Emission modulation of fluorescent turn-on mode dibenzothienyl sulfonyl ethene photoswitches embedded in a polymer film.

For decades photochromic molecules have attracted attention for their potential in using light as an external stimulus to change their photophysical properties. Here we report the spectroscopic characterization of two emissive photochromic molecules that are intrinsically fluorescent and that undergo a photocyclization/cycloreversion reaction upon illumination with light in the UV and VIS spectral ranges. For appropriately adjusted illumination intensities the emission can be modulated between the high- and the low-level with a contrast ratio exceeding 80%. The data are in reasonable agreement with the predictions from a simple kinetic model.

The role of PbI2 in CH3NH3PbI3 perovskite stability, solar cell parameters and device degradation.

We report a systematic investigation on the role of excess PbI2 content in CH3NH3PbI3 perovskite film properties, solar cell parameters and device storage stability. We used the CH3NH3I vapor assisted method for the preparation of PbI2-free CH3NH3PbI3 films under a N2 atmosphere. These pristine CH3NH3PbI3 films were annealed at 165 °C for different time intervals in a N2 atmosphere to generate additional PbI2 in these films. From XRD measurements, the excess of PbI2 was quantified. Detailed characterization using scanning electron microscopy, X-ray diffraction, UV-Visible and photoluminescence for continuous aging of CH3NH3PbI3 films under ambient condition (50% humidity) is carried out for understanding the influence of different PbI2 contents on degradation of the CH3NH3PbI3 films. We find that the rate of degradation of CH3NH3PbI3 is accelerated due to the amount of PbI2 present in the film. A comparison of solar cell parameters of devices prepared using CH3NH3PbI3 samples having different PbI2 contents reveals a strong influence on the current density-voltage hysteresis as well as storage stability. We demonstrate that CH3NH3PbI3 devices do not require any residual PbI2 for a high performance. Moreover, a small amount of excess PbI2, which improves the initial performance of the devices slightly, has undesirable effects on the CH3NH3PbI3 film stability as well as on device hysteresis and stability.

HOMO-HOMO Electron Transfer: An Elegant Strategy for p-Type Doping of Polymer Semiconductors toward Thermoelectric Applications.

Unlike the conventional p-doping of organic semiconductors (OSCs) using acceptors, here, an efficient doping concept for diketopyrrolopyrrole-based polymer PDPP[T]2 -EDOT (OSC-1) is presented using an oxidized p-type semiconductor, Spiro-OMeTAD(TFSI)2 (OSC-2), exploiting electron transfer from HOMOOSC-1 to HOMOOSC-2 . A shift of work function toward the HOMOOSC-1 upon doping is confirmed by ultraviolet photoelectron spectroscopy (UPS). Detailed X-ray photoelectron spectroscopy (XPS) and UV-vis-NIR absorption studies confirm HOMOOSC-1 to HOMOOSC-2 electron transfer. The reduction products of Spiro-OMeTAD(TFSI)2 to Spiro-OMeTAD(TFSI) and Spiro-OMeTAD is also confirmed and their relative amounts in doped samples is determined. Mott-Schottky analysis shows two orders of magnitude increase in free charge carrier density and one order of magnitude increase in the charge carrier mobility. The conductivity increases considerably by four orders of magnitude to a maximum of 10 S m-1 for a very low doping ratio of 8 mol%. The doped polymer films exhibit high thermal and ambient stability resulting in a maximum power factor of 0.07 µW m-1  K-2 at a Seebeck coefficient of 140 µV K-1 for a very low doping ratio of 4 mol%. Also, the concept of HOMOOSC-1 to HOMOOSC-2 electron transfer is a highly efficient, stable and generic way to p-dope other conjugated polymers.