Effect of oxygen vacancies and strain on the phonon spectrum of HfO2 thin films

Gao, Lingyuan; Yalon, Eilam; Chew, Annabel R.; Deshmukh, Sanchit; Salleo, Alberto; Pop, Eric; Demkov, Alexander A.

doi:10.1063/1.4984833

Title: Effect of oxygen vacancies and strain on the phonon spectrum of HfO₂ thin films

Journal Article · Thu Jun 08 00:00:00 EDT 2017 · Journal of Applied Physics

DOI:https://doi.org/10.1063/1.4984833· OSTI ID:1535311

Gao, Lingyuan ^[1];

^[2]; Chew, Annabel R. ^[3]; Deshmukh, Sanchit ^[2]; Salleo, Alberto ^[3];

^[4]; Demkov, Alexander A. ^[1]

Univ. of Texas, Austin, TX (United States). Dept. of Physics
Stanford Univ., Stanford, CA (United States). Dept. of Electrical Engineering
Stanford Univ., Stanford, CA (United States). Dept. of Materials Science and Engineering
Stanford Univ., Stanford, CA (United States). Dept. of Electrical Engineering; Stanford Univ., Stanford, CA (United States). Dept. of Materials Science and Engineering

The effect of strain and oxygen deficiency on the Raman spectrum of monoclinic HfO₂ is investigated theoretically using first-principles calculations. 1% in-plane compressive strain applied to a and c axes is found to blue shift the phonon frequencies, while 1% tensile strain does the opposite. The simulations are compared, and good agreement is found with the experimental results of Raman frequencies greater than 110 cm^-1 for 50 nm HfO₂ thin films. Several Raman modes measured below 110 cm^-1 and previously assigned to HfO₂ are found to be rotational modes of gases present in air ambient (nitrogen and oxygen). However, localized vibrational modes introduced by threefold-coordinated oxygen (O₃) vacancies are identified at 96.4 cm^-1 computationally. Finally, these results are important for a deeper understanding of vibrational modes in HfO₂, which has technological applications in transistors and particularly in resistive random-access memory whose operation relies on oxygen-deficient HfO_x.

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Research Organization:: Univ. of Texas, Austin, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0008877

OSTI ID:: 1535311

Alternate ID(s):: OSTI ID: 1361920

Journal Information:: Journal of Applied Physics, Vol. 121, Issue 22; ISSN 0021-8979

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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References (57)

