the simple porphyrin unit in conventional porphyrin‐based photovoltaic polymers reported in literature, to enhance the coplanarity and to extend the π‐conjugated system of polymer main chains, and consequently to facilitate the intramolecular charge transfer (ICT). The thermal stability, optical, and electrochemical properties as well as the photovoltaic characteristics of the two polymers were systematically investigated. Both the polymers showed high hole mobility, reaching 4.3 × 10?4 cm2 V?1 s?1 for PFTTQP and 2.0 × 10?4 cm2 V?1 s?1 for PBDTTTQP . Polymer solar cells (PSCs) made from PFTTQP and PBDTTTQP demonstrated power conversion efficiencies (PCEs) of 2.39% and 1.53%, both of which are among the highest PCE values in the PSCs based on porphyrin‐based conjugated polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013  相似文献   

14.
We present a study of the optical, structural and device properties of a polyfluorene (PFM)‐based (PFM‐F8BT‐PFM) donor–acceptor triblock copolymer for use in an organic solar cell. Neutron reflectivity is employed to probe the vertical composition profile before and after thermal annealing while the crystallinity was examined using grazing incidence wide‐angle X‐ray. The absorption spectra and photoluminescence emission for the triblock and analogous blend of PFM with F8BT reveal a greater degree of intermixing in the triblock. However, the triblock copolymer exhibits exciplex emission, which necessitates a geminate polar pair; long‐lived exciplex states are detrimental in organic photovoltaic devices. The triplet yield in the triblock and the blend is estimated using photoinduced absorption, with the triblock copolymer generating a triplet population 20 times that of the blend. This is far from ideal as triplets are wasted states in organic photovoltaic devices and they can also act as scavengers of polarons reducing the efficiency even more. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1705–1718  相似文献   

15.
Novel series of conjugated copolymers, incorporating cyclopentadithiophene (CPDT) and the biselenophene ( R‐CPDT‐Se2 ), were synthesized by Pd‐catalyzed Stille coupling polymerization. The optical, electrochemical, field‐effect carrier mobilities, and photovoltaic properties of the R‐CPDT‐Se2 were investigated and compared with cyclopentadithiophene (CPDT) and the bithiophene ( EHex‐CPDT‐T2 ). The highest hole mobility of thin film transistor devices fabricated with new p‐type polymer semiconductors, Oct‐CPDT‐Se2 , was 1.3 × 10?3 cm2/Vs with an on/off ratio of about 105. The maximum power conversion efficiency of polymer solar cell fabricated with the blend of EHex‐CPDT‐Se2 /C71‐PCBM reached 1.86% with an open circuit voltage (VOC) of 0.55 V, a short circuit current density (Jsc) of 7.27 mA/cm2, and a fill factor (FF) of 0.47 under AM 1.5G irradiation (100 mW/cm2). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009  相似文献   

16.
In this study, the maleimide‐thiophene copolymer‐functionalized graphite oxide sheets (PTM21‐GOS) and carbon nanotubes (PTM21‐CNT) were developed for polymer solar cell (PSC) applications. The grafting of PTM21‐OH onto the CNT and GO sheets was confirmed using FTIR spectroscopy. PTM21‐CNT and PTM21‐GOS exhibited excellent dispersal behavior in organic solvents. Better thermal stability was observed for PTM21‐CNT and PTM21‐GOS as compared with that for PTM21‐OH. In addition, the optical band gaps of PTM21‐GOS and PTM21‐CNT were lower than that of PTM21‐OH. We incorporated PTM21‐GOS and PTM21‐CNT individually into poly(3‐hexylthiophene) (P3HT)/[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) blends for use as photoconversion layers of PSCs. Good distributional homogeneity was observed for PTM21‐GOS or PTM21‐CNT in the P3HT/PCBM blend film. The UV–vis absorption peaks of the blend films red‐shifted slightly upon increasing the content of PTM21‐GOS or PTM21‐CNT. The band gap energies and LUMO/HOMO energy levels of the P3HT/PTM21‐GOS and P3HT/PTM21‐CNT blend films were slightly lower than those of the P3HT film. The conjugated polymer‐functionalized PTM21‐GOS and PTM21‐CNT behaved as efficient electron acceptors and as charge‐transport assisters when incorporated into the photoactive layers of the PSCs. PV performance of the PSCs was enhanced after incorporating PTM21‐GOS or PTM21‐CNT in the P3HT/PCBM blend. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013  相似文献   

