Infrared Signatures for Phase Identification in Hafnium Oxide Thin Films

Jaszewski, Samantha T.; Calderon, Sebastian; Shrestha, Bishal; Fields, Shelby S.; Samanta, Atanu; Vega, Fernando J.; Minyard, Jacob D.; Casamento, Joseph A.; Maria, Jon-Paul; Podraza, Nikolas J.; Dickey, Elizabeth C.; Rappe, Andrew M.; Beechem, Thomas E.; Ihlefeld, Jon F.

doi:10.1021/acsnano.3c08371

Title: Infrared Signatures for Phase Identification in Hafnium Oxide Thin Films

Journal Article · 27 November 2023 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.3c08371 · OSTI ID:2222570

^[1]; Calderon, Sebastian ^[2]; Shrestha, Bishal ^[3];

^[4]; Samanta, Atanu ^[5]; Vega, Fernando J. ^[6]; Minyard, Jacob D. ^[6]; Casamento, Joseph A. ^[7]; Maria, Jon-Paul ^[7]; Podraza, Nikolas J. ^[3];

^[2];

^[5];

^[6];

^[4]

University of Virginia, Charlottesville, VA (United States); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); University of Virginia
Carnegie Mellon University, Pittsburgh, PA (United States)
University of Toledo, OH (United States)
University of Virginia, Charlottesville, VA (United States)
University of Pennsylvania, Philadelphia, PA (United States)
Purdue University, West Lafayette, IN (United States)
Pennsylvania State University, University Park, PA (United States)

Phase identification in HfO₂-based thin films is a prerequisite to understanding the mechanisms stabilizing the ferroelectric phase in these materials, which hold great promise in next-generation non-volatile memory and computing technology. While grazing-incidence X-ray diffraction is commonly employed for this purpose, it has difficulty unambiguously differentiating between the ferroelectric phase and other metastable phases that may exist due to similarities in the d-spacings, their low intensities, and the overlapping of reflections. Infrared signatures provide an alternative route. However, their use in phase identification remains limited because phase control has overwhelmingly been accomplished via substituents, thereby convoluting infrared signatures between the substituent and the phase changes they induce. Herein, we report the infrared optical responses of three undoped hafnium oxide films where annealing conditions have been used to create films consisting primarily of the ferroelectric polar orthorhombic Pca2₁, antipolar orthorhombic Pbca, and monoclinic P2₁/c phases, as was confirmed via transmission electron microscopy (TEM), UVvisible optical properties, and electrical property measurements. Vibrational signatures acquired from synchrotron nano-Fourier transform infrared spectroscopy (nano-FTIR) are shown to be capable of differentiating between the phases in a non-destructive, rapid, and nanoscale manner. The utility of nano-FTIR is illustrated for a film exhibiting an antiferroelectric polarization response. In this sample, it is proven that this behavior results from the Pbca phase rather than the often-cited tetragonal phase. Here, by demonstrating that IRspectroscopy can unambiguously distinguish phases in this material, this work establishes a tool needed to isolate the factors dictating ferroelectric phase stability in HfO₂-based materials.

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Research Organization:: Pennsylvania State University, University Park, PA (United States)

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

Grant/Contract Number:: SC0021118; AC02-05CH11231

OSTI ID:: 2222570

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 23 Vol. 17; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Hafnium Oxide
Ferroelectric
Infrared Spectroscopy
Transmission Electron Microscopy
Phases
Differentiation
Electrical Conductivity
Phase Transitions
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Title: Infrared Signatures for Phase Identification in Hafnium Oxide Thin Films

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