p-n Transition in Thermoelectric Semiconductor Eskebornite

热电半导体埃斯克伯恩石的pn转变

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Abstract

Eskebornite (CuFeSe(2)) is a I-III-VI(2) semiconductor with a tetragonal crystal structure, known for its intriguing electrical and magnetic properties. However, experimental studies on this material remain scarce. In this study, Ni-doped eskebornite, Cu(1-x)Ni(x)FeSe(2) (x = 0.02-0.06), was synthesized via solid-state methods by substituting Ni(2+) for Cu(+). Mechanical alloying was employed to prepare the compounds, followed by hot pressing. X-ray diffraction analysis revealed the eskebornite phase alongside a minor secondary phase, identified as penroseite (NiSe(2)) with a cubic crystal structure. Thermoelectric properties were measured over the temperature range of 323-623 K. The Seebeck coefficient exhibited p-type behavior at low temperatures but transitioned to n-type at higher temperatures, indicating a temperature-dependent p-n transition due to changes in the dominant charge carriers. With increasing Ni doping, the Seebeck coefficient increased positively at low temperatures and negatively at high temperatures, with the p-n transition temperature shifting to lower values. Electrical conductivity decreased with higher Ni doping levels, while its positive temperature dependence became more pronounced, reflecting non-degenerate semiconductor behavior. Thermal conductivity showed a negative temperature dependence but increased with higher Ni content. The highest thermoelectric performance was observed for Cu(0.98)Ni(0.02)FeSe(2), achieving ZT(p) = 0.30 × 10(-3) at 523 K, and for Cu(0.94)Ni(0.06)FeSe(2), achieving ZT(n) = 0.55 × 10(-3) at 623 K, where ZT(p) and ZT(n) represent the dimensionless figure of merit for p-type and n-type thermoelectric materials, respectively.

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