Crystal Phase Distribution and Ferroelectricity in Ultrathin HfO 2 –ZrO 2 Bilayers

McBriarty, Martin E.; Narasimhan, Vijay K.; Weeks, Stephen L.; Pal, Ashish; Fang, Huazhi; Petach, Trevor A.; Mehta, Apurva; Davis, Ryan C.; Barabash, Sergey V.; Littau, Karl A.

doi:10.1002/pssb.201900285

Crystal Phase Distribution and Ferroelectricity in Ultrathin HfO ₂ –ZrO ₂ Bilayers

Journal Article · Wed Sep 11 00:00:00 EDT 2019 · Physica Status Solidi B. Basic Solid State Physics

DOI:https://doi.org/10.1002/pssb.201900285· OSTI ID:1561364

^[1]; Narasimhan, Vijay K. ^[1]; Weeks, Stephen L. ^[1]; Pal, Ashish ^[1]; Fang, Huazhi ^[1]; Petach, Trevor A. ^[2]; Mehta, Apurva ^[2]; Davis, Ryan C. ^[2]; Barabash, Sergey V. ^[1]; Littau, Karl A. ^[1]

Technology Group Intermolecular, Inc. 3011 N. 1st Street San Jose CA 95134 USA
Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Center Menlo Park CA 94025 USA

(Hf,Zr)O ₂ ultrathin films are used as ferroelectric layers in emerging digital logic and nonvolatile memory devices. The ferroelectric properties of (Hf,Zr)O ₂ can be improved by interface engineering, such as the formation of nanolaminates with distinct HfO ₂ and ZrO ₂ layers. Herein, the ferroelectric performance of HfO ₂ –ZrO ₂ ultrathin bilayer devices is shown to depend on the stacking order of HfO ₂ and ZrO ₂ , which affects the quantity of the noncentrosymmetric orthorhombic Pca 2 ₁ crystal phase. By combining X‐ray diffraction with a novel extended X‐ray absorption fine structure (EXAFS) analysis procedure, the orthorhombic, tetragonal, and monoclinic phase fractions are quantified for bilayers composed of 3 nm HfO ₂ and 3 nm ZrO ₂ . A significantly larger orthorhombic ZrO ₂ phase fraction is found when ZrO ₂ has an unconstrained surface during annealing, whereas the presence of a ZrO ₂ interface with the substrate results in a substantial tetragonal ZrO ₂ phase fraction and a 2.4× smaller remanent polarization. HfO ₂ is found to be less susceptible than ZrO ₂ to crystal phase templating. The methods presented herein enable mechanistic studies of ferroelectric wake‐up, fatigue, and processing effects in (Hf,Zr)O ₂ films, accelerating the development of electronic devices that rely on ferroelectric oxides.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1561364

Journal Information:: Physica Status Solidi B. Basic Solid State Physics, Journal Name: Physica Status Solidi B. Basic Solid State Physics Journal Issue: 1 Vol. 257; ISSN 0370-1972

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

Country of Publication:: Germany

Language:: English

References (46)

