Lead halide perovskites have recently been used as light absorbers in hybrid organic-inorganic solid-state solar cells, with efficiencies as high as 15% and open-circuit voltages of 1 V. However, a detailed explanation of the mechanisms of operation within this photovoltaic system is still lacking. Here, we investigate the photoinduced charge transfer processes at the surface of the perovskite using time-resolved techniques. Transient laser spectroscopy and microwave photoconductivity measurements were applied to TiO 2 and Al 2 O 3 mesoporous films impregnated with CH 3 NH 3 PbI 3 perovskite and the organic hole-transporting material spiro-OMeTAD. We show that primary charge separation occurs at both junctions, with TiO 2 and the hole-transporting material, simultaneously, with ultrafast electron and hole injection taking place from the photoexcited perovskite over similar timescales. Charge recombination is shown to be significantly slower on TiO 2 than on Al 2 O 3 films.

A systematic study on the photocatalytic activity of well-defined, macroscopic bulk single-crystal TiO(2) anatase and rutile samples has been carried out, which allows us to link photoreactions at surfaces of well-defined oxide semiconductors to an important bulk property with regard to photochemistry, the life time of e-h pairs generated in the bulk of the oxides by photon absorption. The anatase (101) surface shows a substantially higher activity, by an order of magnitude, for CO photo-oxidation to CO(2) than the rutile (110) surface. This surprisingly large difference in activity tracks the bulk e-h pair lifetime difference for the two TiO(2) modifications as determined by contactless transient photoconductance measurements on the corresponding bulk materials.

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The study of charge carrier kinetics in semiconductors by microwave conductivity measurements. II.The study of the excess conductivity induced in a material by pulsed optical excitation yields information on the optoelectronic properties of the material and is receiving increasing attention. As conventional conductivity techniques are hampered by the need to apply electrical contacts, we have investigated the reliability and the possibilities of microwave conductivity measurements. This paper first presents the general background for excess conductivity measurements in the microwave range, and then derives the quantitative relationship between the reflected microwave signal and the change in conductivity for a wafer of single-crystalline Si. For this sample, the theory of excess charge carrier kinetics is also developed. After a short description of our apparatus, kinetic measurements on a nano-and microsecond timescale are compared to theory.

The surface of commercial TiO2 compounds (P25 and ST01) has been modified with Ag nanoparticles induced by radiolysis. On P25, the Ag nanoclusters are very small (1–2 nm) and homogeneous in size while on ST01, two populations of nanoparticles are obtained, small nanoparticles (1–2 nm) and larger ones (mean diameter 7 to 12 nm depending on the silver loading). The photocatalytic properties of Ag-modified TiO2 have been studied for phenol photodegradation in aqueous suspensions under UV and visible light. Their electronic properties have been studied by time resolved microwave conductivity (TRMC) to follow the charge-carrier dynamics. TRMC measurements show that the TiO2 modification (P25 and ST01) with Ag nanoparticles plays a role in charge-carrier separations increasing the activity under UV light. Indeed, Ag nanoparticles act as electron scavengers, decreasing the charge carrier recombination. TRMC measurements show also that more electrons are produced in the conduction band of P25 under UV illumination of Ag-modified P25. Surface modification by silver nanoparticles induces also a modification of the absorption properties of the photocatalyst creating an activity under visible light.