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Secondary ion mass spectrometry

 
Sci-Tech Encyclopedia: Secondary ion mass spectrometry (SIMS)
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An instrumental technique that measures the elemental and molecular composition of solid materials. SIMS provides methods of visualizing the two- and three-dimensional composition of solids at lateral resolutions approaching several hundred nanometers and depth resolutions of 1–10 nm. This technique employs an energetic ion beam to remove or sputter the atomic and molecular constituents from a surface in a very controlled manner. The sputtered products include atoms, molecules, and molecular fragments that are characteristic of the surface composition within each volume element sputtered by the ion beam. A small fraction of the sputtered atoms and molecules are ionized as either positive or negative ions, and a measurement by SIMS determines the mass and intensity of these secondary ions by using various mass analysis or mass spectrometry techniques. In this technique, the sputtering ions are referred to as the primary ions or the primary ion beam, while the ions produced in sputtering the solid are the secondary ions. Most elements in the periodic table produce secondary ions, and SIMS can quantitatively detect elemental concentrations in the part-per-million to part-per-billion range.

Secondary ions are formed by kinetic and chemical ionization processes in which sputtering is achieved by energy transfer from the primary ions to the solid surface. Typically, SIMS primary ions impact the surface with kinetic energies of 5–20 keV, and this energy is ultimately transferred to the sample atoms and molecules. The energy transfer initiates a collision cascade within the solid that ejects atoms and molecules at the solid surface-vacuum interface.

SIMS analyses are divided into two broad categories known as dynamic and static. In the dynamic type, the most common SIMS method, a relatively intense primary ion beam sputters the sample surface at high sputter rates, providing a very useful way to determine the in-depth concentration of different elements in a solid. The most common secondary ions detected in a dynamic secondary ion mass spectrometry analysis are elemental ions or clusters of elemental ions.

Static or molecular SIMS utilizes a very low intensity primary ion beam, and static analyses are typically completed before a single monolayer has been removed from the surface. Most static analyses are stopped before 1% of the top surface layer has been chemically damaged or eroded; under these conditions, molecular and molecular fragment ions characteristic of the chemical structure of the surface are often detected. Thus, static SIMS is best suited for near-surface analysis of molecular composition or chemical structure information, while dynamic SIMS provides the best technique for bulk and in-depth elemental analysis. See also Sputtering.

Instrument designs for SIMS require a primary ion gun or column to generate and transport the primary ion beam to the sample surface, a sample chamber with sample mounting facilities, a mass spectrometer which performs mass-to-charge separation of the different secondary ions, and an ion-detection system. The complete instrument is typically housed in an ultrahigh vacuum chamber. See also Mass spectroscope.

Dynamic SIMS has been successfully utilized in diverse applications. The analytical issues are the detection and localization of specific elements on the surface or in the bulk of the materials. The most important and common application area of dynamic SIMS is the bulk and in-depth analysis of semiconductor materials. Another important contribution of SIMS to materials science is the identification and localization of trace elements in metal grain boundaries, providing detailed insight into the chemistry of welds and alloys. Dynamic SIMS also has the unique ability to detect specific catalyst poisons on the surface and in the bulk of used or spent catalysts. In geological sciences, SIMS has been used to detect isotopic anomalies in the composition of various geological and meteoritic samples to help determine the age of the universe. Dynamic SIMS has found extensive applications to the characterization of both hard and soft biological tissue. See also Semiconductor.

Applications of static secondry ion mass spectrometry to analyses of the near-surface region of solids has become increasingly important as ever more sophisticated materials are developed. The near-surface region is generally defined as the top five monolayers (2–3 nm) of a solid. Examples of technology areas in which the chemistry of the near-surface region plays a critical role include high-performance glass coatings, liquid-crystal displays, manufacturing, semiconductor processing, biopolymer and biocompatible materials development, and polymer adhesives and coatings. See also Mass spectrometry.

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Wikipedia: Secondary ion mass spectrometry
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Secondary ion mass spectrometry

CAMECA IMS3f Magnetic SIMS Instrument
Acronym SIMS
Classification Mass spectrometry
Analytes Solid surfaces, thin films
Other Techniques
Related Fast atom bombardment
Microprobe
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Secondary ion mass spectrometry (SIMS) is a technique used in materials science and surface science 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. These secondary ions are measured with a mass spectrometer to determine the elemental, isotopic, or molecular composition of the surface. SIMS is the most sensitive surface analysis technique, being able to detect elements present in the parts per billion range.

Contents

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.[1] Improved vacuum pump technology in the 1940s enabled the first prototype experiments on SIMS by Herzog and Viehböck[2] in 1949, at the University of Vienna, Austria. 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,[3] the other at the University of Paris-Sud in Orsay by R. Castaing for the PhD thesis of G. Slodzian.[4] 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. Wittmack and C. Magee developed SIMS instruments equipped with quadrupole mass analyzers.[5][6] 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.[7] Instruments of this type use pulsed primary ion sources and time-of-flight mass spectrometers and were developed by Benninghoven, Niehus and Steffens at the University of Munster, Germany and also by Charles Evans & Associates. Recent developments are focusing on novel primary ion species like C60 or ionized clusters of gold and bismuth.[8]

Instrumentation

Typical schematic of a dynamical SIMS instrument. High energy ions are supplied by an ion gun (1 or 2) and focused on to the target sample (3), which ionizes and sputters some atoms off the surface. These secondary ions are then collected by ion lenses (5) and filtered according to atomic mass (6), then projected onto an electron multiplier (7, top), Faraday cup (7, bottom), or CCD screen (8).

Typically, a secondary ion mass spectrometer consists of:

  • primary ion gun generating the primary ion beam
  • 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)
  • high vacuum sample chamber holding the sample and the secondary ion extraction lens
  • mass analyser separating the ions according to their mass to charge ratio
  • ion detection unit.