Hafnia and hafnia-toughened ceramics Wang, J.; Li, H. P.; Stevens, R. Journal of Materials Science, Vol. 27, Issue 20 https://doi.org/10.1007/BF00541601	journal	January 1992
Pressure-induced phase transitions and volume changes in ${HfO}_{2}$ up to 50 GPa Leger, J. M.; Atouf, A.; Tomaszewski, P. E. Physical Review B, Vol. 48, Issue 1 https://doi.org/10.1103/PhysRevB.48.93	journal	July 1993
Atomic layer deposition rate, phase composition and performance of HfO2 films on noble metal and alkoxylated silicon substrates Kukli, Kaupo; Ritala, Mikko; Pilvi, Tero Materials Science and Engineering: B, Vol. 118, Issue 1-3 https://doi.org/10.1016/j.mseb.2004.12.020	journal	April 2005
Vacancy and interstitial defects in hafnia Foster, A. S.; Lopez Gejo, F.; Shluger, A. L. Physical Review B, Vol. 65, Issue 17 https://doi.org/10.1103/PhysRevB.65.174117	journal	May 2002
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
Raman study of oxygen reduced and re-oxidized strontium titanate Tenne, D. A.; Gonenli, I. E.; Soukiassian, A. Physical Review B, Vol. 76, Issue 2 https://doi.org/10.1103/PhysRevB.76.024303	journal	July 2007
Conditions for the existence of phonon localized edge-modes Jiang, Jin-Wu; Wang, Jian-Sheng Physical Review B, Vol. 81, Issue 17 https://doi.org/10.1103/PhysRevB.81.174117	journal	May 2010
Heat Capacities at Low Temperatures and Entropies at 298.16°K. of Hafnium Dioxide and Hafnium Tetrachloride Todd, S. S. Journal of the American Chemical Society, Vol. 75, Issue 12 https://doi.org/10.1021/ja01108a520	journal	June 1953
Uniaxial Strain on Graphene: Raman Spectroscopy Study and Band-Gap Opening Ni, Zhen Hua; Yu, Ting; Lu, Yun Hao ACS Nano, Vol. 2, Issue 11 https://doi.org/10.1021/nn800459e	journal	October 2008
Nucleation and growth study of atomic layer deposited HfO2 gate dielectrics resulting in improved scaling and electron mobility Kirsch, P. D.; Quevedo-Lopez, M. A.; Li, H. -J. Journal of Applied Physics, Vol. 99, Issue 2 https://doi.org/10.1063/1.2161819	journal	January 2006
On the Use of a Fabry-Perot Etalon for the Determination of Rotational Constants of Simple Molecules-The Pure Rotational Raman Spectra of Oxygen and Nitrogen Butcher, R. J.; Willetts, D. V.; Jones, W. J. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 324, Issue 1557 https://doi.org/10.1098/rspa.1971.0137	journal	August 1971
Defect energy levels in HfO2 high-dielectric-constant gate oxide Xiong, K.; Robertson, J.; Gibson, M. C. Applied Physics Letters, Vol. 87, Issue 18 https://doi.org/10.1063/1.2119425	journal	October 2005
Influence of oxygen vacancies on the dielectric properties of hafnia: First-principles calculations Cockayne, Eric Physical Review B, Vol. 75, Issue 9 https://doi.org/10.1103/PhysRevB.75.094103	journal	March 2007
Structure and optical properties of HfO2 thin films on silicon after rapid thermal annealing Tan, Tingting; Liu, Zhengtang; Lu, Hongcheng Optical Materials, Vol. 32, Issue 3 https://doi.org/10.1016/j.optmat.2009.10.003	journal	January 2010
Raman and Brillouin scattering spectroscopy studies of atomic layer-deposited ZrO2 and HfO2 thin films Tkachev, S. N.; Manghnani, M. H.; Niilisk, A. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 61, Issue 10 https://doi.org/10.1016/j.saa.2005.02.025	journal	August 2005
Dynamical response and instability in ceria under lattice expansion Buckeridge, J.; Scanlon, D. O.; Walsh, A. Physical Review B, Vol. 87, Issue 21 https://doi.org/10.1103/PhysRevB.87.214304	journal	June 2013
Pressure-Induced Phase Transformation of HfO2 Arashi, Haruo Journal of the American Ceramic Society, Vol. 75, Issue 4 https://doi.org/10.1111/j.1151-2916.1992.tb04149.x	journal	April 1992
Structural and vibrational properties of high-dielectric oxides, HfO2 and TiO2: A comparative study Debernardi, A.; Fanciulli, M. Materials Science in Semiconductor Processing, Vol. 9, Issue 6 https://doi.org/10.1016/j.mssp.2006.10.036	journal	December 2006
Phase diagram up to 105 GPa and mechanical strength of ${HfO}_{2}$ Al-Khatatbeh, Yahya; Lee, Kanani K. M.; Kiefer, Boris Physical Review B, Vol. 82, Issue 14 https://doi.org/10.1103/PhysRevB.82.144106	journal	October 2010
