Effect of PbSO₄-Oleate Coverage on Cesium Lead Halide Perovskite Quantum Dots to Control Halide Exchange Kinetics

Abstract

The selective control of halide ion exchange in metal halide perovskite quantum dots (PQDs) plays an important role in determining their band gap and composition. In this study, CsPbX3 (X = Cl−, Br−, and I−) PQDs were self-assembled with PbSO4-oleate to form a peapod-like morphology to selectively control halide ion exchange. Considering the distinct absorption and bright luminescence characteristics of these PQDs, in situ UV-Vis. absorption and fluorescence spectroscopies were employed to monitor the time-dependent band gap and compositional changes of the PQDs. We determined that the halide exchange in the capped PQDs is hindered—unlike the rapid anion exchange in noncapped PQDs—by a reduction in the halide exchange kinetic rate depending on the extent of coverage of the PQDs. Thus, we tracked the halide ion exchange kinetics between CsPbBr3 and CsPbI3 PQDs, depending on the coverage, using in situ UV-Vis. absorption/photoluminescence spectroscopy. We regulated the halide exchange reaction rate by varying the capping reaction temperature of the PQDs. The capping hindered the halide exchange kinetics and increased the activation energy. These results will enable the development of white LEDs, photovoltaic cells, and photocatalysts with alternative structural designs based on the divalent composition of CsPbX3 PQDs.

Keywords

• perovskite
• perovskite PQDs
• in situ spectroscopy
• halide exchange