Single Photon Ionization (SPI) via Incoherent VUV-Excimer Light : Robust and Compact Time-of-Flight Mass Spectrometer for On-Line, Real-Time Process Gas Analysis.

Fast on-line detection of organic compounds from complex mixtures, such as industrial process gas streams, require selective and sensitive analytical methods. One feasible approach for this purpose is the use of mass spectrometry (MS) with a selective and soft (fragment-free) ionization technique, such as chemical ionization (CI) or photo ionization (PI). Single photon ionization (SPI) with vacuum ultraviolet (VUV) light is a particularly soft ionization technique, well-suited for detection of both aromatic and aliphatic species. Problematic, however, is the generation of the VUV fight. In general, the vacuum ultraviolet (VUV) light sources for SPI-MS are based either on lasers (e.g., 118-nm radiation generated by frequency-tripling of the third harmonic of a Nd:YAG laser) or on conventional VUV lamps, such as deuterium lamps. Although the laser-based techniques are very sophisticated and expensive, the conventional lamps have serious drawbacks regarding their optical parameters, such as low-output power, low spectral power density, and broad emission bands. In this work, a novel excimer VUV light source, in which an electron beam is used to form rare gas excimer species, is used. The excimer VUV light source produces brilliant and intense VUV light. The novel VUV light source was coupled to a compact and mobile time-of-flight mass spectrometer (TOFMS). A special interface design, including optical (VUV optics) as well as electronic measures (e.g., pulsed ion extraction) was realized. The use of the excimer VUV lamp for SPI will allow the realization of very compact, rugged, and sensitive SPI-TOFMS devices, which preferably will be adapted for process analytical application or monitoring issues (e.g., chemical warfare detection). The excimer VUV-lamp technology delivers VUV light with a good beam quality and high-output power at low costs. Furthermore, it allows changing the emitted wavelength as well as the bandwidth of the excimer VUV lamp in the 100-200-nm region by changing the gas filling. Consequently, SPI-TOFMS with an excimer light source is a fast detection technique that can be used for online monitoring, for example, in environmental studies or industrial manufacturing processes. In this paper, technology and characteristics of the new excimer light source, as well as the combination with the TOFMS, are presented. Furthermore, a first characterization of the SPI-TOFMS instrument, regarding analytical parameters such as detection limits and selectivity, is given. This includes a discussion of potential improvements that probably will be achievable within a future prototype generation. Finally, first applications of the system for on-line measurement of organic trace species in a complex gas mixture (here, motorcycle exhaust gas) are presented