A Kinetic and Phase Analysis of Kesterite Formation : Influence of Chalcogen Availability in the Reaction Pathway
Physical vapor deposition methodologies have gained a lot of interest for the synthesis of kesterites, including sequential processes based on sputtering of metals followed by reactive annealing. Bearing this in mind, understanding the intermediate phases and possible formation routes for these techniques is essential for their further progress. In this work, we have implemented innovative experiments to demonstrate the strong interrelationship between the chalcogen availability in the annealing reactor and the reaction pathways of kesterite formation. We present the first kinetic analysis of the selenization process including slow and fast ramped annealing steps. We observe that at low-medium chalcogen availabilities, kesterite is formed following a pseudo-zero-order kinetic reaction which evolves towards a first-order one with longer annealing times, mainly controlled by the reaction of binary phases. By increasing the chalcogen availability, the kinetic is identified as a first-order one, evolving to a simpler reaction pathway involving the ternary Cu 2 SnSe 3 compound with ZnSe. Nevertheless, our results show that although to a marginal extent, the route involving the binary compounds is always competing with the latter. The phase analysis is extended to the sulfur case, showing the similarities and differences of both chalcogenization processes. This work expands the understanding of the formation reactions and opens interesting perspectives for improving the kesterite synthesis
Year of publication: |
[2022]
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Authors: | Hernández-Martínez, Alejandro ; Giraldo, Sergio ; Alcobé, Xavier ; Becerril-Romero, Ignacio ; Placidi, Marcel ; Izquierdo-Roca, Victor ; Pistor, Paul ; Pérez-Rodríguez, Alejandro ; Saucedo, Edgardo ; Valdes, Matias |
Publisher: |
[S.l.] : SSRN |
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