Prediction of crystallized phases of amorphous Ta$_2$O$_5$-based mixed oxide thin films using density functional theory calculations

TL;DR

This study demonstrates that density functional theory (DFT) calculations can effectively predict the crystalline phases of amorphous Ta$_2$O$_5$-based thin films after annealing, aiding accelerated material discovery.

Contribution

It introduces a method combining DFT calculations with experimental validation to predict crystalline phases of amorphous oxide films, expanding the genomic approach to amorphous materials.

Findings

DFT predictions align well with experimental phases in most cases.

Two cases showed discrepancies due to database limitations and DFT overestimations.

Dopants can act as amorphizers, enhancing thermal stability of Ta$_2$O$_5$.

Abstract

The genomics approach to materials, heralded by increasingly accurate density functional theory (DFT) calculations conducted on thousands of crystalline compounds, has led to accelerated material discovery and property predictions. However, so far amorphous materials have been largely excluded from this as these systems are notoriously difficult to simulate. Here we study amorphous Ta$_2$O$_5$ thin films mixed with Al$_2$O$_3$, SiO$_2$, Sc$_2$O$_3$, TiO$_2$, ZnO, ZrO$_2$, Nb$_2$O$_5$ and HfO$_2$ to identify their crystalline structure upon post-deposition annealing in air both experimentally and with simulations. Using the Materials Project open database, phase diagrams based on DFT calculations are constructed for the mixed oxide systems and the annealing process is evaluated via grand potential diagrams with varying oxygen chemical potential. Despite employing calculations based on crystalline bulk materials, the predictions agree well with the experimentally observed crystallized phases of the amorphous films. Only in two cases the database leads to incorrect predictions: in TiO$_2$-doped Ta$_2$O$_5$ because it does not contain a ternary compound found experimentally, and in Sc$_2$O$_3$-doped Ta$_2$O$_5$ because DFT overestimates the formation enthalpy difference between Sc$_2$O$_3$ and Ta$_2$O$_5$ and thus does not reproduce observed oxygen competition effects. In the absence of ternary phases, the dopant acts as an amorphizer agent increasing the thermal stability of Ta$_2$O$_5$. These results show that DFT calculations can be applied for the prediction of crystallized structures of annealed amorphous materials. This could pave the way for accelerated \textit{in silico} material discovery and property predictions using the powerful genomic approach for amorphous oxide coatings employed in a wide range of applications such as optical coatings, energy storage and electronic devices.