Insight into the collective vibrational modes driving ultralow thermal conductivity of perovskite solar cells

The past few years have witnessed a rapid evolution of hybrid organic-inorganic perovskite solar cells as an unprecedented photovoltaic technology with both relatively low cost and high-power conversion. The fascinating physical and chemical properties of perovskites are benefited from their unique crystal structures represented by the general chemical formula AMX3, where the A cations occupy the hollows formed by the MX3 octahedra and thus balance the charge of the entire network. Despite a vast amount of theoretical and experimental investigations have been dedicated to the structural stability, electrical, and optical properties of hybrid halide perovskite materials in relation to their applications in solar cells, the thermal transport property, another critical parameter to the design and optimization of relevant solar cell modules, receives less attention. In this paper, we evaluate the lattice thermal conductivity of a representative methylammonium lead triiodide perovskite (CH3NH3PbI3) with direct nonequilibrium ab initio molecular dynamics simulation. Resorting to full first-principles calculations, we illustrate the details of the mysterious vibration of the methylammonium cluster (CH3NH3+) and present an unambiguous picture of how the organic cluster interacting with the inorganic cage and how the collective motions of the organic cluster drags the thermal transport, which provide fundamental understanding of the ultralow thermal conductivity of CH3NH3PbI3. We also reveal the strongly localized phonons associated with the internal motions of the CH3NH3+ cluster, which contribute little to the total thermal conductivity. The importance of the CH3NH3+ cluster to the structural instability is also discussed in terms of the unconventional dispersion curves by freezing the partial freedoms of the organic cluster. These results provide more quantitative description of organic-inorganic interaction and coupling dynamics from accurate first-principles calculations, which are expected to underpin the development of emerging photovoltaic devices.