Unusual Thermal Boundary Resistance in Halide Perovskites: A Way To Tune Ultralow Thermal Conductivity for Thermoelectrics.

Halide perovskites have emerged as promising candidates as the active material in photovoltaics and light-emitting diodes. They possess unusual bulk thermal transport properties that have been the focus of a number of studies, but there is much less understanding of thermal transport in thin films where a diverse range of structures and morphologies are accessible. Here, we report on the tuning of in-plane thermal conductivity in methylammonium lead iodide thin films by morphological control. Using 3-ω measurements, we find that the room temperature thermal conductivity of thermally evaporated methylammonium lead iodide perovskite films ranges from 0.31 to 0.59 W/(m K). We measure a discontinuity in thermal conductivity at the orthorhombic-tetragonal phase transition and explore this using density functional theory and attributing it to a collapse in the phonon group velocity along the c-axis of the tetragonal crystal. Moreover, we have quantified the thermal boundary resistance (Kapitza resistance) for thermally evaporated films, allowing us to estimate the Kapitza length, which is 36 ± 2 nm at room temperature and 15 ± 2 nm at 100 K. Curiously, the Kapitza resistance has a strong temperature dependence which we also explore using density functional theory, with these results suggesting an important role of methylammonium rotational modes in scattering phonons at the crystallite boundaries.

Probing structure in submicronic aqueous assemblies of emulsified microemulsions and charged spherical colloids using SANS and cryo-TEM.

The spatial distribution of charged spherical colloids when used as stabilizers of phytantriol-based emulsified microemulsions (EME, L2 symmetry group) is investigated. The coverage of the lipid-based mesophases by the colloids is monitored using small-angle neutron scattering (SANS) in contrast matching conditions and visualized using cryogenic transmission electron microscopy (cryo-TEM) imaging. The results demonstrate that, despite the stability of the emulsion droplets, very few colloids are ever found on the droplets. The stability of the EMEs is suggested to arise from the very slow ripening rates combined with punctual repulsion against coalescence from the isolated charged colloids on the bigger droplet surfaces. We show the possibility of creating a dense cover around the droplets by partially hydrophobizing the colloids by adsorbing a cationic surfactant on their surface. This opens up the possibilities for further modulation of the colloidal coverage in these systems. This is an interesting route for the design of new Colloid-ISAsome assemblies in which dense protective armors could be advantageous such as controlled delivery.