Yb3+ speciation and energy-transfer dynamics in quantum-cutting Yb3+-doped CsPbCl3 perovskite nanocrystals and single crystals

${\mathrm{Yb}}^{3+}$-doped inorganic metal-halide perovskites $(\mathrm{Y}{\mathrm{b}}^{3+}:\mathrm{CsPb}{X}_{3}$, $X=\mathrm{Cl},\mathrm{Br})$ have recently been discovered to display highly efficient quantum cutting, in which the energy from individual blue or UV photons absorbed by the material is reemitted in the form of pairs of near-infrared photons by ${\mathrm{Yb}}^{3+}$ dopants. Experimental photoluminescence quantum yields approaching 200% have been reported. As the first quantum-cutting materials that combine such high-photoluminescence quantum yields with strong, broadband absorption in the visible, these materials offer unique opportunities for enhancing the efficiencies of solar technologies. Little is known about the fundamental origins of this quantum cutting, however. Here, we describe variable-temperature and time-resolved photoluminescence studies of ${\mathrm{Yb}}^{3+}:\mathrm{CsPb}{\mathrm{Cl}}_{3}$ in two disparate forms--colloidal nanocrystals and macroscopic single crystals. Both forms show very similar spectroscopic properties, demonstrating that quantum cutting is an intrinsic property of the ${\mathrm{Yb}}^{3+}:\mathrm{CsPb}{X}_{3}$ composition itself. Diverse ${\mathrm{Yb}}^{3+}$ speciation is observed in both forms by low-temperature photoluminescence spectroscopy, but remarkably, quantum cutting is dominated by the same specific ${\mathrm{Yb}}^{3+}$ species in both cases. Time-resolved photoluminescence measurements provide direct evidence of the previously hypothesized intermediate state in the quantum-cutting mechanism. This intermediate state mediates relaxation from the photogenerated excited state of the perovskite to the emissive excited state of ${\mathrm{Yb}}^{3+}$, and hence is of critical mechanistic importance. At room temperature, this intermediate state is populated within a few picoseconds and has a decay time of only \ensuremath{\sim}7 ns in both nanocrystalline and single-crystal ${\mathrm{Yb}}^{3+}:\mathrm{CsPb}{\mathrm{Cl}}_{3}$. The mechanistic implications of these observations are discussed. These results provide valuable information about characteristics of this unique quantum cutter that will aid its optimization and application in solar technologies.