  Bulk chalcogenide perovskite BaZrS3 (BZS), with a direct band gap in visible
region, is an important photovoltaic material, albeit with limited
applicability owing to its antiferroelectric (AF) nature. Presently,
ferroelectric (FE) perovskite-based photovoltaics are attracting enormous
attention for environmental stability and better energy conversion efficiency
through enhanced charge separation, owing to loss of center of inversion
symmetry. We report on antiferroelectric-ferroelectric (AF-FE) phases of BZS
thin film, grown with chemical vapor deposition (CVD), using
temperature-dependent Raman investigations and first-principles calculations.
The origin of FE phases is established from anomalous behavior of A7g ~ 300
cm-1 and B1g5 ~ 420 cm-1 modes, which involves the vibration of atoms at apical
site of ZrS6 octahedra. Additionally, below 60 K, B1g1 and B2g2 ( ~ 85 cm-1)
modes appear whereas B12g (~ 60 cm-1) disappears to stabilize the Pnma
structure against ferroelectricity by local distortion. Here, B2g2 and B1g2
involve vibrations of Ba atoms in AF manner while B1g1 involves, in addition,
the rotation of octahedra as well. Our first-principles calculations confirm
that FE appears as a result of loss of center of inversion symmetry in ZrS6
octahedra due to existence of oxygen (O) impurities placed locally at apical
sites of sulfur (S) atom.
