Tailoring the thermal conductivity of two-dimensional metal halide perovskites

Proper thermal management of solar cells based on metal halide perovskites (MHPs) is key to increasing their efficiency as well as their durability. Although two-dimensional (2D) MHPs possess enhanced thermal stability as compared to their three-dimensional (3D) counterparts, the lack of comprehensive knowledge of the heat transfer mechanisms dictating their ultralow thermal conductivities is a bottleneck for further improvements in their thermal performance. Here, we experimentally and computationally study the Dion-Jacobson (DJ) and Ruddlesden-Popper (RP) phases of MHPs (n = 1) to demonstrate that the length of the organic spacers has a negligible influence on their thermal transport properties; we experimentally measure thermal conductivities of 0.19 ± 0.03 W m^-1 K^-1 and 0.18 ± 0.03 W m^-1 K^-1 for the RP and DJ phases with 13.6 Å and 6.3 Å interlayer inorganic separations, respectively. In contrast, we show that thermal conductivity is mainly dependent on the separation between the adjacent organic cations. Decreasing the intermolecular distance (by up to 40%) leads to drastically enhanced overall heat conduction (with monotonically increasing thermal conductivity by more than threefold) which is mainly driven by the vibrational hardening of the organic spacers. Although these 2D layered materials constitute a high density of hybrid organic-inorganic interfaces, our results also show that a substantial portion of heat is conducted through coherent phonon transport and that the thermal conductivity of these materials is not solely limited by incoherent interfacial scattering.