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Title: Ferroelectricity in Pb 1+δZrO 3 Thin Films

Antiferroelectric PbZrO 3 is being considered for a wide range of applications where the competition between centrosymmetric and noncentrosymmetric phases is important to the response. Here, we focus on the epitaxial growth of PbZrO 3 thin films and understanding the chemistry structure coupling in Pb 1+δ ZrO 3 (δ = 0, 0.1, 0.2). High-quality, single-phase Pb 1+δZrO 3 films are synthesized via pulsed-laser deposition. Though no significant lattice parameter change is observed in X-ray studies, electrical characterization reveals that while the PbZrO 3 and Pb 1.1ZrO 3 heterostructures remain intrinsically antiferroelectric, the Pb 1.2ZrO 3 heterostructures exhibit a hysteresis loop indicative of ferroelectric response. Furthermore X-ray scattering studies reveal strong quarter-order diffraction peaks in PbZrO 3 and Pb 1.1ZrO 3 heterostructures indicative of antiferroelectricity, while no such peaks are observed for Pb 1.2ZrO 3 heterostructures. Density functional theory calculations suggest the large cation nonstoichiometry is accommodated by incorporation of antisite Pb-Zr defects, which drive the Pb 1.2ZrO 3 heterostructures to a ferroelectric phase with R3c symmetry. In the end, stabilization of metastable phases in materials via chemical nonstoichiometry and defect engineering enables a novel route to manipulate the energy of the ground state of materials and the corresponding material properties.
Authors:
 [1] ;  [2] ;  [1] ;  [1] ;  [3] ;  [1] ;  [1] ;  [1] ; ORCiD logo [1] ;  [4] ;  [5] ;  [6] ; ORCiD logo [7]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry, Materials Sciences Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source; Univ. of Science and Technology, Hefei (China). National Sychrotron Radiation Lab., CAS Key Lab. of Materials for Energy Conversion
  4. Univ. of California, Berkeley, CA (United States). Dept. of Electrical Engineering
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source
  6. Kavli Energy NanoSciences Inst., Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry, Materials Sciences Division
  7. 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:
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 15; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); US Army Research Office (ARO)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; PbZrO3; antiferroelectric/ferroelectric; cation stoichiometry; crystal symmetry; defect engineering
OSTI Identifier:
1394834
Alternate Identifier(s):
OSTI ID: 1436637

Gao, Ran, Reyes-Lillo, Sebastian E., Xu, Ruijuan, Dasgupta, Arvind, Dong, Yongqi, Dedon, Liv R., Kim, Jieun, Saremi, Sahar, Chen, Zuhuang, Serrao, Claudy R., Zhou, Hua, Neaton, Jeffrey B., and Martin, Lane W.. Ferroelectricity in Pb1+δZrO3 Thin Films. United States: N. p., Web. doi:10.1021/acs.chemmater.7b02506.
Gao, Ran, Reyes-Lillo, Sebastian E., Xu, Ruijuan, Dasgupta, Arvind, Dong, Yongqi, Dedon, Liv R., Kim, Jieun, Saremi, Sahar, Chen, Zuhuang, Serrao, Claudy R., Zhou, Hua, Neaton, Jeffrey B., & Martin, Lane W.. Ferroelectricity in Pb1+δZrO3 Thin Films. United States. doi:10.1021/acs.chemmater.7b02506.
Gao, Ran, Reyes-Lillo, Sebastian E., Xu, Ruijuan, Dasgupta, Arvind, Dong, Yongqi, Dedon, Liv R., Kim, Jieun, Saremi, Sahar, Chen, Zuhuang, Serrao, Claudy R., Zhou, Hua, Neaton, Jeffrey B., and Martin, Lane W.. 2017. "Ferroelectricity in Pb1+δZrO3 Thin Films". United States. doi:10.1021/acs.chemmater.7b02506. https://www.osti.gov/servlets/purl/1394834.
@article{osti_1394834,
title = {Ferroelectricity in Pb1+δZrO3 Thin Films},
author = {Gao, Ran and Reyes-Lillo, Sebastian E. and Xu, Ruijuan and Dasgupta, Arvind and Dong, Yongqi and Dedon, Liv R. and Kim, Jieun and Saremi, Sahar and Chen, Zuhuang and Serrao, Claudy R. and Zhou, Hua and Neaton, Jeffrey B. and Martin, Lane W.},
abstractNote = {Antiferroelectric PbZrO3 is being considered for a wide range of applications where the competition between centrosymmetric and noncentrosymmetric phases is important to the response. Here, we focus on the epitaxial growth of PbZrO3 thin films and understanding the chemistry structure coupling in Pb1+δ ZrO3 (δ = 0, 0.1, 0.2). High-quality, single-phase Pb1+δZrO3 films are synthesized via pulsed-laser deposition. Though no significant lattice parameter change is observed in X-ray studies, electrical characterization reveals that while the PbZrO3 and Pb1.1ZrO3 heterostructures remain intrinsically antiferroelectric, the Pb1.2ZrO3 heterostructures exhibit a hysteresis loop indicative of ferroelectric response. Furthermore X-ray scattering studies reveal strong quarter-order diffraction peaks in PbZrO3 and Pb1.1ZrO3 heterostructures indicative of antiferroelectricity, while no such peaks are observed for Pb1.2ZrO3 heterostructures. Density functional theory calculations suggest the large cation nonstoichiometry is accommodated by incorporation of antisite Pb-Zr defects, which drive the Pb1.2ZrO3 heterostructures to a ferroelectric phase with R3c symmetry. In the end, stabilization of metastable phases in materials via chemical nonstoichiometry and defect engineering enables a novel route to manipulate the energy of the ground state of materials and the corresponding material properties.},
doi = {10.1021/acs.chemmater.7b02506},
journal = {Chemistry of Materials},
number = 15,
volume = 29,
place = {United States},
year = {2017},
month = {7}
}