Organic−inorganic hybrid perovskite nanoparticles (OIHP NPs) have attracted scientific attention owing to their efficient photoluminescence with optical tunability, which is highly advantageous for optoelectronic applications. However, the limited long-term stability of OIHP NPs has significantly hindered their practical application. Despite several synthetic strategies and encapsulation methods to stabilize OIHP NPs, complicated multi-step procedures are often required. In this study, we introduce an in situ ligand engineering method for stabilizing and controlling the optical properties of OIHP NPs using tetraalkylammonium (TAA) halides with various molecular structures at different concentrations. Our one-pot ligand engineering substantially enhanced the stability of the OIHP NPs without post-synthetic processes. Moreover, in certain cases, approximately 90% of the initial photoluminescence (PL) intensity was preserved even after a month under ambient conditions (room temperature, 20−50% relative humidity). To determine the role of ligand engineering in stabilizing the OIHP NPs, the surface binding properties of the TAA ligands were thoroughly analyzed using Raman spectroscopy. Specifically, the permanent positive charge of the TAA cations and consequent effective electrostatic interactions with the surfaces of the OIHP NPs are pivotal for preserving the initial PL intensity. Our investigation is beneficial for developing OIHP nanomaterials with improved stability and controlled photoluminescence for various optoelectronic applications, such as light-emitting devices, photosensitizers, photodetectors, photocatalysis, and solar cells.
AgCl nanomaterials recently attracted scientific interest as useful structural building blocks for producing metallic nanomaterials owing to their facile synthesis, controllable morphology, and ease of removal under ambient conditions. However, their complex chemical reactivity has primarily been studied in association with water solubility or reducibility. This study investigates the pivotal role of precursor ligands in the photochemical synthesis of metallic cubic mesh nanostructures on the AgCl templates. The side reactions between AgCl and Au precursors with different ligands are thoroughly discussed along with their influence on the byproduct formation and the structural stability of the resulting metallic nanostructures. Importantly, we introduce for the first time the partial destruction of AgCl and the formation of undesirable byproducts caused by the presence of highly oxidizing and Cl-containing AuCl 4 − . In addition, a synthetic route for producing highly pure and stable metallic nanostructures using a halogen-free Au precursor or Pt-priming is proposed. Further, the photothermal properties of these replicated metallic nanostructures are presented as a new evaluation tool for analyzing their overall structural stability. Discovering the role of precursor ligands in the reaction system will prove useful as a guide for the synthesis of functional noble metal nanomaterials using silver halide templates.
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