Precursor-Dependent Energetics as a Predictive Principle for Polymorph Selection in Thin Films

TL;DR

This paper introduces a predictive framework linking precursor chemistry to polymorph selection in vapor deposition, enabling controlled synthesis of metastable phases by modulating reaction energetics and kinetics.

Contribution

It develops a quantitative model integrating reaction energetics and substrate interactions to predict polymorph outcomes based on precursor chemistry.

Findings

Precursor reaction driving force influences metastable phase stabilization.

Flow rates affect supersaturation and phase stabilization.

Model accurately predicts polymorph competition in Ga2O3 and TiO2 systems.

Abstract

Vapor deposition allows for the synthesis of metastable polymorphs with unique properties, yet polymorph selection remains largely empirical due to the lack of predictive guidelines bridging thermodynamics, kinetics, and synthesis conditions. Here, we show that precursor chemistry can control metastable polymorph selection by modulating the reaction driving force governing nucleation. By integrating first-principles reaction energetics and substrate interactions into classical nucleation theory, we establish a quantitative framework that connects precursor-dependent reaction energetics to polymorph accessibility during vapor deposition. Using Ga2O3 as a model system, we demonstrate that highly reactive precursors with large reaction driving forces kinetically stabilize the metastable {\alpha} phase, whereas low-driving-force precursors permit thermodynamic relaxation to the stable \b{eta} phase. Furthermore, precursor flow rates amplify supersaturation, expanding the kinetic window for stabilizing the elusive \k{appa} phase. The predictive capability of this approach is further validated in the TiO2 system, where precursor-dependent reaction energetics correctly capture the competitive nucleation between rutile and anatase. These results establish precursor chemistry as a tunable chemical lever for controlling nucleation kinetics and provide a predictive design principle for metastable polymorph synthesis in vapor deposition.