Strong Induced Circular Dichroism in a Hybrid Lead‐Halide Semiconductor Using Chiral Amino Acids for Crystallite Surface Functionalization

Abstract

Chirality is a desired property in functional semiconductors for optoelectronic, catalytic, and spintronic applications. Here, introducing enantiomerically‐pure 3‐aminobutyric acid (3‐ABA) into thin films of the 1D semiconductor dimethylammonium lead iodide (DMAPbI3) is found to result in strong circular dichroism (CD) in the optical absorption. X‐ray diffraction and grazing incidence small angle X‐ray scattering (GISAXS) are applied to gain molecular‐scale insights into the chirality transfer mechanism, which is attributed to a chiral surface modification of DMAPbI3 crystallites. This study demonstrates that the CD signal strength can be controlled by the amino‐acid content relative to the crystallite surface area. The CD intensity is tuned by the composition of the precursor solution and the spin‐coating time, thereby achieving anisotropy factors (gabs) as high as 1.75 × 10–2. Grazing incidence wide angle scattering reveals strong preferential ordering that can be suppressed via tailored synthesis conditions. Different contributions to the chiroptical properties are resolved by a detailed analysis of the CD signal utilizing an approach based on the Mueller matrix model. This report of a novel class of chiral hybrid semiconductors with precise control over their optical activity presents a promising approach for the design of circularly polarized light detectors and emitters.

On the nature of optical activity in chiral transition metal complexes: [Pd(Me)2(BINAP)]

“…17,18 We have demonstrated this effect for diverse samples, including silver nanoparticles, thin organic films, tuneable gel structures, and thin-film perovskites. [19][20][21][22][23] In the present case, the experimentally obtained CD spectra of the two enantiomers of the [Pd(Me) 2 (BINAP)]complex in toluene (Fig. 1B) showed a mirror-image relationship as expected: the curves each consisted of two extrema at about 310 and 355 nm, one dip at 335 nm, and a zero crossing at 290 nm.…”

“…17,18 We have demonstrated this effect for diverse samples, including silver nanoparticles, thin organic films, tuneable gel structures, and thin-film perovskites. 19–23…”

Biomolecules incorporated in halide perovskite nanocrystals: synthesis, optical properties, and applications

“…In this regard, a huge number of new HP compositions have been formed using biomolecules including but not limited to alanine, 64,121,122 3-aminobutyric acid, 123 4-aminobutyric acid (GABA), 124,125 5-aminovaleric acid and its derivatives, 122,[126][127][128] cysteine, 129 glycine, 130 histidine, 129 leucine, 122 lysine, 65,131 ornithine, 131 phenylethylamine, 126,[132][133][134][135][136][137] proline, 138 and taurine. 129 While a few of the examples listed above represent novel ABX 3 HPNCs, the vast majority represent novel 2D perovskite layered structures.…”

Optical Properties of Slot‐Die Coated Hybrid Colloid/Cellulose‐Nanofibril Thin Films

“…[49] Extending to molecular arrangements in gratings, the combination with grazing incidence wide-angle X-ray scattering (GIWAXS) allows for correlating optical response, molecular arrangement, and grating morphology. [45,56] In terms of fabricating hybrid thin films, scalable layer-by-layer coating from the liquid phase is especially useful for colloidal and cellulose-based dispersions. To start with, ink-jet printing allows the facile deposition of multi-color functional layers.…”

“…[ 49 ] Extending to molecular arrangements in gratings, the combination with grazing incidence wide‐angle X‐ray scattering (GIWAXS) allows for correlating optical response, molecular arrangement, and grating morphology. [ 45,56 ]…”