Physical Mechanisms behind the Field-Cycling Behavior of HfO ₂ -Based Ferroelectric Capacitors Pešić, Milan; Fengler, Franz Paul Gustav; Larcher, Luca Advanced Functional Materials, Vol. 26, Issue 25 https://doi.org/10.1002/adfm.201600590	journal	May 2016
Direct Observation of Negative Capacitance in Polycrystalline Ferroelectric HfO ₂ Hoffmann, Michael; Pešić, Milan; Chatterjee, Korok Advanced Functional Materials, Vol. 26, Issue 47 https://doi.org/10.1002/adfm.201602869	journal	October 2016
Ferroelectricity and Antiferroelectricity of Doped Thin HfO ₂ -Based Films Park, Min Hyuk; Lee, Young Hwan; Kim, Han Joon Advanced Materials, Vol. 27, Issue 11 https://doi.org/10.1002/adma.201404531	journal	February 2015
Origin of Ferroelectric Phase in Undoped HfO ₂ Films Deposited by Sputtering Mittmann, Terence; Materano, Monica; Lomenzo, Patrick D. Advanced Materials Interfaces https://doi.org/10.1002/admi.201900042	journal	April 2019
Effect of Annealing Ferroelectric HfO ₂ Thin Films: In Situ, High Temperature X-Ray Diffraction Park, Min Hyuk; Chung, Ching-Chang; Schenk, Tony Advanced Electronic Materials, Vol. 4, Issue 7 https://doi.org/10.1002/aelm.201800091	journal	May 2018
Nucleation-Limited Ferroelectric Orthorhombic Phase Formation in Hf _0.5 Zr _0.5 O ₂ Thin Films Lee, Young Hwan; Hyun, Seung Dam; Kim, Hae Jin Advanced Electronic Materials, Vol. 5, Issue 2 https://doi.org/10.1002/aelm.201800436	journal	December 2018
Thermodynamic and Kinetic Origins of Ferroelectricity in Fluorite Structure Oxides Park, Min Hyuk; Lee, Young Hwan; Mikolajick, Thomas Advanced Electronic Materials, Vol. 5, Issue 3 https://doi.org/10.1002/aelm.201800522	journal	December 2018
Prediction of new metastable $$\hbox {HfO}_{2}$$ HfO 2 phases: toward understanding ferro- and antiferroelectric films Barabash, S. V. Journal of Computational Electronics, Vol. 16, Issue 4 https://doi.org/10.1007/s10825-017-1077-5	journal	November 2017
Surface morphology and crystallinity control in the atomic layer deposition (ALD) of hafnium and zirconium oxide thin films Hausmann, Dennis M.; Gordon, Roy G. Journal of Crystal Growth, Vol. 249, Issue 1-2 https://doi.org/10.1016/S0022-0248(02)02133-4	journal	February 2003
Induction of ferroelectricity in nanoscale ZrO2/HfO2 bilayer thin films on Pt/Ti/SiO2/Si substrates Lu, Y. W.; Shieh, J.; Tsai, F. Y. Acta Materialia, Vol. 115 https://doi.org/10.1016/j.actamat.2016.05.029	journal	August 2016
Ab initio theory and calculations of X-ray spectra Rehr, John J.; Kas, Joshua J.; Prange, Micah P. Comptes Rendus Physique, Vol. 10, Issue 6 https://doi.org/10.1016/j.crhy.2008.08.004	journal	July 2009
Field-induced antiferroelectric to ferroelectric transitions in (Pb1–xLax)(Zr0.90Ti0.10)1–x/4O3 investigated by in situ X-ray diffraction Ciuchi, I. V.; Chung, C. C.; Fancher, C. M. Journal of the European Ceramic Society, Vol. 37, Issue 15 https://doi.org/10.1016/j.jeurceramsoc.2017.06.018	journal	December 2017
Structural role of Zr4+ as a nucleating agent in a MgO–Al2O3–SiO2 glass-ceramics: A combined XAS and HRTEM approach Dargaud, Olivier; Cormier, Laurent; Menguy, Nicolas Journal of Non-Crystalline Solids, Vol. 356, Issue 52-54 https://doi.org/10.1016/j.jnoncrysol.2010.05.104	journal	December 2010
Trace Uranium Partitioning in a Multiphase Nano-FeOOH System McBriarty, Martin E.; Soltis, Jennifer A.; Kerisit, Sebastien Environmental Science & Technology, Vol. 51, Issue 9 https://doi.org/10.1021/acs.est.7b00432	journal	April 2017
