Order and randomness in dopant distributions: exploring the thermodynamics of solid solutions from atomically resolved imaging

TL;DR

This paper develops a statistical mechanical modeling approach using atomically resolved microscopy data to understand dopant distributions and structural correlations in solid solutions, especially where traditional mean field theories fail.

Contribution

It introduces a method combining microscopy data, model optimization, and hypothesis testing to derive effective interaction models for complex materials.

Findings

Effective interaction model for Mo$_x$Re$_{1-x}$S$_2$ was proposed.

Atomic configurations generated match experimental observations.

Predictions made for various concentrations and temperatures.

Abstract

Exploration of structure-property relationships as a function of dopant concentration is commonly based on mean field theories for solid solutions. However, such theories that work well for semiconductors tend to fail in materials with strong correlations, either in electronic behavior or chemical segregation. In these cases, the details of atomic arrangements are generally not explored and analyzed. The knowledge of the generative physics and chemistry of the material can obviate this problem, since defect configuration libraries as stochastic representation of atomic level structures can be generated, or parameters of mesoscopic thermodynamic models can be derived. To obtain such information for improved predictions, we use data from atomically resolved microscopic images that visualize complex structural correlations within the system and translate them into statistical mechanical models of structure formation. Given the significant uncertainties about the microscopic aspects of the material's processing history along with the limited number of available images, we combine model optimization techniques with the principles of statistical hypothesis testing. We demonstrate the approach on data from a series of atomically-resolved scanning transmission electron microscopy images of Mo$_x$Re$_{1-x}$S$_2$ at varying ratios of Mo/Re stoichiometries, for which we propose an effective interaction model that is then used to generate atomic configurations and make testable predictions at a range of concentrations and formation temperatures.