194 nm microplasma lamps driven by excitation transfer: optical sources for the ¹⁹⁹Hg ion atomic clock and photochemistry

Abstract A series of miniature, microcavity plasma lamps emitting predominantly at 194 nm has been successfully developed and tested as the optical pump for the microwave 199Hg-ion atomic clock (40.507 GHz), replacing low pressure, RF-powered Ar/Hg discharges. Intense fluorescence on the 6p 2P1/2 → 6s 2S1/2 transition of the singly-charged 202Hg ion at 194.23 nm has been generated in arrays of cylindrical microplasmas through electron-impact excitation of He, followed by three-body formation of He2(a 3 Σ u + ) and Penning ionization of Hg. Emission spectroscopy and kinetic modeling of He/Hg vapor plasmas demonstrate that the population of the Hg+(62P1/2) radiating state (16.82 eV), produced by direct or two-step electron impact processes, is < 1% of that generated by excitation transfer to Hg by H e 2 * . Flat, fused silica lamps having emitting areas as small as 4 mm2 and containing several mg of 202Hg and 50–800 Torr of He have been fabricated and serve as optical drivers for the Hg+ atomic clock cycle. Based on small arrays of 500 μm–1 mm diameter microcavities, these lamps produce peak and average intensities at 194 nm greater than those associated with the Hg resonance transition at ∼ 254 nm, despite the factor of $?> > 3 difference between the energies of the 6p 3P1 and 6p 2P1/2 states of neutral Hg and Hg+, respectively. These lamps are unique in the sense that the desired radiating species is an excited ion and the background He gas pressure can reach 1 atm, both of which contribute to a dense glow plasma placing severe demands on E/N, power conditioning, and materials selection. Nevertheless, with proper attention given to design, vacuum processing, and preparation of the lamps, lifetimes above 1500 h have been realized to date. When these lamps drive Jet Propulsion Laboratory Hg+ clocks, the stability floor has been measured to be ∼ 10 −14. The implications of this lamp for gas-phase and solid-state photochemistry are also discussed.