Discovery of chalcogenides structures and compositions using mixed fluxes

Advancements in many modern technologies rely on the continuous need for materials discovery. However, the design of synthesis routes leading to new and targeted solid-state materials requires understanding of reactivity patterns(1-3). Advances in synthesis science are necessary to increase efficiency and accelerate materials discovery(4-10). We present a highly effective methodology for the rational discovery of materials using high-temperature solutions or fluxes having tunable solubility. This methodology facilitates product selection by projecting the free-energy landscape into real synthetic variables: temperature and flux ratio. We demonstrate the effectiveness of this technique by synthesizing compounds in the chalcogenide system of A(Ba)-Cu-Q(O) (Q = S or Se; A = Na, K or Rb) using mixed AOH/AX (A = Li, Na, K or Rb; X = Cl or I) fluxes. We present 30 unreported compounds or compositions, including more than ten unique structural types, by systematically varying the temperature and flux ratios without requiring changing the proportions of starting materials. Also, we found that the structural dimensionality of the compounds decreases with increasing reactant solubility and temperature. This methodology serves as an effective general strategy for the rational discovery of inorganic solids.

Automated summary

Advancements in modern technologies rely on materials discovery, which in turn requires the development of synthesis science. This study presents an efficient methodology for rational material discovery using high-temperature solutions or fluxes with adjustable solubility. By systematically varying temperature and flux ratios, the researchers were able to synthesize previously unreported compounds and determine their structural characteristics. This methodology provides a general strategy for the rational discovery of inorganic solids.