Particle excitation, surface analysis

Energetic particles interacting can also modify the structure and/or stimulate chemical processes on a surface. Absorbed particles excite electronic and/or vibrational (phonon) states in the near-surface region. Some surface scientists investigate the fiindamental details of particle-surface interactions, while others are concerned about monitormg the changes to the surface induced by such interactions. Because of the importance of these interactions, the physics involved in both surface analysis and surface modification are discussed in this section. 

Both electron microprobe analysis and SAM use an electron beam for excitation of the specimen. The difierence between these techniques is in the detection of emitted x-rays in the microprobe technique while SAM measures emitted electrons. For both techniques, the energy of the detected particles is characteristic of the parent atom and thus identifies the atomic species present. The lateral spatial resolution in SAM is superior due to the much shorter mean free path of the emitted energy (electrons). The escape depth of auger electrons is approximately 10 A versus 1000 A in microprobe analysis. This phenomenon makes SAM a highly specific surface analysis technique. 

Of numerous interaction processes of photons, electrons and ions with solid surfaces resulting in the emission of excited particles and radiation, or in a characteristic change of the incident species properties, those which can be applied for surface analysis are listed in Table 2. The most frequently used techniques are boxed in the table. 

For trace analysis in fluids, some Raman sensors (try to) make use of the SERS effect to increase their sensitivity. While the basic sensor layout for SERS sensors is similar to non-enhanced Raman sensors, somehow the metal particles have to be added. Other than in the laboratory, where the necessary metal particles can be added as colloidal solution to the sample, for sensor applications the particles must be suitably immobilised. In most cases, this is achieved by depositing the metal particles onto the surfaces of the excitation waveguide or the interface window and covering them with a suitable protection layer. The additional layer is required as otherwise washout effects or chemical reactions between e.g. sulphur-compounds and the particles reduce the enhancement effect. Alternatively, it is also possible to disperse the metal particles in the layer material before coating and apply them in one step with the coating. Suitable protection or matrix materials for SERS substrates could be e.g. sol-gel layers or polymer coatings. In either... 

By employing a laser for the photoionization (not to be confused with laser desorption/ ionization, where a laser is irradiating a surface, see Section 2.1.21) both sensitivity and selectivity are considerably enhanced. In 1970 the first mass spectrometric analysis of laser photoionized molecular species, namely H2, was performed [54]. Two years later selective two-step photoionization was used to ionize mbidium [55]. Multiphoton ionization mass spectrometry (MPI-MS) was demonstrated in the late 1970s [56—58]. The combination of tunable lasers and MS into a multidimensional analysis tool proved to be a very useful way to investigate excitation and dissociation processes, as well as to obtain mass spectrometric data [59-62]. Because of the pulsed nature of most MPI sources TOF analyzers are preferred, but in combination with continuous wave lasers quadrupole analyzers have been utilized [63]. MPI is performed on species already in the gas phase. The analyte delivery system depends on the application and can be, for example, a GC interface, thermal evaporation from a surface, secondary neutrals from a particle impact event (see Section 2.1.18), or molecular beams that are introduced through a spray interface. There is a multitude of different source geometries. 

In principle, the neutral desorbed products of dissociation can be detected and mass analyzed, if ionized prior to their introduction into the mass spectrometer. However, such experiments are difficult due to low ejfective ionization efficiencies for desorbed neutrals. Nevertheless, a number of systems have been studied in the groups of Wurm et al. [45], Kimmel et al. [46,47], and Harries et al. [48], for example. In our laboratory, studies of neutral particle desorption have been concentrated on self-assembled monolayer targets at room temperature [27,28]. Under certain circumstances, neutrals desorbed in electronically excited metastable states of sufficient energy can be detected by their de-excitation at the surface of a large-area microchannel plate/detector assembly [49]. Separation of the BSD signal of metastables from UV luminescence can be effected by time of flight analysis [49] however, when the photon signal is small relative to the metastable yield, such discrimination is unnecessary and only the total yield of neutral particles (NP) needs to be measured. 

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