Giant Apparent Optical Circular Dichroism in Thin Films of Bismuth‐Based Hybrid Organic–Inorganic Metal Halide Semiconductor Through Preferred Orientation

Author:

Yan Liang1ORCID,Xie Yi23ORCID,Mitzi David B.34ORCID,Sercel Peter C.5ORCID,Phillips Alan J.67ORCID,Blackburn Jeffrey L.6ORCID,You Wei1ORCID

Affiliation:

1. Department of Chemistry University of North Carolina at Chapel Hill Chapel Hill NC 27599 USA

2. University program in Materials Science and Engineering Duke University Durham North Carolina 27708 USA

3. Department of Mechanical Engineering and Materials Science Duke University Durham NC 27708 USA

4. Department of Chemistry Duke University Durham NC 27708 USA

5. Center for Hybrid Organic Inorganic Semiconductors for Energy Golden CO 80401 USA

6. Materials, Chemistry, and Computation Science Directorate National Renewable Energy Laboratory Golden CO 80401 USA

7. Department of Physics Colorado School of Mines Golden CO 80401 USA

Abstract

AbstractIntroducing chirality into organic/inorganic hybrid materials can impart chiroptical properties such as circular dichroism. The ability to tune chiroptical properties in self‐assembled materials can have important implications for spintronic and optoelectronic applications. Here, a chiral organic cation, (R/S)‐4‐methoxy‐α‐methylbenzylammonium, is incorporated to synthesize the bismuth‐based hybrid organic–inorganic metal halide semiconductor, (R/S‐MeOMePMA)BiI4. Thin films of this Bi‐based compound demonstrate large chiroptical responses, with circular dichroism anisotropy (gCD) values up to ≈0.1, close to the highest value observed in another chiral metal‐halide semiconductor, (R‐MBA2CuCl4). Detailed investigation reveals that this large gCD in (R/S‐MeOMePMA)BiI4 is caused by the apparent CD effect. Careful selection of deposition conditions and the concomitant thin‐film orientation enables the control of gCD, with maximum value observed when its thin film has a well‐crystallized preferred (001) orientation parallel to the substrate. The results support a growing body of evidence that low symmetry plays an important role in achieving unusually large gCD in these chiral metal–halide materials and provides design rules for achieving large chiroptical response via morphology control.

Funder

Office of Science

Basic Energy Sciences

National Science Foundation

Publisher

Wiley

Subject

Atomic and Molecular Physics, and Optics,Electronic, Optical and Magnetic Materials

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