Enhanced ferroelectricity in ultrathin films grown directly on silicon

Cheema, Suraj S.; Kwon, Daewoong; Shanker, Nirmaan; dos Reis, Roberto; Hsu, Shang-Lin; Xiao, Jun; Zhang, Haigang; Wagner, Ryan; Datar, Adhiraj; McCarter, Margaret R.; Serrao, Claudy R.; Yadav, Ajay K.; Karbasian, Golnaz; Hsu, Cheng-Hsiang; Tan, Ava J.; Wang, Li-Chen; Thakare, Vishal; Zhang, Xiang; Mehta, Apurva; Karapetrova, Evguenia; Chopdekar, Rajesh V.; Shafer, Padraic; Arenholz, Elke; Hu, Chenming; Proksch, Roger; Ramesh, Ramamoorthy; Ciston, Jim; Salahuddin, Sayeef

doi:10.1038/s41586-020-2208-x

Enhanced ferroelectricity in ultrathin films grown directly on silicon

Journal Article · Wed Apr 22 00:00:00 EDT 2020 · Nature (London)

DOI:https://doi.org/10.1038/s41586-020-2208-x· OSTI ID:1633850

^[1]; Kwon, Daewoong ^[1]; Shanker, Nirmaan ^[1]; ^[2]; Hsu, Shang-Lin ^[2]; Xiao, Jun ^[1]; Zhang, Haigang ^[3]; Wagner, Ryan ^[3]; Datar, Adhiraj ^[1]; McCarter, Margaret R. ^[1]; Serrao, Claudy R. ^[1]; Yadav, Ajay K. ^[1]; Karbasian, Golnaz ^[1]; Hsu, Cheng-Hsiang ^[1]; Tan, Ava J. ^[1]; ^[1]; Thakare, Vishal ^[1]; Zhang, Xiang ^[1]; Mehta, Apurva ^[4]; Karapetrova, Evguenia ^[5] more »

Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Molecular Foundry (TMF)
Oxford Instruments, Santa Barbara, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Ultrathin ferroelectric materials could potentially enable low-power logic and nonvolatile memories. As ferroelectric materials are made thinner, however, the ferroelectricity is usually suppressed. Size effects in ferroelectrics have been thoroughly investigated in perovskite oxides—the archetypal ferroelectric system. Perovskites, however, have so far proved unsuitable for thickness scaling and integration with modern semiconductor processes. In this paper we report ferroelectricity in ultrathin doped hafnium oxide (HfO₂), a fluorite-structure oxide grown by atomic layer deposition on silicon. We demonstrate the persistence of inversion symmetry breaking and spontaneous, switchable polarization down to a thickness of one nanometre. Our results indicate not only the absence of a ferroelectric critical thickness but also enhanced polar distortions as film thickness is reduced, unlike in perovskite ferroelectrics. This approach to enhancing ferroelectricity in ultrathin layers could provide a route towards polarization-driven memories and ferroelectric-based advanced transistors. This work shifts the search for the fundamental limits of ferroelectricity to simpler transition-metal oxide systems—that is, from perovskite-derived complex oxides to fluorite-structure binary oxides—in which ‘reverse’ size effects counterintuitively stabilize polar symmetry in the ultrathin regime.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS) and The Molecular Foundry (TMF)

Sponsoring Organization:: Defense Advanced Research Projects Agency (DARPA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF); King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research

Grant/Contract Number:: AC02-76SF00515; AC02-06CH11357; AC02-05CH11231

OSTI ID:: 1633850

Alternate ID(s):: OSTI ID: 1770074
OSTI ID: 1894622

Journal Information:: Nature (London), Journal Name: Nature (London) Journal Issue: 7804 Vol. 580; ISSN 0028-0836

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (68)

