Temperature Field, Flow Field, and Temporal Fluctuations Thereof in Ammonothermal Growth of Bulk GaN-Transition from Dissolution Stage to Growth Stage Conditions.

With the ammonothermal method, one of the most promising technologies for scalable, cost-effective production of bulk single crystals of the wide bandgap semiconductor GaN is investigated. Specifically, etch-back and growth conditions, as well as the transition from the former to the latter, are studied using a 2D axis symmetrical numerical model. In addition, experimental crystal growth results are analyzed in terms of etch-back and crystal growth rates as a function of vertical seed position. The numerical results of internal process conditions are discussed. Variations along the vertical axis of the autoclave are analyzed using both numerical and experimental data. During the transition from quasi-stable conditions of the dissolution stage (etch-back process) to quasi-stable conditions of the growth stage, significant temperature differences of 20 K to 70 K (depending on vertical position) occur temporarily between the crystals and the surrounding fluid. These lead to maximum rates of seed temperature change of 2.5 K/min to 1.2 K/min depending on vertical position. Based on temperature differences between seeds, fluid, and autoclave wall upon the end of the set temperature inversion process, deposition of GaN is expected to be favored on the bottom seed. The temporarily observed differences between the mean temperature of each crystal and its fluid surrounding diminish about 2 h after reaching constant set temperatures imposed at the outer autoclave wall, whereas approximately quasi-stable conditions are reached about 3 h after reaching constant set temperatures. Short-term fluctuations in temperature are mostly due to fluctuations in velocity magnitude, usually with only minor variations in the flow direction.

High-Energy Computed Tomography as a Prospective Tool for In Situ Monitoring of Mass Transfer Processes inside High-Pressure Reactors-A Case Study on Ammonothermal Bulk Crystal Growth of Nitrides including GaN.

For the fundamental understanding and the technological development of the ammonothermal method for the synthesis and crystal growth of nitrides, an in situ monitoring technique for tracking mass transport of the nitride throughout the entire autoclave volume is desirable. The feasibility of using high-energy computed tomography for this purpose was therefore evaluated using ex situ measurements. Acceleration voltages of 600 kV were estimated to yield suitable transparency in a lab-scale ammonothermal setup for GaN crystal growth designed for up to 300 MPa operating pressure. The total scan duration was estimated to be in the order of 20 to 40 min, which was sufficient given the comparatively slow crystal growth speed in ammonothermal growth. Even shorter scan durations or, alternatively, lower acceleration voltages for improved contrast or reduced X-ray shielding requirements, were estimated to be feasible in the case of ammonoacidic growth, as the lower pressure requirements for this process variant allow for thinned autoclave walls in an adapted setup designed for improved X-ray transparency. Promising nickel-base and cobalt-base alloys for applications in ammonothermal reactors with reduced X-ray absorption in relation to the maximum operating pressure were identified. The applicability for the validation of numerical simulations of the growth process of GaN, in addition to the applicability of the technique to further nitride materials, as well as larger reactors and bulk crystals, were evaluated.

Ammonothermal Synthesis of Earth-Abundant Nitride Semiconductors ZnSiN2 and ZnGeN2 and Dissolution Monitoring by In Situ X-ray Imaging.

In this contribution, first synthesis of semiconducting ZnSiN2 and ZnGeN2 from solution is reported with supercritical ammonia as solvent and KNH2 as ammonobasic mineralizer. The reactions were conducted in custom-built high-pressure autoclaves made of nickel-based superalloy. The nitrides were characterized by powder X-ray diffraction and their crystal structures were refined by the Rietveld method. ZnSiN2 (a=5.24637(4), b=6.28025(5), c=5.02228(4) Å, Z=4, Rwp =0.0556) and isotypic ZnGeN2 (a=5.46677(10), b=6.44640(12), c=5.19080(10) Å, Z=4, Rwp =0.0494) crystallize in the orthorhombic space group Pna21 (no. 33). The morphology and elemental composition of the nitrides were examined by electron microscopy and energy-dispersive X-ray spectroscopy (EDX). Well-defined single crystals with a diameter up to 7 µm were grown by ammonothermal synthesis at temperatures between 870 and 1070 K and pressures up to 230 MPa. Optical properties have been analyzed with diffuse reflectance measurements. The band gaps of ZnSiN2 and ZnGeN2 were determined to be 3.7 and 3.2 eV at room temperature, respectively. In situ X-ray measurements were performed to exemplarily investigate the crystallization mechanism of ZnGeN2 . Dissolution in ammonobasic supercritical ammonia between 570 and 670 K was observed which is quite promising for the crystal growth of ternary nitrides under ammonothermal conditions.