Size, shape and phase modulation of plasmonic copper sulphide nanocrystals
Mariangela Giancaspro a d, Teresa Sibillano b, Francesca Panzarea a, Cinzia Giannini b, Silvia Schmitzer a, Fabio Vischio a, Nicoletta Depalo c, M. Lucia Curri a c d, Marinella Striccoli c, Elisabetta Fanizza a c
a Dipartimento di Chimica, Università degli Studi di Bari,, Via Orabona 4, 70126 Bari, Italy
b CNR-Istituto di Cristallografia (CNR-IC, Bari, Italy, Via Amendola, 122/O, Bari, Italy
c CNR-Istituto per i Processi chimico Fisici (CNR-IPCF), SS Bari, Via Orabona 4, 70126 Bari, Italy
d National Interuniversity Consortium of Materials Science and Technology (INSTM), Bari, Italy
Proceedings of Internet Conference for Quantum Dots (iCQD)
Online, Spain, 2020 July 14th - 17th
Organizers: Quinten Akkerman, Raffaella Buonsanti, Zeger Hens and Maksym Kovalenko
Poster, Elisabetta Fanizza, 090
Publication date: 3rd July 2020
ePoster: 

Self-doped copper sulphide Cu2-xS nanocrystals (NCs) are semiconductor near infrared absorbing (NIR) plasmonic materials explored in a wide variety of applications from catalysis, energy conversion and sensing to biomedicine. Due to their stoichiometry-, size- and shape- dependent properties, the NCs design is crucial to yield high performances devices. Indeed hexagonal-faceted NC structure has been used as solar cell electrodes, Cu1.94S NCs as cathodes in all-vanadium redox flow batteries, Cu1.8S nanospheres as photoactive agents in photodynamic (PDT) and/or photohermal (PTT) therapy, CuS nanotubes as electrochemical sensors and hollow CuS as chemical storage and drug delivery vectors. Among the synthetic approach, colloidal synthesis by hot-injection offers a toolbox of macroscopic thermodynamic parameters that together with microscopic chemical considerations such as precursor reactivity, ligand binding strengths, valence of metal precursors, can provide a fine control of the NC features. However, within the wide range of Cu2-xS  NC preparatory approaches available, there is still the lack of a priori rationalization of the impact of the synthetic procedure in defining the characteristics of NC. The aim of this work is to fill this gap. By means of systematic investigation of Cu2-xS NCs, prepared under different experimental conditions, we want to outline how the combination of precursors/ligands, their molar ratios shape the final geometry, size, composition and thus crystalline structure and optical properties. Hard-Soft-Acid-Base theory allows to qualitatively predicting the intermediate complex/monomer stability and ligands binding to NC surface, for the kinetic and thermodynamic control of nucleation and growth, with electron affinity of ligand coordinating groups also affecting the plasmonic properties. This study wants to offer through an in-depth and generalized comprehension of the synthetic mechanism, practical guideline for controlling Cu2-xS NC size, shape, phase and plasmonic properties for their future applications.

The authors want to thank the National Interuniversity Consortium of Materials Science and Technology (INSTM), for partial financial support.

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