Dynamic PCBM:Dimer Population in Solar Cells under Light and Temperature Fluctuations

Photoinduced dimerization of phenyl‐C61‐butyric acid methyl ester (PCBM) has a significant impact on the stability of polymer:PCBM organic solar cells (OSCs). This reaction is reversible, as dimers can be thermally decomposed at sufficiently elevated temperatures and both photodimerization and decomposition are temperature dependent. In operando conditions of OSCs evidently involve exposure to both light and heat, following periodic diurnal and seasonal profiles. In this work, the kinetics of dimer formation and decomposition are examined and quantified as a function of temperature, light intensity, blend composition, and time. The activation energy for photodimerization is estimated to be 0.021(3) eV, considerably smaller than that for decomposition (0.96 eV). The findings are benchmarked with a variety of conjugated polymer matrices to propose a descriptive dynamic model of PCBM:dimer population in OSCs, and a framework is proposed to rationalize its interplay with morphology evolution and charge quenching. The model and parameters enable the prediction of the dynamic and long‐term PCBM:dimer populations, under variable temperature and light conditions, which impact the morphological stability of OSCs

Extended conjugated microporous polymers for photocatalytic hydrogen evolution from water

Conjugated microporous polymers (CMPs) have been used as photocatalysts for hydrogen production from water in the presence of a sacrificial electron donor. The relative importance of the linker geometry, the co-monomer linker length, and the degree of planarisation were studied with respect to the photocatalytic hydrogen evolution rate

Evaluation of Surface State Mediated Charge Recombination in Anatase and Rutile TiO2

In nanostructured thin films, photogenerated charge carriers can access the surface more easily than in dense films and thus react more readily. However, the high surface area of these films has also been associated with enhanced recombination losses via surface states. We herein use transient absorption spectroscopy to compare the ultrafast charge carrier kinetics in dense and nanostructured TiO2 films for its two most widely used polymorphs: anatase and rutile. We find that nanostructuring does not enhance recombination rates on ultrafast timescales, indicating that surface state mediated recombination is not a key loss pathway for either TiO2 polymorph. Rutile shows faster, and less intensity-dependent recombination than anatase, which we assign to its higher doping density. For both polymorphs, we conclude that bulk rather than surface recombination is the primary determinant of charge carrier lifetime

Acoustic Enhancement of Polymer/ZnO Nanorod Photovoltaic Device Performance

Leverhulme Trust and EPSRC. Grant Numbers: EP/J500021/1, EP/G037515/1

Acoustic enhancement of polymer/ZnO nanorod photovoltaic device performance

Acoustic vibrations are shown to enhance the photovoltaic efficiency of a P3HT/ZnO nanorod solar cell by up to 45%, correlated to a three‐fold increase in charge carrier lifetime. This is assigned to the generation of piezoelectric dipoles in the ZnO nanorods, indicating that the efficiency of solar cells may be enhanced in the presence of ambient vibrations by the use of piezoelectric materials

Interfacial Engineering of a Carbon Nitride-Graphene Oxide-Molecular Ni Catalyst Hybrid for Enhanced Photocatalytic Activity

Abstract can be found here: https://doi.org/10.1021/acscatal.8b0196

Effect of internal electric fields on charge carrier dynamics in a ferroelectric material for solar energy conversion

Spontaneous polarization is shown to enhance the lifetimes of photogenerated species in BaTiO3. This is attributed to polarization‐induced surface band bending acting as a thermal barrier to electron/hole recombination. The study indicates that the efficiencies of solar cells and solar fuels devices can be enhanced by the use of ferroelectric materials

Evidence for Strong and Weak Phenyl-C61-Butyric Acid Methyl Ester Photodimer Populations in Organic Solar Cells

In polymer/fullerene organic solar cells, the photochemical dimerization of phenyl-C61-butyric acid methyl ester (PCBM) was reported to have either a beneficial or a detrimental effect on device performance and stability. In this work, we investigate the behavior of such dimers by measuring the temperature dependence of the kinetics of PCBM de-dimerization as a function of prior light intensity and duration. Our data reveal the presence of both “weakly” and “strongly” bound dimers, with higher light intensities preferentially generating the latter. DFT simulations corroborate our experimental findings and suggest a distribution of dimer binding energies, correlated with the orientation of the fullerene tail with respect to the dimer bonds on the cage. These results provide a framework to rationalize the double-edged effects of PCBM dimerization on the stability of organic solar cells

Determining the role of oxygen vacancies in the photoelectrocatalytic performance of WO3 for water oxidation

Oxygen vacancies are common to most metal oxides, whether intentionally incorporated or otherwise, and the study of these defects is of increasing interest for solar water splitting. In this work, we examine nanostructured WO3 photoanodes of varying oxygen content to determine how the concentration of bulk oxygen-vacancy states affects the photocatalytic performance for water oxidation. Using transient optical spectroscopy, we follow the charge carrier recombination kinetics in these samples, from picoseconds to seconds, and examine how differing oxygen vacancy concentrations impact upon these kinetics. We find that samples with an intermediate concentration of vacancies (∼2% of oxygen atoms) afford the greatest photoinduced charge carrier densities, and the slowest recombination kinetics across all timescales studied. This increased yield of photogenerated charges correlates with improved photocurrent densities under simulated sunlight, with both greater and lesser oxygen vacancy concentrations resulting in enhanced recombination losses and poorer J–V performances. Our conclusion, that an optimal – neither too high nor too low – concentration of oxygen vacancies is required for optimum photoelectrochemical performance, is discussed in terms of the competing beneficial and detrimental impact these defects have on charge separation and transport, as well as the implications held for other highly doped materials for photoelectrochemical water oxidation