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
Si Doped Hafnium Oxide-A “Fragile” Ferroelectric System Richter, Claudia; Schenk, Tony; Park, Min Hyuk Advanced Electronic Materials, Vol. 3, Issue 10 https://doi.org/10.1002/aelm.201700131	journal	August 2017
Ferroelectric Hf0.5Zr0.5O2 Thin Films: A Review of Recent Advances Kim, Si Joon; Mohan, Jaidah; Summerfelt, Scott R. JOM, Vol. 71, Issue 1 https://doi.org/10.1007/s11837-018-3140-5	journal	September 2018
Multiplet effects in X-ray spectroscopy Groot, Frank de Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.03.018	journal	January 2005
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav Computational Materials Science, Vol. 68 https://doi.org/10.1016/j.commatsci.2012.10.028	journal	February 2013
Growth Window of Ferroelectric Epitaxial Hf _0.5 Zr _0.5 O ₂ Thin Films Lyu, Jike; Fina, Ignasi; Solanas, Raul ACS Applied Electronic Materials, Vol. 1, Issue 2 https://doi.org/10.1021/acsaelm.8b00065	journal	January 2019
Ultrathin Hf _0.5 Zr _0.5 O ₂ Ferroelectric Films on Si Chernikova, Anna; Kozodaev, Maksim; Markeev, Andrei ACS Applied Materials & Interfaces, Vol. 8, Issue 11 https://doi.org/10.1021/acsami.5b11653	journal	March 2016
Differentiating Ferroelectric and Nonferroelectric Electromechanical Effects with Scanning Probe Microscopy Balke, Nina; Maksymovych, Petro; Jesse, Stephen ACS Nano, Vol. 9, Issue 6 https://doi.org/10.1021/acsnano.5b02227	journal	May 2015
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
Tunneling Electroresistance Effect in Ferroelectric Tunnel Junctions at the Nanoscale Gruverman, A.; Wu, D.; Lu, H. Nano Letters, Vol. 9, Issue 10 https://doi.org/10.1021/nl901754t	journal	October 2009
Origin of ferroelectricity in perovskite oxides Cohen, Ronald E. Nature, Vol. 358, Issue 6382 https://doi.org/10.1038/358136a0	journal	July 1992
Critical thickness for ferroelectricity in perovskite ultrathin films Junquera, Javier; Ghosez, Philippe Nature, Vol. 422, Issue 6931, p. 506-509 https://doi.org/10.1038/nature01501	journal	April 2003
Room-temperature ferroelectricity in strained SrTiO₃ Haeni, J. H.; Irvin, P.; Chang, W. Nature, Vol. 430, Issue 7001, p. 758-761 https://doi.org/10.1038/nature02773	journal	August 2004
Origin of the dielectric dead layer in nanoscale capacitors Stengel, Massimiliano; Spaldin, Nicola A. Nature, Vol. 443, Issue 7112 https://doi.org/10.1038/nature05148	journal	October 2006
Surface symmetry-breaking and strain effects on orbital occupancy in transition metal perovskite epitaxial films Pesquera, D.; Herranz, G.; Barla, A. Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms2189	journal	January 2012
Mixed-dimensional van der Waals heterostructures Jariwala, Deep; Marks, Tobin J.; Hersam, Mark C. Nature Materials, Vol. 16, Issue 2 https://doi.org/10.1038/nmat4703	journal	August 2016
Solid-state memories based on ferroelectric tunnel junctions Chanthbouala, André; Crassous, Arnaud; Garcia, Vincent Nature Nanotechnology, Vol. 7, Issue 2 https://doi.org/10.1038/nnano.2011.213	journal	December 2011
Switching of ferroelectric polarization in epitaxial BaTiO3 films on silicon without a conducting bottom electrode Dubourdieu, Catherine; Bruley, John; Arruda, Thomas M. Nature Nanotechnology, Vol. 8, Issue 10 https://doi.org/10.1038/nnano.2013.192	journal	September 2013
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
The era of hyper-scaling in electronics Salahuddin, Sayeef; Ni, Kai; Datta, Suman Nature Electronics, Vol. 1, Issue 8 https://doi.org/10.1038/s41928-018-0117-x	journal	August 2018
High-throughput computational X-ray absorption spectroscopy Mathew, Kiran; Zheng, Chen; Winston, Donald Scientific Data, Vol. 5, Issue 1 https://doi.org/10.1038/sdata.2018.151	journal	July 2018
Surface and grain boundary energy as the key enabler of ferroelectricity in nanoscale hafnia-zirconia: a comparison of model and experiment Park, Min Hyuk; Lee, Young Hwan; Kim, Han Joon Nanoscale, Vol. 9, Issue 28 https://doi.org/10.1039/C7NR02121F	journal	January 2017
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
Principle of ferroelectric domain imaging using atomic force microscope Hong, Seungbum; Woo, Jungwon; Shin, Hyunjung Journal of Applied Physics, Vol. 89, Issue 2, p. 1377-1386 https://doi.org/10.1063/1.1331654	journal	January 2001
