Double-Crucible Vertical Bridgman Technique for Stoichiometry-Controlled Chalcogenide Crystal Growth

Abstract: Precise stoichiometry control in single-crystal growth is essential for both technological applications and fundamental research. However, conventional growth methods often face challenges such as non-stoichiometry, compositional gradients, and phase impurities, particularly in non-congruent melting systems. Even in congruent melting systems like Bi2Se3, deviations from the ideal stoichiometric composition can lead to significant property degradation, such as excessive bulk conductivity, which limits its topological applications. In this study, we introduce the double-crucible vertical Bridgman (DCVB) method, a novel approach that enhances stoichiometry control through the combined use of continuous source material feeding, traveling-solvent growth, and liquid encapsulation, which suppresses volatile element loss under high pressure. Using Bi2Se3 as a model system, we demonstrate that crystals grown via DCVB exhibit enhanced stoichiometric control, significantly reducing defect density and achieving much lower carrier concentrations compared to those produced by conventional Bridgman techniques. Moreover, the continuous feeding of source material enables the growth of large crystals. This approach presents a promising strategy for synthesizing high-quality, large-scale crystals, particularly for metal chalcogenides and pnictides that exhibit challenging non-congruent melting behaviors.