Advances in Chalcogenide Crystal Growth: Flux and Solution Syntheses, and Approaches for Postsynthetic Modifications

Abstract

Chalcogenide-containing materials are important for the semiconductor and thermoelectric industries and are up-and-coming materials for superconductors, catalysis, and battery applications. Challenges in the synthesis of those materials emerge from the chalcogen’s volatility and from the tendencies of chalcogenide materials to react with even trace quantities of oxygen. Nonetheless, many techniques have been applied to the growth of chalcogenide single crystals, which are convenient for structure determinations and intrinsic property measurements. In the current perspective, we highlight flux crystal growth, solution syntheses, and a novel approach, single-crystal-to-single-crystal modifications, as convenient routes for the preparation of single-crystal chalcogenide materials and emphasize recent advances in those synthetic techniques that have resulted in novel chalcogenide materials classes and that exhibit important properties.

Li2MP2S6: Building-Block Approach to a Family of 2D Non-van der Waals-Layered Materials and Their Water, Ammonia, and Ion Intercalation Properties

“…Although the exposure time is the same for all the compounds, the degree of hydration varies from sample to sample. These water intercalation reactions are classic examples of postsynthetic modification of 2D-layered chalcogenides with single crystal-to-single crystal transformation recently reviewed by Berseneva and zur Loye …”

Alkali halide flux synthesis, crystal structure, and photoelectric response of quaternary thiosilicates K3Ga3Si7S20 and K2ZnSi3S8

“…39,40 Because silicon and silicon sulfide have a higher melting point than that of Ge, Sn and their sulfides, the sintering temperature of thiosilicates is higher than that of their Ge/Sn analogues, making the flux synthesis of thiosilicates relatively difficult. [41][42][43][44][45][46] Thus far, most quaternary thiosilicates have been prepared by molten flux methods in which the alkali-polysulfide serves as the molten flux of reaction to help crystal growth and as the source of sulfur and alkali metal. 47,48 However, there are several disadvantages of the use of alkali-polysulfides in terms of cost and operation.…”

Kinetic and Thermodynamic Pathways Via Ion Exchange Metathesis of Cobalt Thiophosphate

“…Efforts to uncover the reaction pathways in the solid state remain highly active. For example, by means of in situ powder X-ray diffraction (pXRD) techniques, “panoramic synthesis” has played a major role in clarifying the optimal conditions for crystal growth and design. − To the best of our knowledge, there has only been one report on solid-state metathesis being used to form transition metal chalchophosphates (transition metal chalcogenophosphates (TMCs)). By reacting M + Cl and M 3+ Cl 3 with MgPSe 3 , Pfeiff et al obtained the corresponding M + M 3+ P 2 Se 6 phases, where M + = Ag + and Cu + , and M 3+ = V 3+ , Cr 3+ , Al 3+ , In 3+ , and Ga 3+ .…”