Effect of oxygen vacancies and strain on the phonon spectrum of HfO2 thin films
Abstract
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 HfOx.
- Authors:
-
- 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
- Publication Date:
- Research Org.:
- Univ. of Texas, Austin, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1535311
- Alternate Identifier(s):
- OSTI ID: 1361920
- Grant/Contract Number:
- SC0008877
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Applied Physics
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 22; Journal ID: ISSN 0021-8979
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; physics
Citation Formats
Gao, Lingyuan, Yalon, Eilam, Chew, Annabel R., Deshmukh, Sanchit, Salleo, Alberto, Pop, Eric, and Demkov, Alexander A. Effect of oxygen vacancies and strain on the phonon spectrum of HfO2 thin films. United States: N. p., 2017.
Web. doi:10.1063/1.4984833.
Gao, Lingyuan, Yalon, Eilam, Chew, Annabel R., Deshmukh, Sanchit, Salleo, Alberto, Pop, Eric, & Demkov, Alexander A. Effect of oxygen vacancies and strain on the phonon spectrum of HfO2 thin films. United States. https://doi.org/10.1063/1.4984833
Gao, Lingyuan, Yalon, Eilam, Chew, Annabel R., Deshmukh, Sanchit, Salleo, Alberto, Pop, Eric, and Demkov, Alexander A. Thu .
"Effect of oxygen vacancies and strain on the phonon spectrum of HfO2 thin films". United States. https://doi.org/10.1063/1.4984833. https://www.osti.gov/servlets/purl/1535311.
@article{osti_1535311,
title = {Effect of oxygen vacancies and strain on the phonon spectrum of HfO2 thin films},
author = {Gao, Lingyuan and Yalon, Eilam and Chew, Annabel R. and Deshmukh, Sanchit and Salleo, Alberto and Pop, Eric and Demkov, Alexander A.},
abstractNote = {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 HfOx.},
doi = {10.1063/1.4984833},
journal = {Journal of Applied Physics},
number = 22,
volume = 121,
place = {United States},
year = {Thu Jun 08 00:00:00 EDT 2017},
month = {Thu Jun 08 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Hafnia and hafnia-toughened ceramics
journal, January 1992
- Wang, J.; Li, H. P.; Stevens, R.
- Journal of Materials Science, Vol. 27, Issue 20
Pressure-induced phase transitions and volume changes in up to 50 GPa
journal, July 1993
- Leger, J. M.; Atouf, A.; Tomaszewski, P. E.
- Physical Review B, Vol. 48, Issue 1
Atomic layer deposition rate, phase composition and performance of HfO2 films on noble metal and alkoxylated silicon substrates
journal, April 2005
- Kukli, Kaupo; Ritala, Mikko; Pilvi, Tero
- Materials Science and Engineering: B, Vol. 118, Issue 1-3
Vacancy and interstitial defects in hafnia
journal, May 2002
- Foster, A. S.; Lopez Gejo, F.; Shluger, A. L.
- Physical Review B, Vol. 65, Issue 17
A Thermodynamic Approach to Selecting Alternative Gate Dielectrics
journal, March 2002
- Schlom, Darrell G.; Haeni, Jeffrey H.
- MRS Bulletin, Vol. 27, Issue 3
Raman study of oxygen reduced and re-oxidized strontium titanate
journal, July 2007
- Tenne, D. A.; Gonenli, I. E.; Soukiassian, A.
- Physical Review B, Vol. 76, Issue 2
Conditions for the existence of phonon localized edge-modes
journal, May 2010
- Jiang, Jin-Wu; Wang, Jian-Sheng
- Physical Review B, Vol. 81, Issue 17
Heat Capacities at Low Temperatures and Entropies at 298.16°K. of Hafnium Dioxide and Hafnium Tetrachloride
journal, June 1953
- Todd, S. S.
