Real-time monitoring of phase transitions in π-SnS nanoparticles.

While the new cubic phase of tin monosulfide, π-SnS, shows potential for various applications, not much work was focused on the phase transitions, thermal stability, and thermal properties of π-SnS. In this work, we addressed these issues using temperature-resolved in situ X-ray diffraction combined with thermo-gravimetric differential scanning calorimetry and thermo-gravimetric infrared spectroscopy. The cubic π-SnS phase nanoparticles capped with polyvinylpyrrolidone were proven stable for 12 hours at 400 °C, pointing out the possible utilization of this new cubic phase at elevated temperatures. At the same time, heating above this temperature resulted in a phase transition to the high-temperature orthorhombic ß-SnS phase. Subsequent cooling to room temperature led to an additional phase transition to the stable orthorhombic α-SnS phase. Interestingly, heating-induced phase transformation of π-SnS nanoparticles always resulted in ß-SnS, even at temperatures below the α- to ß-SnS equilibrium transition temperature. It was shown that surfactant decomposition and evaporation triggers the phase transition. Several thermal parameters were calculated, including the phase transition activation energy and the thermal expansion of the unit cell parameter of π-SnS.

Dynamics of the nanocrystal structure and composition in growth solutions monitored by in situ lab-scale X-ray diffraction.

In situ characterization of nanoparticle (NP) growth has become the state-of-the-art approach for studying their growth mechanisms; there is broad consensus on the reliability and precision of in situ characterization techniques compared to more traditional ex situ ones. Nonetheless, most of the currently available methods require the use of sophisticated setups such as synchrotron-based X-ray sources or an environmental liquid transmission electron microscopy (TEM) cell, which are expensive and not readily accessible. Herein, we suggest a new approach to study NP growth mechanisms: using a commercially available heating chamber for time-resolved X-ray diffraction (TR-XRD) measurements of NP growth in solution. We demonstrate how this lab-scale in situ XRD can be used to study NP growth mechanisms when complemented by standard ex situ techniques such as TEM and UV-vis spectroscopy. TR-XRD reveals the crystallographic phase and real-time evolution of NP size, shape, and composition. A detailed analysis allows determining the growth mechanism and measuring the alloying kinetics of multinary nanocrystals, demonstrated herein for a colloidal CdxZn1-xS system. This approach proves itself as a promising strategy for NP growth research and could be expanded to related fields that study dynamic changes as the formation and evolution of crystalline materials in solutions.