Atom Probe Tomography of Molecular Organic Materials: Sub-Dalton Nanometer-Scale Quantification

Indium-bearing sphalerites from the H&#228;mmerlein skarn deposit, located in the western Erzgebirge (Germany), show complex distribution patterns of major and minor elements on a micrometer to sub-micrometer scale. However, with the spatial resolution of traditional analytical methods, such as SEM-based image analysis and field emission electron probe microanalysis (FE-EPMA), many features in these spalerites cannot be resolved. It remains unclear whether Cu, In and Fe are in solid solution in the sphalerite, are concentrated in nanoparticles or form discrete phases.Atom probe tomography combined with transmission kikuchi diffraction has been used to resolve both the compositional heterogeneity and the nanostructure of these complex In-Cu-Fe-sphalerites. The obtained data indicate a complex structure with micro- to nanometer sized, plate-shaped inclusions of chalcopyrite in the sphalerite. In addition, a nanometer scale In-Cu-sulfide phase forms plate-like segregations in the sphalerite. All types of segregations have similar crystal structure and record the same crystal orientation indicating that they likely formed by exsolution.The results indicate that complex sulfides containing cations of more than one element as minor or major constituents may represent discrete, exsolved phases, rather than solid solutions or being concentrated in nanoparticles. This heterogeneous nature will affect the nanoscale properties of the sphalerite, which may have implications for the economic extraction of precious elements such as In, when processing these minerals for beneficiation. Furthermore these nanoscale properties will open up new perspectives on formation processes of In-Cu-Fe-sphalerites, which might be relevant for other chemically complex minerals as well.&#160;

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An Atom-Probe Tomography Primer

MRS Bulletin ◽

10.1557/mrs2009.194 ◽

2009 ◽

Vol 34 (10) ◽

pp. 717-724 ◽

Cited By ~ 105

Author(s):

David N. Seidman ◽

Krystyna Stiller

Keyword(s):

Atom Probe Tomography ◽

Organic Materials ◽

Ion Beam ◽

Large Data ◽

Laser Pulses ◽

Atom Probe ◽

Femtosecond Laser Pulses ◽

Large Data Sets ◽

Data Sets ◽

Wide Range

AbstractAtom-probe tomography (APT) is in the midst of a dynamic renaissance as a result of the development of well-engineered commercial instruments that are both robust and ergonomic and capable of collecting large data sets, hundreds of millions of atoms, in short time periods compared to their predecessor instruments. An APT setup involves a field-ion microscope coupled directly to a special time-of-flight (TOF) mass spectrometer that permits one to determine the mass-to-charge states of individual field-evaporated ions plus theirx-,y-, andz-coordinates in a specimen in direct space with subnanoscale resolution. The three-dimensional (3D) data sets acquired are analyzed using increasingly sophisticated software programs that utilize high-end workstations, which permit one to handle continuously increasing large data sets. APT has the unique ability to dissect a lattice, with subnanometer-scale spatial resolution, using either voltage or laser pulses, on an atom-by-atom and atomic plane-by-plane basis and to reconstruct it in 3D with the chemical identity of each detected atom identified by TOF mass spectrometry. Employing pico- or femtosecond laser pulses using visible (green or blue light) to ultraviolet light makes the analysis of metallic, semiconducting, ceramic, and organic materials practical to different degrees of success. The utilization of dual-beam focused ion-beam microscopy for the preparation of microtip specimens from multilayer and surface films, semiconductor devices, and for producing site-specific specimens greatly extends the capabilities of APT to a wider range of scientific and engineering problems than could previously be studied for a wide range of materials: metals, semiconductors, ceramics, biominerals, and organic materials.

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