Cubic phase stability, optical and magnetic properties of Cu-stabilized zirconia nanocrystals

Pramanik, Prativa; Singh, Sobhit; Joshi, Deep Chandra; Mallick, Ayan; Pisane, Kelly; Romero, Aldo H.; Thota, Subhash; Seehra, M. S.

doi:10.1088/1361-6463/aac004

Cubic phase stability, optical and magnetic properties of Cu-stabilized zirconia nanocrystals

Journal Article · Mon May 14 00:00:00 EDT 2018 · Journal of Physics. D, Applied Physics

DOI:https://doi.org/10.1088/1361-6463/aac004· OSTI ID:1594022

^[1]; ^[2]; ^[3]; Mallick, Ayan ^[3]; Pisane, Kelly ^[2]; Romero, Aldo H. ^[2]; ^[3]; Seehra, M. S. ^[2]

Indian Inst. of Technology (IIT), Assam (India); West Virginia University
West Virginia Univ., Morgantown, WV (United States)
Indian Inst. of Technology (IIT), Assam (India)

By means of experimental and ab initio investigations, in this article we report on the cubic phase stability of Cu doped zirconia (ZrO₂) at room temperature, and further characterize its structural, optical and magnetic properties. Various compositions of Zr_1–xCu_xO₂ (0.01 ≤ x ≤ 0.25) nanocrystallites of average size ~16 nm were synthesized using co-precipitation technique. Thermal analysis and kinetics of crystallization revealed that the cubic phase at ambient temperature can be stabilized by using a critical calcination temperature of 500 °C for 8 h in air and a critical composition of $$x_c$$ = 0.10 ± 0.05. For $$x < x_c$$, some undigested monoclinic phase of ZrO₂ exists together with the cubic structure. However, for $$x > x_c$$, the monoclinic CuO emerges as a secondary phase with shrinkage of unit-cell volume with increasing the Cu content. At x = 0.05 and 500 °C calcination temperature, we observe a high degree of cubic crystallinity which breaks down into monoclinic phase with increasing calcination temperature beyond 550 °C. Electron magnetic resonance studies provide evidence for the substitution of Cu²⁺ (²D_5/9,3d⁹) ions at Zr⁴⁺ sites with g_∥ = 2.250, g_⊥ = 2.018 and average g_a = (g_∥ + 2g_⊥)/3 ~ 2.1. The temperature dependence of magnetic susceptibility measurements from 2 K to 300 K exhibits Curie–Weiss behaviour whose analysis using g_a = 2.1 and spin S = 1/2 yields x = 0.028 and x = 0.068 for the nominal x = 0.05 and x = 0.20 samples, respectively. This magnetic analysis confirms the findings from x-ray diffraction that only a part of Cu is successfully doped into cubic phase of Cu-doped ZrO₂. The optical bandgap decreases with increasing x, which is due to the emergence of Cu-d states at Fermi-level near the valence bands, thus making Cu-doped zirconia a hole doped (p-type) semiconductor.

View Accepted Manuscript (DOE)

Research Organization:: West Virginia Univ., Morgantown, WV (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0016176

OSTI ID:: 1594022

Alternate ID(s):: OSTI ID: 1540402
OSTI ID: 23091791

Journal Information:: Journal of Physics. D, Applied Physics, Journal Name: Journal of Physics. D, Applied Physics Journal Issue: 22 Vol. 51; ISSN 0022-3727

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

References (59)

