CdCl₂ treatment is a crucial step in development of CdS/CdTe solar cells. Although this processing step has been used over a period of three decades, full understanding is not yet achieved. This paper reports the experimental evidence for improvement of composition of CdTe layers during CdCl₂ treatment. This investigation makes use of four selected analytical techniques; Photo-electro-chemical (PEC) cell, X-ray diffraction (XRD), Raman spectroscopy and Scanning electron microscopy (SEM). CdTe layers used were electroplated using three Cd precursors; CdSO₄, Cd(NO₃)₂ and CdCl₂. Results show the improvement of stoichiometry of CdTe layers during CdCl₂ treatment through chemical reaction between Cd from CdCl₂ and elemental Te that usually precipitate during CdTe growth, due to its natural behaviour. XRD and SEM results show that the low-temperature (~85 °C) electroplated CdTe layers consist of ~(20–60) nm size crystallites, but after CdCl₂ treatment, the layers show drastic recrystallisation with grains becoming a few microns in size. These CdCl₂ treated layers are then comparable to high temperature grown CdTe layers by the size of grains.

Electrodeposition of CdTe thin films was carried out from the late 1970s using the cadmium sulphate precursor. The solar energy group at Sheffield Hallam University has carried out a comprehensive study of CdTe thin films electroplated using cadmium sulfate, cadmium nitrate and cadmium chloride precursors, in order to select the best electrolyte. Some of these results have been published elsewhere, and this manuscript presents the summary of the results obtained on CdTe layers grown from cadmium sulphate precursor. In addition, this research program has been exploring the ways of eliminating the reference electrode, since this is a possible source of detrimental impurities, such as K⁺ and Ag⁺ for CdS/CdTe solar cells. This paper compares the results obtained from CdTe layers grown by three-electrode (3E) and two-electrode (2E) systems for their material properties and performance in CdS/CdTe devices. Thin films were characterized using a wide range of analytical techniques for their structural, morphological, optical and electrical properties. These layers have also been used in device structures; glass/FTO/CdS/CdTe/Au and CdTe from both methods have produced solar cells to date with efficiencies in the region of 5%–13%. Comprehensive work carried out to date produced comparable and superior devices fabricated from materials grown using 2E system.