Theoretical modeling of antiferrodistortive phase transition for $SrTi O_{3}$ ultrathin films Blokhin, E.; Evarestov, R. A.; Gryaznov, D. Physical Review B, Vol. 88, Issue 24 https://doi.org/10.1103/PhysRevB.88.241407	journal	December 2013
Phonon instability and mechanism of superionic conduction in Li $_{2}$ O Gupta, M. K.; Goel, Prabhatasree; Mittal, R. Physical Review B, Vol. 85, Issue 18 https://doi.org/10.1103/PhysRevB.85.184304	journal	May 2012
HfO[sub 2] Gate Dielectrics Deposited via Tetrakis Diethylamido Hafnium Schaeffer, J.; Edwards, N. V.; Liu, R. Journal of The Electrochemical Society, Vol. 150, Issue 4 https://doi.org/10.1149/1.1554729	journal	January 2003
Phase transition in sputtered HfO2 thin films: A qualitative Raman study Belo, G. S.; Nakagomi, F.; Minko, A. Applied Surface Science, Vol. 261 https://doi.org/10.1016/j.apsusc.2012.08.088	journal	November 2012
Memristive devices for computing Yang, J. Joshua; Strukov, Dmitri B.; Stewart, Duncan R. Nature Nanotechnology, Vol. 8, Issue 1, p. 13-24 https://doi.org/10.1038/nnano.2012.240	journal	January 2013
Silicon Nanowire Polytypes: Identification by Raman Spectroscopy, Generation Mechanism, and Misfit Strain in Homostructures Lopez, Francisco J.; Givan, Uri; Connell, Justin G. ACS Nano, Vol. 5, Issue 11 https://doi.org/10.1021/nn2031337	journal	October 2011
X-Ray absorption, photoemission spectroscopy, and Raman scattering analysis of amorphous tantalum oxide with a large extent of oxygen nonstoichiometry Tsuchiya, Takashi; Imai, Hideto; Miyoshi, Shogo Physical Chemistry Chemical Physics, Vol. 13, Issue 38 https://doi.org/10.1039/c1cp21310e	journal	January 2011
The conduction bands of MgO, MgS and Boer, P. K. de; Groot, R. A. de Journal of Physics: Condensed Matter, Vol. 10, Issue 45 https://doi.org/10.1088/0953-8984/10/45/011	journal	November 1998
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
Determination of electron effective mass and electron affinity in HfO2 using MOS and MOSFET structures Monaghan, S.; Hurley, P. K.; Cherkaoui, K. Solid-State Electronics, Vol. 53, Issue 4 https://doi.org/10.1016/j.sse.2008.09.018	journal	April 2009
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Optical characterization of HfO2 thin films grown by atomic layer deposition Aarik, Jaan; Mändar, Hugo; Kirm, Marco Thin Solid Films, Vol. 466, Issue 1-2 https://doi.org/10.1016/j.tsf.2004.01.110	journal	November 2004
Pressure and Temperature Dependence of the Raman Spectra of Zirconia and Hafnia Kourouklis, Gerasimos A.; Liarokapis, Efthymios Journal of the American Ceramic Society, Vol. 74, Issue 3 https://doi.org/10.1111/j.1151-2916.1991.tb04054.x	journal	March 1991
Evidences of oxygen-mediated resistive-switching mechanism in TiN\HfO2\Pt cells Goux, L.; Czarnecki, P.; Chen, Y. Y. Applied Physics Letters, Vol. 97, Issue 24 https://doi.org/10.1063/1.3527086	journal	December 2010
Lithium oxide and superionic behaviour—A study using potentials from periodic ab initio calculations Fracchia, R. M.; Barrera, G. D.; Allan, N. L. Journal of Physics and Chemistry of Solids, Vol. 59, Issue 3 https://doi.org/10.1016/S0022-3697(97)00208-4	journal	March 1998
Raman-scattering measurements and first-principles calculations of strain-induced phonon shifts in monolayer MoS $_{2}$ Rice, C.; Young, R. J.; Zan, R. Physical Review B, Vol. 87, Issue 8 https://doi.org/10.1103/PhysRevB.87.081307	journal	February 2013
Investigation of thermal annealing effects on microstructural and optical properties of HfO2 thin films Modreanu, M.; Sancho-Parramon, J.; Durand, O. Applied Surface Science, Vol. 253, Issue 1 https://doi.org/10.1016/j.apsusc.2006.06.005	journal	October 2006
Annealing and doping effects on the structure of europium-doped HfO2 sol–gel material Villanueva-Ibañez, M.; Le Luyer, C.; Marty, O. Optical Materials, Vol. 24, Issue 1-2 https://doi.org/10.1016/S0925-3467(03)00104-6	journal	October 2003
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Enthalpy of formation of cubic yttria-stabilized hafnia Lee, Theresa A.; Navrotsky, Alexandra Journal of Materials Research, Vol. 19, Issue 6 https://doi.org/10.1557/JMR.2004.0234	journal	June 2004
