We report here the electrochemistry and electrogenerated chemiluminescence (ECL) of a red-emitting dithienylbenzothiadiazole-based molecular fluorophore (4,7-bis(4-(4-sec-butoxyphenyl)-5-(3,5-di(1-naphthyl)phenyl)thiophen-2-yl)-2,1,3-benzothiadiazole, 1b). 1b contains two substituted thiophene groups as strong electron donors at the ends connected directly to a strong electron acceptor, 2,1,3-benzothiadiazole, in the center. Each thiophene moiety is substituted in position 2 by 3,5-di(1-naphthyl)phenyl and in position 3 by 4-sec-butoxyphenyl. Cyclic voltammetry of 1b, with scan rate ranging from 0.05 to 0.75 V/s, shows a single one-electron reduction wave (E°(red) = -1.18 V vs SCE) and two nernstian one-electron oxidation waves (E°(1,ox) = 1.01 V, E°(2,ox) = 1.24 V vs SCE). Reduction of the unsubstituted 2,1,3-benzothiadiazole center shows nernstian behavior with E°(red) = -1.56 V vs SCE. By comparison to a digital simulation, the heterogeneous electron-transfer rate constant for reduction, k(r)° = 1.5 × 10(-3) cm/s, is significantly smaller than those for the oxidations, k(o)° > 0.1 cm/s, possibly indicating that the two substituted end groups have a blocking effect on the reduction of the benzothiadiazole center. The ECL spectrum, produced by electron-transfer annihilation of the reduced and oxidized forms, consists of a single peak with maximum emission at about 635 nm, consistent with the fluorescence of the parent molecule. Relative ECL intensities with respect to 9,10-diphenylanthracene are 330% and 470% for the radical anion-cation and radical anion-dication annihilation, respectively. Radical anion (A(-•))-cation (A(+•)) annihilation produced by potential steps shows symmetric ECL transients during anodic and cathodic pulses, while for anion (A(-•))-dication (A(2+•)) annihilation, transient ECL shows asymmetry in which the anodic pulse is narrower than the cathodic pulse. Digital simulation of the transient ECL experiments showed that the origin of the observed asymmetry is asymmetry in the amount of generated charges rather than instability of the electrogenerated species.

Transparent electrodes (TEs) having electrooptical trade‐offs better than state‐of‐the‐art indium tin oxide (ITO) are continuously sought as they are essential to enable flexible electronic and optoelectronic devices. In this work, a TiO2‐Ag‐ITO (TAI)‐based TE is introduced and its use is demonstrated in an inverted polymer solar cell (I‐PSCs). Thanks to the favorable nucleation and wetting conditions provided by the TiO2, the ultrathin silver film percolates and becomes continuous with high smoothness at very low thicknesses (3–4 nm), much lower than those required when it is directly deposited on a plastic or glass substrate. Compared to conventional ITO‐TE, the proposed TAI‐TE exhibits exceptionally lower electrical sheet resistance (6.2 Ω sq−1), higher optical transmittance, a figure‐of‐merit two times larger, and mechanical flexibility, the latter confirmed by the fact that the resistance increases only 6.6% after 103 tensile bending cycles. The I‐PSCs incorporating the TAI‐TE show record power conversion efficiency (8.34%), maintained at 96% even after 400 bending cycles.

Efficient exciton dissociation and subsequent generation of free charge carriers at the organic donor–acceptor interface requires a number of electron-transfer processes. It is a common view that these steps result in an unavoidable energy loss in organic photovoltaic devices that is not present in other types of solar cells. The currently best performing organic solar cells with power conversion efficiencies over 16% challenge this view, and no interfacial charge-transfer states with energy significantly lower than the strongly absorbing singlet states are detected within the gap of the used donor and acceptor materials. This Perspective will discuss implications, the remaining sources of energy loss, and open questions to be solved to achieve power conversion efficiencies over 20%.

No abstract