In Situ Characterization of Ferroelectric HfO2 During Rapid Thermal Annealing

Narasimhan, Vijay Kris; McBriarty, Martin E.; Passarello, Donata; Adinolfi, Valerio; Toney, Michael F.; Mehta, Apurva; Littau, Karl A.

doi:10.1002/pssr.202000598

In Situ Characterization of Ferroelectric HfO₂ During Rapid Thermal Annealing

Journal Article · Mon Feb 08 00:00:00 EST 2021 · Physica Status Solidi. Rapid Research Letters

DOI:https://doi.org/10.1002/pssr.202000598· OSTI ID:1777416

^[1]; McBriarty, Martin E. ^[1]; Passarello, Donata ^[2]; Adinolfi, Valerio ^[1]; Toney, Michael F. ^[3]; Mehta, Apurva ^[2]; Littau, Karl A. ^[1]

EMD Performance Materials, San Jose, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Univ. of Colorado, Boulder, CO (United States)

Thermal annealing is critical in governing the phase distribution, and ultimately the electrical properties, of ferroelectric hafnium oxide films. In particular, rapid thermal annealing (RTA) has been shown to favor the formation of ferroelectric crystal phases, but the dynamic behavior of the film over the course of the anneal is not well understood. Herein, synchrotron X-ray diffraction is used to characterize the phase distribution of HfO₂ films deposited by atomic layer deposition (ALD) in situ during RTA, revealing complex phase transformations occurring on the scale of seconds. All samples investigated here transform into a nonmonoclinic phase, which is required for ferroelectric films. However, this phase often converts into the more stable monoclinic phase as annealing proceeds. The kinetic barrier to the transformation to the monoclinic phase during heating is higher than 1 eV f.u.^-1 In this work, the initial crystallization into the ferroelectric phase and relatively high barrier to transformation to the nonferroelectric phase suggests that careful control of the thermal annealing profile can greatly increase the ferroelectric fraction of the film. By using a fast ramp rate and a short annealing time above the ferroelectric crystallization temperature, the remanent polarization of a pure HfO₂ film can be increased more than twofold.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

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

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1777416

Alternate ID(s):: OSTI ID: 23019731

Journal Information:: Physica Status Solidi. Rapid Research Letters, Journal Name: Physica Status Solidi. Rapid Research Letters Journal Issue: 5 Vol. 15; ISSN 1862-6254

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (29)

