Tabletop extreme ultraviolet time-of-flight spectrometry for trace analysis of high ionization energy samples

Species with ionization energies beyond what is accessible using state-of-the-art lab sources are affected by poor detection limits in ordinary mass spectrometry setups, whose throughput is also often limited. Extreme ultraviolet (XUV) photoionization mass spectrometry, in combination with linear time-of-flight (TOF), is necessary for the sensitive detection of high ionization energy compounds at trace level. XUV photoionization is available at beamlines, although with limited access. A tabletop setup may fill such a gap.

A self-developed tabletop system, based on a plasma discharge with extreme ultraviolet emission (λ = 5-50 nm) coupled to a TOF mass spectrometer, was used in this study. Simultaneous validation measurements with a reference electron ionization quadrupole mass filter were carried out. An in-house developed hollow toroidal coil (HTC) induction detector was used for concomitant photoelectron detection.

Straightforward XUV mass spectra without fragmentation, thanks to the single-photon ionization, were acquired. The measurements with the reference quadrupole were in agreement with the spectra acquired by XUV-TOF. The resolution obtained for N₂ was at least factor of 2 higher than that measured with the reference quadrupole. Initial energy distributions of photoelectrons were retrieved by cross-correlation that gave access to the photoionization distribution.

The system allows XUV single-photon ionization of elements and molecules with IE >10 eV that are of fundamental interest e.g. for water splitting and catalysis research. The demonstrated performance is now suitable for a prototype platform.