Colloidal Synthesis and Optical Properties of Perovskite-Inspired Cesium Zirconium Halide Nanocrystals

Optoelectronic devices based on lead halide perovskites are processed in facile ways, yet are remarkably efficient. There are extensive research efforts investigating lead-free perovskite and perovskite-related compounds, yet there are challenges to synthesize these materials in forms that can be directly integrated into thin film devices rather than as bulk powders. Here, we report on the colloidal synthesis and characterization of lead-free, antifluorite Cs₂ZrX₆ (X = Cl, Br) nanocrystals that are readily processed into thin films. We use transmission electron microscopy and powder X-ray diffraction measurements to determine their size and structural properties, and solid-state nuclear magnetic resonance measurements reveal the presence of oleate ligand, together with a disordered distribution of Cs surface sites. Density functional theory calculations reveal the band structure and fundamental band gaps of 5.06 and 3.91 eV for Cs₂ZrCl₆ and Cs₂ZrBr₆, respectively, consistent with experimental values. Finally, we demonstrate that the Cs₂ZrCl₆ and Cs₂ZrBr₆ nanocrystal thin films exhibit tunable, broad white photoluminescence with quantum yields of 45% for the latter, with respective peaks in the blue and green spectral regions and mixed systems exhibiting properties between them. Our work represents a critical step toward the application of lead-free Cs₂ZrX₆ nanocrystal thin films into next-generation light-emitting applications.