The immense potential of colossal permittivity (CP) materials for use in modern microelectronics as well as for high-energy-density storage applications has propelled much recent research and development. Despite the discovery of several new classes of CP materials, the development of such materials with the required high performance is still a highly challenging task. Here, we propose a new electron-pinned, defect-dipole route to ideal CP behaviour, where hopping electrons are localized by designated lattice defect states to generate giant defect-dipoles and result in high-performance CP materials. We present a concrete example, (Nb+In) co-doped TiO2 rutile, that exhibits a largely temperature- and frequency-independent colossal permittivity (> 104) as well as a low dielectric loss (mostly < 0.05) over a very broad temperature range from 80 to 450 K. A systematic defect analysis coupled with density functional theory modelling suggests that ‘triangular’ In23+VO••Ti3+ and ‘diamond’ shaped Nb25+Ti3+ATi (A = Ti3+/In3+/Ti4+) defect complexes are strongly correlated, giving rise to large defect-dipole clusters containing highly localized electrons that are together responsible for the excellent CP properties observed in co-doped TiO2. This combined experimental and theoretical work opens up a promising feasible route to the systematic development of new high-performance CP materials via defect engineering.
This is a preview of subscription content, access via your institution
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Homes, C. C., Vogt, T., Shapiro, S. M., Wakimoto, S. & Ramirez, A. P. Optical response of high-dielectric-constant perovskite-related oxide. Science 293, 673–676 (2001).
Krohns, S. et al. The route to resource-efficient novel materials. Nature Mater. 10, 899–901 (2011).
Ikeda, N. et al. Ferroelectricity from iron valence ordering in the charge-frustrated system LuFe2O4 . Nature 436, 1136–1138 (2005).
Shu-Nan, M. & Maki, M. Dielectric anisotropy in the charge-density-wave state of K0.3MoO3 . J. Phys. Soc. Jpn 80, 084706 (2011).
Hess, H. F., Deconde, K., Rosenbaum, T. F. & Thomas, G. A. Giant dielectric constants at the approach to the insulator-metal transition. Phys. Rev. B 25, 5578–5580 (1982).
Wang, C. C. & Zhang, L. W. Surface-layer effect in CaCu3Ti4O12 . Appl. Phys. Lett. 88, 042906 (2006).
Subramanian, M. A., Li, D., Duan, N., Reisner, B. A. & Sleight, A. W. High dielectric constant in ACu3Ti4O12 and ACu3Ti3FeO12 phases. J. Solid State Chem. 151, 323–325 (2000).
Wu, J. B., Nan, C. W., Lin, Y. H. & Deng, Y. Giant dielectric permittivity observed in Li and Ti doped NiO. Phys. Rev. Lett. 89, 217601 (2002).
Krohns, S. et al. Colossal dielectric constant up to gigahertz at room temperature. Appl. Phys. Lett. 94, 122903 (2009).
Lunkenheimer, P. et al. Origin of apparent colossal dielectric constants. Phys. Rev. B 66, 052105 (2002).
Sarkar, S., Jana, P. K. & Chaudhuri, B. K. Colossal internal barrier layer capacitance effect in polycrystalline copper (II) oxide. Appl. Phys. Lett. 92, 022905 (2008).
Lunkenheimer, P. et al. Colossal dielectric constants in transition-metal oxides. Eur. Phys. J. 180, 61–89 (2010).
Buscaglia, M. T. et al. High dielectric constant and frozen macroscopic polarization in dense nanocrystalline BaTiO3 ceramics. Phys. Rev. B 73, 064114 (2006).
Ramirez, A. P. et al. Giant dielectric constant response in a copper-titanate. Solid State Commun. 115, 217–220 (2000).
Li, M., Feteira, A., Sinclair, D. C. & West, A. R. Influence of Mn doping on the semiconducting properties of CaCu3Ti4O12 ceramics. Appl. Phys. Lett. 88, 232903 (2006).
Liu, Y., Withers, R. L. & Wei, X. Y. Structurally frustrated relaxor ferroelectric behavior in CaCu3Ti4O12 . Phys. Rev. B 72, 134104 (2005).
Zhu, Y. et al. Nanoscale disorder in CaCu3Ti4O12: A new route to the enhanced dielectric response. Phys. Rev. Lett. 99, 037602 (2007).
Zhang, L. & Tang, Z. J. Polaron relaxation and variable-range-hopping conductivity in the giant-dielectric-constant material CaCu3Ti4O12 . Phys. Rev. B 70, 174306 (2004).
