Discovery of Nanoscale Electric Field‐Induced Phase Transitions in ZrO 2

Lomenzo, Patrick D.; Collins, Liam; Ganser, Richard; Xu, Bohan; Guido, Roberto; Gruverman, Alexei; Kersch, Alfred; Mikolajick, Thomas; Schroeder, Uwe

doi:10.1002/adfm.202303636

Discovery of Nanoscale Electric Field‐Induced Phase Transitions in ZrO ₂

Journal Article · Thu Jun 08 00:00:00 EDT 2023 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202303636· OSTI ID:1984321

^[1]; ^[2]; Ganser, Richard ^[3]; Xu, Bohan ^[1]; ^[1]; Gruverman, Alexei ^[4]; ^[3]; ^[1]; ^[1]

NaMLab gGmbH Technische Universität Dresden Noethnitzer Str. 64a 01187 Dresden Germany
Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge TN 37831 USA
Department of Applied Sciences and Mechatronics Munich University of Applied Sciences Lothstr. 34 80335 Munich Germany
Department of Physics and Astronomy University of Nebraska‐Lincoln Lincoln lincoln NE 68588 USA

Abstract

The emergence of ferroelectric and antiferroelectric properties in the semiconductor industry's most prominent high‐k dielectrics, HfO ₂ and ZrO ₂ , is leading to technology developments unanticipated a decade ago. Yet the failure to clearly distinguish ferroelectric from antiferroelectric behavior is impeding progress. Band‐excitation piezoresponse force microscopy and molecular dynamics are used to elucidate the nanoscale electric field‐induced phase transitions present in ZrO ₂ ‐based antiferroelectrics. Antiferroelectric ZrO ₂ is clearly distinguished from a closely resembling pinched La‐doped HfO ₂ ferroelectric. Crystalline grains in the range of 3 – 20 nm are imaged independently undergoing reversible electric field induced phase transitions. The electrically accessible nanoscale phase transitions discovered in this study open up an unprecedented paradigm for the development of new nanoelectronic devices.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: German Research Foundation (DFG); Saxon State Parliament; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1984321

Alternate ID(s):: OSTI ID: 1984323
OSTI ID: 1985380

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 41 Vol. 33; ISSN 1616-301X

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (53)