- Journal of the American Chemical Society, Vol. 75, Issue 12
Uniaxial Strain on Graphene: Raman Spectroscopy Study and Band-Gap Opening
journal, October 2008
- Ni, Zhen Hua; Yu, Ting; Lu, Yun Hao
- ACS Nano, Vol. 2, Issue 11
Nucleation and growth study of atomic layer deposited HfO2 gate dielectrics resulting in improved scaling and electron mobility
journal, January 2006
- Kirsch, P. D.; Quevedo-Lopez, M. A.; Li, H. -J.
- Journal of Applied Physics, Vol. 99, Issue 2
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
journal, August 1971
- Butcher, R. J.; Willetts, D. V.; Jones, W. J.
- Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 324, Issue 1557
Defect energy levels in HfO2 high-dielectric-constant gate oxide
journal, October 2005
- Xiong, K.; Robertson, J.; Gibson, M. C.
- Applied Physics Letters, Vol. 87, Issue 18
Influence of oxygen vacancies on the dielectric properties of hafnia: First-principles calculations
journal, March 2007
- Cockayne, Eric
- Physical Review B, Vol. 75, Issue 9
Structure and optical properties of HfO2 thin films on silicon after rapid thermal annealing
journal, January 2010
- Tan, Tingting; Liu, Zhengtang; Lu, Hongcheng
- Optical Materials, Vol. 32, Issue 3
Raman and Brillouin scattering spectroscopy studies of atomic layer-deposited ZrO2 and HfO2 thin films
journal, August 2005
- Tkachev, S. N.; Manghnani, M. H.; Niilisk, A.
- Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 61, Issue 10
Dynamical response and instability in ceria under lattice expansion
journal, June 2013
- Buckeridge, J.; Scanlon, D. O.; Walsh, A.
- Physical Review B, Vol. 87, Issue 21
Pressure-Induced Phase Transformation of HfO2
journal, April 1992
- Arashi, Haruo
- Journal of the American Ceramic Society, Vol. 75, Issue 4
Structural and vibrational properties of high-dielectric oxides, HfO2 and TiO2: A comparative study
journal, December 2006
- Debernardi, A.; Fanciulli, M.
- Materials Science in Semiconductor Processing, Vol. 9, Issue 6
Phase diagram up to 105 GPa and mechanical strength of
journal, October 2010
- Al-Khatatbeh, Yahya; Lee, Kanani K. M.; Kiefer, Boris
- Physical Review B, Vol. 82, Issue 14
Theoretical modeling of antiferrodistortive phase transition for ultrathin films
journal, December 2013
- Blokhin, E.; Evarestov, R. A.; Gryaznov, D.
- Physical Review B, Vol. 88, Issue 24
Phonon instability and mechanism of superionic conduction in Li O
journal, May 2012
- Gupta, M. K.; Goel, Prabhatasree; Mittal, R.
- Physical Review B, Vol. 85, Issue 18
HfO[sub 2] Gate Dielectrics Deposited via Tetrakis Diethylamido Hafnium
journal, January 2003
- Schaeffer, J.; Edwards, N. V.; Liu, R.
- Journal of The Electrochemical Society, Vol. 150, Issue 4
Phase transition in sputtered HfO2 thin films: A qualitative Raman study
journal, November 2012
- Belo, G. S.; Nakagomi, F.; Minko, A.
- Applied Surface Science, Vol. 261
Memristive devices for computing
journal, January 2013
- Yang, J. Joshua; Strukov, Dmitri B.; Stewart, Duncan R.
- Nature Nanotechnology, Vol. 8, Issue 1, p. 13-24
Silicon Nanowire Polytypes: Identification by Raman Spectroscopy, Generation Mechanism, and Misfit Strain in Homostructures
journal, October 2011
- Lopez, Francisco J.; Givan, Uri; Connell, Justin G.