First-principles study of structural, vibrational, and lattice dielectric properties of hafnium oxide Zhao, Xinyuan; Vanderbilt, David Physical Review B, Vol. 65, Issue 23 https://doi.org/10.1103/PhysRevB.65.233106	journal	June 2002
Structural, electronic, optical, elastic properties and Born effective charges of monoclinic HfO ₂ from first-principles calculations Liu, Qi-Jun; Zhang, Ning-Chao; Liu, Fu-Sheng Chinese Physics B, Vol. 23, Issue 4 https://doi.org/10.1088/1674-1056/23/4/047101	journal	April 2014
Monoclinic to tetragonal transformations in hafnia and zirconia: A combined calorimetric and density functional study Luo, Xuhui; Zhou, Wei; Ushakov, Sergey V. Physical Review B, Vol. 80, Issue 13 https://doi.org/10.1103/PhysRevB.80.134119	journal	October 2009
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
Raman spectrometry study of phonon anharmonicity of hafnia at elevated temperatures Li, Chen W.; McKerns, Michael M.; Fultz, B. Physical Review B, Vol. 80, Issue 5 https://doi.org/10.1103/PhysRevB.80.054304	journal	August 2009
High-κ gate dielectrics: Current status and materials properties considerations Wilk, G. D.; Wallace, R. M.; Anthony, J. M. Journal of Applied Physics, Vol. 89, Issue 10 https://doi.org/10.1063/1.1361065	journal	May 2001
Energetics of rare-earth-doped hafnia Simoncic, Petra; Navrotsky, Alexandra Journal of Materials Research, Vol. 22, Issue 4 https://doi.org/10.1557/jmr.2007.0133	journal	April 2007
Raman Scattering Cross Sections in Gases and Liquids Schrötter, H. W.; Klöckner, H. W. Raman Spectroscopy of Gases and Liquids https://doi.org/10.1007/978-3-642-81279-8_4	book	January 1979
Effect of static uniaxial stress on the Raman spectrum of silicon Anastassakis, E.; Pinczuk, A.; Burstein, E. Solid State Communications, Vol. 8, Issue 2 https://doi.org/10.1016/0038-1098(70)90588-0	journal	January 1970
Oxygen vacancy in monoclinic HfO2: A consistent interpretation of trap assisted conduction, direct electron injection, and optical absorption experiments Broqvist, Peter; Pasquarello, Alfredo Applied Physics Letters, Vol. 89, Issue 26 https://doi.org/10.1063/1.2424441	journal	December 2006
High dielectric constant oxides Robertson, J. The European Physical Journal Applied Physics, Vol. 28, Issue 3, p. 265-291 https://doi.org/10.1051/epjap:2004206	journal	December 2004
First-principles calculations of the ferroelastic transition between rutile-type and ${CaCl}_{2}$ -type ${SiO}_{2}$ at high pressures Togo, Atsushi; Oba, Fumiyasu; Tanaka, Isao Physical Review B, Vol. 78, Issue 13 https://doi.org/10.1103/PhysRevB.78.134106	journal	October 2008
X-ray diffraction study of Hafnia under high pressure using synchrotron radiation Adams, David M.; Leonard, Simon; Russell, David R. Journal of Physics and Chemistry of Solids, Vol. 52, Issue 9 https://doi.org/10.1016/0022-3697(91)90052-2	journal	January 1991
Comparative Lattice-Dynamical Study of the Raman Spectra of Monoclinic and Tetragonal Phases of Zirconia and Hafnia Quintard, Pierre E.; Barbéris, Pierre; Mirgorodsky, Andrei P. Journal of the American Ceramic Society, Vol. 85, Issue 7 https://doi.org/10.1111/j.1151-2916.2002.tb00346.x	journal	July 2002
Effect of static uniaxial stress on the Raman spectrum of silicon Anastassakis, E.; Pinczuk, A.; Burstein, E. Solid State Communications, Vol. 88, Issue 11-12 https://doi.org/10.1016/0038-1098(93)90294-w	journal	December 1993
High-resolution X-ray luminescence extension imaging Ou, Xiangyu; Qin, Xian; Huang, Bolong Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-021-03251-6	journal	February 2021
Uniaxial Strain on Graphene: Raman Spectroscopy Study and Band-Gap Opening Ni, Zhen Hua; Yu, Ting; Lu, Yun Hao ACS Nano, Vol. 3, Issue 2 https://doi.org/10.1021/nn8008323	journal	January 2009
First-principles study of structural, vibrational and lattice dielectric properties of hafnium oxide Zhao, Xinyuan; Vanderbilt, David arXiv https://doi.org/10.48550/arxiv.cond-mat/0202454	text	January 2002

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Title: Effect of oxygen vacancies and strain on the phonon spectrum of HfO₂ thin films