Large tetragonality and room temperature ferroelectricity in compressively strained CaTiO3 thin films
Abstract
We report that ferroelectricity and piezoelectricity are desirable for a variety of high-temperature applications such as actuators and sensors in heat engines, high-temperature manufacturing, and space technologies; however, the number of such material candidates is currently limited. Here, we demonstrate that CaTiO3, the first discovered perovskite mineral that is abundantly found in the Earth, as a non-polar bulk form, becomes a high-temperature ferroelectric oxide under compression. A strain-phase-temperature diagram of CaTiO3 is created by growing a series of thin films with a range of compressive and tensile strains. Using temperature dependent optical second harmonic generation analysis, we show that tensile strained films exhibit predominantly in-plane polarization with orthorhombic-like point group symmetry with a phase transition below room temperature. On the other hand, compressively strained CaTiO3 films exhibit a neartetragonal unit cell with a c/a ratio of 1.03, larger than that of classic ferroelectric, e.g. BaTiO3 (c/a~1.01). These films exhibit a robust and switchable out-of-plane polarization at room temperature, with a ferroelectric transition temperature up to ~800 K. Density functional theory calculations reveal that compressive strain gives rise to a large out-of-plane displacement of Ti-cations inside the TiO6 octahedral cages responsible for the strain induced polarization of ~ 9μC/cm2. Given thatmore »
- Authors:
-
- Pennsylvania State Univ., University Park, PA (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1560045
- Alternate Identifier(s):
- OSTI ID: 1512339
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- APL Materials
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 5; Journal ID: ISSN 2166-532X
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; CaTiO3; Ferroelectric; Hybrid molecular beam epitaxy; Piezoresponse force microscopy; Second harmonic generation; Strain engineering; Thin film
Citation Formats
Haislmaier, Ryan C., Lu, Yanfu, Lapano, Jason, Zhou, Hua, Alem, Nasim, Sinnott, Susan B., Engel-Herbert, Roman, and Gopalan, Venkatraman. Large tetragonality and room temperature ferroelectricity in compressively strained CaTiO3 thin films. United States: N. p., 2019.
Web. doi:10.1063/1.5090798.
Haislmaier, Ryan C., Lu, Yanfu, Lapano, Jason, Zhou, Hua, Alem, Nasim, Sinnott, Susan B., Engel-Herbert, Roman, & Gopalan, Venkatraman. Large tetragonality and room temperature ferroelectricity in compressively strained CaTiO3 thin films. United States. https://doi.org/10.1063/1.5090798
Haislmaier, Ryan C., Lu, Yanfu, Lapano, Jason, Zhou, Hua, Alem, Nasim, Sinnott, Susan B., Engel-Herbert, Roman, and Gopalan, Venkatraman. Mon .
"Large tetragonality and room temperature ferroelectricity in compressively strained CaTiO3 thin films". United States. https://doi.org/10.1063/1.5090798. https://www.osti.gov/servlets/purl/1560045.
