Detailed insights into the formation pathway of CdS and ZnS in solution: a multi-modal in situ characterisation approach†
The high stability, high availability, and wide size-dependent bandgap energy of sulphidic semiconductor nanoparticles (NPs) render them promising for applications in optoelectronic devices and solar cells. However, the tunability of their optical properties depends on the strict control of their crystal structure and crystallisation process. Herein, we studied the structural evolution during the formation of CdS and ZnS in solution by combining in situ luminescence spectroscopy, synchrotron-based X-ray diffraction (XRD) and pair distribution function (PDF) analyses for the first time. The influence of precursor type, concentration, temperature and heating program on the product formation and on the bandgap or trap emission were investigated in detail. In summary, for CdS, single-source precursor (SSP) polyol strategies using the dichlorobis(thiourea)cadmium(II) complex and double-source precursor approaches combining Cd(CH3COO)2·2H2O and thiourea led to the straightforward product at 100 °C, while the catena((m2-acetato-O,O′)-(acetate-O,O′)-(m2-thiourea)-cadmium) complex was formed at 25 and 80 °C. For ZnS, the reaction between Zn(CH3COO)2·2H2O and thiourea at 100 °C led to the product formation after the crystallisation and dissolution of an unknown intermediate. At 180 °C, besides an unknown phase, the acetato-bis(thiourea)-zinc(II) complex was also detected as a reaction intermediate. The formation of such reaction intermediates, which generally remain undetected applying only ex situ characterisation approaches, reinforce the importance of in situ analysis for promoting the advance on the production of tailored semiconductor materials.