Homomeric chains of intermolecular bonds scaffold octahedral germanium perovskites

Amin Morteza Najarian, Filip Dinic, Hao Chen, Randy Sabatini, Chao Zheng, Alan Lough, Thierry Maris, Makhsud I. Saidaminov, F. Pelayo García de Arquer, Oleksandr Voznyy, Sjoerd Hoogland and Edward H. Sargent ()
Additional contact information
Amin Morteza Najarian: University of Toronto
Filip Dinic: University of Toronto Scarborough
Hao Chen: University of Toronto
Randy Sabatini: University of Toronto
Chao Zheng: University of Toronto
Alan Lough: University of Toronto
Thierry Maris: Université de Montréal
Makhsud I. Saidaminov: University of Victoria
F. Pelayo García de Arquer: The Barcelona Institute of Science and Technology
Oleksandr Voznyy: University of Toronto Scarborough
Sjoerd Hoogland: University of Toronto
Edward H. Sargent: University of Toronto

Nature, 2023, vol. 620, issue 7973, 328-335

Abstract: Abstract Perovskites with low ionic radii metal centres (for example, Ge perovskites) experience both geometrical constraints and a gain in electronic energy through distortion; for these reasons, synthetic attempts do not lead to octahedral [GeI6] perovskites, but rather, these crystallize into polar non-perovskite structures1–6. Here, inspired by the principles of supramolecular synthons7,8, we report the assembly of an organic scaffold within perovskite structures with the goal of influencing the geometric arrangement and electronic configuration of the crystal, resulting in the suppression of the lone pair expression of Ge and templating the symmetric octahedra. We find that, to produce extended homomeric non-covalent bonding, the organic motif needs to possess self-complementary properties implemented using distinct donor and acceptor sites. Compared with the non-perovskite structure, the resulting [GeI6]4− octahedra exhibit a direct bandgap with significant redshift (more than 0.5 eV, measured experimentally), 10 times lower octahedral distortion (inferred from measured single-crystal X-ray diffraction data) and 10 times higher electron and hole mobility (estimated by density functional theory). We show that the principle of this design is not limited to two-dimensional Ge perovskites; we implement it in the case of copper perovskite (also a low-radius metal centre), and we extend it to quasi-two-dimensional systems. We report photodiodes with Ge perovskites that outperform their non-octahedral and lead analogues. The construction of secondary sublattices that interlock with an inorganic framework within a crystal offers a new synthetic tool for templating hybrid lattices with controlled distortion and orbital arrangement, overcoming limitations in conventional perovskites.

Date: 2023
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DOI: 10.1038/s41586-023-06209-y

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