Domain structure study of SrBi2Ta2O9 ferroelectric thin films by scanning capacitance microscopy Leu, Ching-Chich; Chen, Chih-Yuan; Chien, Chao-Hsin Applied Physics Letters, Vol. 82, Issue 20 https://doi.org/10.1063/1.1576308	journal	May 2003
Quantitative mapping of switching behavior in piezoresponse force microscopy Jesse, Stephen; Lee, Ho Nyung; Kalinin, Sergei V. Review of Scientific Instruments, Vol. 77, Issue 7 https://doi.org/10.1063/1.2214699	journal	July 2006
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
Role of measurement voltage on hysteresis loop shape in Piezoresponse Force Microscopy Strelcov, E.; Kim, Y.; Yang, J. C. Applied Physics Letters, Vol. 101, Issue 19 https://doi.org/10.1063/1.4764939	journal	November 2012
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
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
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
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
Ferroelectric or non-ferroelectric: Why so many materials exhibit “ferroelectricity” on the nanoscale Vasudevan, Rama K.; Balke, Nina; Maksymovych, Peter Applied Physics Reviews, Vol. 4, Issue 2 https://doi.org/10.1063/1.4979015	journal	June 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
Evolution of ferroelectric HfO2 in ultrathin region down to 3 nm Tian, Xuan; Shibayama, Shigehisa; Nishimura, Tomonori Applied Physics Letters, Vol. 112, Issue 10 https://doi.org/10.1063/1.5017094	journal	March 2018
High dielectric constant gate oxides for metal oxide Si transistors Robertson, John Reports on Progress in Physics, Vol. 69, Issue 2 https://doi.org/10.1088/0034-4885/69/2/R02	journal	December 2005
Dual-frequency resonance-tracking atomic force microscopy Rodriguez, Brian J.; Callahan, Clint; Kalinin, Sergei V. Nanotechnology, Vol. 18, Issue 47, Article No. 475504 https://doi.org/10.1088/0957-4484/18/47/475504	journal	October 2007
The Effect of Hydrostatic Pressure on the Curie Point of Barium Titanate Single Crystals Merz, W. J. Physical Review, Vol. 78, Issue 1 https://doi.org/10.1103/PhysRev.78.52	journal	April 1950
Oxygen 1 s x-ray-absorption edges of transition-metal oxides de Groot, F. M. F.; Grioni, M.; Fuggle, J. C. Physical Review B, Vol. 40, Issue 8 https://doi.org/10.1103/PhysRevB.40.5715	journal	September 1989
Structural properties and electronic structure of HfO 2 -ZrO 2 composite films Cho, Deok-Yong; Jung, Hyung-Suk; Hwang, Cheol Seong Physical Review B, Vol. 82, Issue 9 https://doi.org/10.1103/PhysRevB.82.094104	journal	September 2010
Strain and composition dependence of orbital polarization in nickel oxide superlattices Wu, M.; Benckiser, E.; Haverkort, M. W. Physical Review B, Vol. 88, Issue 12 https://doi.org/10.1103/PhysRevB.88.125124	journal	September 2013
Orbital Engineering in Symmetry-Breaking Polar Heterostructures Disa, Ankit S.; Kumah, Divine P.; Malashevich, Andrei Physical Review Letters, Vol. 114, Issue 2 https://doi.org/10.1103/PhysRevLett.114.026801	journal	January 2015
Intrinsic Two-Dimensional Ferroelectricity with Dipole Locking Xiao, Jun; Zhu, Hanyu; Wang, Ying Physical Review Letters, Vol. 120, Issue 22 https://doi.org/10.1103/PhysRevLett.120.227601	journal	May 2018
Ferroelectricity and Tetragonality in Ultrathin P b T i O 3 Films Lichtensteiger, Céline; Triscone, Jean-Marc; Junquera, Javier Physical Review Letters, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevLett.94.047603	journal	February 2005
Physics of thin-film ferroelectric oxides Dawber, M.; Rabe, K. M.; Scott, J. F. Reviews of Modern Physics, Vol. 77, Issue 4 https://doi.org/10.1103/RevModPhys.77.1083	journal	October 2005
xrayutilities : a versatile tool for reciprocal space conversion of scattering data recorded with linear and area detectors Kriegner, Dominik; Wintersberger, Eugen; Stangl, Julian Journal of Applied Crystallography, Vol. 46, Issue 4 https://doi.org/10.1107/S0021889813017214	journal	July 2013
Variable linear polarization from an X-ray undulator Young, A. T.; Arenholz, E.; Marks, S. Journal of Synchrotron Radiation, Vol. 9, Issue 4 https://doi.org/10.1107/S0909049502007161	journal	June 2002
