X-ray photoelectron spectroscopy uses X-ray excitation to investigate Electron removal energies, including those of core electrons. The common name electron spectroscopy for chemical analysis emphasizes its use in distinguishing chemical surroundings. The whole recorded spectrum can also contain Electrons produced by processes other than direct photoionization; a peak assignment must identify the emission process as well as the chemical element.
In a modern implementation, a quartz crystal selects aluminum characteristic X-rays according to Bragg's law and focuses them onto the sample. Vacuum reduces gas collisions and contamination; a separately pumped entry chamber limits exposure to air. Lenses collect photoelectrons; an electrostatic electron energy analyzer transmits a narrow kinetic energy band. Stepping that band and counting detector pulses produces the spectrum. An electron flood source can compensate positive electric charge on insulating samples. Ion cleaning can alter vulnerable samples.[ref]
For a scan with count and dwell time at setting , compare rates , rather than raw counts when dwell times differ. Under an independent Poisson distribution model, the count standard deviation is approximately for a sufficiently populated bin. Longer acquisition reduces this relative counting measurement uncertainty; it does not automatically improve separation of overlapping peaks. Photoelectron peak overlap and resolution gives an example in which the same chemical separation produces either two maxima or one.
Figure 1.
Photoelectron energy selection and the analyzer energy reference
. Original functional diagram for an unbiased electrical conductor in electrical contact with an electron energy analyzer. The lower panel uses a common Fermi level; the two vacuum levels differ because the work functions differ. Vertical distances are schematic. The outgoing Electron's total energy is measured above the analyzer's vacuum level to obtain its kinetic energy. This is an explanatory model, not a reconstruction of one historical instrument. Details.