Ag_2Se to KAg_3Se_2: Suppressing Order-Disorder Transitions via Reduced Dimensionality

摘要

We report an order–disorder phase transition in the 2D semiconductor KAg_(3)Se_(2), which is a dimensionally reduced derivative of 3D Ag_(2)Se. At ∼695 K, the room temperature β-phase (CsAg_(3)S_(2) structure type, monoclinic space group C2/m ) transforms to the high temperature α-phase (new structure type, hexagonal space group R 3̅m , a = 4.5638(5) Å, c = 25.4109(6) Å), as revealed by in situ temperature-dependent X-ray diffraction. Significant Ag~(+) ion disorder accompanies the phase transition, which resembles the low temperature (∼400 K) superionic transition in the 3D parent compound. Ultralow thermal conductivity of ∼0.4 W m~(–1) K~(–1) was measured in the “ordered” β-phase, suggesting anharmonic Ag motion efficiently impedes phonon transport even without extensive disordering. The optical and electronic properties of β-KAg_(3)Se_(2) are modified as expected in the context of the dimensional reduction framework. UV–vis spectroscopy shows an optical band gap of ∼1 eV that is indirect in nature as confirmed by electronic structure calculations. Electronic transport measurements on β-KAg_(3)Se_(2) yielded n -type behavior with a high electron mobility of ∼400 cm~(2) V~(–1) s~(–1) at 300 K due to a highly disperse conduction band. Our results thus imply that dimensional reduction may be used as a design strategy to frustrate order–disorder phenomena while retaining desirable electronic and thermal properties.