Ferroelectric hafnium oxide: A CMOS-compatible and highly scalable approach to future ferroelectric memories Muller, J.; Boscke, T. S.; Muller, S. 2013 IEEE International Electron Devices Meeting (IEDM) https://doi.org/10.1109/IEDM.2013.6724605	conference	December 2013
Physical thickness 1.x nm ferroelectric HfZrOx negative capacitance FETs Lee, M. H.; Fan, S. -T.; Tang, C. -H. 2016 IEEE International Electron Devices Meeting (IEDM) https://doi.org/10.1109/IEDM.2016.7838400	conference	December 2016
Negative Capacitance Transistors Wong, Justin C.; Salahuddin, Sayeef Proceedings of the IEEE, Vol. 107, Issue 1 https://doi.org/10.1109/JPROC.2018.2884518	journal	January 2019
Improved Subthreshold Swing and Short Channel Effect in FDSOI n-Channel Negative Capacitance Field Effect Transistors Kwon, Daewoong; Chatterjee, Korok; Tan, Ava J. IEEE Electron Device Letters, Vol. 39, Issue 2 https://doi.org/10.1109/LED.2017.2787063	journal	February 2018
Negative Capacitance FET With 1.8-nm-Thick Zr-Doped HfO ₂ Oxide Kwon, Daewoong; Cheema, Suraj; Shanker, Nirmaan IEEE Electron Device Letters, Vol. 40, Issue 6 https://doi.org/10.1109/LED.2019.2912413	journal	June 2019
First demonstration and performance improvement of ferroelectric HfO2-based resistive switch with low operation current and intrinsic diode property Fujii, Shosuke; Kamimuta, Yuuichi; Ino, Tsunehiro 2016 IEEE Symposium on VLSI Technology https://doi.org/10.1109/VLSIT.2016.7573413	conference	June 2016
Phase Relations and Volume Changes of Hafnia under High Pressure and High Temperature Ohtaka, Osamu; Fukui, Hiroshi; Kunisada, Taichi Journal of the American Ceramic Society, Vol. 84, Issue 6 https://doi.org/10.1111/j.1151-2916.2001.tb00843.x	journal	June 2001
Probing Ferroelectrics Using Optical Second Harmonic Generation Denev, Sava A.; Lummen, Tom T. A.; Barnes, Eftihia Journal of the American Ceramic Society, Vol. 94, Issue 9 https://doi.org/10.1111/j.1551-2916.2011.04740.x	journal	August 2011
Ferroelectricity at the Nanoscale: Local Polarization in Oxide Thin Films and Heterostructures Ahn, C. H. Science, Vol. 303, Issue 5657 https://doi.org/10.1126/science.1092508	journal	January 2004
Ferroelectricity in Ultrathin Perovskite Films Fong, Dillon D.; Stephenson, G. Brian; Streiffer, Stephen K. Science, Vol. 304, Issue 5677, p. 1650-1653 https://doi.org/10.1126/science.1098252	journal	June 2004
Probing Nanoscale Ferroelectricity by Ultraviolet Raman Spectroscopy Tenne, D. A.; Bruchhausen, A.; Lanzillotti-Kimura, N. D. Science, Vol. 313, Issue 5793 https://doi.org/10.1126/science.1130306	journal	September 2006
A Ferroelectric Oxide Made Directly on Silicon Warusawithana, M. P.; Cen, C.; Sleasman, C. R. Science, Vol. 324, Issue 5925 https://doi.org/10.1126/science.1169678	journal	April 2009
Flexoelectric Effect in Solids Zubko, Pavlo; Catalan, Gustau; Tagantsev, Alexander K. Annual Review of Materials Research, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-matsci-071312-121634	journal	July 2013
Strain Tuning of Ferroelectric Thin Films Schlom, Darrell G.; Chen, Long-Qing; Eom, Chang-Beom Annual Review of Materials Research, Vol. 37, Issue 1 https://doi.org/10.1146/annurev.matsci.37.061206.113016	journal	August 2007
Review and perspective on ferroelectric HfO2-based thin films for memory applications Park, Min Hyuk; Lee, Young Hwan; Mikolajick, Thomas MRS Communications, Vol. 8, Issue 03 https://doi.org/10.1557/mrc.2018.175	journal	August 2018
Elastic strain engineering of ferroic oxides Schlom, Darrell G.; Chen, Long-Qing; Fennie, Craig J. MRS Bulletin, Vol. 39, Issue 2 https://doi.org/10.1557/mrs.2014.1	journal	February 2014
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
A Thermodynamic Approach to Selecting Alternative Gate Dielectrics Schlom, Darrell G.; Haeni, Jeffrey H. MRS Bulletin, Vol. 27, Issue 3 https://doi.org/10.1557/mrs2002.71	journal	March 2002
Gate Oxides Beyond SiO ₂ Schlom, Darrell G.; Guha, Supratik; Datta, Suman MRS Bulletin, Vol. 33, Issue 11 https://doi.org/10.1557/mrs2008.221	journal	November 2008
Crystallisation and Tetragonal-Monoclinic Transformation in ZrO₂ and HfO₂ Dielectric Thin Films Zhao, Chao; Roebben, Gert; Heyns, Marc M. Key Engineering Materials, Vol. 206-213 https://doi.org/10.4028/www.scientific.net/KEM.206-213.1285	journal	December 2001

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