Band splitting and plurality of excitons in Ruddlesden-Popper metal halides


The organic-inorganic interactions within the hybrid lattice of two-dimensional Ruddlesden-Popper metal halides(RPMH) have consequences on the structural and electronic properties of the material. Such interactions have been primarily investigated through a library of organic cations, keeping the inorganic lead halide lattice component intact. Here, we demonstrate that the role of the organic-inorganic interactions in electronic processes can also be effectively manipulated by the metal cation, particularly moving from heavier lead to lighter tin. We perform in-depth spectroscopic and theoretical analysis of prototypical tin-based RPMH, in which we identify the presence multiple resonances in the optical spectra, which correspond to distinct exciton series. We show that the higher energy excitonic series are composed of electronic transitions from a lower lying valence band which originates from variations in the coordination geometries of the metal halide octahedra induced by subtle changes in the organic-inorganic interactions. Our studies indicate that the deformation induced splitting of the carrier bands is ubiquitous to the Ruddlesden-Popper architectures, although the splitting energies are substantially higher in the tin based systems.

Version notes

Additional calculations have been added to substantiate the origin of multiple electronic bands to lattice deformations (summarized in Fig 3 of the revised manuscript). Extensive details and clarifications on sample stability and spectral assignment have also been added.


Supplementary material

Supplemental Information for Band splitting and plurality of excitons in Ruddlesden-Popper metal halides
The SI contains the following: Computational details Assignment of transient absoprtion features at 5 K Temperature dependent transient absorption dataset Details of DT modeling Details on the sample stability during the measurments