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Title: Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs

Abstract

Site-specific preparation of specimens using focused ion beam instruments for transmission electron microscopy is at the forefront of targeting regions of interest for nanoscale characterization. Typical methods of pinpointing desired features include electron backscatter diffraction for differentiating crystal structures and energy-dispersive X-Ray spectroscopy for probing compositional variations. Yet there are situations, notably in the titanium dioxide system, where these techniques can fail. Differentiating between the brookite and anatase polymorphs of titania is either excessively laborious or impossible with the aforementioned techniques. However, due to differences in bonding structure, Raman spectroscopy serves as an ideal candidate for polymorph differentiation. In this work, a correlative approach utilizing Raman spectroscopy for targeted focused ion beam specimen preparation was employed. Dark field imaging and diffraction in the transmission electron microscope confirmed the region of interest located via Raman spectroscopy and demonstrated the validity of this new method. Correlative Raman spectroscopy, scanning electron microscopy, and focused ion beam is shown to be a promising new technique for identifying site-specific preparation of nanoscale specimens in cases where conventional approaches do not suffice.

Authors:
 [1];  [2];  [3]; ORCiD logo [4];  [4];  [1]
  1. Colorado School of Mines, Golden, CO (United States)
  2. TESCAN USA Inc., Warrendale, PA (United States)
  3. WITec GmbH, Ulm (Germany)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1431039
Report Number(s):
NREL/JA-5K00-71234
Journal ID: ISSN 0304-3991
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Ultramicroscopy
Additional Journal Information:
Journal Volume: 188; Journal Issue: C; Journal ID: ISSN 0304-3991
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; raman spectroscopy; focused ion beam; transmission electron; microscopy; correlative; site-specific preparation; polymorphs

Citation Formats

Mangum, John S., Chan, Lisa H., Schmidt, Ute, Garten, Lauren M., Ginley, David S., and Gorman, Brian P.. Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs. United States: N. p., 2018. Web. https://doi.org/10.1016/j.ultramic.2018.02.007.
Mangum, John S., Chan, Lisa H., Schmidt, Ute, Garten, Lauren M., Ginley, David S., & Gorman, Brian P.. Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs. United States. https://doi.org/10.1016/j.ultramic.2018.02.007
Mangum, John S., Chan, Lisa H., Schmidt, Ute, Garten, Lauren M., Ginley, David S., and Gorman, Brian P.. Fri . "Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs". United States. https://doi.org/10.1016/j.ultramic.2018.02.007. https://www.osti.gov/servlets/purl/1431039.
@article{osti_1431039,
title = {Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs},
author = {Mangum, John S. and Chan, Lisa H. and Schmidt, Ute and Garten, Lauren M. and Ginley, David S. and Gorman, Brian P.},
abstractNote = {Site-specific preparation of specimens using focused ion beam instruments for transmission electron microscopy is at the forefront of targeting regions of interest for nanoscale characterization. Typical methods of pinpointing desired features include electron backscatter diffraction for differentiating crystal structures and energy-dispersive X-Ray spectroscopy for probing compositional variations. Yet there are situations, notably in the titanium dioxide system, where these techniques can fail. Differentiating between the brookite and anatase polymorphs of titania is either excessively laborious or impossible with the aforementioned techniques. However, due to differences in bonding structure, Raman spectroscopy serves as an ideal candidate for polymorph differentiation. In this work, a correlative approach utilizing Raman spectroscopy for targeted focused ion beam specimen preparation was employed. Dark field imaging and diffraction in the transmission electron microscope confirmed the region of interest located via Raman spectroscopy and demonstrated the validity of this new method. Correlative Raman spectroscopy, scanning electron microscopy, and focused ion beam is shown to be a promising new technique for identifying site-specific preparation of nanoscale specimens in cases where conventional approaches do not suffice.},
doi = {10.1016/j.ultramic.2018.02.007},
journal = {Ultramicroscopy},
number = C,
volume = 188,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Figure 1 Figure 1: Crystal structures of TiO2 polymorphs; (a) anatase and (b) brookite.

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Works referenced in this record:

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    Works referencing / citing this record:

    Utilizing TiO 2 amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics
    journal, December 2019

    • Mangum, John S.; Garten, Lauren M.; Ginley, David S.
    • Journal of the American Ceramic Society, Vol. 103, Issue 4
    • DOI: 10.1111/jace.16965

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.