Structures and Properties of High-Concentration Doped Th:CaF₂ Single Crystals for Solid-State Nuclear Clock Materials

Thorium-doped vacuum ultraviolet (VUV) transparent crystals is a promising candidate for establishing a solid-state nuclear clock. Here, we report the research results on high-concentration doping of ²³²Th:CaF₂ single crystals. The structures, defects, and VUV transmittance performances of highly doped Th:CaF₂ crystals are investigated by theoretical and experimental methods. The defect configurations formed by Th and the charge compensation mechanism (Ca vacancy or interstitial F atoms) located at its first nearest neighbor position are mainly considered and studied. The preferred defect configuration is identified according to the doping concentration dependence of structural changes caused by the defects and the formation energies of the defects at different Ca or F chemical potentials. The cultivated Th:CaF₂ crystals maintain considerable high VUV transmittance levels while accommodating high doping concentrations, showcasing an exceptional comprehensive performance. The transmittances of 1-mm-thick samples with doping concentrations of 1.91 × 10²⁰ and 2.76 × 10²⁰ cm^-3 can reach ∼62% and 53% at 150 nm, respectively. The VUV transmittance exhibits a weak negative doping concentration dependence. The system factors that may cause distortion and additional deterioration of the VUV transmittance are discussed. Balancing and controlling the impacts of various factors will be of great significance for fully exploiting the advantages of Th:CaF₂ and other Th-doped crystals for a solid-state nuclear optical clock.