Successful growth of low carrier density $\alpha$-In${}_2$Se${}_3$ single crystals using Se-flux in a modified Bridgman furnace

Abstract

Indium selenide (In${}_2$Se${}_3$) has garnered significant attention for its intriguing properties and applications in batteries, solar cells, photodetectors and ferroelectric devices. However, the controlled synthesis of single phase $\alpha$-In${}_2$Se${}_3$ remains challenging owing to its complex phase diagram, presence of multiple polymorphs and the high volatility of selenium that induces non-stoichiometry and unintentional carrier doping. For ferroelectric α-In2Se3, minimizing the carrier density is essential because leakage current can obscure polarization switching. Here, we report the growth of $\alpha$-In${}_2$Se${}_3$ single crystals using a unique approach, the Se-flux assisted modified vertical Bridgman technique combined with liquid encapsulation under high pressure. This approach creates a high-pressure, Se-rich environment that effectively minimizes Se-vaporization. Structural and compositional analysis using X-ray diffraction, transmission electron microscopy and energy-dispersive X-ray spectroscopy confirm the formation of pure $\alpha$-In${}_2$Se${}_3$ single crystals with 3R stacking. Furthermore, the crystals exhibit remarkably low carrier density of 1.5-3.2 $\times$ 10${}^{16}$ cm${}^{-3}$ at 300K$-$the lowest reported to date, reflecting a significant suppression of Se-vacancies relative to the conventional Bridgman or melt-grown crystals. Through transport and ARPES measurements on different batches of crystals, we also demonstrate that the amount of Se-flux plays a crucial role in controlling Se-vacancies. Our results thus establish this modified Bridgman method as an effective strategy for synthesizing large $\alpha$-In${}_2$Se${}_3$ single crystals with reduced intrinsic defects. This technique can be broadly applied to grow other volatile chalcogenides with reduced defects and controlled stoichiometry.