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HAXPES measurements wereperformed at both the GALAXIES beamline at the Soleil synchrotron(France)16 and at the I09 beamline at theDiamond Light Source (UK)17 to gain informationabout the chemical and electronic properties of CZTS and ZTO/CZTS.The photoemission spectra for the ZTO/CZTS interface measurementswere performed at GALAXIES employing a VG Scienta EW4000 energy electronanalyzer at normal emission and excitation energies of hν = 3 keV and hν = 9 keV, respectively.A pass energy of 200 eV yielding an analyzer resolution of 150 meVwas used for all measurements, and the binding energy was calibratedby measuring the 4f spectrum of a grounded clean Au foil and settingthe Au 4f7/2 binding energy to 84.0 eV, if not otherwisementioned in the text. XPS line intensities were quantified by fittingthem with Voigt profiles and a linear background using Igor Pro softwareand taking into account the respective values for the inelastic meanfree path18,19 and photoionization cross-section20,21 including the asymmetry parameters of photoelectric angular distributions.21,22 The analyzer transmission function has not been taken into account,which may introduce an error in the calculation of the absolute values,but the aim of this study is to compare relative amounts between theinvestigated samples, and the method was therefore found to give reliableresults, as we previously discussed.8,23