Low-temperature synthesis of superconducting iron selenide using a triphenylphosphine flux

Many functional materials have relatively low decomposition temperatures (T≤ 400 °C), which makes their synthesis challenging using conventional high-temperature solid-state chemistry. Therefore, non-conventional techniques such as metathesis, hydrothermal, and solution chemistry are often employed to access low-temperature phases; the discovery of new chemistries is needed to expand access to these phases. This contribution discusses the use of triphenylphosphine (PPh₃) as a molten flux to synthesize superconducting iron selenide (Fe_1+δSe) at low temperature (T = 325 °C). Powder X-ray diffraction and magnetism measurements confirm the successful formation of superconducting iron selenide while nuclear magnetic resonance spectroscopy and in situ X-ray diffraction show that the formation of superconducting FeSe at low temperatures is enabled by an adduct between the triphenylphosphine and selenium. Exploration of the Fe-Se-PPh₃ phase space indicates that the PPh₃-Se adduct effectively reduces the chemical potential of the selenium at high concentrations of triphenylphosphine. This contribution demonstrates that the use of a poorly-solvating yet reactive flux has the potential to enable the synthesis of new low-temperature phases of solid materials.