Nonvolatile Random Access Memory and Energy Storage Based on Antiferroelectric Like Hysteresis in ZrO ₂ Pešić, Milan; Hoffmann, Michael; Richter, Claudia Advanced Functional Materials, Vol. 26, Issue 41 https://doi.org/10.1002/adfm.201603182	journal	September 2016
Quantification of the Electromechanical Measurements by Piezoresponse Force Microscopy Buragohain, Pratyush; Lu, Haidong; Richter, Claudia Advanced Materials, Vol. 34, Issue 47 https://doi.org/10.1002/adma.202206237	journal	October 2022
Toward Advanced High‐ k and Electrode Thin Films for DRAM Capacitors via Atomic Layer Deposition Kim, Se Eun; Sung, Ju Young; Jeon, Jae Deock Advanced Materials Technologies https://doi.org/10.1002/admt.202200878	journal	October 2022
Harnessing Phase Transitions in Antiferroelectric ZrO ₂ Using the Size Effect Lomenzo, Patrick D.; Materano, Monica; Mittmann, Terence Advanced Electronic Materials, Vol. 8, Issue 1 https://doi.org/10.1002/aelm.202100556	journal	October 2021
Temperature‐Dependent Phase Transitions in Hf _x Zr _1‐x O ₂ Mixed Oxides: Indications of a Proper Ferroelectric Material Schroeder, Uwe; Mittmann, Terence; Materano, Monica Advanced Electronic Materials, Vol. 8, Issue 9 https://doi.org/10.1002/aelm.202200265	journal	May 2022
Modulation of ferroelectricity and antiferroelectricity of nanoscale ZrO2 thin films using ultrathin interfacial layers Yi, Sheng-Han; Lin, Bo-Ting; Hsu, Tzu-Yao Journal of the European Ceramic Society, Vol. 39, Issue 14 https://doi.org/10.1016/j.jeurceramsoc.2019.05.065	journal	November 2019
Ferroelectric phase transitions in nanoscale HfO 2 films enable giant pyroelectric energy conversion and highly efficient supercapacitors Hoffmann, Michael; Schroeder, Uwe; Künneth, Christopher Nano Energy, Vol. 18 https://doi.org/10.1016/j.nanoen.2015.10.005	journal	November 2015
Lanthanum-Doped Hafnium Oxide: A Robust Ferroelectric Material Schroeder, Uwe; Richter, Claudia; Park, Min Hyuk Inorganic Chemistry, Vol. 57, Issue 5 https://doi.org/10.1021/acs.inorgchem.7b03149	journal	February 2018
Depolarization as Driving Force in Antiferroelectric Hafnia and Ferroelectric Wake-Up Lomenzo, Patrick D.; Richter, Claudia; Mikolajick, Thomas ACS Applied Electronic Materials, Vol. 2, Issue 6 https://doi.org/10.1021/acsaelm.0c00184	journal	May 2020
Recent Progress on Energy-Related Applications of HfO ₂ -Based Ferroelectric and Antiferroelectric Materials Ali, Faizan; Zhou, Dayu; Ali, Mohsin ACS Applied Electronic Materials, Vol. 2, Issue 8 https://doi.org/10.1021/acsaelm.0c00304	journal	July 2020
Emerging Fluorite-Structured Antiferroelectrics and Their Semiconductor Applications Park, Geun Hyeong; Lee, Dong Hyun; Choi, Hyojun ACS Applied Electronic Materials, Vol. 5, Issue 2 https://doi.org/10.1021/acsaelm.2c01615	journal	February 2023
Phase-Exchange-Driven Wake-Up and Fatigue in Ferroelectric Hafnium Zirconium Oxide Films Fields, Shelby S.; Smith, Sean W.; Ryan, Philip J. ACS Applied Materials & Interfaces, Vol. 12, Issue 23 https://doi.org/10.1021/acsami.0c03570	journal	May 2020
Steep-Slope Transistor with an Imprinted Antiferroelectric Film Lee, Sangho; Lee, Yongsun; Kim, Taeho ACS Applied Materials & Interfaces, Vol. 14, Issue 47 https://doi.org/10.1021/acsami.2c10610	journal	November 2022
Fluid Imprint and Inertial Switching in Ferroelectric La:HfO ₂ Capacitors Buragohain, Pratyush; Erickson, Adam; Kariuki, Pamenas ACS Applied Materials & Interfaces, Vol. 11, Issue 38 https://doi.org/10.1021/acsami.9b11146	journal	August 2019
Quantitative Electromechanical Atomic Force Microscopy Collins, Liam; Liu, Yongtao; Ovchinnikova, Olga S. ACS Nano, Vol. 13, Issue 7 https://doi.org/10.1021/acsnano.9b02883	journal	July 2019
Ferroelectricity in Simple Binary ZrO ₂ and HfO ₂ Müller, Johannes; Böscke, Tim S.; Schröder, Uwe Nano Letters, Vol. 12, Issue 8 https://doi.org/10.1021/nl302049k	journal	July 2012
The order of the quantum chromodynamics transition predicted by the standard model of particle physics Aoki, Y.; Endrődi, G.; Fodor, Z. Nature, Vol. 443, Issue 7112 https://doi.org/10.1038/nature05120	journal	October 2006
