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Abstract: Low‐bandgap conjugated polymers have provided a considerable increase in organic photovoltaic efficiencies, however, an understanding of class‐specific nanostructures, necessary to further improve device qualities, remains scarce. Their self‐assembly and associated electronic behaviors in Langmuir−Blodgett (LB) films are used here to provide relationships specific to each polymer, clarifying their structure−property characteristics. The behavior of two low‐bandgap polymers based on cyclopentadithiophene (PCPDTBT) and dithienosilole (Si‐PCPDTBT) units in the Langmuir trough were investigated and it is shown that it is possible to fabricate nanostructured films of low‐bandgap polymers on solid substrates with the LB deposition technique. The polymers were mixed with amphiphilic molecules at well‐defined concentrations to improve the formation of the LB films. The polymers were also deposited by drop‐casting and LB techniques onto interdigitated electrodes to evaluate their electrical properties, and the LB films were characterized for their optical and morphological properties. It was found that both LB and drop‐cast films of PCPDTBT showed higher electrical conductivities than those of Si‐PCPDTBT. Importantly, LB films resulted in higher electrical conductivities – by an order of magnitude − compared to their equivalent mixtures with stearic acid in drop‐cast films, although drop‐cast films without stearic acid gave higher conductivities. This fine‐tuning of the molecular architectures of the films is thus demonstrated to directly affect the physical properties and may lead to an improvement in device efficiencies in future applications. © 2018 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

To achieve highly efficient organic photovoltaic (OPV) devices, the interface between the photoactive layer and the electrode must be modified to afford the appropriate alignment of the energy levels and to ensure efficient charge extraction at the same time as suppressing charge recombination and accumulation. Recently, p -type conjugated polyelectrolytes (CPEs) have emerged as new hole-transporting materials that can be deposited on electrodes through simple solution processes without additional heat treatment. However, the applications of CPEs have been limited so far because the high electron richness of their conjugated backbones result in low work functions, ∼5.0 eV. Here, by inserting a donor−acceptor (D−A) building block into the CPE backbone, we successfully synthesized a new p -type CPE (PhNa-DTBT), which shows a deep work function above 5.3 eV on several electrodes including Au, Ag, and indium tin oxide. More importantly, PhNa-DTBT produces stable polarons on the polymer backbone and thus achieves a high electrical conductivity of 5.7 × 10 −4 S cm −1 . As a result, an OPV incorporating PhNa-DTBT as a hole-transporting layer was found to exhibit a high performance with a power conversion efficiency of 9.29%. Also, the OPV device shows improved stability in air due to the neutral characteristics of the CPE which is favorable for stabilizing neighbored active and electrode layers. [ABSTRACT FROM AUTHOR]

A series of donor–acceptor (D–A) polymers ( P1 – P3 ) based on benzodithiophene (BDT) and electron-accepting benzotriazole (BTZ) units containing thiophene linkers with/without alkyl side-chains were designed and synthesized via Stille coupling polymerization method. The effects of polymers with multiple fluorinated BTZ groups on their thermal, optical, electrochemical, and photovoltaic properties were investigated. These polymers possessed the highest occupied molecular orbital (HOMO) levels ranged −5.38 to −5.6 eV and the lowest unoccupied molecular orbital (LUMO) levels ranged −3.55 to −3.57 eV, which covered broad absorption ranges with low optical bandgaps. The bulk heterojunction (BHJ) polymer solar cell (PSC) devices containing an active layer of D-A polymers blended with different weight ratios of electron-acceptor [6,6]-phenyl-C 71 -butyric acid methyl ester (PC 71 BM) were explored under 100 mW cm −2 of AM 1.5 white-light illumination, where the maximum power conversion efficiency (PCE) value of 3% (with J sc = 7.70 mA/cm 2 , FF = 54.04, and V oc = 0.72 V) was obtained in the PSC device consisting of polymer P3 . [ABSTRACT FROM AUTHOR]

Molybdenum oxide (MoO x ) has been widely used as a hole transport layer in organic photovoltaic cells (OPVs), whose performance can be improved by inserting a MoO x layer between an organic active layer and a transparent anode because of efficient carrier dissociation. In this study, the influence of thermally annealed MoO x on the photovoltaic performance of OPVs was first investigated using low-bandgap polymer and [6,6]-phenyl C 71 -butyric acid methyl ester (PC 71 BM) blend films as the active layer. We used three low-bandgap polymers: poly[2,6-(4,4-bis-(2-ethylhexyl)-4 H -cyclopenta[2,1- b ;3,4- b ′]dithiophene)- alt -4,7(2,1,3-benzothiadiazole)] (PCPDTBT), poly(4,8-bis[(2-ethylhexyl)oxy]benzo[1,2- b :4,5- b ′]dithiophene-2,6-diyl3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl) (PTB7), and poly([2,6′-4,8-di(5-ethylhexylthienyl)benzo[1,2-b,3,3-b]dithiophene]3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl) (PTB7-Th). Power conversion efficiencies were drastically increased for all investigated polymers when the as-deposited MoO x layer was annealed at 160 °C for 5 min. In particular, a high efficiency of 6.57% was achieved when PTB7 was used; for comparison, the efficiency of a reference device with an as-deposited MoO x layer (not subjected to annealing) was 1.40%. Specifically, the short-circuit current density and fill factor were remarkably improved after annealing, which means that efficient carrier dissociation was achieved in the active layer. We evaluated optical absorption and surface morphology to elucidate reasons behind the improved photovoltaic performance, and these parameters only slightly changed after annealing. In contrast, angle-dependent X-ray photoelectron spectroscopy revealed that the MoO x layer was oxidized after annealing. In general, the oxygen vacancies of MoO x act as carrier traps; a reduction in the number of carrier traps causes high hole mobility in the organic layer, which, in turn, results in an improved photovoltaic performance. Therefore, our results indicate that the annealing-induced oxidation of MoO x is useful for achieving high photovoltaic performance. [ABSTRACT FROM AUTHOR]

