Flow Stability, Convective Heat Transfer and Chemical Reactions in Ammonothermal Autoclaves—Insights by In Situ Measurements of Fluid Temperatures

Saskia Schimmel,Eberhard Schlücker,Anna-Carina L Kimmel,Thomas G Steigerwald,Peter Wellmann,Lukas Heinlein,Ines Kobelt

doi:10.3390/cryst10090723

Abstract

A variety of functional nitride materials, including the important wide bandgap semiconductor GaN, can be crystallized in exceptionally good structural quality by the ammonothermal method. However, the further development of this method is hindered by a lack of access to internal process parameters including fluid temperatures, flow stability and reaction kinetics. Internal temperature measurements are thus introduced as a tool for in situ monitoring of fluid flow stability in ammonothermal reactors as well as chemical reactions associated with enthalpy changes. The temperature change of an internal thermocouple is studied numerically in order to estimate possible errors due to heat conduction along thermocouples as well as due to their heat capacity. Results from otherwise identical experiments conducted with air at ambient pressure and ammonothermal reaction medium, respectively, are compared. The comparison indicates that internal temperature distributions during ammonothermal growth of GaN cannot be determined by measurements using ambient pressure air instead of supercritical ammonia. Even an approximate determination is not feasible, given that the internal temperature gradients differ by a factor of seven, and that the Grashof- and Rayleigh numbers differ by approximately four orders of magnitude. Most importantly, convective heat transfer by supercritical ammonia is found to greatly influence the temperature distribution inside the reaction chamber and its walls, suggesting that it probably needs to be taken into account in numerical simulations of the global thermal field of ammonothermal reactors.

Highlights

The ammonothermal method has evolved as a promising route for the synthesis of major quantities of high-quality bulk GaN crystals
Alt et al demonstrated internal temperature measurements as well as further in situ monitoring technologies [16], but did not discuss information beyond temperature itself that is contained in the measurement signal of internal thermocouples
As will be discussed in Section 3.3., the results shown in Figure 6 suggest turbulent flow for the experiments with supercritical ammonia inside the autoclave

Summary

Introduction

The ammonothermal method has evolved as a promising route for the synthesis of major quantities of high-quality bulk GaN crystals. The method has proven to be a valuable tool for exploratory syntheses of nitride materials [7,8] including earth-abundant semiconductors [9,10] For both bulk and exploratory syntheses, the internal temperature distribution inside the high-pressure autoclaves is very important. Alt et al show a method for flow monitoring through optical in situ monitoring [16] While this is promising for visualizing flow fields in principle, this technique cannot be applied to most crystal growth reactors because it requires the use of autoclave windows, which poses special geometrical constraints on the reactor design. Griffiths et al [17] performed internal temperature measurements but focused on the direct information on temperatures rather than on indirectly contained information on fluid flow

Results

Discussion

Conclusion