- ACS Nano, Vol. 5, Issue 11
X-Ray absorption, photoemission spectroscopy, and Raman scattering analysis of amorphous tantalum oxide with a large extent of oxygen nonstoichiometry
journal, January 2011
- Tsuchiya, Takashi; Imai, Hideto; Miyoshi, Shogo
- Physical Chemistry Chemical Physics, Vol. 13, Issue 38
The conduction bands of MgO, MgS and
journal, November 1998
- Boer, P. K. de; Groot, R. A. de
- Journal of Physics: Condensed Matter, Vol. 10, Issue 45
The simulated vibrational spectra of HfO 2 polymorphs
journal, February 2014
- Zhou, B.; Shi, H.; Zhang, X. D.
- Journal of Physics D: Applied Physics, Vol. 47, Issue 11
Determination of electron effective mass and electron affinity in HfO2 using MOS and MOSFET structures
journal, April 2009
- Monaghan, S.; Hurley, P. K.; Cherkaoui, K.
- Solid-State Electronics, Vol. 53, Issue 4
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Optical characterization of HfO2 thin films grown by atomic layer deposition
journal, November 2004
- Aarik, Jaan; Mändar, Hugo; Kirm, Marco
- Thin Solid Films, Vol. 466, Issue 1-2
Pressure and Temperature Dependence of the Raman Spectra of Zirconia and Hafnia
journal, March 1991
- Kourouklis, Gerasimos A.; Liarokapis, Efthymios
- Journal of the American Ceramic Society, Vol. 74, Issue 3
Evidences of oxygen-mediated resistive-switching mechanism in TiN\HfO2\Pt cells
journal, December 2010
- Goux, L.; Czarnecki, P.; Chen, Y. Y.
- Applied Physics Letters, Vol. 97, Issue 24
Lithium oxide and superionic behaviour—A study using potentials from periodic ab initio calculations
journal, March 1998
- Fracchia, R. M.; Barrera, G. D.; Allan, N. L.
- Journal of Physics and Chemistry of Solids, Vol. 59, Issue 3
Raman-scattering measurements and first-principles calculations of strain-induced phonon shifts in monolayer MoS
journal, February 2013
- Rice, C.; Young, R. J.; Zan, R.
- Physical Review B, Vol. 87, Issue 8
Investigation of thermal annealing effects on microstructural and optical properties of HfO2 thin films
journal, October 2006
- Modreanu, M.; Sancho-Parramon, J.; Durand, O.
- Applied Surface Science, Vol. 253, Issue 1
Annealing and doping effects on the structure of europium-doped HfO2 sol–gel material
journal, October 2003
- Villanueva-Ibañez, M.; Le Luyer, C.; Marty, O.
- Optical Materials, Vol. 24, Issue 1-2
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Enthalpy of formation of cubic yttria-stabilized hafnia
journal, June 2004
- Lee, Theresa A.; Navrotsky, Alexandra
- Journal of Materials Research, Vol. 19, Issue 6
First-principles study of structural, vibrational, and lattice dielectric properties of hafnium oxide
journal, June 2002
- Zhao, Xinyuan; Vanderbilt, David
- Physical Review B, Vol. 65, Issue 23
Structural, electronic, optical, elastic properties and Born effective charges of monoclinic HfO 2 from first-principles calculations
journal, April 2014
- Liu, Qi-Jun; Zhang, Ning-Chao; Liu, Fu-Sheng
- Chinese Physics B, Vol. 23, Issue 4
Monoclinic to tetragonal transformations in hafnia and zirconia: A combined calorimetric and density functional study
journal, October 2009
- Luo, Xuhui; Zhou, Wei; Ushakov, Sergey V.
- Physical Review B, Vol. 80, Issue 13
Phase Relations and Volume Changes of Hafnia under High Pressure and High Temperature
journal, June 2001
- Ohtaka, Osamu; Fukui, Hiroshi; Kunisada, Taichi
- Journal of the American Ceramic Society, Vol. 84, Issue 6
Raman spectrometry study of phonon anharmonicity of hafnia at elevated temperatures
journal, August 2009
- Li, Chen W.; McKerns, Michael M.; Fultz, B.
