Arsole-containing conjugated polymers are a practically unexplored class of materials despite the high interest in their phosphole analogues. Herein we report the synthesis of the first dithieno[3,2-b;2′,3′-d]arsole derivative, and demonstrate that it is stable to ambient oxidation in its +3 oxidation state. A soluble copolymer is obtained by a palladium-catalyzed Stille polymerization and demonstrated to be a p-type semiconductor with promising hole mobility, which was evaluated by field-effect transistor measurements.

Arsole-containing conjugated polymers are a practically unexplored class of materials despite the high interest in their phosphole analogues. Herein we report the synthesis of the first dithieno[3,2-b;2′,3′-d]arsole derivative, and demonstrate that it is stable to ambient oxidation in its +3 oxidation state. A soluble copolymer is obtained by a palladium-catalyzed Stille polymerization and demonstrated to be a p-type semiconductor with promising hole mobility, which was evaluated by field-effect transistor measurements.

Dithienogermole-co-thieno[3,4-c]pyrroledione (DTG-TPD) polymers incorporating chemically cross-linkable sidechains are reported and their properties compared to a parent polymer with simple octyl sidechains. Two cross-linking groups and mechanisms are investigated, UV-promoted radical cross-linking of an alkyl bromide cross-linker and acid-promoted cationic cross-linking of an oxetane cross-linker. It is found that random copolymers with a 20% incorporation of the cross-linker demonstrate a higher performance in bulk heterojunction solar cells than the parent polymer, while 100% cross-linker incorporation results in deterioration in device efficiency. The use of 1,8-diiodooctane (DIO) as a processing additive improves as-cast solar cell performance, but is found to have a significant deleterious impact on solar cell efficiency after UV exposure. The instability to UV can be overcome by the use of an alternative additive, 1-chloronapthalene, which also promotes high device efficiency. Cross-linking of the polymer is investigated in the presence and absence of fullerene highlighting significant differences in behavior. Intractable films cannot be obtained by radical cross-linking in the presence of fullerene, whereas cationic cross-linking is successful.

The synthesis of a novel 3,3′-difluoro-4,4′-dihexadecyl-2,2′-bithiophene monomer and its copolymerization with thieno[3,2-b]thiophene to afford the fluorinated analogue of the well-known poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]-thiophene) (PBTTT) polymer is reported. Fluorination is found to have a significant influence on the physical properties of the polymer, enhancing aggregation in solution and increasing melting point by over 100 °C compared to nonfluorinated polymer. On the basis of DFT calculations these observations are attributed to inter and intramolecular S…F interactions. As a consequence, the fluorinated polymer PFBTTT exhibits a fourfold increase in charge carrier mobility compared to the nonfluorinated polymer and excellent ambient stability for a nonencapsulated transistor device.

The effects of heteroatom substitution from a silicon atom to a germanium atom in donor-acceptor type low band gap copolymers, poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (PSiBTBT) and poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]germole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (PGeBTBT), are studied. The optoelectronic and charge transport properties of these polymers are investigated with a particular focus on their use for organic photovoltaic (OPV) devices in blends with phenyl-C₇₀-butyric acid methyl ester (PC₇₀BM). It is found that the longer C-Ge bond length, in comparison to C-Si, modifies the molecular conformation and leads to a more planar chain conformation in PGeBTBT than PSiBTBT. This increase in molecular planarity leads to enhanced crystallinity and an increased preference for a face-on backbone orientation, thus leading to higher charge carrier mobility in the diode configuration. These results provide important insight into the impact of the heavy atom substitution on the molecular packing and device performance of polymers based on the poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole) (PCPDTBT) backbone.

A series of donor–acceptor (D–A) conjugated polymers utilizing 4,4-bis(2-ethylhexyl)-4H-germolo[3,2-b:4,5-b′]dithiophene (DTG) as the electron rich unit and three electron withdrawing units of varying strength, namely 2-octyl-2H-benzo[d][1,2,3]triazole (BTz), 5,6-difluorobenzo[c][1,2,5]thiadiazole (DFBT) and [1,2,5]thiadiazolo[3,4-c]pyridine (PT) are reported. It is demonstrated how the choice of the acceptor unit (BTz, DFBT, PT) influences the relative positions of the energy levels, the intramolecular transition energy (ICT), the optical band gap (E_g^opt), and the structural conformation of the DTG-based co-polymers. Moreover, the photovoltaic performance of poly[(4,4-bis(2-ethylhexyl)-4H-germolo[3,2-b:4,5-b′]dithiophen-2-yl)-([1,2,5]thiadiazolo[3,4-c]pyridine)] (PDTG-PT), poly[(4,4-bis(2-ethylhexyl)-4H-germolo[3,2-b:4,5-b′]dithiophen-2-yl)-(2-octyl-2H-benzo[d][1,2,3]triazole)] (PDTG-BTz), and poly[(4,4-bis(2-ethylhexyl)-4H-germolo[3,2-b:4,5-b′]dithiophen-2-yl)-(5,6-difluorobenzo[c][1,2,5]thiadiazole)] (PDTG-DFBT) is studied in blends with [6,6]-phenyl-C₇₀-butyric acid methyl ester (PC₇₀BM). The highest power conversion efficiency (PCE) is obtained by PDTG-PT (5.2%) in normal architecture. The PCE of PDTG-PT is further improved to 6.6% when the device architecture is modified from normal to inverted. Therefore, PDTG-PT is an ideal candidate for application in tandem solar cells configuration due to its high efficiency at very low band gaps (E_g^opt = 1.32 eV). Finally, the 6.6% PCE is the highest reported for all the co-polymers containing bridged bithiophenes with 5-member fused rings in the central core and possessing an E_g^opt below 1.4 eV.

The use of thermoelectric technology is attractive in many potential applications, such as energy scavenging from waste heat. The basic principles for harvesting electricity from a temperature gradient were first discovered around 180 years ago, but the contemporary technology utilising inorganic semiconductors was only developed since the early 1950s. The widespread use of this platform has so far been limited by a combination of relatively low efficiency in energy conversion or by issues related to the utilisation of rare, expensive and/or toxic elements that can be difficult to process. Recently much interest has been focused on the use of organic materials in thermoelectric devices, prompted by the possibility of developing large-area, low-cost devices. Considerable research in the last 20 years has been focused on understanding and improving organic thermoelectric properties, with remarkable progress recently published for compounds such as PEDOT and others. Here we provide an overview into thermoelectricity, from the initial discoveries made by Johann Seebeck to modern practical applications including the current trends in organic thermoelectric research.

A method is reported for the controlled synthesis of device-grade semiconducting polymers, utilizing a droplet-based microfluidic reactor. Using poly(3-hexylthiophene) (P3HT) as a test material, the reactor is shown to provide a controlled and stable environment for polymer synthesis, enabling control of molecular weight via tuning of flow conditions, reagent composition or temperature. Molecular weights of up to 92 000 Da are readily attainable, without leakage or reactor fouling. The method avoids the usual deterioration in materials quality that occurs when conventional batch syntheses are scaled from the sub-gram level to higher quantities, with a prototype five-channel reactor producing material of consistent molecular weight distribution and high regioregularity (>98%) at a rate of ≈60 g/day. The droplet-synthesized P3HT compares favorably with commercial material in terms of absorption spectrum, polydispersity, regioregularity, and crystallinity, yielding power conversion efficiencies of up to 4% in bulk heterojunction solar cells with [6,6]-phenyl-C61-butyric acid methyl ester.