Piezoresponse force microscopy and nanoferroic phenomena Gruverman, Alexei; Alexe, Marin; Meier, Dennis Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09650-8	journal	April 2019
Piezoelectricity in hafnia Dutta, Sangita; Buragohain, Pratyush; Glinsek, Sebastjan Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-27480-5	journal	December 2021
Compact artificial neuron based on anti-ferroelectric transistor Cao, Rongrong; Zhang, Xumeng; Liu, Sen Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-34774-9	journal	November 2022
Ultrathin ferroic HfO2–ZrO2 superlattice gate stack for advanced transistors Cheema, Suraj S.; Shanker, Nirmaan; Wang, Li-Chen Nature, Vol. 604, Issue 7904 https://doi.org/10.1038/s41586-022-04425-6	journal	April 2022
An ultrathin integrated nanoelectromechanical transducer based on hafnium zirconium oxide Ghatge, Mayur; Walters, Glen; Nishida, Toshikazu Nature Electronics, Vol. 2, Issue 11 https://doi.org/10.1038/s41928-019-0305-3	journal	October 2019
Superhigh energy storage density on-chip capacitors with ferroelectric Hf_0.5Zr_0.5O₂/antiferroelectric Hf_0.25Zr_0.75O₂ bilayer nanofilms fabricated by plasma-enhanced atomic layer deposition He, Yuli; Zheng, Guang; Wu, Xiaohan Nanoscale Advances, Vol. 4, Issue 21 https://doi.org/10.1039/D2NA00427E	journal	January 2022
Removal of 90° domain pinning in (100) Pb(Zr0.15Ti0.85)O3 thin films by pulsed operation Kohli, Markus; Muralt, Paul; Setter, Nava Applied Physics Letters, Vol. 72, Issue 24 https://doi.org/10.1063/1.121554	journal	June 1998
Evolution of phases and ferroelectric properties of thin Hf _0.5 Zr _0.5 O ₂ films according to the thickness and annealing temperature Hyuk Park, Min; Joon Kim, Han; Jin Kim, Yu Applied Physics Letters, Vol. 102, Issue 24 https://doi.org/10.1063/1.4811483	journal	June 2013
Wake-up effects in Si-doped hafnium oxide ferroelectric thin films Zhou, Dayu; Xu, Jin; Li, Qing Applied Physics Letters, Vol. 103, Issue 19 https://doi.org/10.1063/1.4829064	journal	November 2013
About the deformation of ferroelectric hystereses Schenk, T.; Yurchuk, E.; Mueller, S. Applied Physics Reviews, Vol. 1, Issue 4 https://doi.org/10.1063/1.4902396	journal	December 2014
The origin of ferroelectricity in Hf _1−x Zr _x O ₂ : A computational investigation and a surface energy model Materlik, R.; Künneth, C.; Kersch, A. Journal of Applied Physics, Vol. 117, Issue 13 https://doi.org/10.1063/1.4916707	journal	April 2015
Modeling ferroelectric film properties and size effects from tetragonal interlayer in Hf _1– _x Zr _x O ₂ grains Künneth, Christopher; Materlik, Robin; Kersch, Alfred Journal of Applied Physics, Vol. 121, Issue 20 https://doi.org/10.1063/1.4983811	journal	May 2017
Doped ZrO ₂ for future lead free piezoelectric devices Starschich, S.; Böttger, U. Journal of Applied Physics, Vol. 123, Issue 4 https://doi.org/10.1063/1.4997681	journal	January 2018
Antiferroelectricity in lanthanum doped zirconia without metallic capping layers and post-deposition/-metallization anneals Wang, Zheng; Gaskell, Anthony Arthur; Dopita, Milan Applied Physics Letters, Vol. 112, Issue 22 https://doi.org/10.1063/1.5037185	journal	May 2018
Ferroelectric and pyroelectric properties of polycrystalline La-doped HfO ₂ thin films Mart, C.; Kühnel, K.; Kämpfe, T. Applied Physics Letters, Vol. 114, Issue 10 https://doi.org/10.1063/1.5089821	journal	March 2019
Physical chemistry of the TiN/Hf _0.5 Zr _0.5 O ₂ interface Hamouda, W.; Pancotti, A.; Lubin, C. Journal of Applied Physics, Vol. 127, Issue 6 https://doi.org/10.1063/1.5128502	journal	February 2020
Piezoresponse amplitude and phase quantified for electromechanical characterization Neumayer, Sabine M.; Saremi, Sahar; Martin, Lane W. Journal of Applied Physics, Vol. 128, Issue 17 https://doi.org/10.1063/5.0011631	journal	November 2020
Doping concentration dependent piezoelectric behavior of Si:HfO₂ thin-films Kirbach, S.; Lederer, M.; Eßlinger, S. Applied Physics Letters, Vol. 118, Issue 1 https://doi.org/10.1063/5.0026990	journal	January 2021
Ab initio interphase characteristics in HfO₂ and ZrO₂ and nucleation of the polar phase Falkowski, Max; Kersch, Alfred Applied Physics Letters, Vol. 118, Issue 3 https://doi.org/10.1063/5.0029610	journal	January 2021
