Microwave-Enhanced Chemistry at Solid-Liquid Interfaces: Synthesis of All-Inorganic CsPbX3 Nanocrystals and Unveiling the Anion-Induced Evolution of Structural and Optical Properties.

Abstract

We demonstrate how microwaves could enhance the chemistry at interfaces of heterogeneous reactions involved in the microwave-solvothermal (MW-ST) synthesis of all-inorganic CsPbX3 (X = Cl, Br, I) perovskite nanocrystals (PNCs) within 6 min, unlike a conventional hot-injection method that requires 3 h. The enhanced MW-ST reaction rate was quantitatively analyzed by the Eyring equation, and it has been observed that the decreased activation free energy (ΔG⧧) and increased activation entropy (ΔS⧧) are caused by changes in the relative energies of reactants at their solid-liquid interfaces, leading to the formation of "hot spots", where microwave energy absorption is at its maximum. This rapid and homogeneous microwave heating could facilitate the self-assembly of uniformly distributed CsPbX3 nanocubes with precise control over the stoichiometric ratio, as confirmed by high-resolution transmission electron microscopy and energy-dispersive X-ray analyses. X-ray diffraction and Raman results indicate that lattice contraction and expansion in CsPbBr3-yXy have occurred because of an increase in the metal-halide bond length upon moving down the groups Cl → Br → I, as further ascertained by the Rietveld refinement studies. These anion-induced structural variations accordingly affected the electronic properties of MW-ST-synthesized CsPbX3 PNCs, which is apparent from the shifts in their conduction-band (CB) and valence-band (VB) positions. Consequently, the optical properties were also altered, resulting in a color-tuned emission from blue to red, with excellent photoluminescence quantum yields (up to 92%) and narrow emission line widths, as is evident from UV-vis and photoluminescence spectroscopy. The MW-ST-synthesized CsPbX3 PNCs were used as color-conversion layers for the fabrication of light-emitting diodes (LEDs) with commercial 456 nm UV-LED chips.