Electron Paramagnetic Resonance Study of Copper(II) Ions in Single Crystals of Thallium Magnesium Sulphate Hexahydrate Krishna, R. M.; Rao, J. L.; Chand, Prem physica status solidi (b), Vol. 151, Issue 2 https://doi.org/10.1002/pssb.2221510222	journal	February 1989
Electronic structure and optical properties of zirconia Kul’kova, S. E.; Muryzhnikova, O. N. Inorganic Materials, Vol. 36, Issue 1 https://doi.org/10.1007/BF02758377	journal	March 2000
ZrO2 and Cu/ZrO2 Sol?Gel Materials Spectroscopic Characterization L�pez, T.; Alvarez, M.; G�mez, R. Journal of Sol-Gel Science and Technology, Vol. 33, Issue 1 https://doi.org/10.1007/s10971-005-6706-y	journal	January 2005
X-ray line broadening from filed aluminium and wolfram Williamson, G. K.; Hall, W. H. Acta Metallurgica, Vol. 1, Issue 1 https://doi.org/10.1016/0001-6160(53)90006-6	journal	January 1953
Preparation and characterization of dispersed Rh2O3 on tetragonal ZrO2 Zhang, Y-C.; Dwight, K.; Wold, A. Materials Research Bulletin, Vol. 21, Issue 7 https://doi.org/10.1016/0025-5408(86)90171-6	journal	July 1986
Preparation and characterization of members of the systems and Luo, X-M.; Wu, P.; Kershaw, R. Materials Research Bulletin, Vol. 23, Issue 12 https://doi.org/10.1016/0025-5408(88)90181-X	journal	December 1988
On the structural chemistry of zirconium oxide Ho, Shih-Ming Materials Science and Engineering, Vol. 54, Issue 1 https://doi.org/10.1016/0025-5416(82)90026-X	journal	June 1982
Optical properties of cubic stabilized zirconia Camagni, P.; Galinetto, P.; Samoggia, G. Solid State Communications, Vol. 83, Issue 11 https://doi.org/10.1016/0038-1098(92)90916-W	journal	September 1992
Oxygen sensors Takeuchi, Takashi Sensors and Actuators, Vol. 14, Issue 2 https://doi.org/10.1016/0250-6874(88)80058-1	journal	June 1988
Influence of pH on the stability of low temperature t-ZrO2 Štefanić, G.; Musić, S.; Gržeta, B. Journal of Physics and Chemistry of Solids, Vol. 59, Issue 6-7 https://doi.org/10.1016/S0022-3697(98)00028-6	journal	June 1998
Electron Paramagnetic Resonance investigation of the nature of active species involved in carbon black oxidation on ZrO2 and Cu/ZrO2 catalysts Labaki, M.; Laversin, H.; Zhilinskaya, E. A. Catalysis Communications, Vol. 17 https://doi.org/10.1016/j.catcom.2011.10.016	journal	January 2012
Synthesis and optical properties of yttria-doped ZrO2 nanopowders Yang, Huaming; Ouyang, Jing; Zhang, Xiaolong Journal of Alloys and Compounds, Vol. 458, Issue 1-2 https://doi.org/10.1016/j.jallcom.2007.04.011	journal	June 2008
In situ investigations of structure–activity relationships of a Cu/ZrO2 catalyst for the steam reforming of methanol Szizybalski, A.; Girgsdies, F.; Rabis, A. Journal of Catalysis, Vol. 233, Issue 2 https://doi.org/10.1016/j.jcat.2005.04.024	journal	July 2005
An overview of zirconia ceramics: Basic properties and clinical applications Manicone, Paolo Francesco; Rossi Iommetti, Pierfrancesco; Raffaelli, Luca Journal of Dentistry, Vol. 35, Issue 11 https://doi.org/10.1016/j.jdent.2007.07.008	journal	November 2007
Investigation of the vibrational properties of cubic yttria-stabilized zirconia: A combined experimental and theoretical study Cousland, G. P.; Mole, R. A.; Elcombe, M. M. Journal of Physics and Chemistry of Solids, Vol. 75, Issue 3 https://doi.org/10.1016/j.jpcs.2013.10.012	journal	March 2014
Development of hafnium based high-k materials—A review Choi, J. H.; Mao, Y.; Chang, J. P. Materials Science and Engineering: R: Reports, Vol. 72, Issue 6 https://doi.org/10.1016/j.mser.2010.12.001	journal	July 2011
Absence of ferromagnetism in Mn- and Fe-stabilized zirconia nanoparticles Yu, J.; Duan, L. B.; Wang, Y. C. Physica B: Condensed Matter, Vol. 403, Issue 23-24 https://doi.org/10.1016/j.physb.2008.09.015	journal	December 2008
Elastic, electronic and thermal properties of YSZ from first principles Jin, Lei; Yu, Qinghe; Rauf, Abdul Solid State Sciences, Vol. 14, Issue 1 https://doi.org/10.1016/j.solidstatesciences.2011.11.003	journal	January 2012
