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The Electrochemical Atomic Layer Deposition (ECALD) methodology has been recently employed to synthesize thin films of ternary Cu-Zn sulfides, technologically relevant for photovoltaic semiconductors. This approach, which represents probably the first successful synthesis of a ternary Cu-Zn sulfide, consisted in alternate ECALD depositions of CuS and ZnS layers that yielded a compound with a Cu/Zn ratio of about 6, thus confirming the low contribution of Zn in ternary compound already evidenced in previous studies. This paper, which represents the logical sequel, shows that it is possible to establish a well defined relationship between deposition sequence and stoichiometry as done for the other ternary compounds containing Zn.

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Electrodeposition is known as a low-cost semiconductor growth technique for applications in electronic devices such as display and photovoltaic components. Surface limited electrodeposition of metals and non-metals single-layers can be performed exploiting their underpotential deposition by EC-ALD (ElectroChemical Atomic Layer Deposition) technique to obtain calchogenide thin films. The main advantage of this technique lies in the possibility of choosing the number of deposition cycles in order to perform an accurate control of the thickness and composition of the film, mainly valuable for the preparation of nanostructured materials. For this reason, a wide number of semiconductors in the form of thin films were obtained by EC-ALD. Initially the study was concerned with zinc and cadmium compounds, because of their suitable optical and electronic proprieties. In particular cadmium calchogenides thin-films are used in manufacturing of last generation photovoltaic components. Toxicity and shortage of the involved elements must be considered in the advancement of technology. Hence scientific community is focusing attention on new compounds based on economic and low-environmental impact elements such as Cu, Sn, Fe and Zn. In particular, quaternary semiconducting materials based on the kesterite (Cu2ZnSnS4) mineral structure are the most promising candidates to overtake the current generation of light-absorbing materials for thin-film solar cells.