Temperature-Dependent Selection of Reaction Pathways, Reactive Species, and Products during Postsynthetic Selenization of Copper Sulfide Nanoparticles.

Rational design of elaborate, multicomponent nanomaterials is important for the development of many technologies such as optoelectronic devices, photocatalysts, and ion batteries. Combination of metal chalcogenides with different anions, such as in CdS/CdSe structures, is particularly effective for creating heterojunctions with valence band offsets. Seeded growth, often coupled with cation exchange, is commonly used to create various core/shell, dot-in-rod, or multipod geometries. To augment this library of multichalcogenide structures with new geometries, we have developed a method for postsynthetic transformation of copper sulfide nanorods into several different classes of nanoheterostructures containing both copper sulfide and copper selenide. Two distinct temperature-dependent pathways allow us to select from several outcomes-rectangular, faceted Cu2-xS/Cu2-xSe core/shell structures, nanorhombuses with a Cu2-xS core, and triangular deposits of Cu2-xSe or Cu2-x(S,Se) solid solutions. These different outcomes arise due to the evolution of the molecular components in solution. At lower temperatures, slow Cu2-xS dissolution leads to concerted morphology change and Cu2-xSe deposition, while Se-anion exchange dominates at higher temperatures. We present detailed characterization of these Cu2-xS-Cu2-xSe nanoheterostructures by transmission electron microscopy (TEM), powder X-ray diffraction, energy-dispersive X-ray spectroscopy, and scanning TEM-energy-dispersive spectroscopy. Furthermore, we correlate the selenium species present in solution with the roles they play in the temperature dependence of nanoheterostructure formation by comparing the outcomes of the established reaction conditions to use of didecyl diselenide as a transformation precursor.

Thermally Induced Domain Migration and Interfacial Restructuring in Cation Exchanged ZnS-Cu1.8S Heterostructured Nanorods.

Partial cation exchange reactions can be used to rationally design and synthesize heterostructured nanoparticles that are useful targets for applications in photocatalysis, nanophotonics, thermoelectrics, and medicine. Such reactions introduce intraparticle frameworks that define the spatial arrangements of different materials within a heterostructured nanoparticle, as well as the orientations and locations of their interfaces. Here, we show that upon heating to temperatures relevant to their synthesis and applications, the ZnS regions and Cu1.8S/ZnS interfaces of heterostructured ZnS-Cu1.8S nanorods migrate and restructure. We first use partial cation exchange reactions to synthesize a library of seven distinct samples containing various patches, bands, and tips of ZnS embedded within Cu1.8S nanorods. Upon annealing in solution or in air, ex situ TEM analysis shows evidence that the ZnS domains migrate in different ways, depending upon their sizes and locations. Using differential scanning calorimetry, we correlate the threshold temperature for ZnS migration to the superionic transition temperature of Cu1.8S, which facilitates rapid diffusion throughout the nanorods. We then use in situ thermal TEM to study the evolution of individual ZnS-Cu1.8S nanorods upon heating. We find that ZnS domain migration occurs through a ripening process that minimizes small patches with higher-energy interfaces in favor of larger bands and tips having lower-energy interfaces, as well as through restructuring of higher-energy Cu1.8S/ZnS interfaces. Notably, Cu1.8S nanorods containing multiple patches of ZnS thermally transform into ZnS-Cu1.8S heterostructured nanorods having ZnS tips and/or central bands, which provides mechanistic insights into how these commonly observed products form during synthesis.