Quantitative X-Ray Fluorescence Determination of Elemental Composition of Micro-Constituents Smaller Than the Electron Probe Volume

"Often referred to as SEM-EDX, energy-dispersive spectroscopic analysis of characteristic fluorescence x-ray is a standard technique for semi-quantitative elemental composition analysis in scanning electron microscopy. It is quick and extremely useful for identification of phases in the sample microstructure, as long as the constituents are significantly larger than the probe volume from which the fluorescence x-rays originate. The probe volume ranges from a few to several microns, depending on the electron beam spot size and the acceleration voltage. We report on a new variant of an EDX technique developed to overcome this limitation and allow quantitative elemental analysis of smaller phase constituents, down to a size of several nanometers. This variant involves the calculation of compositions of individual phases from multiple analyses of areas containing phases of interest. This significantly increases the usefulness of EDX for quantitative analysis of new nano-structured materials.IntroductionIn any elemental micro-analytical method, the sample material is illuminated by a probe beam that excites an interaction volume of a sample to emit a characteristic signal. This signal in turn interacts with the sample material through absorption and fluorescence mechanisms before a portion of it is collected by a suitable detector and analyzed for elemental composition. The spatial resolution of the method depends on the minimum interaction volume between the probe beam and the sample material.Laser light beams can be tightly focused to a spot size limited by the photon wavelength and can be used to sample the surface of any material. In micro-LIBS (laser-induced plasma spectroscopy) a focused laser beam ablates and vaporizes a small volume of material from the sample surface, creating a plasma spark. Spectral analysis of the light emission from the plasma spark allows the semi-quantitative determination of the elemental composition of the material removed from the sample surface. The smallest reproducible craters achieved are ~ 3mm in diameter and a few nanometers in depth. [l]Particle probe beams of ions or electrons can be focused to a diameter of a few nanometers at the point of impact on the sample. Ions sputter the sample atoms from the point of impact, and the sputtered ionized material is analyzed by mass spectroscopy in a secondary ion mass spectrometer (SIMS). [2] This gives SIMS resolution in a nanometer range. SIMS equipment, however, is expensive and not readily available."