Ytterbium charge state and stabilization in the Ba(Ca)F$_2$ host by electron paramagnetic resonance and infrared photoluminescence

Abstract

Lanthanide-doped fluorides are promising materials for advanced photonic and quantum applications due to their wide bandgap, low phonon energy, and chemical stability. In this work, we present a systematic comparative study of ytterbium incorporation at low doping levels (0.05--0.2 mol\%) in BaF$_2$ and CaF$_2$ single crystals, focusing on the interplay between host lattice properties, charge-state stabilization, and defect formation mechanisms. Using a combination of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), transmittance, and infrared photoluminescence (IR PL), we explore how host lattice properties affect the stabilization of Yb$^{3+}$ and Yb$^{2+}$ ions. XRD confirmed cubic phase purity and lattice parameter stability in both hosts, while XPS revealed surface chemical composition variations associated with charge-compensating defects and trace impurities. EPR spectra indicated that BaF$_2$ favored perturbed Yb$^{3+}$ environments with increasing dopant levels, while CaF$_2$ maintained predominantly unperturbed sites, suggesting a more favorable ionic match for Yb$^{2+}$. Photothermal deflection spectroscopy (PDS) and IR PL results showed host-specific optical responses, with CaF$_2$ exhibiting crystal-field splitting and broader local field effects. These results reveal a clear decoupling between long-range structural stability and local lattice perturbations, and demonstrate that host cation identity governs the balance between Yb$^{2+}$ and Yb$^{3+}$ stabilization as well as defect-driven optical behavior. This offers valuable insights for optimizing rare-earth-doped fluoride crystals in laser, scintillator, and quantum device applications.