LMFIT: Non-Linear Least-Square Minimization and Curve-Fitting for Python Newville, Matthew; Stensitzki, Till; Allen, Daniel B. Zenodo https://doi.org/10.5281/zenodo.11813	software	September 2014
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
Crystal Phase Distribution and Ferroelectricity in Ultrathin HfO ₂ –ZrO ₂ Bilayers McBriarty, Martin E.; Narasimhan, Vijay K.; Weeks, Stephen L. physica status solidi (b), Vol. 257, Issue 1 https://doi.org/10.1002/pssb.202070010	journal	September 2019
Kinetics of non-isothermal crystallization process and activation energy for crystal growth in amorphous materials Matusita, Kazumasa; Komatsu, Takayuki; Yokota, Ryosuke Journal of Materials Science, Vol. 19, Issue 1 https://doi.org/10.1007/BF02403137	journal	January 1984
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
Kinetics of non-isothermal crystallization Ozawa, T. Polymer, Vol. 12, Issue 3 https://doi.org/10.1016/0032-3861(71)90041-3	journal	March 1971
Modification of the Kolmogorov–Johnson–Mehl–Avrami rate equation for non-isothermal experiments and its analytical solution Farjas, J.; Roura, P. Acta Materialia, Vol. 54, Issue 20 https://doi.org/10.1016/j.actamat.2006.07.037	journal	December 2006
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
The Occurrence of Metastable Tetragonal Zirconia as a Crystallite Size Effect Garvie, Ronald C. The Journal of Physical Chemistry, Vol. 69, Issue 4 https://doi.org/10.1021/j100888a024	journal	April 1965
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
Kinetic Parameters from Thermogravimetric Data Coats, A. W.; Redfern, J. P. Nature, Vol. 201, Issue 4914 https://doi.org/10.1038/201068a0	journal	January 1964
The formation mechanism for printed silver-contacts for silicon solar cells Fields, Jeremy D.; Ahmad, Md. Imteyaz; Pool, Vanessa L. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11143	journal	April 2016
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
Enhanced ferroelectricity in ultrathin films grown directly on silicon Cheema, Suraj S.; Kwon, Daewoong; Shanker, Nirmaan Nature, Vol. 580, Issue 7804 https://doi.org/10.1038/s41586-020-2208-x	journal	April 2020
Low-power linear computation using nonlinear ferroelectric tunnel junction memristors Berdan, Radu; Marukame, Takao; Ota, Kensuke Nature Electronics, Vol. 3, Issue 5 https://doi.org/10.1038/s41928-020-0405-0	journal	May 2020
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
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
Rapid thermal processing chamber for in-situ x-ray diffraction Ahmad, Md. Imteyaz; Van Campen, Douglas G.; Fields, Jeremy D. Review of Scientific Instruments, Vol. 86, Issue 1 https://doi.org/10.1063/1.4904848	journal	January 2015
Ferroelectricity in undoped hafnium oxide Polakowski, Patrick; Müller, Johannes Applied Physics Letters, Vol. 106, Issue 23 https://doi.org/10.1063/1.4922272	journal	June 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 phase in tungsten capped Hf _0.8 Zr _0.2 O ₂ Karbasian, Golnaz; dos Reis, Roberto; Yadav, Ajay K. Applied Physics Letters, Vol. 111, Issue 2 https://doi.org/10.1063/1.4993739	journal	July 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
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Crystal Structure of Monoclinic Hafnia and Comparison with Monoclinic Zirconia Ruh, Robert; Corfield, Peter W. R. Journal of the American Ceramic Society, Vol. 53, Issue 3 https://doi.org/10.1111/j.1151-2916.1970.tb12052.x	journal	March 1970
Low-Temperature Aging of Y-TZP Ceramics Chevalier, Jérôme; Cales, Bernard; Drouin, Jean Michel Journal of the American Ceramic Society, Vol. 82, Issue 8 https://doi.org/10.1111/j.1151-2916.1999.tb02055.x	journal	August 1999
(Invited) Opportunity for Phase-Controlled Higher-k HfO ₂ Toriumi, Akira; Nakajima, Yasuhiro; Kita, Koji ECS Transactions, Vol. 41, Issue 7 https://doi.org/10.1149/1.3633292	journal	October 2011
Ferroelectric Hafnium Oxide Based Materials and Devices: Assessment of Current Status and Future Prospects Müller, J.; Polakowski, P.; Mueller, S. ECS Journal of Solid State Science and Technology, Vol. 4, Issue 5 https://doi.org/10.1149/2.0081505jss	journal	January 2015
On-the-fly segmentation approaches for x-ray diffraction datasets for metallic glasses Ren, Fang; Williams, Travis; Hattrick-Simpers, Jason MRS Communications, Vol. 7, Issue 3 https://doi.org/10.1557/mrc.2017.76	journal	August 2017
Ferroelectric hafnium oxide for ferroelectric random-access memories and ferroelectric field-effect transistors Mikolajick, Thomas; Slesazeck, Stefan; Park, Min Hyuk MRS Bulletin, Vol. 43, Issue 5 https://doi.org/10.1557/mrs.2018.92	journal	May 2018

Similar Records

Mixed Al and Si doping in ferroelectric HfO{sub 2} thin films

Journal Article · Sun Dec 13 23:00:00 EST 2015 · Applied Physics Letters · OSTI ID:22486242

The effects of layering in ferroelectric Si-doped HfO{sub 2} thin films

Journal Article · Mon Aug 18 00:00:00 EDT 2014 · Applied Physics Letters · OSTI ID:22310900

Ferroelectricity in undoped hafnium oxide

Journal Article · Mon Jun 08 00:00:00 EDT 2015 · Applied Physics Letters · OSTI ID:22412559

Related Subjects

36 MATERIALS SCIENCE
ferroelectrics
hafnium oxide
phase transformation
rapid thermal annealing

In Situ Characterization of Ferroelectric HfO2 During Rapid Thermal Annealing

Citation Formats

References (29)

Similar Records

Related Subjects

In Situ Characterization of Ferroelectric HfO₂ During Rapid Thermal Annealing