Iron Vacancies Accommodate Uranyl Incorporation into Hematite McBriarty, Martin E.; Kerisit, Sebastien; Bylaska, Eric J. Environmental Science & Technology, Vol. 52, Issue 11 https://doi.org/10.1021/acs.est.8b00297	journal	May 2018
Engineering of Ferroelectric HfO ₂ –ZrO ₂ Nanolaminates Weeks, Stephen L.; Pal, Ashish; Narasimhan, Vijay K. ACS Applied Materials & Interfaces, Vol. 9, Issue 15 https://doi.org/10.1021/acsami.7b00776	journal	April 2017
Electric Field Cycling Behavior of Ferroelectric Hafnium Oxide Schenk, Tony; Schroeder, Uwe; Pešić, Milan ACS Applied Materials & Interfaces, Vol. 6, Issue 22 https://doi.org/10.1021/am504837r	journal	October 2014
EXAFS Studies on the Size Dependence of Structural and Dynamic Properties of CdS Nanoparticles Rockenberger, Jörg; Tröger, Larc; Kornowski, Andreas The Journal of Physical Chemistry B, Vol. 101, Issue 14 https://doi.org/10.1021/jp963266u	journal	April 1997
Use of Negative Capacitance to Provide Voltage Amplification for Low Power Nanoscale Devices Salahuddin, Sayeef; Datta, Supriyo Nano Letters, Vol. 8, Issue 2 https://doi.org/10.1021/nl071804g	journal	February 2008
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
A rhombohedral ferroelectric phase in epitaxially strained Hf0.5Zr0.5O2 thin films Wei, Yingfen; Nukala, Pavan; Salverda, Mart Nature Materials, Vol. 17, Issue 12 https://doi.org/10.1038/s41563-018-0196-0	journal	October 2018
Understanding the formation of the metastable ferroelectric phase in hafnia–zirconia solid solution thin films Park, Min Hyuk; Lee, Young Hwan; Kim, Han Joon Nanoscale, Vol. 10, Issue 2 https://doi.org/10.1039/C7NR06342C	journal	January 2018
A comprehensive study on the structural evolution of HfO ₂ thin films doped with various dopants Park, M. H.; Schenk, T.; Fancher, C. M. Journal of Materials Chemistry C, Vol. 5, Issue 19 https://doi.org/10.1039/C7TC01200D	journal	January 2017
Characterizing crystalline polymorph transitions in HfO2 by extended x-ray absorption fine-structure spectroscopy Lysaght, Patrick S.; Woicik, Joseph C.; Alper Sahiner, M. Applied Physics Letters, Vol. 91, Issue 12 https://doi.org/10.1063/1.2789180	journal	September 2007
Ferroelectricity in hafnium oxide thin films Böscke, T. S.; Müller, J.; Bräuhaus, D. Applied Physics Letters, Vol. 99, Issue 10 https://doi.org/10.1063/1.3634052	journal	September 2011
Ferroelectricity in yttrium-doped hafnium oxide Müller, J.; Schröder, U.; Böscke, T. S. Journal of Applied Physics, Vol. 110, Issue 11 https://doi.org/10.1063/1.3667205	journal	December 2011
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
The effects of crystallographic orientation and strain of thin Hf _0.5 Zr _0.5 O ₂ film on its ferroelectricity Hyuk Park, Min; Joon Kim, Han; Jin Kim, Yu Applied Physics Letters, Vol. 104, Issue 7 https://doi.org/10.1063/1.4866008	journal	February 2014
On the structural origins of ferroelectricity in HfO ₂ thin films Sang, Xiahan; Grimley, Everett D.; Schenk, Tony Applied Physics Letters, Vol. 106, Issue 16 https://doi.org/10.1063/1.4919135	journal	April 2015
Enhancing ferroelectricity in dopant-free hafnium oxide Pal, Ashish; Narasimhan, Vijay Kris; Weeks, Stephen Applied Physics Letters, Vol. 110, Issue 2 https://doi.org/10.1063/1.4973928	journal	January 2017
Stabilization of ferroelectric Hf _x Zr _1−x O ₂ films using a millisecond flash lamp annealing technique O’Connor, Éamon; Halter, Mattia; Eltes, Felix APL Materials, Vol. 6, Issue 12 https://doi.org/10.1063/1.5060676	journal	December 2018