ABSTRACT The low-bandgap polymer poly{[4,4-bis(2-ethylhexyl)-cyclopenta-(2,1- b;3,4- b′)dithiophen]-2,6-diyl- alt-(2,1,3-benzo-thiadiazole)−4,7-diyl} (PCPDTBT) is widely used for organic solar cell applications. Here, we present a comprehensive study of the optical properties as a function of temperature for PCPDTBT in solution and in thin films with two distinct morphologies. Using absorption and photoluminescence spectroscopy as well as Franck-Condon analyses, we show that PCPDTBT in solution undergoes a phase transformation at 300 K from a disordered to a truly aggregated state on cooling. The saturation value of aggregates in solution is reached in PCPDTBT thin films at any temperature. In addition, we demonstrate that the photophysical properties of the aggregates in films are similar to those in solution and that a low percentage of thermally activated excimer states is present in the films at temperatures above 200 K. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1416-1430 [ABSTRACT FROM AUTHOR]

We developed a novel all-optical method for monitoring the diffusion of a small quencher molecule through a polymer layer in a bilayer architecture. Experimentally, we injected C 60 molecules from a C 60 layer into the adjacent donor layer by stepwise heating, and we measured how the photoluminescence (PL) of the donor layer becomes gradually quenched by the incoming C 60 molecules. By analyzing the temporal evolution of the PL, the diffusion coefficient of C 60 can be extracted, as well as its activation energy and an approximate concentration profile in the film. We applied this technique to three carbazole-based low-bandgap polymers with different glass temperatures with a view to study the impact of structural changes of the polymer matrix on the diffusion process. We find that C 60 diffusion is thermally activated and not driven by WFL-type collective motion above T g but rather by local motions mediated by the sidechains. The results are useful as guidance for material design and device engineering, and the approach can be adapted to a wide range of donor and acceptor materials.

In this Article, low-bandgap pTTDPP-BT polymers based on electron-accepting pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) and benzothiadiazole (BT) and electron-donating thienothiophene (TT) moieties were synthesized. Phototransistors have been fabricated using ambipolar-behaving pTTDPP-BT polymers as active channel materials. The electrical and photoresponsive properties of the pTTDPP-BT phototransistors were strongly dependent on the film annealing temperature. As-spun pTTDPP-BT phototransistors exhibited a low hole mobility of 0.007 cm 2 /(V·s) and a low electron mobility of 0.005 cm 2 /(V·s), which resulted in low photocurrent detection due to the limited transport of the charge carriers. Thermal treatment of the polymer thin films led to a significant enhancement in the carrier mobilities (hole and electron mobilities of 0.066 and 0.115 cm 2 /(V·s), respectively, for 200 °C annealing) and thus significantly improved photoresponsive properties. The 200 °C-annealed phototransistors showed a wide-range wavelength (405-850 nm) of photoresponse, and a high photocurrent/dark-current ratio of 150 with a fast photoswitching speed of less than 100 ms. This work demonstrates that a dual acceptor-containing low band gap polymer can be an important class of material in broadband photoresponsive transistors, and the crystallinity of the semiconducting polymer layer has a significant effect on the photoresponse characteristics.

The development of thick organic photovoltaics (OPV) could increase absorption in the active layer and ease manufacturing constraints in large-scale solar panel production. However, the efficiencies of most low-bandgap OPVs decrease substantially when the active layers exceed ∼100 nm in thickness (because of low crystallinity and a short exciton diffusion length). Herein, we report the use of solvent additive diphenyl ether (DPE) that facilitates the fabrication of thick (180 nm) active layers and triples the power conversion efficiency (PCE) of conventional thienothiophene-co-benzodithiophene polymer (PTB7)-based OPVs from 1.75 to 6.19%. These results demonstrate a PCE 20% higher than those of conventional (PTB7)-based OPV devices using 1,8-diiodooctane. Morphology studies reveal that DPE promotes the formation of nanofibrillar networks and ordered packing of PTB7 in the active layer that facilitate charge transport over longer distances. We further demonstrate that DPE improves the fill factor and photocurrent collection by enhancing the overall optical absorption, reducing the series resistance, and suppressing bimolecular recombination.