Surface Ionization Methods

The photodetachment threshold values for Ga, As, and Pb (0.30(15), 0.81(3), and 1.10(5) eV, respectively) were determined by an older photodetachment technique [30]. The PES values for Ga, 0.43(3), and As, 0.814(8), are more precise, but are supported by the PD values [31, 32]. The PES value for Pb, 0.364(8), is significantly lower than the PD value, 1.10(5) eV. The photodetachment values for the majority of the other main group elements have also been confirmed by photoelectron spectroscopy. The values for the halogens have been determined by most methods photodetachment thresholds, photoabsorption, ion pair photodissociation, relative and absolute surface ionization methods, and the Born Haber cycle. Values for H, Li, C, F, Cl, Cu, Ge, Br, Nb, Ag, Sn, I, W, Re, Au, and Pb have also been determined by relative and absolute surface ionization methods, as shown in Table 8.2. 

Rasulev, U.K. Khasanov, U. Pahtcin, V.V., Surface-ionization methods and devices of indication and identification of nitrogen-containing base molecules, J. Chromatogr. A 2000, 896, 3-18. 

Atmospheric pressure ionization (API). The need to analyze polar componnds and the necessity to interface LC with MS led to the development of techniqnes where the ionization occurs at atmospheric pressure outside the vacuum chamber, and the resulting ions are transferred directly into the mass analyzer. Electrospray ionization (ESI) is the most successful of the API methods because of the range of molecular masses to which it can be applied, from small molecules to proteins. Other API methods include atmospheric pressure chemical ionization (APCI) and atmospheric pressure photo-ionization (APPI), and also the recently developed surface ionization methods such as desorption electrospray ionization (DESI) and direct analysis in real time (DART) (see below and Sections 2.2.2 and 2.2.3). 

Because the vast majority of samples are complex mixtures, they generally require the separation of their components, by GC or LC, prior to their introduction into the ion source. GC is usually carried out on fused silica capillary columns. LC is available in two formats in conventional LC the flow rates are O.l-l.O ml/min, while nano-LC operates at sub pl/min flow rates. Capillary electrophoresis (CE) can be interfaced to mass spectrometers (similarly to LC). Thin-layer chromatography (TLC) is compatible with the newer surface ionization methods. 

DART has been used to vaporize and ionize a large variety of analytes, e.g., drugs, explosive residues, plant metabolites, peptides, and oligosaccharides, from a variety of surfaces, including glass, paper, fruits, fabrics, medicinal tablets, and thin-layer chromatography plates. Limitations of DART include that it is useful only for small molecule analysis and cannot be combined with chromatography because it is a surface ionization method. 

The term surface ionization is frequently used to describe the process in which ionization takes place within some critical distance from the surface. A number of surface-dependent ionization methods, such as field desorption, fast atom bombardment, and laser desorption, are described as surface ionization methods. Another use of this term is more restricted surface ionization (SI) is defined as the ionization process, which can be interpreted by use of the Saha-Langmuir equation. 

The precision of the atomic beam magnetic resonance method naturally led to the proposal that it could be used as the basis of an atomic clock. Of the many available elements, cesium was chosen because it combines a hyperfine transition of very high frequency with simplicity of experimental details an atomic beam can be obtained from a cesium oven at only 200°C, the high atomic mass gives a relatively low thermal velocity of 2 5 x lo cm s and the beam is easily detected by the surface ionization method. 

The previous discussion demonstrates that measurement of precise isotope ratios requires a substantial amount of operator experience, particularly with samples that have not been examined previously. A choice of filament metal must be made, the preparation of the sample on the filament surface is important (particularly when activators are used), and the rate of evaporation (and therefore temperature control) may be crucial. Despite these challenges, this method of surface ionization is a useful technique for measuring precise isotope ratios for multiple isotopes. Other chapters in this book discuss practical details and applications. 

Desorption Electrospray Ionization (DESI). DESI is a novel gentle ionization method for surface analysis (Figure 2.6).[19,20] Like classical ESI, it operates at atmospheric pressure. No sample preparation is required. A solvent passes through the capillary of the electrospray source charged droplets are produced (primary ions) and they are directed to a solid sample. Their impact with the surface causes sample molecules to be ionized and... 

Offline-surface mediated approach Collect effluent from multiple LCs on surface place surface in MS interface use fast, surface-mediated ionization methods such as MALDI, DESI, etc. to sample effluents... 

Field desorption (FD) was introduced by Beckey in 1969 [76]. FD was the first soft ionization method that could generate intact ions from nonvolatile compounds, such as small peptides [77]. The principal difference between FD and FI is the sample injection. Rather than being in the gas phase as in FI, analytes in FD are placed onto the emitter and desorbed from its surface. Application of the analyte onto the emitter can be performed by just dipping the activated emitter in a solution. The emitter is then introduced into the ion source of the spectrometer. The positioning of the emitter is cmcial for a successful experiment, and so is the temperature setting. In general, FI and FD are now replaced by more efficient ionization methods, such as MALDI and ESI. For a description of FD (and FI), see Reference 78. 

