Auger electron spectroscopy

thumb|A [[Hanford Site|Hanford scientist uses an Auger electron spectrometer to determine the elemental composition of surfaces.]]

Auger electron spectroscopy (AES; pronounced in French) is a common analytical technique used specifically in the study of surfaces and, more generally, in the area of materials science. It is a form of electron spectroscopy that relies on the Auger effect, based on the analysis of energetic electrons emitted from an excited atom after a series of internal relaxation events. The Auger effect was discovered independently by both Lise Meitner and Pierre Auger in the 1920s. Though the discovery was made by Meitner and initially reported in the journal Zeitschrift für Physik in 1922, Auger is credited with the discovery in most of the scientific community. Until the early 1950s Auger transitions were considered nuisance effects by spectroscopists, not containing much relevant material information, but studied so as to explain anomalies in X-ray spectroscopy data. Since 1953 however, AES has become a practical and straightforward characterization technique for probing chemical and compositional surface environments and has found applications in metallurgy, gas-phase chemistry, and throughout the microelectronics industry.

Electron transitions and the Auger effect

The Auger effect is an electronic process at the heart of AES resulting from the inter- and intrastate transitions of electrons in an excited atom. When an atom is probed by an external mechanism, such as a photon or a beam of electrons with energies in the range of several eV to 50 keV, a core state electron can be removed leaving behind a hole. As this is an unstable state, the core hole can be filled by an outer shell electron, whereby the electron moving to the lower energy level loses an amount of energy equal to the difference in orbital energies. The transition energy can be coupled to a second outer shell electron, which will be emitted from the atom if the transferred energy is greater than the orbital binding energy. An emitted electron will have a kinetic energy of:

:<math>E_{\text{kin=E_{\text{Core State-E_B-E_{C}'</math>

where <math>E_{\text{Core State</math>, <math>E_B</math>, <math>E_C'</math> are respectively the core level, first outer shell, and second outer shell electron binding energies (measured from the vacuum level) which are taken to be positive. The apostrophe (tic) denotes a slight modification to the binding energy of the outer shell electrons due to the ionized nature of the atom; often, however, this energy modification is ignored in order to ease calculations. Since orbital energies are unique to an atom of a specific element, analysis of the ejected electrons can yield information about the chemical composition of a surface. Figure 1 illustrates two schematic views of the Auger process.

thumb|340px|Figure 1. Two views of the Auger process. (a) illustrates sequentially the steps involved in Auger deexcitation. An incident electron creates a core hole in the 1s level. An electron from the 2s level fills in the 1s hole and the transition energy is imparted to a 2p electron that is emitted. The final atomic state thus has two holes, one in the 2s orbital and the other in the 2p orbital. (b) illustrates the same process using [[X-ray notation, <math>KL_1L_{2,3}</math>.]]

The types of state-to-state transitions available to electrons during an Auger event are dependent on several factors, ranging from initial excitation energy to relative interaction rates, yet are often dominated by a few characteristic transitions. Because of the interaction between an electron's spin and orbital angular momentum (spin-orbit coupling) and the concomitant energy level splitting for various shells in an atom, there are a variety of transition pathways for filling a core hole. Energy levels are labeled using a number of different schemes such as the j-j coupling method for heavy elements (Z ≥ 75), the Russell–Saunders L-S method for lighter elements (Z < 20), and a combination of both for intermediate elements. The j-j coupling method, which is historically linked to X-ray notation, is almost always used to denote Auger transitions. Thus for a <math>KL_1L_{2,3}</math> transition, <math>K</math> represents the core level hole, <math>L_1</math> the relaxing electron's initial state, and <math>L_{2,3}</math> the emitted electron's initial energy state. Figure 1(b) illustrates this transition with the corresponding spectroscopic notation. The energy level of the core hole will often determine which transition types will be favored. For single energy levels, i.e. K, transitions can occur from the L levels, giving rise to strong KLL type peaks in an Auger spectrum. Higher level transitions can also occur, but are less probable. For multi-level shells, transitions are available from higher energy orbitals (different n, ℓ quantum numbers) or energy levels within the same shell (same n, different ℓ number).

Since the intensity of the Auger peaks may be small compared to the noise level of the background, AES is often run in a derivative mode that serves to highlight the peaks by modulating the electron collection current via a small applied AC voltage. Since this <math>\Delta V=k\sin(\omega t)</math>, the collection current becomes <math>I(V+k\sin(\omega t))</math>. Taylor expanding  gives:

:<math>I(V+k\sin(\omega t))\approx I_0+I'(V+k\sin(\omega t))+O(I)</math>

Using the setup in figure 2, detecting the signal at frequency ω will give a value for <math>I'</math> or <math>\frac{dN}{dE}</math>. SAM images are obtained by stepping a focused electron beam across a sample surface and measuring the intensity of the Auger peak above the background of scattered electrons. The intensity map is correlated to a gray scale on a monitor with whiter areas corresponding to higher element concentration. In addition, sputtering is sometimes used with Auger spectroscopy to perform depth profiling experiments. Sputtering removes thin outer layers of a surface so that AES can be used to determine the underlying composition. Theoretically, Auger spectra can also be utilized to distinguish between protonation states. When a molecule is protonated or deprotonated, the geometry and electronic structure is changed, and AES spectra reflect this. In general, as a molecule becomes more protonated, the ionization potentials increase and the kinetic energy of the emitted outer shell electrons decreases.

Despite the advantages of high spatial resolution and precise chemical sensitivity attributed to AES, there are several factors that can limit the applicability of this technique, especially when evaluating solid specimens. One of the most common limitations encountered with Auger spectroscopy are charging effects in non-conducting samples. This method has been debated, with claims that the thinning process leaves elemental artifacts on a surface and/or creates damaged layers that distort bonding and promote chemical mixing in the sample. As a result, the compositional AES data is considered suspect. The most common setup to minimize charging effects includes use of a glancing angle (~10°) electron beam and a carefully tuned bombarding energy (between 1.5 keV and 3 keV). Control of both the angle and energy can subtly alter the number of emitted electrons vis-à-vis the incident electrons and thereby reduce or altogether eliminate sample charging.

Despite these sometimes substantial drawbacks, Auger electron spectroscopy is a widely used surface analysis technique that has been successfully applied to many diverse fields ranging from gas phase chemistry to nanostructure characterization. A new class of high-resolving electrostatic energy analyzers, face-field analyzers (FFA) can be used for remote electron spectroscopy of distant surfaces or surfaces with large roughness or even with deep dimples. These instruments are designed as if to be specifically used in combined scanning electron microscopes (SEMs). "FFA" in principle have no perceptible end-fields, which usually distort focusing in most of analysers known, for example, well known CMA.

Auger electron spectroscopy

Electron transitions and the Auger effect

See also

References

Further reading