We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.

Excitonic solar cells, within which bound electron-hole pairs have a central role in energy harvesting, have represented a hot field of research over the last two decades due to the compelling prospect of low-cost solar energy. However, in such cells, exciton dissociation and charge collection occur with significant losses in energy, essentially due to poor charge screening. Organic-inorganic perovskites show promise for overcoming such limitations. Here, we use optical spectroscopy to estimate the exciton binding energy in the mixed-halide crystal to be in the range of 50 meV. We show that such a value is consistent with almost full ionization of the exciton population under photovoltaic cell operating conditions. However, increasing the total photoexcitation density, excitonic species become dominant, widening the perspective of this material for a host of optoelectronic applications.

We report a colloidal synthesis approach to CsPbBr3 nanoplatelets (NPLs). The nucleation and growth of the platelets, which takes place at room temperature, is triggered by the injection of acetone in a mixture of precursors that would remain unreactive otherwise. The low growth temperature enables the control of the plate thickness, which can be precisely tuned from 3 to 5 monolayers. The strong two-dimensional confinement of the carriers at such small vertical sizes is responsible for a narrow PL, strong excitonic absorption, and a blue shift of the optical band gap by more than 0.47 eV compared to that of bulk CsPbBr3. We also show that the composition of the NPLs can be varied all the way to CsPbBr3 or CsPbI3 by anion exchange, with preservation of the size and shape of the starting particles. The blue fluorescent CsPbCl3 NPLs represent a new member of the scarcely populated group of blue-emitting colloidal nanocrystals. The exciton dynamics were found to be independent of the extent of 2D confinement in these platelets, and this was supported by band structure calculations.

We report about the relationship between the morphology and luminescence properties of methylammonium lead trihalide perovskite thin films. By tuning the average crystallite dimension in the film from tens of nanometers to a few micrometers, we are able to tune the optical band gap of the material along with its photoluminescence lifetime. We demonstrate that larger crystallites present smaller band gap and longer lifetime, which correlates to a smaller radiative bimolecular recombination coefficient. We also show that they present a higher optical gain, becoming preferred candidates for the realization of CW lasing devices.

We present an investigation into incorporating core-shell Au-SiO(2) nanoparticles into dye-sensitized solar cells. We demonstrate plasmon-enhanced light absorption, photocurrent, and efficiency for both iodide/triiodide electrolyte based and solid-state dye-sensitized solar cells. Our spectroscopic investigation indicates that plasmon-enhanced photocarrier generation competes well with plasmons oscillation damping with in the first tens of femtoseconds following light absorption.

photovoltaic properties of MAPbI 3 perovskites across the tetragonal to cubic transition, due to structural fluctuations on a sub-picosecond timescale that make the instantaneous electronic energy levels and band-gap of the formally cubic, high temperature structure, to differ only slightly from those of the room temperature stable tetragonal phase. disordered position of the Cl anions 45 and the presence of a Raman signal at 66 cm -1 in the high temperature phase of MAPbCl 3 . 47 From a technological perspective, these results help to explain the lack of an observable abrupt change in photovoltaic device performance above room temperature 23 as would be expected to be observable if the light-harvester undergoes a phase transition. This is also further evidence indicating that ferroelectricity contributions to the optoelectronic properties, as in traditional inorganic materials, 54-57 are negligible, since the ferroelectric polarizability is expected to change dramatically across the transition between two different crystalline structures.On the contrary, this view supports other proposed mechanisms, as the spatial charge localization 50, 58 and/or stable band bending effects at the interfaces and grain boundaries, 59 as the basis of the impressive inherent performance of hybrid lead halide perovskites. ASSOCIATED CONTENT Supplementary InformationExperimental methods; theoretical methods and models; EQE measurements on different MAPbI3 devices; corresponding JV measurements of the devices; EQE of a cell with MAPbI 3-xClx ; comparison between theoretical and experimental radial distribution function of MAPbI 3 perovskite; theoretical fluctuation of the band edges.

Recent reports on high-mobility organic field-effect transistors (FETs) based on donor-acceptor semiconducting co-polymers have indicated an apparently strong deviation from the paradigm, valid for a series of semi-crystalline polymers, which has been strictly correlating charges mobility to crystalline order. This poses a severe limit on the control of mobility and a fundamental question on the critical length scale which is dominating charge transport. Here we focus on a well-known model material for electron transport, a naphthalene-diimide based copolymer, and we demonstrate that mobility can be controlled over two orders of magnitude, with maximum saturation mobility exceeding 1 cm2/Vs at high gate voltages, by controlling the extent of orientational domains through a deposition process as simple as spin-coating. High mobility values can be achieved by adopting solvents inducing a higher amount of pre-aggregates in the solution, which through the interaction with the substrate, provide the polymer with liquid-crystalline like ordering properties.

Structural inhomogeneity on a micrometer-scale across a CH3NH3PbI3 single crystal is responsible for a local modulation of the optical band gap, which is also highly sensitive to humidity.