Towards lead-free perovskite device architectures: interface simulations of tin-based heterostructures (2021)

Following the emergence of lead halide perovskites as record-breaking materials for emerging photovoltaic applications, lead-free perovskites are gaining interest as novel materials which are compatible with inkjet-printing based technologies<sup>1,</sup><sup>2,3</sup>. Bulk properties are of the prime importance, but charge transport can be rapidly altered across the interface of perovskite/ (hole or electron) transport layer (HTL or ETL). Yet, due to the size and complexity of the interface systems, a thorough ab initio modeling of the interfaces remains elusive to-date. Within this work, to explore the atomic-scale details of the structural and electronic properties of these materials, we employ state-of-the-art density functional theory (DFT) based calculations of model tin-based heterostructures. We investigate in particular three-dimensional corner-sharing Sn-based perovskites, their surface and interface properties and calculate the interaction of the materials with charge transport layers (CTLs). Our approach reveals the electronic band alignments and dielectric mismatches between perovskite layers and the most important hole and electron transport layers that have been used in prototype thin film device architectures<sup>4,5</sup>. In an effort to understand the fundamental physico-chemical mechanisms that govern the interactions between the photo-active absorber material and CTLs, we also probe the influence of surface termination on structural and electronic properties at FASnI<sub>3</sub>/C<sub>60</sub> (as ETL) interfaces and FASnI<sub>3</sub>/NiO<sub>x</sub> (as ETL) interfaces. Our findings give a detailed insight into the interface engineering necessary for optimizing the next generation of environmental-friendly high-performing opto-electronic devices. This DROP-IT project<sup>1</sup> has received funding from the European Union’s Horizon 2020 research and innovation Program under the grant agreement N<sup>o</sup> 862656. The information and views set out in the abstracts and presentations are those of the authors and do not necessarily reflect the official opinion of the European Union. Neither the European Union institutions and bodies nor any person acting on their behalf may be held responsible for the use which may be made of the information contained herein. <strong>References:</strong> (1) DROPIT https://www.uv.es/dropit/ (accessed June 22, 2021). (2) Volonakis, G.; Filip, M. R.; Haghighirad, A. A.; Sakai, N.; Wenger, B.; Snaith, H. J.; Giustino, F. Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals. <em>J. Phys. Chem. Lett.</em> <strong>2016</strong>, <em>7</em> (7), 1254–1259. https://doi.org/10.1021/acs.jpclett.6b00376. (3) Volonakis, G.; Haghighirad, A. A.; Milot, R. L.; Sio, W. H.; Filip, M. R.; Wenger, B.; Johnston, M. B.; Herz, L. M.; Snaith, H. J.; Giustino, F. Cs2InAgCl6: A New Lead-Free Halide Double Perovskite with Direct Band Gap. <em>J. Phys. Chem. Lett.</em> <strong>2017</strong>, <em>8</em> (4), 772–778. https://doi.org/10.1021/acs.jpclett.6b02682. (4) Traore, B.; Pedesseau, L.; Blancon, J.-C.; Tretiak, S.; Mohite, A. D.; Even, J.; Katan, C.; Kepenekian, M. Importance of Vacancies and Doping in Hole Transporting Nickel Oxide Interface with Halide Perovskites. <em>ACS Appl. Mater. Interfaces</em> <strong>2020</strong>. https://doi.org/10.1021/acsami.9b19457. (5) Canicoba, N. D.; Zagni, N.; Liu, F.; McCuistian, G.; Fernando, K.; Bellezza, H.; Traoré, B.; Rogel, R.; Tsai, H.; Le Brizoual, L.; et al. Halide Perovskite High-k Field Effect Transistors with Dynamically Reconfigurable Ambipolarity. <em>ACS Materials Lett.</em> <strong>2019</strong>, <em>1</em> (6), 633–640. https://doi.org/10.1021/acsmaterialslett.9b00357.