X-rays IN – Electrons OUT
X-ray photoelectron spectroscopy (XPS) is a surface-sensitive quantitative spectroscopic technique that measures the elemental composition at the parts per thousand range, empirical formula, chemical state and electronic state of the elements that exist within a material. Put more simply, XPS is a useful measurement technique because it not only shows what elements are within a film but also what other elements they are bonded to. This means if you have a metal oxide and you want to know if the metal is in a +1 or +2 state, using XPS will allow you to find that ratio. However at most the instrument will only probe 20 nm into a sample.
XPS spectra are obtained by irradiating a material with a beam of X-rays while simultaneously measuring the kinetic energy and number of electrons that escape from the top 0 to 10 nm of the material being analyzed. XPS requires high vacuum (P ~ 10−8 millibar) or ultra-high vacuum (UHV; P < 10−9 millibar) conditions, although a current area of development is ambient-pressure XPS, in which samples are analyzed at pressures of a few tens of millibar.
XPS can be used to analyze the surface chemistry of a material in its as-received state, or after some treatment, for example: fracturing, cutting or scraping in air or UHV to expose the bulk chemistry, ion beam etching to clean off some or all of the surface contamination (with mild ion etching) or to intentionally expose deeper layers of the sample (with more extensive ion etching) in depth-profiling XPS, exposure to heat to study the changes due to heating, exposure to reactive gases or solutions, exposure to ion beam implant, exposure to ultraviolet light.
- In principle XPS detects all elements. In practice, using typical laboratory-scale X-ray sources, XPS detects all elements with an atomic number (Z) of 3 (lithium) and above. It cannot easily detect hydrogen (Z = 1) or helium (Z = 2).
- Detection limits for most of the elements (on a modern instrument) are in the parts per thousand range. Detection limits of parts per million (ppm) are possible, but require special conditions: concentration at top surface or very long collection time (overnight).
- XPS is routinely used to analyze inorganic compounds, metal alloys, semiconductors, polymers, elements, catalysts, glasses, ceramics, paints, papers, inks, woods, plant parts, make-up, teeth, bones, medical implants, bio-materials, viscous oils, glues, ion-modified materials and many others. XPS is less routinely used to analyze the hydrated forms of some of the above materials by freezing the samples in their hydrated state in an ultra pure environment, and allowing or causing multilayers of ice to sublime away prior to analysis. Such hydrated XPS analysis allows hydrated sample structures, which may be different from vacuum-dehydrated sample structures, to be studied in their more relevant as-used hydrated structure. Many biomaterials such as hydrogels are examples of such samples.
Advantages of XPS