A novel technique is introduced for probing charging/discharging dynamics of dielectric materials in which X-ray photoemission data is recorded while the sample rod is subjected to (10.0 V square-wave pulses with varying frequencies in the range of 10 -3 to 10 3 Hz. For a clean silicon sample, the Si2p(Si 0 ) peak appears at correspondingly -10.0 eV and +10.0 eV binding energy positions (20.0 eV difference) with no frequency dependence. However, the corresponding peak of the oxide (Si 4+ ) appears with less than 20.0 eV difference and exhibits a strong frequency dependence due to charging of the oxide layer, which is faithfully reproduced by a theoretical model. In the simplest application of this technique, we show that the two O1s components can be assigned to SiO x and TiO y moeties by correlating their dynamical shifts to those of the Si2p and Ti2p peaks in a composite sample. Our pulsing technique turns the powerful X-ray photoemission into an even more powerful impedance spectrometer with an added advantage of chemical resolution and specificity.Charge accumulation and dissipation (charging/discharging) in dielectric materials are vital processes for design and function of various devices and sensors. 1 This is especially important for SiO 2 , as the thickness of the dielectric layer is expected to shrink down to few atomic layers for the next generation of metal oxide semiconductor (MOS) devices. 2 Charge accumulation in the oxide layer occurs via various trapping mechanisms and is normally probed by electrical current-voltage and/or current-capacitance measurements. [3][4][5][6] Photoemission utilizing UV, X-rays, and lasers has also been employed for probing very fast (<10 -9 s) charging dynamics. 7-9 Core-level X-ray photoemission, XPS, is especially attractive, since additional chemical information can also be derived from the line positions of the corresponding peaks. However, the measured line positions are severely altered by local potentials developed due to the uncompensated charges resulting from photoelectron emission, especially for poorly conducting samples or regions (layers or domains) within such samples. [10][11][12][13][14][15][16] Various methods of charge compensation have been developed using low-energy electrons, ions, and/or photons. 17,18 On the other hand, one can also utilize XPS for understanding the mechanisms leading to and/or controlling of the charging/ discharging processes in materials which offer great possibilities for researchers in all fields. 19 Several applications have been reported, which utilize the charging, called controlled surface charging, for extracting chemical, physical, structural, and electrical parameters of various surface species. 20-26 Using a slightly different strategy and by applying voltage stress to the sample rod while recording XPS spectra, we have shown that the extent of charging can be controlled and various analytical and electrical information can be extracted. [27][28][29][30][31][32] In addition to static information derived from applic...