Charge generation and transport in (CH₃NH₃)PbI_3−xCl_x sensitized mesostructured solar cells are investigated. A highly efficient charge generation is directly proven by time correlated single photon counting analysis. Photoinduced absorption and transient photovoltage investigations depict double charge recombination dynamics. To explain the high device performances according to those spectroscopic observations, we suggest the existence of two complementary paths for electron transport, involving either TiO₂ or perovskite matrixes.

Hybrid halide perovskites have emerged as promising active constituents of next generation solution processable optoelectronic devices. During their assembling process, perovskite components undergo very complex dynamic equilibria starting in solution and progressing throughout film formation. Finding a methodology to control and affect these equilibria, responsible for the unique morphological diversity observed in perovskite films, constitutes a fundamental step towards a reproducible material processability. Here we propose the exploitation of polymer matrices as cooperative assembling components of novel perovskite CH₃NH₃PbI₃ : polymer composites, in which the control of the chemical interactions in solution allows a predictable tuning of the final film morphology. We reveal that the nature of the interactions between perovskite precursors and polymer functional groups, probed by Nuclear Magnetic Resonance (NMR) spectroscopy and Dynamic Light Scattering (DLS) techniques, allows the control of aggregates in solution whose characteristics are strictly maintained in the solid film, and permits the formation of nanostructures that are inaccessible to conventional perovskite depositions. These results demonstrate how the fundamental chemistry of perovskite precursors in solution has a paramount influence on controlling and monitoring the final morphology of CH₃NH₃PbI₃ (MAPbI₃) thin films, foreseeing the possibility of designing perovskite : polymer composites targeting diverse optoelectronic applications.