@article{osti_1560045,
title = {Large tetragonality and room temperature ferroelectricity in compressively strained CaTiO3 thin films},
author = {Haislmaier, Ryan C. and Lu, Yanfu and Lapano, Jason and Zhou, Hua and Alem, Nasim and Sinnott, Susan B. and Engel-Herbert, Roman and Gopalan, Venkatraman},
abstractNote = {We report that ferroelectricity and piezoelectricity are desirable for a variety of high-temperature applications such as actuators and sensors in heat engines, high-temperature manufacturing, and space technologies; however, the number of such material candidates is currently limited. Here, we demonstrate that CaTiO3, the first discovered perovskite mineral that is abundantly found in the Earth, as a non-polar bulk form, becomes a high-temperature ferroelectric oxide under compression. A strain-phase-temperature diagram of CaTiO3 is created by growing a series of thin films with a range of compressive and tensile strains. Using temperature dependent optical second harmonic generation analysis, we show that tensile strained films exhibit predominantly in-plane polarization with orthorhombic-like point group symmetry with a phase transition below room temperature. On the other hand, compressively strained CaTiO3 films exhibit a neartetragonal unit cell with a c/a ratio of 1.03, larger than that of classic ferroelectric, e.g. BaTiO3 (c/a~1.01). These films exhibit a robust and switchable out-of-plane polarization at room temperature, with a ferroelectric transition temperature up to ~800 K. Density functional theory calculations reveal that compressive strain gives rise to a large out-of-plane displacement of Ti-cations inside the TiO6 octahedral cages responsible for the strain induced polarization of ~ 9μC/cm2. Given that nearly half of the perovskites exhibit the bulk symmetry of CaTiO3, compressive strain tuning of this family may prove to be a fertile ground for the discovery of strain-induced piezoelectrics and ferroelectrics at high-temperatures. High-temperature piezoelectric sensors are important for many industries such as automotive, aircraft, and aerospace, as well as nuclear and geothermal energy, where dynamic structural monitoring of high-speed rotors in engines, turbines, and power generators is critical for safety and reliability.[1, 2] Modern sensors are however limited, where the main challenges are maximizing operating temperatures while maintaining good sensing capability and low electrical leakage.[3] High-temperature piezoelectric materials are typically derived from BaTiO3 or PbTiO3 based ceramics and single crystals, as these materials are also ferroelectric, meaning that they have a built-in spontaneous polarization (Ps). In bulk, these standard ferroelectric perovskite materials yield maximum operating temperatures ranging from 250-450 °C.[4], where above these temperatures the spontaneous polarization (P) and piezoelectric properties disappear due to the onset of a ferroelectric-to-paraelectric phase transition (TC). As next-generation engines, turbines, and reactors require hotter operating temperatures above 500 °C, materials with enhanced ferroelectric properties and increased ferroelectric transition temperatures will be needed in such extreme conditions. A promising way of boosting ferroelectric transition temperatures and polarization is through epitaxial strain engineering,[5] where tremendous in-plane distortions can be applied to thin film crystal materials, well beyond the point at which their bulk ceramic and single crystal counterparts would crack. Strain engineering has proven to drastically enhance ferroelectric polarizations and transition temperatures in classic ferroelectric materials such as BaTiO3 [6] and PbTiO3 [7], and strain can even turn on ferroelectricity in otherwise non-polar materials such as SrTiO3 and CaTiO3,[8] although reported strain-induced ferroelectric transition temperatures are only at room temperature or below.[9-12] In this work, we will focus on strain-induced ferroelectricity in CaTiO3, the first discovered perovskite mineral and long known to be a simple nonpolar insulating crystal.},
doi = {10.1063/1.5090798},
journal = {APL Materials},
number = 5,
volume = 7,
place = {United States},
year = {Mon May 13 00:00:00 EDT 2019},
month = {Mon May 13 00:00:00 EDT 2019}
}
Web of Science
Works referenced in this record:
Room-temperature ferroelectricity in strained SrTiO3
journal, August 2004
- Haeni, J. H.; Irvin, P.; Chang, W.
- Nature, Vol. 430, Issue 7001, p. 758-761
Probing Ferroelectrics Using Optical Second Harmonic Generation
journal, August 2011
- Denev, Sava A.; Lummen, Tom T. A.; Barnes, Eftihia
- Journal of the American Ceramic Society, Vol. 94, Issue 9
Human health and ecological toxicity potentials due to heavy metal content in waste electronic devices with flat panel displays
journal, May 2010
- Lim, Seong-Rin; Schoenung, Julie M.
- Journal of Hazardous Materials, Vol. 177, Issue 1-3
Frontiers in the Growth of Complex Oxide Thin Films: Past, Present, and Future of Hybrid MBE
journal, December 2017
- Brahlek, Matthew; Gupta, Arnab Sen; Lapano, Jason
- Advanced Functional Materials, Vol. 28, Issue 9
Self-regulated growth of CaVO 3 by hybrid molecular beam epitaxy
journal, November 2017
- Eaton, Craig; Lapano, Jason; Zhang, Lei
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 35, Issue 6
Unleashing Strain Induced Ferroelectricity in Complex Oxide Thin Films via Precise Stoichiometry Control
journal, September 2016
- Haislmaier, Ryan C.; Grimley, Everett D.; Biegalski, Michael D.
