Single crystal growth and physical property characterization of ternary phosphide chalcogenide ZrP1.49Se0.51

Li, Meng; Meng, Yan; Yi, Xiaolei; Xing, Xiangzhuo; Xu, Chunqiang; Feng, Jiajia; Lin, Bing; Li, Wenchong; Tamegai, T.; Shi, Zhixiang

doi:10.1016/j.jpcs.2020.109423

Cited by 2 publications

(1 citation statement)

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“…Using CVT, crystal growth can be achieved for bulk crystals , as well as micro- and nanostructures , with minimum experimental effort. The determination of optimum conditions for crystal growth in a regarded substance system mostly happens on the basis of experiences from similar systems, “trial-and-error”, or thermodynamic calculation, whereas the latter is limited to the availability of consistent thermodynamic data. , Only a few analytic methods are feasible for the investigation of the solid–gas equilibria or the monitoring of transport processes in closed systems.…”

Section: Introductionmentioning

confidence: 99%

Crystal Growth by Chemical Vapor Transport: Process Screening by Complementary Modeling and Experiment

Heinemann

Schmidt

2020

Crystal Growth & Design

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Despite chemical vapor transport (CVT) being a widely used method for crystal growth of inorganic substances, detailed mechanistic studies on the course of the crystallization process are rather few. In this study, an elaborated experimental screening run combined with sophisticated modeling of the respective heterogeneous equilibria is presented: Crystal growth of germanium by vapor transport with the addition of iodine has been chosen as a model system for validation of the applied method spectrum. In order to record the course and the interplay of heterogeneous equilibrium and nonequilibrium reactions in the system Ge−I, the experimental setup of high-temperature gasbalance (HTGB) is applied. Additionally, the observed evaporation processes are compared with saturation curves of corresponding volatile substances and, thus, can be assigned to individual species within the system. In this experimental screening, a phase sequence means to examine how the condensed phases undergo iodine depletion and how the gaseous phase undergoes a germanium enrichment when the temperature is increased. This phase screening combined with annealing experiments in the course of the phase sequence helps to analyze stepwise nonequilibrium products and to identify the characteristic species. Subsequently, for the evaluation of the composition of the gaseous phase, and for the deduction of the vapor transport mechanism, thermodynamic modeling by the CalPhaD method is performed. For the reference system, it is confirmed that iodine does not act as the transport agent. Instead, GeI 4 is responsible for the volatilization of germanium, forming GeI 2 . Nevertheless, investigations clearly illustrate how GeI 4 forms naturally in the phase sequence in the system Ge−I, which makes direct addition of it unnecessary. The recommended temperature range for vapor transport of germanium spans from 460 to 800 °C. Modeling shows that migration rates for germanium reaches a maximum at a mean temperature between 540 and 550 °C. Finally, vapor transport experiments were performed from 565 to 515 °C and from 690 to 590 °C. By increasing the deposition temperature, a slight decrease of the migration rate was observed, though a positive impact on the crystal's morphology was also found.

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