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Abstract Glycol sidechains are often used to enhance the performance of organic photoconversion and electrochemical devices. Herein, we study their effects on electronic states and electronic properties. We find that polymer glycolation not only induces more disordered packing, but also results in a higher reorganisation energy due to more localised π-electron density. Transient absorption spectroscopy and femtosecond stimulated Raman spectroscopy are utilised to monitor the structural relaxation dynamics coupled to the excited state formation upon photoexcitation. Singlet excitons are initially formed, followed by polaron pair formation. The associated structural relaxation slows down in glycolated polymers (5 ps vs. 1.25 ps for alkylated), consistent with larger reorganisation energy. This slower vibrational relaxation is found to drive ultrafast formation of the polaron pair state (5 ps vs. 10 ps for alkylated). These results provide key experimental evidence demonstrating the impact of molecular structure on electronic state formation driven by strong vibrational coupling.

Abstract Among the various photoanode materials investigated for photoelectrochemical water splitting cells, TiO2 stands out due to its abundance, stability, and favorable valence band edge for water oxidation. In this study, the importance of introducing and combining oxygen and titanium vacancy point defects in anatase TiO2 photoanodes to improve their performance is unveiled, achieving a photocurrent density of 0.73 (±0.015) mA cm−2 at +1.23 VRHE under 100 mW cm−2 of simulated sunlight or 26.4 mA cm−2 at +1.23 VRHE under 100 mW cm−2 of 365 nm light. The characterization by X‐ray photoelectron spectroscopy, surface photovoltage, and electron paramagnetic resonance demonstrates that these oxygen and titanium vacancies can have both collective and localized positive effects on the material, leading to a narrowing of the bandgap, an increase in donor density, and an increase in hydroxyl groups on the surface of TiO2. These result in enhanced light absorption, conductivity, and photovoltage, as well as a more negative flat‐band potential and increase in hole flux to the semiconductor–electrolyte interface. These findings provide valuable insights into the role of point defects in modulating the properties of TiO2 and have important implications for the development of high‐performance TiO2‐based devices.

Abstract Herein, a new ternary strategy to fabricate efficient and photostable inverted organic photovoltaics (OPVs) is introduced by combining a bulk heterojunction (BHJ) blend and a fullerene self‐assembled monolayer (C60‐SAM). Time‐of‐flight secondary‐ion mass spectrometry ‐ analysis reveals that the ternary blend is vertically phase separated with the C60‐SAM at the bottom and the BHJ on top. The average power conversion efficiency ‐ of OPVs based on the ternary system is improved from 14.9% to 15.6% by C60‐SAM addition, mostly due to increased current density (Jsc) and fill factor ‐. It is found that the C60‐SAM encourages the BHJ to make more face‐on molecular orientation because grazing incidence wide‐angle X‐ray scattering ‐ data show an increased face‐on/edge‐on orientation ratio in the ternary blend. Light‐intensity dependent Jsc data and charge carrier lifetime analysis indicate suppressed bimolecular recombination and a longer charge carrier lifetime in the ternary system, resulting in the enhancement of OPV performance. Moreover, it is demonstrated that device photostability in the ternary blend is enhanced due to the vertically self‐assembled C60‐SAM that successfully passivates the ZnO surface and protects BHJ layer from the UV‐induced photocatalytic reactions of the ZnO. These results suggest a new perspective to improve both performance and photostability of OPVs using a facial ternary method.

The power conversion efficiencies of most organic solar cells roll off quickly with thickness more than 100 nm. Here, Wu et al. show that avoiding excessive charge accumulation in the intra-bandgap tail states is vital to maintain the photocurrent generation at high thickness.

Solution-processed organic small molecule solar cells (SMSCs) have achieved efficiency over 11%. However, very few studies have focused on their stability under illumination and the origin of the degradation during the so-called burn-in period. Here, we studied the burn-in period of a solution-processed SMSC using benzodithiophene terthiophene rhodamine:[6,6]-phenyl C71 butyric acid methyl ester (BTR:PC71BM) with increasing solvent vapour annealing time applied to the active layer, controlling the crystallisation of the BTR phase. We find that the burn-in behaviour is strongly correlated to the crystallinity of BTR. To look at the possible degradation mechanisms, we studied the fresh and photo-aged blend films with grazing incidence X-ray diffraction, UV–vis absorbance, Raman spectroscopy and photoluminescence (PL) spectroscopy. Although the crystallinity of BTR affects the performance drop during the burn-in period, the degradation is found not to originate from the crystallinity changes of the BTR phase, but correlates with changes in molecular conformation – rotation of the thiophene side chains, as resolved by Raman spectroscopy which could be correlated to slight photobleaching and changes in PL spectra.

Indium tin oxide (ITO) is commonly used as the transparent bottom electrode for organic solar cells. However, it is known that the cost of the ITO is quite high due to the indium element, and in some studies ITO coated glass substrate is found to be the most expensive component of device fabrication. Moreover, indium migration from ITO can cause stability issues in organic solar cells. Nevertheless, the use of ITO as the bottom electrode is still dominating in the field. Here, we explore the possibility of using fluorine doped tin oxide (FTO) as an alternative to ITO for the bottom electrode of organic solar cells particularly on semi-transparent cells. We present side-by-side comparisons on their optical, morphological and device properties and suggest that FTO could be more suitable than ITO as the bottom electrode for glass substrate based organic photovoltaic devices.