- Physical Review B, Vol. 80, Issue 5
High-κ gate dielectrics: Current status and materials properties considerations
journal, May 2001
- Wilk, G. D.; Wallace, R. M.; Anthony, J. M.
- Journal of Applied Physics, Vol. 89, Issue 10
Energetics of rare-earth-doped hafnia
journal, April 2007
- Simoncic, Petra; Navrotsky, Alexandra
- Journal of Materials Research, Vol. 22, Issue 4
Raman Scattering Cross Sections in Gases and Liquids
book, January 1979
- Schrötter, H. W.; Klöckner, H. W.
- Raman Spectroscopy of Gases and Liquids
Effect of static uniaxial stress on the Raman spectrum of silicon
journal, January 1970
- Anastassakis, E.; Pinczuk, A.; Burstein, E.
- Solid State Communications, Vol. 8, Issue 2
Oxygen vacancy in monoclinic HfO2: A consistent interpretation of trap assisted conduction, direct electron injection, and optical absorption experiments
journal, December 2006
- Broqvist, Peter; Pasquarello, Alfredo
- Applied Physics Letters, Vol. 89, Issue 26
High dielectric constant oxides
journal, December 2004
- Robertson, J.
- The European Physical Journal Applied Physics, Vol. 28, Issue 3, p. 265-291
First-principles calculations of the ferroelastic transition between rutile-type and -type at high pressures
journal, October 2008
- Togo, Atsushi; Oba, Fumiyasu; Tanaka, Isao
- Physical Review B, Vol. 78, Issue 13
X-ray diffraction study of Hafnia under high pressure using synchrotron radiation
journal, January 1991
- Adams, David M.; Leonard, Simon; Russell, David R.
- Journal of Physics and Chemistry of Solids, Vol. 52, Issue 9
Comparative Lattice-Dynamical Study of the Raman Spectra of Monoclinic and Tetragonal Phases of Zirconia and Hafnia
journal, July 2002
- Quintard, Pierre E.; Barbéris, Pierre; Mirgorodsky, Andrei P.
- Journal of the American Ceramic Society, Vol. 85, Issue 7
Effect of static uniaxial stress on the Raman spectrum of silicon
journal, December 1993
- Anastassakis, E.; Pinczuk, A.; Burstein, E.
- Solid State Communications, Vol. 88, Issue 11-12
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
Uniaxial Strain on Graphene: Raman Spectroscopy Study and Band-Gap Opening
journal, January 2009
- Ni, Zhen Hua; Yu, Ting; Lu, Yun Hao
- ACS Nano, Vol. 3, Issue 2
First-principles study of structural, vibrational and lattice dielectric properties of hafnium oxide
text, January 2002
- Zhao, Xinyuan; Vanderbilt, David
- arXiv
Works referencing / citing this record:
Synthesis, structural, Raman scattering and magnetic properties of Fe -doped HfO 2 nanoparticles
journal, July 2019
- Singhal, Rahul; Singh, Manoj K.; Kumar, Aditya
- Materials Research Express, Vol. 6, Issue 9
Investigation of HfO2 Thin Films on Si by X-ray Photoelectron Spectroscopy, Rutherford Backscattering, Grazing Incidence X-ray Diffraction and Variable Angle Spectroscopic Ellipsometry
journal, June 2018
- Luo, Xuguang; Li, Yao; Yang, Hong
- Crystals, Vol. 8, Issue 6
Spatially Resolved Thermometry of Resistive Memory Devices
journal, November 2017
- Yalon, Eilam; Deshmukh, Sanchit; Muñoz Rojo, Miguel
- Scientific Reports, Vol. 7, Issue 1
Micro-Raman Spectroscopy for Monitoring of Deposition Quality of High-k Stack Protective Layer onto Nanowire FET Chips for Highly Sensitive miRNA Detection
journal, July 2018
- Malsagova, Kristina; Pleshakova, Tatyana; Kozlov, Andrey
- Biosensors, Vol. 8, Issue 3