Secondary ions, detection

Effects of Primary Beam Species Prediction of FABMS source sputtering yields can be generally supported by available data on secondary ion emission coefficients. For secondary ions detected at zero angle with respect to the surface normal, the secondary ion emission yield generally increases with the mass of the primary ions because of the... 

Simultaneous secondary ion detection is limited to the number of detectors placed in the transmission plane of the magnetic sector. Quasi-simultaneous detection of two or more ions may be achieved by programming electrostatic deflection plates to switch ions rapidly within a fairly narrow mass range (see Fig. 4.6). Simultaneous or quasisimultaneous collection of ions is especially helpful for measurement of isotopic ratios. 

The cells were coated with a thin layer of Au/Pd to enhance their electrical conductivity for SIMS analysis. In the positive secondary ion detection mode, images of masses 12, 23, 39, 40, and 195 provided the subcellular distribution of Na, Ca, and secondary ions, respectively. 

The primary advantage associated with PCs lies in their robusmess and the fact that these detectors have essentially no upper counting limit (the limit typically stipulated is a result of the associated electronics). As a result, these are the only detectors used for both primary and secondary ion detection in SIMS instruments. As amplification is not carried out within these units, a current of > 1000 ions per second must strike the detector if a signal is to be recorded. Note 626 cps equates to lxlO A and the lower detection limit of the most sensitive electrometers is around a factor of two times this value. The practical lower limit of these detectors is, however, signal to noise dependent, hence, will also be a function of, among other things, the dwell time applied. 

Ar, Cs, Ga or other elements with energies between 0.5 and 10 keV), energy is deposited in the surface region of the sample by a collisional cascade. Some of the energy will return to the surface and stimulate the ejection of atoms, ions and multi-atomic clusters (figure Bl.25.8). In SIMS, secondary ions (positive or negative) are detected directly with a mass spectrometer. 

Lasers are used to deliver a focused, high density of monochromatic radiation to a sample target, which is vaporized and ionized. The ions are detected in the usual way by any suitable mass spectrometer to produce a mass spectrum. The yield of ions is often increased by using a secondary ion source or a matrix. 

Mass spectral analysis of quaternary ammonium compounds can be achieved by fast-atom bombardment (fab) ms (189,190). This technique rehes on bombarding a solution of the molecule, usually in glycerol [56-81-5] or y -nitroben2yl alcohol [619-25-0], with argon and detecting the parent cation plus a proton (MH ). A more recent technique has been reported (191), in which information on the stmcture of the quaternary compounds is obtained indirectly through cluster-ion formation detected via Hquid secondary ion mass spectrometry (Isims) experiments. 

The use of separation techniques, such as gel permeation and high pressure Hquid chromatography interfaced with sensitive, silicon-specific aas or ICP detectors, has been particularly advantageous for the analysis of siUcones in environmental extracts (469,483—486). Supercritical fluid chromatography coupled with various detection devices is effective for the separation of siUcone oligomers that have molecular weights less than 3000 Da. Time-of-flight secondary ion mass spectrometry (TOF-sims) is appHcable up to 10,000 Da (487). 

Environment. Detection of environmental degradation products of nerve agents directly from the surface of plant leaves using static secondary ion mass spectrometry (sims) has been demonstrated (97). Pinacolylmethylphosphonic acid (PMPA), isopropylmethylphosphonic acid (IMPA), and ethylmethylphosphonic acid (EMPA) were spiked from aqueous samples onto philodendron leaves prior to analysis by static sims. The minimum detection limits on philodendron leaves were estimated to be between 40 and 0.4 ng/mm for PMPA and IMPA and between 40 and 4 ng/mm for EMPA. Sims analyses of IMPA adsorbed on 10 different crop leaves were also performed in order to investigate general apphcabiflty of static sims for... 

The instrumentation for SSIMS can be divided into two parts (a) the primary ion source in which the primary ions are generated, transported, and focused towards the sample and (b) the mass analyzer in which sputtered secondary ions are extracted, mass separated, and detected. 

To minimize surface damage, static SIMS mass spectrometers should be as efficient as possible for detecting the total yield of secondary ions from a surface. Also, to be able to separate elemental from molecular species, and molecular species from each other, the mass resolution usually given as the mass m divided by the separable mass Am, should be very high. With this in mind, two types of mass spectrometer have been used - in early work mainly quadrupole mass filters and, more recently, time-of-flight mass spectrometers. 

The Mattauch-Herzoggeometry (Fig. 3.20) enables detection of several masses simultaneously and is, therefore, ideal for scanning instruments [3.49]. Up to five detectors are adjusted mechanically to locations in the detection plane, and thus to masses of interest. Because of this it is possible to detect, e. g., all isotopes of one element simultaneously in a certain mass range. Also fast, sensitive, and precise measurements of the distributions of different isotopes are feasible. This enables calculation of isotope ratios of small particles visible in the image. The only commercial instrument of this type (Cameca Nanosims 50) uses an ion gun of coaxial optical design, and secondary ion extraction the lateral resolution is 50 nm. 

Fig. 3.21. SIMS spectra obtained from a high-speed steei. (A) primary ions OJ no secondary ion energy iimitation eiec-tropositive eiements are sensitive many moiecuie ions are visibie. (B) same conditions but 300 Voffset was used the moiecuie ion intensities are reduced significantiy. (C) Primary ions Cs" 300 Voffset was used therefore eiectronegative eiements are detected more sen-sit iveiy.

For detection of secondary ions a laterally resolving detector is necessary. In the first step a channel plate for amplification is used secondary electrons from the output of this device are accelerated either to a fluorescent screen or to a resistive anode. If a fluorescent screen is used the image is picked up by a CCD camera and summed frame by frame by use of a computer. The principal advantage of this system is unlimited secondary ion intensities, but compared with the digital detection of the resistive anode encoder the lateral and intensity linearity is not as well-defined. 

The limitations of SIMS - some inherent in secondary ion formation, some because of the physics of ion beams, and some because of the nature of sputtering - have been mentioned in Sect. 3.1. Sputtering produces predominantly neutral atoms for most of the elements in the periodic table the typical secondary ion yield is between 10 and 10 . This leads to a serious sensitivity limitation when extremely small volumes must be probed, or when high lateral and depth resolution analyses are needed. Another problem arises because the secondary ion yield can vary by many orders of magnitude as a function of surface contamination and matrix composition this hampers quantification. Quantification can also be hampered by interferences from molecules, molecular fragments, and isotopes of other elements with the same mass as the analyte. Very high mass-resolution can reject such interferences but only at the expense of detection sensitivity. 

SIMS has superb surface sensitivity since most of the secondary ions originate within a few nanometers of the surface and since high detection efficiency enables as little as 10 " of a monolayer to be detected for most elements. Because of its very high surface sensitivity, SIMS can be used to obtain depth profiles with exceptionally high depth resolution (<5 nm). Since the beam of primary ions can be focused to a small spot, SIMS can be used to characterize the surface of a sample with lateral resolution that is on the order of micrometers. Elements with low atomic numbers, such as H and He, can be detected, isotope analysis can be conducted, and images showing the distribution of chemical species across... 

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