Prof Laura Herz FRS

Abstract:

Covalent organic frameworks (COFs), crystalline and porous conjugated structures, are of great interest for sustainable energy applications. Organic building blocks in COFs with suitable electronic properties can feature strong optical absorption, whereas the extended crystalline network can establish a band structure enabling long-range coherent transport. This peculiar combination of both molecular and solid-state materials properties makes COFs an interesting platform to study and ultimately utilize photoexcited charge carrier diffusion. Herein, we investigated the charge carrier diffusion in a two-dimensional COF thin film generated through condensation of the building blocks benzodithiophene-dialdehyde (BDT) and N,N,N′,N′-tetra(4-aminophenyl)benzene-1,4-diamine (W). We visualized the spatiotemporal evolution of photogenerated excited states in the 2D WBDT COF thin film using remote-detected time-resolved PL measurements (RDTR PL). Combined with optical pump terahertz probe (OPTP) studies, we identified two diffusive species dominating the process at different time scales. Initially, short-lived free charge carriers diffuse almost temperature-independently before relaxing into bound states at a rate of 0.7 ps^–1. Supported by theoretical simulations, these long-lived bound states were identified as excitons. We directly accessed the lateral exciton diffusion within the oriented and crystalline film, revealing remarkably high diffusion coefficients of up to 4 cm² s^–1 (200 K) and diffusion lengths of several hundreds of nanometers and across grain boundaries. Temperature-dependent exciton transport analysis showed contributions from both incoherent hopping and coherent band-like transport. In the transport model developed based on these findings, we discuss the complex impact of order and disorder on charge carrier diffusion within the WBDT COF thin film.

Abstract:

Inorganic semiconductors based on heavy pnictogen cations (Sb3+ and Bi3+) have gained significant attention as potential nontoxic and stable alternatives to lead-halide perovskites for solar cell applications. A limitation of these novel materials, which is being increasingly commonly found, is carrier localization, which substantially reduces mobilities and diffusion lengths. Herein, CuSbSe2 is investigated and discovered to have delocalized free carriers, as shown through optical pump terahertz probe spectroscopy and temperature-dependent mobility measurements. Using a combination of theory and experiment, the critical enabling factors are found to be: 1) having a layered structure, which allows distortions to the unit cell during the propagation of an acoustic wave to be relaxed in the interlayer gaps, with minimal changes in bond length, thus limiting deformation potentials; 2) favourable quasi-bonding interactions across the interlayer gap giving rise to higher electronic dimensionality; 3) Born effective charges not being anomalously high, which, combined with the small bandgap (≤1.2 eV), result in a low ionic contribution to the dielectric constant compared to the electronic contribution, thus reducing the strength of Fröhlich coupling. These insights can drive forward the rational discovery of perovskite-inspired materials that can avoid carrier localization.