Insights into Nucleation and Growth of Colloidal Quaternary Nanocrystals by Multimodal X-ray Analysis.

Copper chalcogenide nanocrystals find applications in photovoltaic inks, bio labels, and thermoelectric materials. We reveal insights in the nucleation and growth during synthesis of anisotropic Cu2ZnSnS4 nanocrystals by simultaneously performing in situ X-ray absorption spectroscopy (XAS) and small-angle X-ray scattering (SAXS). Real-time XAFS reveals that upon thiol injection into the reaction flask, a key copper thiolate intermediate species is formed within fractions of seconds, which decomposes further within a narrow temperature and time window to form copper sulfide nanocrystals. These nanocrystals convert into Cu2ZnSnS4 nanorods by sequentially incorporating Sn and Zn. Real-time SAXS and ex situ TEM of aliquots corroborate these findings. Our work demonstrates how combined in situ X-ray absorption and small-angle X-ray scattering enables the understanding of mechanistic pathways in colloidal nanocrystal formation.

Investigation into the Selenization Mechanisms of Wurtzite CZTS Nanorods.

Here, we report the first detailed investigation into the selenization mechanism of thin films of wurtzite copper zinc tin sulfide (CZTS) nanorods (NRs), giving particular emphasis to the role of the long-chain organic ligands surrounding each NR. During selenization, the NRs undergo a selenium-mediated phase change from wurtzite to kesterite, concurrent with the replacement of sulfur with selenium in the lattice and in situ grain growth, along with the recrystallization of larger copper zinc tin selenide kesterite grains on top of the existing film. By utilizing a facile ligand removal technique, we demonstrate that the formation of a large-grain overlayer is achievable without the presence of ligands. In addition, we demonstrate an elegant ligand-exchange-based method for controlling the thickness of the fine-grain layer. This report emphasizes the key role played by ligands in determining the structural evolution of CZTS nanocrystal films during selenization, necessitating the identification of optimal ligand chemistries and processing conditions for desirable grain growth.

Compound Copper Chalcogenide Nanocrystals.

This review captures the synthesis, assembly, properties, and applications of copper chalcogenide NCs, which have achieved significant research interest in the last decade due to their compositional and structural versatility. The outstanding functional properties of these materials stems from the relationship between their band structure and defect concentration, including charge carrier concentration and electronic conductivity character, which consequently affects their optoelectronic, optical, and plasmonic properties. This, combined with several metastable crystal phases and stoichiometries and the low energy of formation of defects, makes the reproducible synthesis of these materials, with tunable parameters, remarkable. Further to this, the review captures the progress of the hierarchical assembly of these NCs, which bridges the link between their discrete and collective properties. Their ubiquitous application set has cross-cut energy conversion (photovoltaics, photocatalysis, thermoelectrics), energy storage (lithium-ion batteries, hydrogen generation), emissive materials (plasmonics, LEDs, biolabelling), sensors (electrochemical, biochemical), biomedical devices (magnetic resonance imaging, X-ray computer tomography), and medical therapies (photochemothermal therapies, immunotherapy, radiotherapy, and drug delivery). The confluence of advances in the synthesis, assembly, and application of these NCs in the past decade has the potential to significantly impact society, both economically and environmentally.

Colloidal synthesis of Cu2SnSe3 tetrapod nanocrystals.

The formation of Cu2SnSe3 tetrapod nanocrystals is reported using a hot injection colloidal synthesis. The ternary copper chalcogenide nanocrystals nucleate with a cubic core with four short wurzite arms.

Assembly of CuIn(1-x)Ga(x)S2 nanorods into highly ordered 2D and 3D superstructures.

Here, we report self- and directed assembly of CuIn(1-x)Ga(x)S(2) (CIGS) nanorods into highly ordered 2D and 3D superstructures. The assembly protocol is dictated by the ligand environment and is hence chemically tunable. Thiol capped nanorods spontaneously assemble into 3D aligned nanorod clusters over a period of hours with end to end and side to side order. These clusters can be disassembled by ligand exchange with an amine and subsequently reassembled either at a substrate interface or as free floating 2D sheets by directed assembly protocols. This dimensional control of CIGS nanorod assembly, extending over device scale areas with high degrees of order, is highly attractive for applications utilizing these important quaternary photoabsorbers.

A facile spin-cast route for cation exchange of multilayer perpendicularly-aligned nanorod assemblies.

A facile spin cast route was developed to convert perpendicularly aligned nanorod assemblies of cadmium chalcogenides into their silver and copper analogues. The assemblies are rapidly cation exchanged without affecting either the individual rod dimensions or collective superlattice order extending over several multilayers.