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Structural Asymmetry and Chiral-Induced Spin Selectivity in Chiral Palladium-Halide Semiconductors

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.3c14491· OSTI ID:2371673
 [1];  [2];  [1];  [1];  [3];  [4];  [1];  [2];  [1]
  1. Hanyang Univ., Seoul (Korea, Republic of)
  2. Chungnam National Univ., Daejeon (Korea, Republic of)
  3. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  4. National Renewable Energy Laboratory (NREL), Golden, Colorado 80401, United States
+ Show Author Affiliations
Chiral Pb-free metal-halide semiconductors (MHSs) have attracted considerable attention in the field of spintronics due to various interesting spin-related properties and chiral-induced spin selectivity (CISS) effect. Despite their excellent chemical and structural tunability, the material scope and crystal structure of Pb-free chiral MHSs exhibiting the CISS effect are still limited; chiral MHSs that have metal-halide structures of octahedra and tetrahedra are only reported. Here, we report a new class of chiral MHSs, of which palladium (Pd)-halides are formed in 1D square-pyramidal structures or 0D square-planar structures, with a general formula of ((R/S-MBA)2PdBr4)1-x((R/S-MBA)2PdCl4)x (MBA = methylbenzylammonium; x = 0, 0.25, 0.5, 0.75, and 1) for the first time. The crystals adopt the 1D helical chain of Pd-halide square-pyramid (for x = 0, 0.25, 0.5, and 0.75) and 0D structure of Pd-halide square-plane (for x = 1). All the Pd-halides are distorted by the interaction between the halide and the chiral organic ammonium and arranged in a noncentrosymmetric position. Circular dichroism (CD) for ((R/S-MBA)2PdBr4)1-x((R/S-MBA)2PdCl4)x indicates that chirality was transferred from chiral organic ammonium to Pd-halide inorganics. ((R-MBA)2PdBr4)1-x((R-MBA)2PdCl4)x (x = 0, 0.25, 0.5, and 0.75) shows a distortion index of 0.127-0.128, which is the highest value among the previously reported chiral MHSs to the best of our knowledge. We also find that (R/S-MBA)2Pd(Br1-xClx)4 crystals grow along the out-of-plane direction during spin coating and have high c-axis orientation and crystallinity, and (R/S-MBA)2Pd(Br1-xClx)4 (x = 0 and 0.5) crystals exhibit a CISS effect in polycrystalline bulk films. In conclusion, these results demonstrate the possibility of a new metal-halide series with square-planar structures or square-pyramidal structures for future spintronic applications.
Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
National Research Foundation of Korea (NRF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
2371673
Report Number(s):
NREL/JA--5F00-90158; MainId:91936; UUID:d86acd1e-fd1c-46f8-890c-517995bfd0fe; MainAdminId:72787
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 22 Vol. 146; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
cations
chiral metal halide
chiral-induced spin-selectivity
crystal structure
crystals
diffraction
distortion index
palladium
quantum mechanics
square-plane
square-pyramid