A system for characterizing a film comprising a metal or atomic element species, said system comprising: an X-ray source for generating an X-ray beam having an energy below the absorption edge (k-edge) of silicon; a sample holder for positioning a sample in a pathway of said X-ray beam; a first detector for collecting an X-ray photoelectron spectroscopy (XPS) signal generated by bombarding said sample with said X-ray beam; a second detector for collecting an X-ray fluorescence (XRF) signal generated by bombarding said sample with said X-ray beam; and a processor configured to calibrate said XPS signal with said XRF signal , the processor being configured to: determine a quantity of said metal or atomic element species from said XRF signal ; and, subsequently, determine a thickness of said film comprising said metal or atomic element species from said XPS signal and said quantity, or wherein said film comprising said metal or atomic element species is disposed below one or more other films, wherein said XPS signal comprises an attenuated intensity signal of said metal or atomic element species, and wherein said XRF signal comprises a non-attenuated signal of said metal or atomic element species and, optionally, determine a quantity of said metal or atomic element species from said XRF signal ; and, subsequently, determine, from said XPS signal and said quantity, a depth of said film below said one or more other films. an X-ray source for generating an X-ray beam having an energy below the absorption edge (k-edge) of silicon; a sample holder for positioning a sample in a pathway of said X-ray beam; a first detector for collecting an X-ray photoelectron spectroscopy (XPS) signal generated by bombarding said sample with said X-ray beam; a second detector for collecting an X-ray fluorescence (XRF) signal generated by bombarding said sample with said X-ray beam; and a processor configured to calibrate said XPS signal with said XRF signal , the processor being configured to: determine a quantity of said metal or atomic element species from said XRF signal ; and, subsequently, determine a thickness of said film comprising said metal or atomic element species from said XPS signal and said quantity, or wherein said film comprising said metal or atomic element species is disposed below one or more other films, wherein said XPS signal comprises an attenuated intensity signal of said metal or atomic element species, and wherein said XRF signal comprises a non-attenuated signal of said metal or atomic element species and, optionally, determine a quantity of said metal or atomic element species from said XRF signal ; and, subsequently, determine, from said XPS signal and said quantity, a depth of said film below said one or more other films. determine a quantity of said metal or atomic element species from said XRF signal ; and, subsequently, determine a thickness of said film comprising said metal or atomic element species from said XPS signal and said quantity, or wherein said film comprising said metal or atomic element species is disposed below one or more other films, wherein said XPS signal comprises an attenuated intensity signal of said metal or atomic element species, and wherein said XRF signal comprises a non-attenuated signal of said metal or atomic element species and, optionally, determine a quantity of said metal or atomic element species from said XRF signal ; and, subsequently, determine, from said XPS signal and said quantity, a depth of said film below said one or more other films. <EOS>