Ultrasensitive microwave spectroscopy of paramagnetic impurities in sapphire crystals at millikelvin temperatures

Progress in the emerging field of engineered quantum systems requires the development of devices that can act as quantum memories. The realization of such devices by doping solid-state cavities with paramagnetic ions imposes a tradeoff between ion concentration and cavity coherence time. Here, we investigate an alternative approach involving interactions between photons and naturally occurring impurity ions in ultrapure crystalline microwave cavities exhibiting exceptionally high quality factors. We implement a hybrid whispering gallery/electron spin resonance method to perform rigorous spectroscopy of an undoped single-crystal sapphire resonator over the frequency range 8--19 GHz, and at external applied DC magnetic fields up to 0.9 T. Measurements of high-purity sapphire cooled close to 100 mK reveal the presence of Fe³⁺, Cr³⁺, and V²⁺ impurities. A host of electron transitions are measured and identified, including the two-photon classically forbidden quadrupole transition (Δmₛ=2) for Fe³⁺, as well as hyperfine transitions of V²⁺.