Secondary-ion mass spectrometry (SIMS) is a technique used to analyze the composition of solid surfaces and thin films by sputtering the surface of the specimen with a focused primary ion beam and collecting and analyzing ejected secondary ions. The mass/charge ratios of these secondary ions are measured with a mass spectrometer to determine the elemental, isotopic, or molecular composition of the surface to a depth of 1 to 2 nm. Due to the large variation in ionization probabilities among elements sputtered from different materials, comparison against well-calibrated standards is necessary to achieve accurate quantitative results. SIMS is the most sensitive elemental surface analysis technique, with elemental detection limits ranging from parts per million to parts per billion.
History In 1910, British physicist J. J. Thomson observed a release of positive ions and neutral atoms from a solid surface induced by ion bombardment. Improved vacuum pump technology in the 1940s enabled the first prototype experiments on SIMS by Herzog and Viehböck in 1949, at the University of Vienna, Austria. In the mid-1950s, Honig constructed a SIMS instrument at RCA Laboratories in Princeton, New Jersey. Then in the early 1960s, two SIMS instruments were developed independently. One was an American project, led by Liebel and Herzog, which was sponsored by NASA at GCA Corp, Massachusetts, for analyzing Moon rocks, and the other was at the University of Paris-Sud in Orsay by R. Castaing for the PhD thesis of G. Slodzian. These first instruments were based on a magnetic double-focusing sector field mass spectrometer and used argon for the primary-beam ions. In the 1970s, K. Wittmaack and C. Magee developed SIMS instruments equipped with quadrupole mass analyzers. Around the same time, A. Benninghoven introduced the method of static SIMS, where the primary ion current density is so small that only a negligible fraction (typically 1%) of the first surface layer is necessary for surface analysis. Instruments of this type use pulsed primary ion sources and time-of-flight mass spectrometers and were developed by Benninghoven, Niehuis, and Steffens at the University of Münster, Germany and also by Charles Evans & Associates. The Castaing and Slodzian design was developed in the 1960s by the French company CAMECA S.A.S. and used in materials science and surface science. Recent developments are focusing on novel primary ion species like C60+, ionized clusters of gold and bismuth, or large gas-cluster ion beams (e.g., Ar700+). The sensitive high-resolution ion microprobe (SHRIMP) is a large-diameter, double-focusing SIMS sector instrument based on the Liebl and Herzog design, and produced by Australian Scientific Instruments in Canberra, Australia.
Instrumentation
A secondary-ion mass spectrometer consists of (1) a primary ion gun generating the primary ion beam, (2) a primary ion column, accelerating and focusing the beam onto the sample (and in some devices an opportunity to separate the primary ion species by Wien filter or to pulse the beam), (3) high-vacuum sample chamber holding the sample and the secondary-ion extraction lens, (4) a mass analyzer separating the ions according to their mass-to-charge ratios, and (5) a detector.
Vacuum SIMS requires a high vacuum with pressures below 10−4 Pa (roughly 10−6 mbar or torr). This is needed to ensure that secondary ions do not collide with background gases on their way to the detector (i.e., the mean free path of gas molecules within the detector must be large compared to the size of the instrument), and it also limits surface contamination by adsorption of background gas particles during measurement.
Primary ion source Three types of ion guns are employed. In one, ions of gaseous elements are usually generated with duoplasmatrons or by electron ionization, for instance noble gases (40Ar+, Xe+), oxygen (16O−, 16O2+, 16O2−), or even ionized molecules such as SF5+ (generated from SF6) or C60+ (fullerene). This type of ion gun is easy to operate and generates roughly focused but high-current ion beams. A second source type, the surface ionization source, generates 133Cs+ primary ions. Caesium atoms vaporize through a porous tungsten plug and are ionized during evaporation. Depending on the gun design, fine focus or high current can be obtained. A third source type, the liquid metal ion gun (LMIG), operates with metals or metallic alloys, which are liquid at room temperature or slightly above. The liquid metal covers a tungsten tip and emits ions under influence of an intense electric field. While a gallium source is able to operate with elemental gallium, recently developed sources for gold, indium, and bismuth use alloys which lower their melting points. The LMIG provides a tightly focused ion beam (<50 nm) with moderate intensity and is additionally able to generate short pulsed ion beams. It is therefore commonly used in static SIMS devices. The choice of the ion species and ion gun respectively depends on the required current (pulsed or continuous), the required beam dimensions of the primary ion beam, and on the sample which is to be analyzed. Oxygen primary ions are often used to investigate electropositive elements due to an increase of the generation probability of positive secondary ions, while caesium primary ions often are used when electronegative elements are being investigated. For short pulsed ion beams in static SIMS, LMIGs are most often deployed for analysis; they can be combined with either an oxygen gun or a caesium gun during elemental depth profiling, or with a C60+ or gas-cluster ion source during molecular depth profiling.
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