Crystal structures and photoluminescence characteristics of cesium lead bromide perovskite nanoplatelets depending on the antisolvent and ligand used in their syntheses.

Cesium lead bromide (CsPbBr3) nanocrystals (NCs) with nanoplatelet shapes and different crystal structures were synthesized via the ligand-assisted reprecipitation (LARP) method using different pairs of ligands and antisolvents, namely oleic acid (OA) or linoleic acid (LA) as the ligand and toluene or chloroform as the antisolvent. The XRD data revealed that the obtained CsPbBr3 NCs have different crystal structures, namely orthorhombic, tetragonal, and cubic, depending on the ligand and antisolvent pair, which exhibited significantly different photoluminescence (PL) characteristics. From the XPS data, these CsPbBr3 nanoplatelets showed two doublet peaks of the Br-3d orbital at different binding energies, representing two different chemical environments of the Br bonds. The doublet peak apparent at a higher binding energy was associated with the Br chemical states at the crystal surface, which appeared because of the distorted crystal structure resulting from the interaction of the solvent and ligand with Br ions. The PL emission consists of three luminescence centers: a PL band peaked at 520 nm (A band), a PL band peaked at 540 nm (B band), and a PL band tail, which can be discussed in terms of exciton models. Stable and intense luminescence was observed in CsPbBr3 nanoplatelets synthesized using a pair of toluene antisolvent and LA ligand, namely CsPbBr3#(Tl/LA). The orthorhombic crystal structure and distorted crystal surface in this sample may lead to confinement of the photogenerated small exciton-polaron and weak phonon interactions, which effectively hinder exciton dissociation, particularly at the crystal surface, resulting in intense PL. The results of this study may provide additional important insights into the role of the antisolvent and ligand in the formation of CsPbBr3 NCs and the exciton behavior in their PL characteristics, which may also be found in other types of halide perovskites.

Characterization of citrates on gold and silver nanoparticles.

In this paper, we report different coordinations of citrates on gold (AuNP) and silver (AgNP) nanoparticles, as determined using Fourier transform infrared spectroscopy (FTIR) and molecular orbital (MO) calculations. AuNPs and AgNPs are found to have completely different interactions with the carboxylate anchoring groups, as indicated by their unique asymmetric stretching vibrations in the FTIR spectra. The ν(as) (COO(-)) of citrate exhibits a high-frequency shift resulting from the formation of a unidentate coordination on AuNPs, whereas this vibration exhibits a low-frequency shift as a result of ionic bond formation on AgNPs, as predicted from the MO calculations of the corresponding metal complex salts. The enhancement in the IR signals when their vibration direction was perpendicular to the nanoparticle surface revealed the influence of localized surface plasmons excited on the metal nanoparticles.