Thermodynamic Tetragonal Phase Stability in Sol−Gel Derived Nanodomains of Pure Zirconia Shukla, Satyajit; Seal, Sudipta The Journal of Physical Chemistry B, Vol. 108, Issue 11 https://doi.org/10.1021/jp037532x	journal	March 2004
Thermal conductivity of dense and porous yttria-stabilized zirconia Schlichting, K. W.; Padture, N. P.; Klemens, P. G. Journal of Materials Science, Vol. 36, Issue 12, p. 3003-3010 https://doi.org/10.1023/A:1017970924312	journal	June 2001
Cu/ZnO and Cu/ZrO 2 interactions studied by contact angle measurement with TEM Kasatkin, Igor; Kniep, Benjamin; Ressler, Thorsten Phys. Chem. Chem. Phys., Vol. 9, Issue 7 https://doi.org/10.1039/B616795K	journal	January 2007
The atomistic structure of yttria stabilised zirconia at 6.7 mol%: an ab initio study Parkes, Michael A.; Tompsett, David A.; d'Avezac, Mayeul Physical Chemistry Chemical Physics, Vol. 18, Issue 45 https://doi.org/10.1039/C6CP04694K	journal	January 2016
Cu–ZrO2 nanocomposite catalyst for selective hydrogenation of levulinic acid and its ester to γ-valerolactone Hengne, Amol M.; Rode, Chandrashekhar V. Green Chemistry, Vol. 14, Issue 4 https://doi.org/10.1039/c2gc16558a	journal	January 2012
Nature of magnetism in copper-doped oxides: ZrO2, TiO2, MgO, SiO2, Al2O3, and ZnO Dutta, P.; Seehra, M. S.; Zhang, Y. Journal of Applied Physics, Vol. 103, Issue 7 https://doi.org/10.1063/1.2830555	journal	April 2008
On the resistive switching mechanisms of Cu/ZrO2:Cu/Pt Guan, Weihua; Liu, Ming; Long, Shibing Applied Physics Letters, Vol. 93, Issue 22 https://doi.org/10.1063/1.3039079	journal	December 2008
Effect of ZrOx/HfOx bilayer structure on switching uniformity and reliability in nonvolatile memory applications Lee, Joonmyoung; Bourim, El Mostafa; Lee, Wootae Applied Physics Letters, Vol. 97, Issue 17 https://doi.org/10.1063/1.3491803	journal	October 2010
Absence of ferromagnetism in Mn-doped tetragonal zirconia Srivastava, S. K.; Lejay, P.; Barbara, B. Journal of Applied Physics, Vol. 110, Issue 4 https://doi.org/10.1063/1.3626788	journal	August 2011
Room temperature ferromagnetism in monoclinic Mn-doped ZrO 2 thin films Hoa Hong, Nguyen; Park, C. -K.; Raghavender, A. T. Journal of Applied Physics, Vol. 111, Issue 7 https://doi.org/10.1063/1.3670577	journal	April 2012
From zirconia to yttria: Sampling the YSZ phase diagram using sputter-deposited thin films Götsch, Thomas; Wallisch, Wolfgang; Stöger-Pollach, Michael AIP Advances, Vol. 6, Issue 2 https://doi.org/10.1063/1.4942818	journal	February 2016
Size-dependent structural, magnetic, and optical properties of MnCo 2 O 4 nanocrystallites Singh, S.; Pramanik, P.; Sangaraju, S. Journal of Applied Physics, Vol. 121, Issue 19 https://doi.org/10.1063/1.4983360	journal	May 2017
Molecular dynamics calculations of anion diffusion in nitrogen-doped yttria-stabilized zirconia Kilo, M.; Homann, T.; Bredow, T. Philosophical Magazine, Vol. 87, Issue 6 https://doi.org/10.1080/14786430600993349	journal	January 2007
Physical interpretation and accuracy of the Kubelka–Munk theory Kokhanovsky, Alexander A. Journal of Physics D: Applied Physics, Vol. 40, Issue 7 https://doi.org/10.1088/0022-3727/40/7/053	journal	March 2007
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Experimental and theoretical determination of the electronic structure and optical properties of three phases of ZrO 2 French, R. H.; Glass, S. J.; Ohuchi, F. S. Physical Review B, Vol. 49, Issue 8 https://doi.org/10.1103/PhysRevB.49.5133	journal	February 1994
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
Structural properties and quasiparticle band structure of zirconia Králik, Balázs; Chang, Eric K.; Louie, Steven G. Physical Review B, Vol. 57, Issue 12 https://doi.org/10.1103/PhysRevB.57.7027	journal	March 1998
Relative stability, structure, and elastic properties of several phases of pure zirconia Dewhurst, J. K.; Lowther, J. E. Physical Review B, Vol. 57, Issue 2 https://doi.org/10.1103/PhysRevB.57.741	journal	January 1998
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
*Ab initio* study of structural and electronic properties of yttria-stabilized cubic zirconia Stapper, G.; Bernasconi, M.; Nicoloso, N. Physical Review B, Vol. 59, Issue 2 https://doi.org/10.1103/PhysRevB.59.797	journal	January 1999