Vacuum

SIMS requires a high vacuum with pressures below 10-4 Pascal (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 prevents surface contamination by adsorption of background gas particles during measurement.

Primary ion sources

There are three basic types of ion guns. In one, ions of gaseous elements are usually generated with Duoplasmatrons or by electron ionization, for instance noble gases (Ar+, Xe+), oxygen (O-, O2+), or even ionized molecules such as SF5+ (generated from SF6) or C60+. 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 Cs+ 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 source (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, only LMIGs are deployable, but they are often combined with either an oxygen gun or a caesium gun for sample depletion.

Mass analyzers

Dependent on the SIMS type, there are three basic analyzers available: sector, quadrupole, and time-of-flight. A sector field mass spectrometer uses a combination of an electrostatic analyzer and a magnetic analyzer to separate the secondary ions by their mass to charge ratio. A quadrupole mass analyzer separates the masses by resonant electric fields, which allow only the selected masses to pass through. The time of flight mass analyzer separates the ions in a field-free drift path according to their kinetic energy. It requires pulsed secondary ion generation using either a pulsed primary ion gun or a pulsed secondary ion extraction. It is the only analyzer type able to detect all generated secondary ions simultaneously, and is the standard analyzer for static SIMS instruments.

Detectors

A Faraday cup measures the ion current hitting a metal cup, and is sometimes used for high current secondary ion signals. With an electron multiplier an impact of a single ion starts off an electron cascade, resulting in a pulse of 108 electrons which is recorded directly. A microchannel plate detector is similar to an electron multiplier, with lower amplification factor but with the advantage of laterally-resolved detection. Usually it is combined with a fluorescent screen, and signals are recorded either with a CCD-camera or with a fluorescence detector.

Detection limits and sample degradation

Detection limits for most trace elements are between 1012 and 1016 atoms per cubic centimeter,[9] depending on the type of instrumentation used, the primary ion beam used and the analytical area, and other factors. Samples as small as individual pollen grains and microfossils can yield results by this technique.[10]

The amount of surface cratering created by the process depends on the current (pulsed or continuous) and dimensions of the primary ion beam. While only charged secondary ions emitted from the material surface through the sputtering process are used to analyze the chemical composition of the material, these represent a small fraction of the particles emitted from the sample.

Static and dynamic modes

In the field of surface analysis, it is usual to distinguish static SIMS and dynamic SIMS. Static SIMS is the process involved in surface atomic monolayer analysis, usually with a pulsed ion beam and a time of flight mass spectrometer, while dynamic SIMS is the process involved in bulk analysis, closely related to the sputtering process, using a DC primary ion beam and a magnetic sector or quadrupole mass spectrometer.

Applications

The COSIMA instrument onboard Rosetta will be the first instrument to determine the composition of cometary dust with secondary ion mass spectrometry in 2014.[11]

See also

References

  1. ^ Thomson, J. J. "Rays of positive electricity". Phil. Mag. 20(1910), 752–767.. 
  2. ^ Herzog, R. F. K., Viehboeck, F. "Ion source for mass spectrography". Phys. Rev. 76(1949), 855–856. 
  3. ^ Liebl, H. J. "Ion microprobe mass analyzer". J. Appl. Phys. 38(1967), 5277–5280. 
  4. ^ Castaing, R. & Slodzian, G. J. "Optique corpusculaire—premiers essais de microanalyse par emission ionique secondaire". Microscopie 1(1962), 395–399.. 
  5. ^ Wittmaack, K.. "Pre-equilibrium variation of secondary ion yield". Int. J. Mass Spectrom. Ion Phys. 17(1975), 39–50. 
  6. ^ Magee, C. W. et al.. "Secondary ion quadrupole mass spectrometer for depth profiling design and performance evaluation". Rev. Scient. Instrum. 49(1978), 477–485. 
  7. ^ Benninghoven, A. "Analysis of sub-monolayers on silver by secondary ion emission". Physica Status Solidi 34(1969), K169–171. 
  8. ^ S.Hofmann. "Sputter-depth profiling for thin-film analysis". Phil. Trans. R. Soc. Lond. A (2004) 362, 55–75. 
  9. ^ "SIMS Detection Limits of Selected Elements in Si and SIO2 Under Normal Depth Profiling Conditions". Evans Analytical Group. May 4, 2007. http://www.eaglabs.com/files/appnotes/AN339.pdf. Retrieved on 2007-11-22. 
  10. ^ Kaufman, A.J.; Xiao, S. (2003). "High CO 2 levels in the Proterozoic atmosphere estimated from analyses of individual microfossils". Nature 425: 279–282. doi:10.1038/nature01902. 
  11. ^ C. Engrand, J. Kissel, F. R. Krueger, P. Martin, J. Silén, L. Thirkell, R. Thomas, K. Varmuza (2006). "Chemometric evaluation of time-of-flight secondary ion mass spectrometry data of minerals in the frame of future in situ analyses of cometary’s material by COSIMA onboard ROSETTA". Rapid Communications in Mass Spectrometry 20: 1361–1368. doi:10.1002/rcm.2448. 

Bibliography

  • Benninghoven, A., F. G. Rüdenauer, and H. W. Werner, "Secondary Ion Mass Spectrometry: Basic Concepts, Instrumental Aspects, Applications, and Trends", Wiley, New York, 1987 (1227 pages) ISBN 0471519456
  • Bubert, H., Jenett, H., "Surface and Thin Film Analysis; A compenium of Principles, Instrumentation, and Applications", p. 86-121, Wiley-VCH, Weinheim, Germany 2002 ISBN 3-527-30458-4

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