Atomic-scale insights in the interplay of chemical composition and chirality in two-dimensional chiral perovskites

Author(s)

Inui, Guilherme K. ; Besse, Rafael ; Gonzalez, Jose E. ; Da Silva, Juarez L. F.

• Document type: Journal article
• Source: Physical Chemistry Chemical Physics; v. 26, n. 23, p. 13-pg., 2024-05-23.

Abstract

The incorporation of chiral molecules (A) in materials based on hybrid ABX3 perovskites has opened new paths to tune the optoelectronic properties of perovskites through the transfer of chirality to the inorganic BX framework. However, our atomistic understanding of the role of chemical BX composition in the magnitude of the chirality transfer is far from complete. In this study, we use density functional theory calculations and the experimental Ruddlesden-Popper chiral (R-/S-NEA)2PbBr4 structure (R-/S-NEA = R-/S-1-(1-naphthyl)ethylammonium) to investigate the effects induced by chemical substitution of Pb by Ge or Sn and Br by Cl or I on the transfer of chirality and physical-chemical properties. We have observed that different enantiomers result in opposing orientations of octahedral tiltings within the inorganic framework, thus transferring chirality to the inorganic structure. The tilts are greater in perovskites based on Pb and decrease in the sequence of Cl to Br to I, as a consequence of the decrease in the halide electronegativity that weakens the interactions between X and the -N+H3 group of the NEA chiral cation. The chirality transfer is also evident in the Rashba-Dresselhaus effects on the electronic band structure, in which we found magnitudes directly correlated to the trends of octahedra tilting. The band offsets of substitutions B and X are predominantly influenced by their natural atomic energy levels, while organic molecules play a pivotal role in modulating the ionic potential and electron affinity in systems containing light atoms. The band gap values range from 1.91 up to 3.77 eV, with chirality and anion electronegativity providing significant tuning effects on whether the band gaps are direct or indirect. Transfer of chirality, inducing octahedral distortions in two-dimensional chiral perovskites, impacts the electronic structure via Rashba-Dresselhaus effects, and is influenced by chemical compositions, which also dictates band offsets. (AU)

• FAPESP's process: 22/06925-5 - Theoretical investigation of chiral molecules in the physicochemical properties of hybrid perovskites
• Grantee: Guilherme Kazuo Inui
• Support Opportunities: Scholarships in Brazil - Master
• FAPESP's process: 18/21401-7 - Multi-User Equipment approved in grant 2017/11631-2: cluster computational de alto desempenho - ENIAC
• Grantee: Juarez Lopes Ferreira da Silva
• Support Opportunities: Multi-user Equipment Program
• FAPESP's process: 17/11631-2 - CINE: computational materials design based on atomistic simulations, meso-scale, multi-physics, and artificial intelligence for energy applications
• Grantee: Juarez Lopes Ferreira da Silva
• Support Opportunities: Research Grants - Research Centers in Engineering Program