17.
A novel fused ladder alternating D–A copolymer, PIDT–DPP, with alkyl substituted indacenodithiophene (IDT) as donor unit and diketopyrrolopyrrole (DPP) as acceptor unit, was designed and synthesized by Pd‐catalyzed Stille‐coupling method. The copolymer showed good solubility and film‐forming ability combining with good thermal stability. PIDT–DPP exhibited a broad absorption band from 350 to 900 nm with an absorption peak centered at 735 nm. The optical band gap determined from the onset of absorption of the polymer film was 1.37 eV. The highest occupied molecular orbital level of the polymer is as deep as ?5.32 eV. The solution‐processed organic field‐effect transistor (OFETs) was fabricated with bottom gate/top contact geometry. The highest FET hole mobility of PIDT–DPP reached 0.065 cm2 V?1 s?1 with an on/off ratio of 4.6 × 105. This mobility is one of the highest values for narrow band gap conjugated polymers. The power conversion efficiency of the polymer solar cell based on the polymer as donor was 1.76% with a high open circuit voltage of 0.88 V. To the best of our knowledge, this is the first report on the photovoltaic properties of alkyl substituted IDT‐based polymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

18.
The synthesis and characterization of a soluble high molecular weight copolymer based on 4,8‐bis(1‐pentylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene and 2,1,3‐benzoxadiazole is presented. High efficiency organic photovoltaic (OPV) devices comprised of this polymer and phenyl‐C71‐butyric acid methyl ester (PC71BM) were fabricated by additive processing with 1‐chloronapthalene (CN). When the active layer is cast from pristine chlorobenzene (CB), power conversion efficiencies (PCEs) average 1.41%. Our best condition—using 2% chloronapthalene as a solvent additive in CB—results in an average PCE of 5.65%, with a champion efficiency of 6.05%.

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19.
We have synthesized a narrow‐bandgap conjugated polymer ( PCTDPP ) containing alternating cyclopentadithiophene (CT) and diketo‐pyrrolo‐pyrrole (DPP) units by Suzuki coupling. This PCTDPP exhibits a low band gap of 1.31 eV and a broad absorption band from 350 to 1000 nm, which allows it to absorb more available photons from sunlight. A bulk heterojunction polymer solar cell incorporating PCTDPP and C70 at a blend ratio of 1:3 exhibited a high short‐circuit current of 10.87 mA/cm2 and a power conversion efficiency of 2.27%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1669–1675, 2010  相似文献   

20.
A new coil‐rod‐coil copolymer is synthesized via Sonogashira coupling using one‐step methodology. The copolymer PEG‐OEPETPT‐PEG constitutes of poly(ethylene glycol) (PEG) as the coil block, and oligo[p‐(ethynylenephenyleneethynylene)‐alt‐(thienylenepyridazinylenethienylene)] (OEPETPT) as the rod segment. The conjugated polymer PEPETPT with the same conjugated building blocks is also synthesized for comparison. The structures of both polymers are confirmed by NMR, combined with other characterizations. PEG‐OEPETPT‐PEG has a 12 nm blue‐shift in the emission maximum compared with that of PEPETPT, and a higher quantum yield of fluorescence in THF. PEG‐OEPETPTE‐PEG tolerates up to 20% water content in H2O/THF mixed solvent without significantly changing the emission wavelength and intensity, while the fluorescence of PEPETPT is dramatically quenched by a very small quantity of water. Further photophysical studies about these two polymers indicate that the introduction of PEG coils onto the conjugated block retards the water‐induced‐aggregation and therefore improves the fluorescence stability of PEG‐OEPETPT‐PEG. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

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