Quantifying Intrinsic, Extrinsic, Dielectric, and Secondary Pyroelectric Responses in PbZr1–xTixO3 Thin Films

Velarde, Gabriel; Pandya, Shishir; Zhang, Lei; Garcia, David; Lupi, Eduardo; Gao, Ran; Wilbur, Joshua D.; Dames, Chris; Martin, Lane W.

doi:10.1021/acsami.9b12191

Title: Quantifying Intrinsic, Extrinsic, Dielectric, and Secondary Pyroelectric Responses in PbZr_1–xTi_xO₃ Thin Films

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Abstract

Applications such as solid-state waste-heat energy conversion, infrared sensing, and thermally-driven electron emission rely on pyroelectric materials (a subclass of dielectric piezoelectrics) which exhibit temperature-dependent changes in polarization. Although enhanced dielectric and piezoelectric responses are typically found at polarization instabilities such as temperature- and chemically induced phase boundaries, large pyroelectric effects have been primarily limited in study to temperature-induced phase boundaries. Here in this paper, we directly identify the magnitude and sign of the intrinsic, extrinsic, dielectric, and secondary pyroelectric contributions to the total pyroelectric response as a function of chemistry in thin films of the canonical ferroelectric PbZr$$_{1-x}$$Ti$$_x$$O$$_3$$ (x = 0.40, 0.48, 0.60, and 0.80) across the morphotropic phase boundary. Using phase-sensitive frequency and applied dc-bias methods, the various pyroelectric contributions were measured. It is found that the total pyroelectric response decreases systematically as one moves from higher to lower titanium contents. This arises from a combination of decreasing intrinsic response (-232 to -97 μC m$$^{-2}$$ K$$^{-1}$$) and a sign inversion (+33 to -17 μC m$$^{-2}$$ K$$^{-1}$$)) of the extrinsic contribution upon crossing the morphotropic phase boundary. Additionally, the measured secondary and dielectric contributions span between -70 and -29 and 10-115 μC m$$^{-2}$$K$$^{-1}$$) under applied fields, respectively, following closely trends in the piezoelectric and dielectric susceptibility. These findings and methodologies provide novel insights into the understudied realm of pyroelectric response.

Authors:

^[1]; Pandya, Shishir ^[1];

^[1]; Garcia, David ^[1]; Lupi, Eduardo ^[1]; Gao, Ran ^[1]; Wilbur, Joshua D. ^[1]; Dames, Chris ^[1];

^[2]

Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Wed Sep 04 00:00:00 EDT 2019

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1633244

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Materials and Interfaces

Additional Journal Information:: Journal Volume: 11; Journal Issue: 38; Journal ID: ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; pyroelectric; ferroelectric; PbZr1−xTixO3; morphotropic phase boundary; thin films

Citation Formats


                    Velarde, Gabriel, Pandya, Shishir, Zhang, Lei, Garcia, David, Lupi, Eduardo, Gao, Ran, Wilbur, Joshua D., Dames, Chris, and Martin, Lane W. Quantifying Intrinsic, Extrinsic, Dielectric, and Secondary Pyroelectric Responses in PbZr1–xTixO3 Thin Films.  United States: N. p., 2019. 
Web.  doi:10.1021/acsami.9b12191.

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                    Velarde, Gabriel, Pandya, Shishir, Zhang, Lei, Garcia, David, Lupi, Eduardo, Gao, Ran, Wilbur, Joshua D., Dames, Chris, & Martin, Lane W. Quantifying Intrinsic, Extrinsic, Dielectric, and Secondary Pyroelectric Responses in PbZr1–xTixO3 Thin Films.  United States.  https://doi.org/10.1021/acsami.9b12191

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                    Velarde, Gabriel, Pandya, Shishir, Zhang, Lei, Garcia, David, Lupi, Eduardo, Gao, Ran, Wilbur, Joshua D., Dames, Chris, and Martin, Lane W. Wed .  
"Quantifying Intrinsic, Extrinsic, Dielectric, and Secondary Pyroelectric Responses in PbZr1–xTixO3 Thin Films".  United States.  https://doi.org/10.1021/acsami.9b12191.  https://www.osti.gov/servlets/purl/1633244.

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@article{osti_1633244,

  title        = {Quantifying Intrinsic, Extrinsic, Dielectric, and Secondary Pyroelectric Responses in PbZr1–xTixO3 Thin Films},

  author       = {Velarde, Gabriel and Pandya, Shishir and Zhang, Lei and Garcia, David and Lupi, Eduardo and Gao, Ran and Wilbur, Joshua D. and Dames, Chris and Martin, Lane W.},

  abstractNote = {Applications such as solid-state waste-heat energy conversion, infrared sensing, and thermally-driven electron emission rely on pyroelectric materials (a subclass of dielectric piezoelectrics) which exhibit temperature-dependent changes in polarization. Although enhanced dielectric and piezoelectric responses are typically found at polarization instabilities such as temperature- and chemically induced phase boundaries, large pyroelectric effects have been primarily limited in study to temperature-induced phase boundaries. Here in this paper, we directly identify the magnitude and sign of the intrinsic, extrinsic, dielectric, and secondary pyroelectric contributions to the total pyroelectric response as a function of chemistry in thin films of the canonical ferroelectric PbZr$_{1-x}$Ti$_x$O$_3$ (x = 0.40, 0.48, 0.60, and 0.80) across the morphotropic phase boundary. Using phase-sensitive frequency and applied dc-bias methods, the various pyroelectric contributions were measured. It is found that the total pyroelectric response decreases systematically as one moves from higher to lower titanium contents. This arises from a combination of decreasing intrinsic response (-232 to -97 μC m$^{-2}$ K$^{-1}$) and a sign inversion (+33 to -17 μC m$^{-2}$ K$^{-1}$)) of the extrinsic contribution upon crossing the morphotropic phase boundary. Additionally, the measured secondary and dielectric contributions span between -70 and -29 and 10-115 μC m$^{-2}$K$^{-1}$) under applied fields, respectively, following closely trends in the piezoelectric and dielectric susceptibility. These findings and methodologies provide novel insights into the understudied realm of pyroelectric response.},

  doi          = {10.1021/acsami.9b12191},

  journal      = {ACS Applied Materials and Interfaces},

  number       = 38,

  volume       = 11,

  place        = {United States},

  year         = {Wed Sep 04 00:00:00 EDT 2019},

  month        = {Wed Sep 04 00:00:00 EDT 2019}

}

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Title: Quantifying Intrinsic, Extrinsic, Dielectric, and Secondary Pyroelectric Responses in PbZr1–xTixO3 Thin Films

Abstract

Citation Formats

Title: Quantifying Intrinsic, Extrinsic, Dielectric, and Secondary Pyroelectric Responses in PbZr_1–xTi_xO₃ Thin Films