Stoichiometry of tetragonal and hexagonal Fe xSe: Phase relations

Precise compositional analyses at spatial resolution xSe and δ-FexSe form as solids in a two-phase field above and below the apparent peritectic temperature of 457 ?C. Microstructures show that β-FexSe and δ-FexSe form together via exsolution when cooled from this two-phase field; evident when annealing time and temperature are optimised. Using a facile one-pot method with elemental Fe:Se reactant ratios ranging from 0.95 to 1.14, β-FexSe occurs as the predominant phase in association with hexagonal δ-FexSe in the temperature range 330 ?C max max is the sintering temperature. Maximum yield of β-FexSe occurs after sintering at Tmax > 690 ?C with annealing at 420 ?C for ∼24 h. We define a modified phase diagram that includes this two phase field with β-FexSe and δ-FexSe for 1.02 xSe and α-Fe for 1.08 < x < 1.02. This revised phase diagram for Fe:Se ∼ 1.0 suggests that the peretectic transition nominally identified at x = 1.04 is not evident.