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In this work we use Auger electron spectroscopy depth profiling and grazing incidence X‐ray diffraction (GIXRD) to study chemical composition and structure of the CdTe/CdS/ITO/glass heterostructure. The CdS layer was deposited on ITO (In2Sn2O7–x) substrates by chemical bath deposition and the CdTe film was deposited by double‐step close space sublimation. We found by AES profiling a strong intermixing at the CdS/ITO and CdS/CdTe interfaces, confirmed by GIXRD and evidences of two diffusion steps for the CdS into the ITO matrix. Additionally, the CdS/ITO structure was separately investigated in order to know the influence of the substrate roughness on the heterostructure conformation. The morphology of the ITO substrate and the as‐deposited CdS layer was studied by atomic force microscopy. The use of GIXRD showed to be useful to study the entire CdTe/CdS/ITO/glass heterostructure. The ITO roughness has proved to be an influencing factor in the structural features and suggested that CdS roughness can also influence the observed composition profiles.

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The chemical composition of CdTe surfaces has been studied for In over polycrystalline CdTe using I–V measurement. The obtained barrier height presents a spatial distribution on CdTe surface and an inhomogeneous barrier height is the cause of the ideal behavior deviation in the I–V curves. Multi‐level Fermi pinning within the contact that is produced by aggregate of Te‐rich and Cd‐rich areas is a consistent explanation for the barrier height inhomogeneities.

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