- Advanced Functional Materials, Vol. 26, Issue 40
Stoichiometry as key to ferroelectricity in compressively strained SrTiO 3 films
journal, July 2016
- Haislmaier, R. C.; Engel-Herbert, R.; Gopalan, V.
- Applied Physics Letters, Vol. 109, Issue 3
ELATE: an open-source online application for analysis and visualization of elastic tensors
journal, May 2016
- Gaillac, Romain; Pullumbi, Pluton; Coudert, François-Xavier
- Journal of Physics: Condensed Matter, Vol. 28, Issue 27
Phenomenological thermodynamic potential for CaTiO single crystals
journal, February 2012
- Gu, Yijia; Rabe, Karin; Bousquet, Eric
- Physical Review B, Vol. 85, Issue 6
Materials for high temperature piezoelectric transducers
journal, October 1998
- Damjanovic, Dragan
- Current Opinion in Solid State and Materials Science, Vol. 3, Issue 5
Induced Magnetoelectric Response in Perovskites
journal, November 2011
- Bousquet, Eric; Spaldin, Nicola
- Physical Review Letters, Vol. 107, Issue 19
Strain-induced ferroelectricity in orthorhombic from first principles
journal, June 2009
- Eklund, C. -J.; Fennie, C. J.; Rabe, K. M.
- Physical Review B, Vol. 79, Issue 22
Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals
journal, January 2019
- Ramirez, Mariola O.; Lummen, Tom T. A.; Carrasco, Irene
- APL Materials, Vol. 7, Issue 1
Perovskite CaTiO3 as an incipient ferroelectric
journal, May 1999
- Lemanov, V. V.; Sotnikov, A. V.; Smirnova, E. P.
- Solid State Communications, Vol. 110, Issue 11
Three-dimensional atomic scale electron density reconstruction of octahedral tilt epitaxy in functional perovskites
journal, December 2018
- Yuan, Yakun; Lu, Yanfu; Stone, Greg
- Nature Communications, Vol. 9, Issue 1
Piezoelectric Materials for High Temperature Sensors
journal, August 2011
- Zhang, Shujun; Yu, Fapeng
- Journal of the American Ceramic Society, Vol. 94, Issue 10
Quantitative mapping of switching behavior in piezoresponse force microscopy
journal, July 2006
- Jesse, Stephen; Lee, Ho Nyung; Kalinin, Sergei V.
- Review of Scientific Instruments, Vol. 77, Issue 7
Enhancement of Ferroelectricity in Strained BaTiO3 Thin Films
journal, November 2004
- Choi, K. J.; Biegalski, M.; Li, Y. L.
- Science, Vol. 306, Issue 5698, p. 1005-1009
Structure and properties of CaTiO3
journal, March 1957
- Kay, H. F.; Bailey, P. C.
- Acta Crystallographica, Vol. 10, Issue 3
Impact of symmetry on the ferroelectric properties of CaTiO3 thin films
journal, April 2015
- Biegalski, Michael D.; Qiao, Liang; Gu, Yijia
- Applied Physics Letters, Vol. 106, Issue 16
Observation of ferroelectricity induced by defect dipoles in the strain-free epitaxial CaTiO3 thin film
journal, May 2014
- Yang, Sang Mo; Moon, Soon Jae; Kim, Tae Heon
- Current Applied Physics, Vol. 14, Issue 5
Acute barium poisoning with respiratory failure and rhabdomyolysis
journal, October 1991
- Johnson, Charles H.; VanTassell, V. Jefferson
- Annals of Emergency Medicine, Vol. 20, Issue 10
Switching spectroscopy piezoresponse force microscopy of ferroelectric materials
journal, February 2006
- Jesse, Stephen; Baddorf, Arthur P.; Kalinin, Sergei V.
- Applied Physics Letters, Vol. 88, Issue 6
Why Are There So Few Perovskite Ferroelectrics?
journal, May 2013
- Benedek, Nicole A.; Fennie, Craig J.
- The Journal of Physical Chemistry C, Vol. 117, Issue 26
Strain Tuning of Ferroelectric Thin Films
journal, August 2007
- Schlom, Darrell G.; Chen, Long-Qing; Eom, Chang-Beom
- Annual Review of Materials Research, Vol. 37, Issue 1