The simulated vibrational spectra of HfO ₂ polymorphs Zhou, B.; Shi, H.; Zhang, X. D. Journal of Physics D: Applied Physics, Vol. 47, Issue 11 https://doi.org/10.1088/0022-3727/47/11/115502	journal	February 2014
Atomic-layer-deposited silver and dielectric nanostructures for plasmonic enhancement of Raman scattering from nanoscale ultrathin films Ko, Chung-Ting; Yang, Po-Shuan; Han, Yin-Yi Nanotechnology, Vol. 26, Issue 26 https://doi.org/10.1088/0957-4484/26/26/265702	journal	June 2015
X-ray-absorption fine-structure standards: A comparison of experiment and theory Li, G. G.; Bridges, F.; Booth, C. H. Physical Review B, Vol. 52, Issue 9 https://doi.org/10.1103/PhysRevB.52.6332	journal	September 1995
Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure Ankudinov, A. L.; Ravel, B.; Rehr, J. J. Physical Review B, Vol. 58, Issue 12 https://doi.org/10.1103/PhysRevB.58.7565	journal	September 1998
XANES and EXAFS study of the local order in nanocrystalline yttria-stabilized zirconia Dura, O. J.; Boada, R.; López de la Torre, M. A. Physical Review B, Vol. 87, Issue 17 https://doi.org/10.1103/PhysRevB.87.174109	journal	May 2013
XAFS atomistic insight of the oxygen gettering in Ti / HfO 2 based OxRRAM Viennet, R.; Roussel, H.; Rapenne, L. Physical Review Materials, Vol. 2, Issue 5 https://doi.org/10.1103/PhysRevMaterials.2.055002	journal	May 2018
Theoretical approaches to x-ray absorption fine structure Rehr, J. J.; Albers, R. C. Reviews of Modern Physics, Vol. 72, Issue 3 https://doi.org/10.1103/RevModPhys.72.621	journal	July 2000
Local atomic structure in tetragonal pure ZrO ₂ nanopowders Acuña, Leandro M.; Lamas, Diego G.; Fuentes, Rodolfo O. Journal of Applied Crystallography, Vol. 43, Issue 2 https://doi.org/10.1107/S0021889809054983	journal	February 2010
Structures of ZrO ₂ polymorphs at room temperature by high-resolution neutron powder diffraction Howard, C. J.; Hill, R. J.; Reichert, B. E. Acta Crystallographica Section B Structural Science, Vol. 44, Issue 2 https://doi.org/10.1107/S0108768187010279	journal	April 1988
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Overview of emerging nonvolatile memory technologies Meena, Jagan; Sze, Simon; Chand, Umesh Nanoscale Research Letters, Vol. 9, Issue 1 https://doi.org/10.1186/1556-276X-9-526	journal	January 2014
Structural Correlation of Ferroelectric Behavior in Mixed Hafnia-Zirconia High-k Dielectrics for FeRAM and NCFET Applications Mukundan, Vineetha; Beckmann, Karsten; Tapily, Kandabara MRS Advances, Vol. 4, Issue 09 https://doi.org/10.1557/adv.2019.148	journal	January 2019
Microstructural evolution of ZrO ₂ –HfO ₂ nanolaminate structures grown by atomic layer deposition Kim, Hyoungsub; McIntyre, Paul C.; Saraswat, Krishna C. Journal of Materials Research, Vol. 19, Issue 2 https://doi.org/10.1557/jmr.2004.19.2.643	journal	February 2004
Stability of the orthorhombic phase in (111)-oriented YO_1.5-substituted HfO₂ films Shimizu, Takao; Katayama, Kiliha; Funakubo, Hiroshi Journal of the Ceramic Society of Japan, Vol. 126, Issue 5 https://doi.org/10.2109/jcersj2.17247	journal	January 2018
Improvement in ferroelectricity of Hf _x Zr ₁₋ _x O ₂ thin films using ZrO ₂ seed layer Onaya, Takashi; Nabatame, Toshihide; Sawamoto, Naomi Applied Physics Express, Vol. 10, Issue 8 https://doi.org/10.7567/APEX.10.081501	journal	July 2017

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