Iron selenide obtained by mild hydrothermal reaction is not superconducting and exhibits a triclinic crystal structure below 60 K unlike superconducting FeSe from conventional solid state synthesis which is orthorhombic. In contrast, tetragonal iron sulphide FeS from hydrothermal synthesis is superconducting but undergoes no structural change on cooling.
Hybrid organic–inorganic networks that incorporate
chiral
molecules have attracted great attention due to their potential in
semiconductor lighting applications and optical communication. Here,
we introduce a chiral organic molecule (R)/(S)-1-cyclohexylethylamine (CHEA) into bismuth-based lead-free
structures with an edge-sharing octahedral motif, to synthesize chiral
lead-free (R)/(S)-CHEA4Bi2Br
x
I10–x
crystals and thin films. Using single-crystal X-ray
diffraction measurements and density functional theory calculations,
we identify crystal and electronic band structures. We investigate
the materials’ optical properties and find circular dichroism,
which we tune by the bromide–iodide ratio over a wide wavelength
range, from 300 to 500 nm. We further employ transient absorption
spectroscopy and time-correlated single photon counting to investigate
charge carrier dynamics, which show long-lived excitations with optically
induced chirality memory up to tens of nanosecond timescales. Our
demonstration of chirality memory in a color-tunable chiral lead-free
semiconductor opens a new avenue for the discovery of high-performance,
lead-free spintronic materials with chiroptical functionalities.
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.
We used second harmonic generation (SHG) spectroscopy to study the chiroptical properties of R-, S- and racemic (RAC-) 1,1'-Bi-2-naphthol (BINOL) films with various thicknesses, incidence angles and degrees of crystallization...
We present aspects of emerging optical activity in thin racemic 1,1 0-Bi-2-naphthol films upon irradiation with circularly polarized light and subsequent resonant two-photon absorption in the sample. Thorough analysis of the sample morphology is conducted by means of (polarization-resolved) optical microscopy and scanning electron microscopy (SEM). The influence of crystallization on the nonlinear probing technique (second harmonic generation circular dichroism [SHG-CD]) is investigated. Optical activity and crystallization are brought together by a systematic investigation in different crystallization regimes. We find crystallization to be responsible for two counteracting effects, which arise for different states of crystallization. Measuring crystallized samples offers the best signal-to-noise ratio, but it limits generation of optical activity due to self-assembly effects. For suppression of crystallization on the other hand, there is a clear indication that enantiomeric selective desorption is responsible for the generation of optical activity in the sample. We reach the current resolution limit of probing with SHG-CD, as we suppress the crystallization in the racemic sample during desorption. In addition, intensitydependent measurements on the induced optical activity reveal an onset threshold (≈0.7 TW cm −2), above which higher order nonlinear processes impair the generation of optical activity by desorption with CPL.
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