Chiral nanostructures exhibiting different absorption of right- and left-handed circularly polarized light are of rapidly growing interest due to their potential applications in various fields. Here, we have studied the induction of chirality in atomically thin (0.6–1.2 nm thick) ZnSe and CdSe nanoplatelets grown by a colloidal method and coated with L-cysteine and N-acetyl-L-cysteine ligands. We conducted an analysis of the optical and chiroptical properties of atomically thin ZnSe and CdSe nanoplatelets, which was supplemented by a detailed analysis of the composition and coordination of ligands. Different signs of circular dichroism were shown for L-cysteine and N-acetyl-L-cysteine ligands, confirmed by different coordination of these ligands on the basal planes of nanoplatelets. A maximum value of the dissymmetry factor of (2–3) × 10−3 was found for N-acetyl-L-cysteine ligand in the case of the thinnest nanoplatelets.
Chiral semiconductor nanostructures and nanoparticles are promising materials for applications in biological sensing, enantioselective separation, photonics, and spin-polarized devices. Here, we studied the induction of chirality in atomically thin only two-monolayer-thick CdSe nanoplatelets (NPLs) grown using a colloidal method and exchanged with L-alanine and L-phenylalanine as model thiol-free chiral ligands. We have developed a novel two-step approach to completely exchange the native oleic acid ligands for chiral amino acids at the basal planes of NPLs. We performed an analysis of the optical and chiroptical properties of the chiral CdSe nanoplatelets with amino acids, which was supplemented by an analysis of the composition and coordination of ligands. After the exchange, the nanoplatelets retained heavy-hole, light-hole, and spin-orbit split-off exciton absorbance and bright heavy-hole exciton luminescence. Capping with thiol-free enantiomer amino acid ligands induced the pronounced chirality of excitons in the nanoplatelets, as proven by circular dichroism spectroscopy, with a high dissymmetry g-factor of up to 3.4 × 10−3 achieved for heavy-hole excitons in the case of L-phenylalanine.
In recent years, wide bandgap metal oxide semiconductors have become the base materials of choice for semiconductor gas sensor design. In this work, nanocrystalline ZnO, In2O3, and SnO2 were investigated when detecting NO2 under UV-photoactivation conditions. The materials were characterized by XRD, low-temperature nitrogen adsorption, and electron microscopy. The article considers the mechanism of sensor signal formation, as well as the mechanism of action of UV-light photoactivation, using an in situ multi-method approach. In situ mass spectrometry and in situ TR-DRIFTS were employed to study the impact of UV-light photoactivation on target gas adsorption equilibrium as well as the electrical and gas-sensing properties of the materials.
Semiconductor colloidal nanostructures capped with chiral organic molecules are a research hotspot due to their wide range of important implications for photonic and spintronic applications. However, to date, the study of chiral ligands has been limited almost exclusively to naturally occurring chiral amino and hydroxy acids, which typically contain only one stereocenter. Here, we show the pronounced induction of chirality in atomically thin CdSe nanoplatelets (NPLs) by capping them with enantiopure menthol derivatives as multi-stereocenter molecules. L-(−)/D-(+)-menthyl thioglycolate, easily synthesized from L-(−)/D-(+)-menthol, is attached to Cd-rich (001) basal planes of 2- and 3-monolayer (ML) CdSe NPLs. We show the appearance of narrow sign-alternating bands in the circular dichroism (CD) spectra of 2 ML NPLs corresponding to heavy-hole (HH) and light-hole (LH) excitons with maximal dissymmetry g-factor up to 2.5 × 10−4. The most intense CD bands correspond to the lower-energy HH exciton, and in comparison with the N-acetyl-L-Cysteine ligand, the CD bands for L-(−)-menthyl thioglycolate have the opposite sign. The CD measurements are complemented with magnetic CD measurements and first-principles modeling. The obtained results may be of interest for designing new chiral semiconductor nanostructures and improving understanding of their chiroptical properties.
Sensors based on nanocomposites of quantum dots (QDs) and wide-gap metal oxides are of exceptional interest for photoactivated detection of toxic and pollutant gases without thermal heating. However, the class of detecting gases has been limited almost exclusively to oxidizing gases like NO2. Here, we designed a photoactivated sensor for the selective detection of primary alcohols at room temperature using CdSe quantum dots coupled to a wide-gap SnO2 semiconductor matrix. Our concept of the sensor operations is based on the photochemical reaction of primary alcohols via photoactivated QD-SnO2 charge transfer and does not involve chemisorbed oxygen, which is traditional for the operation of metal oxide sensors. We demonstrated an efficient sensor response to C1–C4 primary alcohols of ppm concentration under photoexcitation with a yellow LED in the absence of a signal from other volatile organic compounds (VOCs). We believe that proposed sensor concept opens up new ways to design photoactivated sensors without heating for the detection of VOCs.
Chiral semiconductor nanostructures and nanoparticles are promising materials for applications in biological sensing, enantioselective separation, photonics, and spin-polarized devices. Here, we have studied the induction of chirality in atomically thin only 2 monolayers thick CdSe nanoplatelets (NPLs) grown by a colloidal method and exchanged with L-alanine and L-phenylalanine as model thiol-free chiral ligands. We have developed a novel two-step approach to completely exchange the native oleic acid ligands for chiral amino acids at the basal planes of NPLs. We performed an analysis of the optical and chiroptical properties of the chiral CdSe nanoplatelets with amino acids, which was supplemented by an analysis of the composition and coordination of ligands. After the exchange, the nanoplatelets retain HH, LH and SO exciton absorbance and bright HH exciton luminescence. Capping with thiol-free enantiomer amino acid ligands induce pronounced chirality of excitons in the nanoplatelets, as proven by circular dichroism spectroscopy, with high dissymmetry g-factor up to 3.4 × 10−3 achieved for HH excitons in the case of L-phenylalanine.