The process of peak-fitting high energy resolution XPS spectra is a mixture of scientific knowledge and experience. The process is affected by instrument design, instrument components, experimental settings and sample variables. Before starting any peak-fit effort, the analyst performing the peak-fit needs to know if the topmost 15 nm of the sample is expected to be a homogeneous material or is expected to be a mixture of materials. If the top 15 nm is a homogeneous material with only very minor amounts of adventitious carbon and adsorbed gases, then the analyst can use theoretical peak area ratios to enhance the peak-fitting process. Peak fitting results are affected by overall peak widths (at half maximum, FWHM), possible chemical shifts, peak shapes, instrument design factors and experimental settings, as well as sample properties:
* The full width at half maximum (FWHM) values are useful indicators of chemical state changes and physical influences. Their increase may indicate a change in the number of chemical bonds, a change in the sample condition (x-ray damage) or differential charging of the surface (localised differences in the charge state of the surface). However, the FWHM also depends on the detector, and can also increase due to the sample getting charged. When using high energy resolution experiment settings on an XPS equipped with a monochromatic Al K-alpha X-ray source, the FWHM of the major XPS peaks range from 0.3 eV to 1.7 eV. The following is a simple summary of FWHM from major XPS signals:   Main metal peaks (e.g. 1s, 2p3, 3d5, 4f7) from pure metals have FWHMs that range from 0.30 eV to 1.0 eV  Main metal peaks (e.g. 1s, 2p3, 3d5, 4f7) from binary metal oxides have FWHMs that range from 0.9 eV to 1.7 eV  The O (1s) peak from binary metal oxides have FWHMs that, in general, range from 1.0 eV to 1.4 eV  The C (1s) peak from adventitious hydrocarbons have FWHMs that, in general, range from 1.0 eV to 1.4 eV
* Chemical shift values depend on the degree of electron bond polarization between nearest-neighbor atoms. A specific chemical shift is the difference in BE values of one specific chemical state versus the BE of one form of the pure element, or of a particular agreed-upon chemical state of that element. Component peaks derived from peak-fitting a raw chemical state spectrum can be assigned to the presence of different chemical states within the sampling volume of the sample.
* Peak shapes depend on instrument parameters, experimental parameters and sample characteristics.
* Instrument design factors include linewidth and purity of X-rays used (monochromatic Al, non-monochromatic Mg, Synchrotron, Ag, Zr), as well as properties of the electron analyzer.
* Settings of the electron analyzer (e.g. pass energy, step size)
* Sample factors that affect the peak fitting are the number of physical defects within the analysis volume (from ion etching, or laser cleaning), and the very physical form of the sample (single crystal, polished, powder, corroded)