There are several methods of producing gas-phase inorganic ions, the starting materials in mass spectrometric studies. The properties of the source of the ions required for study are important in the choice of ionization method. The production of bare metal ions from an involatile nonmolecular source requires a large amount of energy deposited on the surface of the material. The processes that occur after the initial ionization process may also affect the ions finally observed (e.g., clustering). At the other end of the ionization energy spectrum, gas-phase ions of a complexity similar to those observed in the condensed phases require a soft ionization process. A brief description of some of the ionization methods follows. 

The surface ionization (SI) method refers to ions thermally evolving from the surface of a hot filament. The vapor of a volatile inorganic compound may be passed over a heated filament where it decomposes and ionizes to form bare metal... 

Direct analysis of solid samples or analytes present on solid surfaces without any sample preparation has always been a topic of interest. Desorption electrospray ionization (DESI) is an atmospheric pressure desorption ionization method introduced by Cooks et al., producing ions directly from the surface to be analyzed, which are then sampled with the mass spectrometer [22, 37]. DESI is based on charged liquid droplets that are directed by a high velocity gas jet (in the order of 300 m s ) to the surface to be analyzed. Analytes are desorbed from the surface and analyzed by mass spectrometer (Eig. 1.15). 

The fast atom bombardment ionization (FAB) technique is a soft ionization method, typically requiring the use of a direct insertion probe for sample introduction in which a high energy beam of Xe atoms, Cs+ ions, or massive glycerol-NH4+ clusters sputter the sample and matrix from the probe surface (Figure 8). 

A variety of ion species, from light to heavy ions, namely, from protons to uranium ions, are utilized for the ion beam applications. Wide diversity of ion species, charge state, and beam currents is required to meet the requirements for the research of the ion beam applications. Various types of ion sources [3], using different ionization methods, such as field ionization and surface ionization, have been developed to provide optimum ion beams. An ion source... 

Different mass spectrometric techniques can be classified according to the evaporation and ionization methods applied. Evaporation of solid samples can be performed, for example, by thermal (e.g., on a hot tantalum filament or in a heated graphite furnace) or laser-induced evaporation, and by electron or ion bombardment. Electron ionizaton (El), ionization during the sputtering process with a primary ion beam, resonant or non-resonant laser ionization or thermal surface ionization... 

Production of Ions. Several methods are used (11 by bombardment with electrons from a heated filament (2 by application of a strong electrostatic field (field ionization, field desorption) Ot by reaction with an ionized reagent gas (chemical ionization) (4 by direct emission of ions from a solid sample that is deposited on a heated filament (surface ionization) (SI by vaporization from a crucible and subsequent electron bombardment (e.g.. Knudsen cell for high-lcmperalure sludies id solids and (6) by radio-frequency spark bomhardmenl of sample fur parts-per-biliion (ppb) elemental analysis of solids as encountered in metallurgical, semiconductor, ceramics, and geological studies. Ions also are produced by photoion izution and laser ionizalion. 

TYPES OF IONS leaving the surface are approximately independent of the ionization method. 

This paper focuses on special ionization methods such as secondary ion MS (SIMS) (1, 13, 24-28) and ZCf plasma desorption (PD), and on MS/MS methods for characterizing primary ions, such as surface induced dissociation (SID), laser photodissociation, and neutralization of multiply charged ions. A Hadamard transform method for more efficient recording of multiple MS-II spectra is also proposed. 

The ionization methods reported for IMS included MALDI [41,76-80], Secondary Ion Mass Spectrometry (SIMS) [19, 81-86], Matrix-enhanced (ME)-SIMS [87, 88], Desorption Electrospray Ionization (DESI) [89-99], Nanostructure Initiator Mass Spectrometry (NIMS) [100-102], Atmospheric Pressure Infrared MALDI Mass Spectrometry (AP-IR-MALDI-MS) [103], Laser Ablation-inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) [104-106], Laser Desorption Postionization (LDPI) [107], Laser Ablation Electrospray Ionization Mass Spectrometry (LAESI) [108, 109], and Surface-assisted Laser Desorption/ioniza-tion Mass Spectrometry (SALDI) [110-112], Another method was called probe electrospray ionization (PESI) that was used for both liquid solution and the direct sampling on wet samples. 

Other early attempts at quantification from first principles included use of the Dobretsov equation for surface ionization through nonequilibrium thermodynamics [87], use of quantum mechanical models [88,89], and others, including surface bond breaking and dissociative [90] or chemical ionization [91]. None of these led to successful quantification schemes. An evaluation of several of these methods was made by Rudat and Morrison [92]. 

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