Chiroptical Properties of Semiconducting Nanoplatelets Functionalized by Tartrate Derivatives

Inducing chirality in semiconductor nanoparticles is a recent trend motivated by the possible applications in circularly polarized light emission, spintronics, or stereoselective synthesis. However, the previous reports on CdSe nanoplatelets (NPLs) exclusively rely on cysteine or its derivatives as chiral ligands to induce optical activity. Here, we show a strong induction of chirality with derivatives of tartaric acid obtained by a single-step synthesis. The ligand exchange procedure in organic solvent was optimized for five-monolayer (5 ML) NPLs but can also be performed on 4, 3, and 2 ML. We show that the features of the CD spectra change with structural modification of the ligands and that these chiral ligands interact mainly with the first light-hole (lh1) band rather than the first heavy-hole (hh1) band, contrary to cysteine. This result suggests that chiroptical properties could be used to probe CdSe nanoplatelets’ surface ligands

Gold Nanoparticle Superlattices: Conditions for Long-Range Order, Moiré Patterns, and Binary Phase from a Single Population

We report the two-dimensional self-assembly at the liquid–air interface of spherical gold nanoparticles (NPs) with diameters between 2 and 14 nm. By exploring the self-assembly conditions, such as the dispersing solvent and the coating ligand (thiols with different lengths, oleylamine, polystyrene), we identify suitable conditions for long-range close-packed monolayers obtention. We show that though NPs with diameters below 3 nm yield glassy films or fuse during self-assembly depending on the ligand length, NPs with larger sizes dispersed in toluene yield well-ordered monolayers over distances that can span tens of micrometers. Adding a free ligand in solution before the self-assembly triggers long-range ordering into close-packed structures of otherwise amorphous films. The equilibrium distance between the NPs within the monolayers is compared to predictions by packing models, and the OTM displays qualitative agreement. We also observed a CaCu5 phase in few-layers assemblies which results from the size segregation of a monomodal population of NPs into two populations of different mean sizes occupying the two different sites of this complex lattice. In some instances, Moiré patterns consisting of two close-packed hexagonal monolayers superimposed with a twist angle are evidenced. By comparing the experimental structures with numerically simulated patterns, we show that a twist angle of 30° yields a quasicrystalline order with 12-fold rotational symmetry. Our work provides insights into fundamental processes behind the self-assembly of colloidal nanocrystals into ordered mono- and few-layers as well as more complex assemblies such as quasicrystalline or Frank–Kasper phases. These structures are of great significance for bottom-up fabrication of functional devices that take advantage of (collective) plasmonic properties or surface enhanced Raman scattering

Self-Assembly of CdSe Nanoplatelets into Giant Micrometer-Scale Needles Emitting Polarized Light

We report on the self-assembly of colloidal CdSe nanoplatelets into micrometers long anisotropic needle-like superparticles (SPs), which are formed in solution upon addition of an antisolvent to a stable colloidal dispersion. Optical fluorescence microscopy, transmission electron microscopy, and small-angle X-ray scattering provide detailed structural characterization and show that each particle is composed of 10⁶ nanoplatelets organized in highly aligned columns. Within the SPs, the nanoplatelets are stacked on each other to maximize the contact surface between the ligands. When deposited on a substrate, the planes of the platelets are oriented perpendicularly to its surface and the SPs exhibit polarized emission properties

Optimized Synthesis of CdTe Nanoplatelets and Photoresponse of CdTe Nanoplatelets Films

We study in detail the synthesis of CdTe nanoplatelets. Three populations of nanoplatelets with a thickness defined with atomic precision are obtained. We show that CdTe nanoplatelets can be extended laterally to obtain nanosheets with lateral dimensions in the micrometer range. We present the study of the reaction conditions for the formation of CdTe nanoplatelets and for their lateral extension. The reaction products are analyzed with optical spectroscopy, transmission electron microscopy, and small-angle X-ray scattering. We investigate the electro-optical properties of films formed with CdTe nanoplatelets, and we show that their current photoresponse is better than the one of comparable films formed with CdTe spherical nanocrystals

Real-Time in Situ Probing of High-Temperature Quantum Dots Solution Synthesis

Understanding the formation mechanism of colloidal nanocrystals is of paramount importance in order to design new nanostructures and synthesize them in a predictive fashion. However, reliable data on the pathways leading from molecular precursors to nanocrystals are not available yet. We used synchrotron-based time-resolved <i>in situ</i> small and wide-angle X-ray scattering to experimentally monitor the formation of CdSe quantum dots synthesized in solution through the heating up of precursors in octadecene at 240 °C. Our experiment yields a complete movie of the structure of the solution from the self-assembly of the precursors to the formation of the quantum dots. We show that the initial cadmium precursor lamellar structure melts into small micelles at 100 °C and that the first CdSe nuclei appear at 218.7 °C. The size distributions and concentration in nanocrystals are measured in a quantitative fashion as a function of time. We show that a short nucleation burst lasting 30 s is followed by a slow decrease of nanoparticle concentration. The rate-limiting process of the quantum dot formation is found to be the thermal activation of selenium