UV-enhanced environmental charge compensation in near ambient pressure XPS

In this work, we discuss the possibility of improving charge neutralization in near ambient pressure X-ray photoelectron spectroscopy by co-irradiating the sample with He I photons of 21.2 eV. This UV-enhanced neutralization of charges is a variation of the so-called environmental charge compensation, which uses the electrons produced by the photoionization of the ambient gas to neutralize the positive charges built at the sample surface. Adding an additional ionization source generates more charges at the sample but also larger amounts of electrons available for neutralization. The final surface charge equilibrium depends on different aspects of the experiment, such as the sample composition and geometry, the total ionization cross sections of the gas compared to the surface materials, the gas used, the luminosity and spot size of the sources used for photoionization, and the energy of the electrons present in the gas phase. Here we illustrate the efficiency of the UV-enhanced neutralization using three different dielectric samples with different geometries (a porous SiO₂ monolith with an irregular surface, a flat mica sample, and a thin SiO₂ film deposited onto a Si substrate), different X-ray spot sizes, and two different gases (N₂ and Ar). The effect of biasing on the efficiency of the sample surface to attract electrons produced in the gas phase is also discussed.