The electron transport layer (ETL) plays a fundamental role in perovskite solar cells. Recently, graphene-based ETLs have been proved to be good candidate for scalable fabrication processes and to achieve higher carrier injection with respect to most commonly used ETLs. In this work we experimentally study the effects of different graphene-based ETLs in sensitized MAPI solar cells. By means of time-integrated and picosecond time-resolved photoluminescence techniques, the carrier recombination dynamics in MAPI films embedded in different ETLs is investigated. Using graphene doped mesoporous TiO 2 (G+mTiO 2 ) with the addition of a lithium-neutralized graphene oxide (GO-Li) interlayer as ETL, we find that the carrier collection efficiency is increased by about a factor two with respect to standard mTiO 2 . Taking advantage of the absorption coefficient dispersion, we probe the MAPI layer morphology, along the thickness, finding that the MAPI embedded in the ETL composed by G+mTiO 2 plus GO-Li brings to a very good crystalline quality of the MAPI layer with a trap density about one order of magnitude lower than that found with the other ETLs. In addition, this ETL freezes MAPI at the tetragonal phase, regardless of the temperature. Graphene-based ETLs can open the way to significant improvement of perovskite solar cells.

We present a detailed experimental investigation of the carrier recombination dynamics in CsPbBr 3 films by means of picosecond time-resolved photoluminescence. Temperaturedependent measurements show that carrier capture and release from the nanocrystals (NCs) surfaces determine the observed increase of the recombination lifetime with the increase of temperature. This result opens the way to probe the surface of the NCs, which is of the utmost relevance for optoelectronic applications, and to eventually give feedback for surface treatments of NCs.

Intrinsic defects in CsPbBr3 microcrystalline films have been studied using thermally stimulated current (TSC) technique in a wide temperature range (100–400 K). Below room temperature, TSC emission is composed by a set of several energy levels, in the range 0.11–0.27 eV, suggesting a quasi-continuum distribution of states with almost constant density. Above room temperature, up to 400 K, the temperature range of interest for solar cells, both dark current and photocurrent, are mainly dominated by energy levels in the range 0.40–0.45 eV. Even if measured trap densities are high, in the range 1013–1016 cm−3, the very small capture cross-sections, about 10−26 m2, agree with the high defect tolerance characterizing this material.

By means of time-resolved photoluminescence (TR-PL) spectroscopy, we present a detailed investigation of the carrier relaxation dynamics in a CsPbBr3 bulk sample and microcrystal ensemble at cryogenic temperature on a picosecond time scale. We provide evidence of a long temperature-dependent cooling rate for the excitons and free carriers population, with an initial cooling time constant of a few tens of picoseconds. A relaxation bottleneck in the thermalization process was found that cannot be explained by the Auger effect or hot phonon population, since we address a very low excitation regime, not commonly investigated in literature, where such processes are not effective. Adding a continuous wave optical bias to the picosecond excitation, we probed the photoinduced PL decrease of the localized states and the photoinduced PL increase of the population in the high energy states. A long recovery time from the photoinduced PL decrease was found for localized states and quite significant differences were detected, depending on the resonance/off resonance bias used in the experiment.

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