With all this talk about averaging of pixels, it is important to keep in mind that pixel averaging only works when averaging quantitative x-ray map pixels (or points for that matter!). Now these x-ray maps could be elemental weight percents, oxide weight percents, atomic percents, formula atoms, detection limits, etc., etc., etc., but they must be already corrected for matrix effects prior to averaging.
Why? Because we know from physics that matrix correction of x-ray intensities are extremely non-linear. If we instead average raw intensities of a heterogeneous interaction volume, whether that heterogeneity be due to scanning the beam or defocusing it, we will obtain inaccurate results, when that average is subsequently quantified. See the attachments to this post here for additional details:
https://probesoftware.com/smf/index.php?topic=44.msg145#msg145An easy way to think about this is to consider an interaction volume that is at the boundary of a pure Cu phase and a pure Al phase. From geometry we know that most of the copper x-rays are being emitted from pure Cu and most of the aluminum x-rays are being emitted from pure Al, but our software sees both emitted intensities and has to assume that this is (roughly) a 50-50 Cu-Al "alloy" (since the software knows nothing about the sample geometry).
The matrix correction for copper in a CuAl alloy is similar to that of the pure element (because Cu Ka is very energetic and suffers little absorption in this "alloy"), but Al Ka is highly absorbed in such a composition, and is therefore is greatly overcorrected resulting in totals of around 150-160 wt%.
SAMPLE: 32767, TOA: 40, ITERATIONS: 0, Z-BAR: 24.23118
ELEMENT ABSCOR FLUCOR ZEDCOR ZAFCOR STP-POW BKS-COR F(x)u Ec Eo/Ec MACs
Cu ka .9996 1.0000 1.0555 1.0551 1.0739 .9828 .9903 8.9790 1.6706 49.0723
Al ka 2.0289 1.0000 .9199 1.8664 .8478 1.0851 .4374 1.5600 9.6154 3320.82
ELEMENT K-RAW K-VALUE ELEMWT% OXIDWT% ATOMIC% FORMULA KILOVOL
Cu ka .00000 .66532 70.195 ----- 50.000 .500 15.00
Al ka .00000 .15969 29.805 ----- 50.000 .500 15.00
TOTAL: 100.000 ----- 100.000 1.000
By the way, this is also why one cannot characterize thin film compositions if any substrate elements are detected. Because if the beam energy is sufficient, and the electrons penetrate to the substrate, not only will the homogeneous volume assumption be invalid, but the substrate can fluoresce elements in the thin film layer if any absorption edges of slightly lower energy than the substrate x-rays are present.
Unless of course one acquires intensities using multiple beam energies, and applies a thin film geometry model such as Pouchou and Pichoir! See here for more discussion on quantification of thin film geometries:
https://probesoftware.com/smf/index.php?topic=111.msg405#msg405