Decoupling Li out-diffusion and surface diffusion in the lithiation-assisted epitaxial growth of lithium tungstate

Shi, Jueli; Samarakoon, Widitha S.; Choi, Min-Ju; Wang, Le; Dhas, Jeffrey A.; Yang, Zhenzhong; Zhang, Zhan; Tao, Jinhui; Bowden, Mark E.; Zhu, Zihua; Zhou, Hua; Feng, Zhenxing; Du, Yingge

doi:10.1103/bk4y-qds8

Title: Decoupling Li out-diffusion and surface diffusion in the lithiation-assisted epitaxial growth of lithium tungstate

Journal Article · Mon Dec 08 00:00:00 UTC 2025 · Physical Review Materials

DOI: https://doi.org/10.1103/bk4y-qds8 · OSTI ID:3010851

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Oregon State Univ., Corvallis, OR (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); East China Normal Univ. (ECNU), Shanghai (China)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Oregon State Univ., Corvallis, OR (United States)

Lithiation-assisted epitaxy offers a flexible and robust approach for synthesizing high-quality Li-containing materials and interfaces with precise control. Here, in this study, we use lithium tungstate (Li_xWO_3+x/2, where x = 0 to 2) as a model system to investigate the intertwined effects of Li out-diffusion-induced compositional changes and surface-diffusion-induced morphological changes. By systematically varying synthesis and processing conditions, we uncover their impact on lithium tungstate film formation. Comprehensive characterizations, including X-ray diffraction, atomic force microscopy, X-ray photoemission spectroscopy and time-of-flight secondary ion mass spectrometry, reveal that low-temperature growth (< 300 °C) followed by high-temperature annealing yields continuous lithium tungstate films with significantly reduced surface roughness. In contrast, high-temperature deposition (≥ 300 °C) accelerates surface diffusion and Li out-diffusion, leading to island formation. Furthermore, in situ scanning transmission electron microscopy demonstrates the beam sensitivity of Li₂WO₄ and reveals a phase transition from Li₂WO₄ to LiWO_3.5 under prolonged electron beam exposure. These findings deepen our understanding of how to control composition and morphology of Li-containing films, providing valuable insights for the design and integration of energy materials.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 3010851

Report Number(s):: PNNL-SA--210171

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 12 Vol. 9; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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