Synthesis and Optical Properties of One Year Air-Stable Chiral Sb(III) Halide Semiconductors

Azmy, Ali and Konovalova, Daria M and Lepore, Leah and Fyffe, Alexander and Kim, Doyun and Wojtas, Lukasz and Tu, Qing and Trinh, Minh Tuan and Zibouche, Nourdine and Spanopoulos, Ioannis (2023) Synthesis and Optical Properties of One Year Air-Stable Chiral Sb(III) Halide Semiconductors. Inorganic Chemistry, 62 (49). pp. 20142-20152. ISSN 0020-1669

Text (manuscript)
manuscript.pdf - Accepted Version
Available under License Creative Commons Attribution.
Download (10MB)

Abstract

Chiral hybrid metal-halide semiconductors (MHS) pose as ideal candidates for spintronic applications owing to their strong spin-orbit coupling (SOC), and long spin relaxation times. Shedding light on the underlying structure-property relationships is of paramount importance for the targeted synthesis of materials with an optimum performance. Herein, we report the synthesis and optical properties of 1D chiral ( -/ -THBTD)SbBr (THBTD = 4,5,6,7-tetrahydro-benzothiazole-2,6-diamine) semiconductors using a multifunctional ligand as a countercation and a structure directing agent. ( -/ -THBTD)SbBr feature direct and indirect band gap characteristics, exhibiting photoluminescence (PL) light emission at RT that is accompanied by a lifetime of a few ns. Circular dichroism (CD), second harmonic generation (SHG), and piezoresponse force microscopy (PFM) studies validate the chiral nature of the synthesized materials. Density functional theory (DFT) calculations revealed a Rashba/Dresselhaus (R/D) spin splitting, supported by an energy splitting ( ) of 23 and 25 meV, and a Rashba parameter (α ) of 0.23 and 0.32 eV·Å for the and analogs, respectively. These values are comparable to those of the 3D and 2D perovskite materials. Notably, ( -THBTD)SbBr has been air-stable for a year, a record performance among chiral lead-free MHS. This work demonstrates that low-dimensional, lead-free, chiral semiconductors with exceptional air stability can be acquired, without compromising spin splitting and manipulation performance.