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you can definitely use x-ray photoelectron spectroscopy for surface analysis.    This technique provides valuable chemical state and quantitative information from the surface of the material that is under study.

  You can use XPS technique for surface analysis. Physical Electronics or XPS instruments work similar    to SEM/EDS instruments. Here the finely focused electron beam is used to develop SEM images for sample viewing    and for point spectra for compositional analysis. With XPS instruments, finely focused x-ray beam will be scanned    to develop secondary electron images for point spectra for compositional analysis and sample viewing.    The x-ray beam size can be increased to support the analysis of huge samples with homogeneous composition.

  I don’t think there is any alternate method for surface analysis of a material. Use XPS technique itself.    XPS is achieved by exciting a sample surface using mono-energetic kα x-rays that causes photoelectrons to    emit from the surface of the sample. An electron energy analyser will be used to measure the energy of emitted photoelectrons.    From the intensity and the binding energy of a photoelectron peak, chemical state, the elemental identity, and quantity of a detected element can be measured.

  Visit https://www.mccrone.com/mm/surface-properties-using-xps/, https://www.youtube.com/watch?v=FasXWyuKK3M.