Origin of Degradation in Perovskite Solar Cells by Intensity Modulated Photovoltage Spectroscopy Measurement (IMVS)

Perovskite solar cells (PSCs) based on lead halide perovskite have attracted much attention owing to the fast development of their power conversion efficiency (PCE) from 3.8% to 25%. Various factors play important roles in affecting the conversion efficiency of PSCs, such as charge carrier generation, transport, recombination, and collection. In addition, the presence of interfacial defects has also a crucial effect in charge carrier transfer and recombination processes. However, the origin and mechanism of interfacial charge recombinations in PSCs are still not comprehensively investigated. For that purpose, we have performed intensity-modulated photovoltage spectroscopy (IMVS) and transient photovoltage (TPV) measurements of PSCs, which were fabricated with FTO/c-TiO2/mp-TiO2/Perovskite/PTAA/Au cell structure. The solar cell (J-V) characteristics of the PSCs on the day-1, day-2, day-3, and day-6 after the cell fabrication, indicating a significant degradation of the cell with time. The Nyquist plots of IMVS measurement on the same day as the J-V measurement seem to be composed of two semicircles at a lower frequency range and a higher frequency range. The semicircle at the lower frequency range enlarged on the day-6 measurement, but the semicircle at higher frequency decreased. The change of this Nyquist plot is in agreement with a significant decrease in the J-V curves. The semicircle at lower frequency may be assigned to the ion diffusion or migration. Therefore, cell degradation may be caused by the liberation of ions (including iodide) from the surface of the perovskite crystal structure. It then increases recombination loss due to back charge transfer from TiO2 to perovskite as indicated by the changing of the semicircle at high frequency into a smaller semicircle. Therefore, the present results reemphasize that the improvement of PSC stability needs the prevention of ions liberations from the surface by introducing passivation substances. In addition, the results also show the practical usefulness of IMVS for inspecting PSC degradation due to such an ion liberation process.

A metal-free photocatalyst for highly efficient hydrogen peroxide photoproduction in real seawater

Artificial photosynthesis of H2O2 from H2O and O2, as a spotless method, has aroused widespread interest. Up to date, most photocatalysts still suffer from serious salt-deactivated effects with huge consumption of photogenerated charges, which severely limit their wide application. Herein, by using a phenolic condensation approach, carbon dots, organic dye molecule procyanidins and 4-methoxybenzaldehyde are composed into a metal-free photocatalyst for the photosynthetic production of H2O2 in seawater. This catalyst exhibits high photocatalytic ability to produce H2O2 with the yield of 1776 μmol g−1h−1 (λ ≥ 420 nm; 34.8 mW cm−2) in real seawater, about 4.8 times higher than the pure polymer. Combining with in-situ photoelectrochemical and transient photovoltage analysis, the active site and the catalytic mechanism of this composite catalyst in seawater are also clearly clarified. This work opens up an avenue for a highly efficient and practical, available catalyst for H2O2 photoproduction in real seawater.

Revealing the charge carrier kinetics in perovskite solar cells affected by mesoscopic structures and defect states from simple transient photovoltage measurements

This report shows that, by using simple transient photovoltage (TPV) measurements, we can reveal a significant correlation between the TPV decay characteristics and the performance of these perovskite solar cells. TPV decay seems to be composed of a rising part in a short interval after photoexcitation and a long decaying part that extends up to tens of milliseconds. These decay behaviors look different depending on the mesoscopic structures and the perovskite morphology formed therein, as seen from their Scanning Electron Microcopy images and X-ray diffraction patterns. The decay part can be fitted with a three-exponential decay, which reflects different kinetics of electrons in the perovskite/TiO2 layer. On the other hand, the rising part must be fit by a decay equation derived by employing the convolution theorem, where the rising part can be assigned to the electron transport process inside the perovskite layer and the decaying part can be assigned to electron back-transfer. The characteristics can be then understood by considering the effect of crystal defects and trap states in the perovskite grains and perovskite interface with its transport layer, which is TiO2 in this study. Although the TPV decay occurs in a time range much longer than the primary process of photoexcitation as commonly observed in transient photoluminescence spectroscopy, the processes involved in this TPV strongly correlates with the performance of these perovskite solar cells.

Photo-Induced Charge Transfer on Pt/Bi2WO6 Composite Photocatalysts

Pt/Bi2WO6 composite photocatalysts were prepared by a facile photoreduction method. Pt nanoparticles with an average size of 5–8 nm were successfully deposited on the surface of Bi2WO6 microspheres and the photocatalytic activity of Bi2WO6 was greatly improved by Pt nanoparticles. The photo-induced charge transfer properties of samples were studied by means of surface photovoltage (SPV) and transient photovoltage (TPV) techniques, giving an insight into the intrinsic reasons of the improvement in photocatalytic activity. The SPV and TPV results revealed that the deposited Pt nanoparticles could trap photo-induced electrons and then largely enhance the separation efficiency of photo-induced charge carriers.