Eliminating surface charging in X-ray photoelectron spectroscopy of insulators for reliable bonding assignments

Sample charging during X-ray photoelectron spectroscopy analyses of electrically insulating samples is a widely recognized challenge of this essential technique. If the electron loss caused by the photoelectric effect is not compensated due to specimens’ poor electrical conductivity, the positive charge building up in the surface region results in an uncontrolled shift of detected core level peaks to higher binding energy (BE). This seriously complicates chemical bonding assignment, which is based on measured peak positions, and accounts for a large spread in reported core level BE values. Here, we show that peaks from several industry-relevant oxides, serving as model insulators, typically displaced by several eV due to charging, shift back to positions characteristic of electrically-neutral samples following ex-situ capping with a few nm thick metallic layer with low affinity to oxygen. The effect is present only if the capping layers contain sufficiently large non-oxidized volume that provides long-range conduction paths to grounded Cu clamps, while being thin enough to allow for recording high quality spectra from the underlying insulators. The versatility of the charging elimination is demonstrated for different oxides/cap combinations, air exposure times, and sample types (including thin film and bulk specimens).