Crystal Growth of Chalcogenides and Oxy-Chalcogenides Using Chloride Exchange Reaction

TL;DR

This paper introduces a novel chloride exchange reaction method for rapid growth of high-quality single crystals of chalcogenides and oxy-chalcogenides, enhancing material synthesis for electronic and photonic applications.

Contribution

The study presents a new, efficient crystal growth technique using chloride exchange reactions, enabling large, high-quality crystals with short reaction times for complex chalcogenide materials.

Findings

Successful growth of ZrS₂, HfS₂, BaZrS₃, and ZrOS crystals

Crystals exhibit low mosaicity and high structural quality

Optical properties characterized by photoluminescence and Raman spectroscopy

Abstract

Chalcogenides and oxy-chalcogenides, including complex chalcogenides and transition metal dichalcogenides, are emerging semiconductors with direct or indirect band gaps within the visible spectrum. These materials are being explored for various photonic and electronic applications, such as photodetectors, photovoltaics, and phase-change electronics. Understanding the fundamental properties of these materials is crucial for optimizing their functionalities. Therefore, the availability of large, high-quality single crystals of chalcogenides and oxy-chalcogenides is essential for a better comprehension of their structure and properties. In this study, we present a novel crystal growth method that utilizes the exchange reaction between BaS and ZrCl$_4$/ HfCl$_4$. By carefully controlling the stoichiometric ratio of the binary sulfide to the chloride, we can grow single crystals of several materials, such as ZrS$_2$, HfS$_2$, BaZrS$_3$, and ZrOS. This method results in large single crystals with a short reaction time of 24 to 48 hours. High-resolution thin film diffraction and single-crystal X-ray diffraction confirm the quality of the crystals produced through this exchange reaction. We also report the optical properties of these materials investigated using photoluminescence and Raman measurements. The chloride exchange reaction method paves the way for the synthesis of single crystals of chalcogenides and oxy-chalcogenide systems with a short reaction time but with low mosaicity and can be an alternative growth technique for single crystals of materials that are difficult to synthesize using conventional growth techniques.