Next generation ferroelectric materials for semiconductor process integration and their applications Mikolajick, T.; Slesazeck, S.; Mulaosmanovic, H. Journal of Applied Physics, Vol. 129, Issue 10 https://doi.org/10.1063/5.0037617	journal	March 2021
Large thermal hysteresis of ferroelectric transition in HfO₂-based ferroelectric films Mimura, Takanori; Shimizu, Takao; Sakata, Osami Applied Physics Letters, Vol. 118, Issue 11 https://doi.org/10.1063/5.0040934	journal	March 2021
Antiferroelectric properties of ZrO₂ ultra-thin films prepared by atomic layer deposition Luo, Xuan; Toprasertpong, Kasidit; Takenaka, Mitsuru Applied Physics Letters, Vol. 118, Issue 23 https://doi.org/10.1063/5.0051068	journal	June 2021
Band excitation in scanning probe microscopy: sines of change Jesse, Stephen; Kalinin, Sergei V. Journal of Physics D: Applied Physics, Vol. 44, Issue 46 https://doi.org/10.1088/0022-3727/44/46/464006	journal	November 2011
The band excitation method in scanning probe microscopy for rapid mapping of energy dissipation on the nanoscale Jesse, Stephen; Kalinin, Sergei V.; Proksch, Roger Nanotechnology, Vol. 18, Issue 43 https://doi.org/10.1088/0957-4484/18/43/435503	journal	September 2007
Fluorite-structure antiferroelectrics Park, Min Hyuk; Hwang, Cheol Seong Reports on Progress in Physics, Vol. 82, Issue 12 https://doi.org/10.1088/1361-6633/ab49d6	journal	November 2019
Piezo- and Pyroelectricity in Zirconia: A Study with Machine-Learned Force Fields Ganser, Richard; Bongarz, Simon; von Mach, Alexander Physical Review Applied, Vol. 18, Issue 5 https://doi.org/10.1103/PhysRevApplied.18.054066	journal	November 2022
Pathways towards ferroelectricity in hafnia Huan, Tran Doan; Sharma, Vinit; Rossetti, George A. Physical Review B, Vol. 90, Issue 6 https://doi.org/10.1103/PhysRevB.90.064111	journal	August 2014
Antiferroelectricity in thin-film ZrO 2 from first principles Reyes-Lillo, Sebastian E.; Garrity, Kevin F.; Rabe, Karin M. Physical Review B, Vol. 90, Issue 14 https://doi.org/10.1103/PhysRevB.90.140103	journal	October 2014
Deep Potential Molecular Dynamics: A Scalable Model with the Accuracy of Quantum Mechanics Zhang, Linfeng; Han, Jiequn; Wang, Han Physical Review Letters, Vol. 120, Issue 14 https://doi.org/10.1103/PhysRevLett.120.143001	journal	April 2018
Giant negative electrostriction and dielectric tunability in a van der Waals layered ferroelectric Neumayer, Sabine M.; Eliseev, Eugene A.; Susner, Michael A. Physical Review Materials, Vol. 3, Issue 2 https://doi.org/10.1103/PhysRevMaterials.3.024401	journal	February 2019
Steep Slope and Near Non-Hysteresis of FETs With Antiferroelectric-Like HfZrO for Low-Power Electronics Lee, M. H.; Wei, Y. -T.; Chu, K. -Y. IEEE Electron Device Letters, Vol. 36, Issue 4 https://doi.org/10.1109/LED.2015.2402517	journal	April 2015
Electrical Investigation of Wake-Up in High Endurance Fatigue-Free La and Y Doped HZO Metal–Ferroelectric–Metal Capacitors Walke, Amey M.; Popovici, Mihaela I.; Banerjee, Kaustuv IEEE Transactions on Electron Devices, Vol. 69, Issue 8 https://doi.org/10.1109/TED.2022.3186869	journal	August 2022
Primordial Gravitational Waves and Cosmology Krauss, L. M.; Dodelson, S.; Meyer, S. Science, Vol. 328, Issue 5981 https://doi.org/10.1126/science.1179541	journal	May 2010
Toward attojoule switching energy in logic transistors Datta, Suman; Chakraborty, Wriddhi; Radosavljevic, Marko Science, Vol. 378, Issue 6621 https://doi.org/10.1126/science.ade7656	journal	November 2022
Phase Transitions in the Early and Present Universe Boyanovsky, D.; de Vega, H. J.; Schwarz, D. J. Annual Review of Nuclear and Particle Science, Vol. 56, Issue 1 https://doi.org/10.1146/annurev.nucl.56.080805.140539	journal	November 2006
Substrate-dependent differences in ferroelectric behavior and phase diagram of Si-doped hafnium oxide Lederer, Maximilian; Mertens, Konstantin; Olivo, Ricardo Journal of Materials Research, Vol. 36, Issue 21 https://doi.org/10.1557/s43578-021-00415-y	journal	November 2021

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