Theoretical investigation of nitrogen substitution in cubic zirconia Bredow, Thomas Physical Review B, Vol. 75, Issue 14 https://doi.org/10.1103/PhysRevB.75.144102	journal	April 2007
First-principles study of the effect of pressure on the five zirconia polymorphs. I. Structural, vibrational, and thermoelastic properties Fadda, Giuseppe; Zanzotto, Giovanni; Colombo, Luciano Physical Review B, Vol. 82, Issue 6 https://doi.org/10.1103/PhysRevB.82.064105	journal	August 2010
First-principles study of the effect of pressure on the five zirconia polymorphs. II. Static dielectric properties and Raman spectra Fadda, Giuseppe; Zanzotto, Giovanni; Colombo, Luciano Physical Review B, Vol. 82, Issue 6 https://doi.org/10.1103/PhysRevB.82.064106	journal	August 2010
Defect-induced ferromagnetism in undoped and Mn-doped zirconia thin films Zippel, Jan; Lorenz, Michael; Setzer, Annette Physical Review B, Vol. 82, Issue 12 https://doi.org/10.1103/PhysRevB.82.125209	journal	September 2010
Ferroelastic switching of doped zirconia: Modeling and understanding from first principles Carbogno, Christian; Levi, Carlos G.; Van de Walle, Chris G. Physical Review B, Vol. 90, Issue 14 https://doi.org/10.1103/PhysRevB.90.144109	journal	October 2014
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Mn-Stabilized Zirconia: From Imitation Diamonds to a New Potential High- T C Ferromagnetic Spintronics Material Ostanin, S.; Ernst, A.; Sandratskii, L. M. Physical Review Letters, Vol. 98, Issue 1 https://doi.org/10.1103/PhysRevLett.98.016101	journal	January 2007
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
The crystal structure of baddeleyite (monoclinic ZrO2) McCullough, J. D.; Trueblood, K. N. Acta Crystallographica, Vol. 12, Issue 7 https://doi.org/10.1107/S0365110X59001530	journal	July 1959
Nonpolar Nonvolatile Resistive Switching in Cu Doped $\hbox{ZrO}_{2}$ Guan, Weihua; Long, Shibing; Liu, Qi IEEE Electron Device Letters, Vol. 29, Issue 5 https://doi.org/10.1109/LED.2008.919602	journal	May 2008
The Cubic Field in the System CaO-ZrO 2 Garvie, Ronald C. Journal of the American Ceramic Society, Vol. 51, Issue 10 https://doi.org/10.1111/j.1151-2916.1968.tb13320.x	journal	October 1968
Structure and Thermomechanical Properties of Partially Stabilized Zirconia in the CaO-ZrO2 System Garvie, Ronald C.; Nicholson, Patrick S. Journal of the American Ceramic Society, Vol. 55, Issue 3 https://doi.org/10.1111/j.1151-2916.1972.tb11241.x	journal	March 1972
Phase Analysis in Zirconia Systems Garvie, Ronald C.; Nicholson, Patrick S. Journal of the American Ceramic Society, Vol. 55, Issue 6 https://doi.org/10.1111/j.1151-2916.1972.tb11290.x	journal	June 1972
Subsolidus Phase Equilibria and Ordering in the System ZrO2-Y2O3 Pascual, Carmen; Duran, Pedro Journal of the American Ceramic Society, Vol. 66, Issue 1 https://doi.org/10.1111/j.1151-2916.1983.tb09961.x	journal	January 1983
Influence of Thermal Decomposition on the Mechanical Properties of Magnesia-Stabilized Cubic Zirconia Swain, Michael V.; Garvie, Ronald C.; Hannink, Richard H. J. Journal of the American Ceramic Society, Vol. 66, Issue 5 https://doi.org/10.1111/j.1151-2916.1983.tb10049.x	journal	May 1983
Size driven thermodynamic crossovers in phase stability in zirconia and hafnia Sharma, Geetu; Ushakov, Sergey V.; Navrotsky, Alexandra Journal of the American Ceramic Society, Vol. 101, Issue 1 https://doi.org/10.1111/jace.15200	journal	September 2017
Indirect band gap in α‐ZrO 2 Kwok, Chee‐Kin; Aita, Carolyn Rubin Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 8, Issue 4 https://doi.org/10.1116/1.576548	journal	July 1990
Exploiting magnetic properties of Fe doping in zirconia: From first-principles simulations to the experimental growth and characterization of thin films Sangalli, Davide; Cianci, Elena; Lamperti, Alessio The European Physical Journal B, Vol. 86, Issue 5 https://doi.org/10.1140/epjb/e2013-30669-3	journal	May 2013

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