Resolving local structural motifs across the phase evolution of zinc titanates with computational x-ray absorption spectroscopy

Jiang, Xuance; Li, Ruoshui; Stacchiola, Dario J.; Stavitski, Eli; Qu, Xiaohui; Hybertsen, Mark S.; Liu, Mingzhao; Lu, Deyu

doi:10.1103/physrevmaterials.9.023802

Title: Resolving local structural motifs across the phase evolution of zinc titanates with computational x-ray absorption spectroscopy

Journal Article · 21 February 2025 · Physical Review Materials

DOI: https://doi.org/10.1103/physrevmaterials.9.023802 · OSTI ID:2525845

^[1]; Li, Ruoshui ^[2]; Stacchiola, Dario J. ^[2];

^[3];

^[2];

^[2]; Liu, Mingzhao ^[2];

^[2]

Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Stony Brook Univ., NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Resolving the local structure motifs that characterize phase evolution as a function of composition is a key challenge in structure characterization of complex materials. Here, in this study, we combine first-principles simulations and x-ray absorption near-edge structures (XANES) analysis to gain insights into the structure evolution revealed by measurements across a combinatorial zinc titanate thin film, which was grown with smoothly varying composition over a wide range of the Ti:Zn ratio. Specifically, we propose a cluster blind-signal-separation (cBSS) method for XANES spectral analysis based on a library of the structures and spectra of representative local motifs. In addition to motifs from zinc titanate crystals, two types of Ti-defect models constructed in this study are key to the understanding of the structure characteristics in the Zn-rich region. The cBSS method makes use of both spectral clustering of the simulated site-XANES spectra library and the BSS procedure to construct high-fidelity spectral basis functions from an experimental spectral sequence. The method provides a rigorous measure of the spectral sensitivity and basis completeness. The results of the XANES analysis are corroborated with other experimental modalities, including x-ray diffraction and spectroscopic ellipsometry, to validate the cBSS method. The calculated motif weights resulting from fitting the XANES spectra with the cBSS basis probe the atomic structure characteristics of both crystalline and amorphous phases as a function of the Ti/Zn composition. The insights of the local structure motif evolution are pivotal to the understanding of the nonmonotonic trend in the optical gap, which may lead to potential applications through tuning the optical properties of zinc titanate. The workflow of the XANES spectral analysis developed in this work can be generalized to construct the structure-property relationship in a broad material space.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2525845

Report Number(s):: BNL--227631-2025-JAAM

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 2 Vol. 9; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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