Ligand Tail Controls the Conformation of Indium Sulfide Ultrathin Nanoribbons.

We report the conformational control of 2D ultrathin indium sulfide nanoribbons by tuning their amine ligands' alkyl chain. The initial orthorhombic InS nanoribbons bare n-octylamine ligands and display a highly curved geometry with a characteristic figure of eight shapes. Exchanging the native ligand by oleylamine induces their complete unfolding to yield flat board-shaped nanoribbons. Significant strain variations in the InS crystal structure accompany this shape-shifting. By tuning the linear alkyl chain length from 4 to 18 carbon atoms, we show using small-angle X-ray scattering in solution and transmission electron microscopy that the curvature of the nanoribbon subtly depends on the ligand-ligand interactions at the nanoribbon's surface. The curvature decreases gradually as the chain length increases, while carbon unsaturation has an unexpectedly significant effect at constant chain length. These experiments shed light on the critical role of the ligand monolayer on the curvature of ultrathin 2D crystalline nanosheets and demonstrate that weak supramolecular forces within the organic part of colloidal nanocrystals can dramatically impact their shape. This transduction mechanism, in which changes in the organic monolayer impact the shape of a nanocrystal, will help to devise new strategies to design stimuli-responsive systems that take advantage of both the flexibility of organic moieties and the physical properties of the inorganic core.

Metal Fluorides Passivate II-VI and III-V Quantum Dots.

Quantum dots (QDs) with metal fluoride surface ligands were prepared via reaction with anhydrous oleylammonium fluoride. Carboxylate terminated II-VI QDs underwent carboxylate for fluoride exchange, while InP QDs underwent photochemical acidolysis yielding oleylamine, PH3, and InF3. The final photoluminescence quantum yield (PLQY) reached 83% for InP and near unity for core-shell QDs. Core-only CdS QDs showed dramatic improvements in PLQY, but only after exposure to air. Following etching, the InP QDs were bound by oleylamine ligands that were characterized by the frequency and breadth of the corresponding ν(N-H) bands in the infrared absorption spectrum. The fluoride content (1.6-9.2 nm-2) was measured by titration with chlorotrimethylsilane and compared with the oleylamine content (2.3-5.1 nm-2) supporting the formation of densely covered surfaces. The influence of metal fluoride adsorption on the air stability of QDs is discussed.

Persistent nucleation and size dependent attachment kinetics produce monodisperse PbS nanocrystals.

Modern syntheses of colloidal nanocrystals yield extraordinarily narrow size distributions that are believed to result from a rapid "burst of nucleation" (La Mer, JACS, 1950, 72(11), 4847-4854) followed by diffusion limited growth and size distribution focusing (Reiss, J. Chem. Phys., 1951, 19, 482). Using a combination of in situ X-ray scattering, optical absorption, and 13C nuclear magnetic resonance (NMR) spectroscopy, we monitor the kinetics of PbS solute generation, nucleation, and crystal growth from three thiourea precursors whose conversion reactivity spans a 2-fold range. In all three cases, nucleation is found to be slow and continues during >50% of the precipitation. A population balance model based on a size dependent growth law (1/r) fits the data with a single growth rate constant (k G) across all three precursors. However, the magnitude of the k G and the lack of solvent viscosity dependence indicates that the rate limiting step is not diffusion from solution to the nanoparticle surface. Several surface reaction limited mechanisms and a ligand penetration model that fits data our experiments using a single fit parameter are proposed to explain the results.

Curvature and self-assembly of semi-conducting nanoplatelets.

Semi-conducting nanoplatelets are two-dimensional nanoparticles whose thickness is in the nanometer range and controlled at the atomic level. They have come up as a new category of nanomaterial with promising optical properties due to the efficient confinement of the exciton in the thickness direction. In this perspective, we first describe the various conformations of these 2D nanoparticles which display a variety of bent and curved geometries and present experimental evidences linking their curvature to the ligand-induced surface stress. We then focus on the assembly of nanoplatelets into superlattices to harness the particularly efficient energy transfer between them, and discuss different approaches that allow for directional control and positioning in large scale assemblies. We emphasize on the fundamental aspects of the assembly at the colloidal scale in which ligand-induced forces and kinetic effects play a dominant role. Finally, we highlight the collective properties that can be studied when a fine control over the assembly of nanoplatelets is achieved.

Long Range Energy Transfer in Self-Assembled Stacks of Semiconducting Nanoplatelets.

Fluorescent emitters like ions, dye molecules, or semiconductor nanoparticles are widely used in optoelectronic devices, usually within densely packed layers. Their luminescence properties can then be very different from when they are isolated, because of short-range interparticle interactions such as Förster resonant energy transfer (FRET). Understanding these interactions is crucial to mitigate FRET-related losses and could also lead to new energy transfer strategies. Exciton migration by FRET hopping between consecutive neighbor fluorophores has been evidenced in various systems but was generally limited to distances of tens of nanometers and involved only a few emitters. Here, we image self-assembled linear chains of CdSe nanoplatelets (colloidal quantum wells) and demonstrate exciton migration over 500 nm distances, corresponding to FRET hopping over 90 platelets. By comparing a diffusion-equation model to our experimental data, we measure a (1.5 ps)-1 FRET rate, much faster than all decay mechanisms, so that strong FRET-mediated collective photophysical effects can be expected.

Induction of Chirality in Two-Dimensional Nanomaterials: Chiral 2D MoS2 Nanostructures.

Two-dimensional (2D) nanomaterials have been intensively investigated due to their interesting properties and range of potential applications. Although most research has focused on graphene, atomic layered transition metal dichalcogenides (TMDs) and particularly MoS2 have gathered much deserved attention recently. Here, we report the induction of chirality into 2D chiral nanomaterials by carrying out liquid exfoliation of MoS2 in the presence of chiral ligands (cysteine and penicillamine) in water. This processing resulted in exfoliated chiral 2D MoS2 nanosheets showing strong circular dichroism signals, which were far past the onset of the original chiral ligand signals. Using theoretical modeling, we demonstrated that the chiral nature of MoS2 nanosheets is related to the presence of chiral ligands causing preferential folding of the MoS2 sheets. There was an excellent match between the theoretically calculated and experimental spectra. We believe that, due to their high aspect ratio planar morphology, chiral 2D nanomaterials could offer great opportunities for the development of chiroptical sensors, materials, and devices for valleytronics and other potential applications. In addition, chirality plays a key role in many chemical and biological systems, with chiral molecules and materials critical for the further development of biopharmaceuticals and fine chemicals, and this research therefore should have a strong impact on relevant areas of science and technology such as nanobiotechnology, nanomedicine, and nanotoxicology.