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Title: Pyroelectric and electrocaloric effects in ferroelectric silicon-doped hafnium oxide thin films

Abstract

The emergent ferroelectricity in HfO 2 -based systems has attracted significant attention as this simple binary high- k dielectric now offers the possibility of nonvolatile function. Here we employ zero-field and field-dependent pyroelectricity to show that thin films of silicon-doped HfO 2 do exhibit a broken-inversion symmetry and are indeed ferroelectric. In addition, the pyroelectric response is found to exhibit a wake-up behavior akin to the wake-up phenomenon observed in the ferroelectric polarization with electric-field cycling. Using polarization-electric field hysteresis measurements, this wake-up phenomenon is attributed to the presence of defect dipoles which explains the measured pyroelectric response. Finally, direct electrocaloric measurements are performed on these silicon-doped HfO 2 thin films, revealing an electrocaloric coefficient ~ 4 times larger in magnitude than that expected for the measured pyroelectric coefficient. This enhancement is explained using the plausible role played by defect dipoles that contribute to additional configurational or dipolar entropy.

Authors:
 [1];  [1];  [1];  [2]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  2. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; US Army Research Office (ARO); National Science Foundation (NSF)
OSTI Identifier:
1633226
Alternate Identifier(s):
OSTI ID: 1489071
Grant/Contract Number:  
AC02-05CH11231; SC-0012375; W911NF-14-1-0104; DMR-1708615
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 12; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; electrocaloric effect; ferroelectricity; pyroelectricity; thin films

Citation Formats

Pandya, Shishir, Velarde, Gabriel, Zhang, Lei, and Martin, Lane W. Pyroelectric and electrocaloric effects in ferroelectric silicon-doped hafnium oxide thin films. United States: N. p., 2018. Web. doi:10.1103/physrevmaterials.2.124405.
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Pandya, Shishir, Velarde, Gabriel, Zhang, Lei, & Martin, Lane W. Pyroelectric and electrocaloric effects in ferroelectric silicon-doped hafnium oxide thin films. United States. https://doi.org/10.1103/physrevmaterials.2.124405
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Pandya, Shishir, Velarde, Gabriel, Zhang, Lei, and Martin, Lane W. Fri . "Pyroelectric and electrocaloric effects in ferroelectric silicon-doped hafnium oxide thin films". United States. https://doi.org/10.1103/physrevmaterials.2.124405. https://www.osti.gov/servlets/purl/1633226.
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@article{osti_1633226,
title = {Pyroelectric and electrocaloric effects in ferroelectric silicon-doped hafnium oxide thin films},
author = {Pandya, Shishir and Velarde, Gabriel and Zhang, Lei and Martin, Lane W.},
abstractNote = {The emergent ferroelectricity in HfO2-based systems has attracted significant attention as this simple binary high-k dielectric now offers the possibility of nonvolatile function. Here we employ zero-field and field-dependent pyroelectricity to show that thin films of silicon-doped HfO2 do exhibit a broken-inversion symmetry and are indeed ferroelectric. In addition, the pyroelectric response is found to exhibit a wake-up behavior akin to the wake-up phenomenon observed in the ferroelectric polarization with electric-field cycling. Using polarization-electric field hysteresis measurements, this wake-up phenomenon is attributed to the presence of defect dipoles which explains the measured pyroelectric response. Finally, direct electrocaloric measurements are performed on these silicon-doped HfO2 thin films, revealing an electrocaloric coefficient ~4 times larger in magnitude than that expected for the measured pyroelectric coefficient. This enhancement is explained using the plausible role played by defect dipoles that contribute to additional configurational or dipolar entropy.},
doi = {10.1103/physrevmaterials.2.124405},
journal = {Physical Review Materials},
number = 12,
volume = 2,
place = {United States},
year = {Fri Dec 28 00:00:00 EST 2018},
month = {Fri Dec 28 00:00:00 EST 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1103/physrevmaterials.2.124405
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Cited by: 29 works
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Figures / Tables:

FIG. 1 FIG. 1: (a)–(e) Schematic illustration showing the fabrication of the electrothermal device through the various processing steps. (f) Cross-section view of the final device showing the various layers in the heterostructure.
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    Works referencing / citing this record:

    Pyroelectric Energy Conversion in Doped Hafnium Oxide (HfO 2 ) Thin Films on Area‐Enhanced Substrates
    journal, July 2019

    • Hanrahan, Brendan; Mart, Clemens; Kämpfe, Thomas
    • Energy Technology, Vol. 7, Issue 10
    • DOI: 10.1002/ente.201900515

    Enhanced electrocaloric effect in a Si-doped PbZr 0.95 Ti 0.05 O 3 film deposited on FTO substrate
    journal, July 2019

    • Wang, Jinxin; Jiang, Guicheng; Huang, Weicheng
    • Applied Physics Letters, Vol. 115, Issue 5
    • DOI: 10.1063/1.5093697

    Stabilization of ferroelectric phase of Hf 0.58 Zr 0.42 O 2 on NbN at 4 K
    journal, March 2019

    • Henry, M. D.; Smith, S. W.; Lewis, R. M.
    • Applied Physics Letters, Vol. 114, Issue 9
    • DOI: 10.1063/1.5052435

    Ferroelectric and pyroelectric properties of polycrystalline La-doped HfO 2 thin films
    journal, March 2019

    • Mart, C.; Kühnel, K.; Kämpfe, T.
    • Applied Physics Letters, Vol. 114, Issue 10
    • DOI: 10.1063/1.5089821

    Pyroelectric Energy Conversion in Doped Hafnium Oxide (HfO 2 ) Thin Films on Area‐Enhanced Substrates
    journal, August 2019

    • Hanrahan, Brendan; Mart, Clemens; Kämpfe, Thomas
    • Energy Technology, Vol. 7, Issue 10
    • DOI: 10.1002/ente.201980371

    Enhanced pyroelectric properties of Bi 1−x La x FeO 3 thin films
    journal, November 2019

    • Zhang, Lei; Huang, Yen-Lin; Velarde, Gabriel
    • APL Materials, Vol. 7, Issue 11
    • DOI: 10.1063/1.5128413
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