Krohns, S., Lunkenheimer, P., Ebbinghaus, S. G. & Loidl, A. Colossal dielectric constants in single-crystalline and ceramic CaCu3Ti4O12 investigated by broadband dielectric spectroscopy. J. Appl. Phys. 103, 084107 (2008).
Guillemet-Fritsch, S. et al. Colossal permittivity in ultrafine grain size BaTiO3−x and Ba0.95La0.05TiO3−x materials. Adv. Mater. 20, 551–555 (2008).
Jonscher, A. K. The universal dielectric response. Nature 267, 673–679 (1977).
Whangbo, M. H. & Subramanian, M. A. Structural model of planar defects in CaCu3Ti4O12 exhibiting a giant dielectric constant. Chem. Mater. 18, 3257–3260 (2006).
Wuttig, M. et al. The role of vacancies and local distortions in the design of new phase-change materials. Nature Mater. 6, 122–128 (2007).
Balke, N. et al. Enhanced electric conductivity at ferroelectric vortex cores in BiFeO3 . Nature Phys. 8, 81–88 (2012).
Zheng, J. C. et al. Nanoscale disorder and local electronic properties of CaCu3Ti4O12: An integrated study of electron, neutron, and X-ray diffraction, X-ray absorption fine structure, and first-principles calculations. Phys. Rev. B 81, 144203 (2010).
Morgan, B. J. & Watson, G. W. A density functional theory plus U study of oxygen vacancy formation at the (110), (100), (101), and (001) surfaces of rutile TiO2 . J. Phys. Chem. C 113, 7322–7328 (2009).
Parker, R. A. Static dielectric constant of rutile (TiO2), 1.6–1060 K. Phys. Rev. 124, 1719–1722 (1961).
Jonscher, A. K. Universal Relaxation Law (Chelsea Dielectrics, 1996).
Morris, D. et al. Photoemission and STM study of the electronic structure of Nb-doped TiO2 . Phys. Rev. B 61, 13445–13457 (2000).
Li, G. S., Boerio-Goates, J., Woodfield, B. F. & Li, L. P. Evidence of linear lattice expansion and covalency enhancement in rutile TiO2 nanocrystals. Appl. Phys. Lett. 85, 2059–2061 (2004).
Ramos-Moore, E., Ferrari, P., Diaz-Droguett, D. E., Lederman, D. & Evans, J. T. Raman and X-ray photoelectron spectroscopy study of ferroelectric switching in Pb(Nb,Zr,Ti)O3 thin films. J. Appl. Phys. 111, 014108 (2012).
Valigi, M. et al. A structural, thermogravimetric, magnetic, electron spin resonance, and optical reflectance study of the NbOx–TiO2 system. J. Solid State Chem. 77, 255–263 (1988).
Khomenko, V. M., Langer, K., Rager, H. & Fett, A. Electronic absorption by Ti3+ ions and electron delocalization in synthetic blue rutile. Phys. Chem. Miner. 25, 338–346 (1998).
Deford, J. W. & Johnson, O. W. Electron transport properties in rutile from 6 to 40 K. J. Appl. Phys. 54, 889–897 (1983).
Janotti, A., Franchini, C., Varley, J. B., Kresse, G. & Van de Walle, C. G. Dual behavior of excess electrons in rutile TiO2 . Phys. Status Solidi Rapid Res. Lett. 7, 199–203 (2013).
Yu, J. D. et al. Giant dielectric constant of hexagonal BaTiO3 crystal grown by containerless processing. Chem. Mater. 16, 3973–3975 (2004).
Kimura, T., Sekio, Y., Nakamura, H., Siegrist, T. & Ramirez, A. P. Cupric oxide as an induced-multiferroic with high- TC . Nature Mater. 7, 291–294 (2008).
Sheng, Z., Nakamura, M., Kagawa, F., Kawasaki, M. & Tokura, Y. Dynamics of multiple phases in a colossal-magnetoresistive manganite as revealed by dielectric spectroscopy. Nature Commun. 3, 944 (2012).
Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Perdew, J. P. et al. Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B 46, 6671–6687 (1992).
Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study. Phys. Rev. B 57, 1505–1509 (1998).
Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).
Glassford, K. M. & Chelikowsky, J. R. Structural and electronic properties of titanium dioxide. Phys. Rev. B 46, 1284–1298 (1992).
W.H., Y.L., R.L.W., A.S. and J.W.L. acknowledge the supports of the Australian Research Council (ARC) in the form of Discovery and Linkage Projects, and of the Australian National University Connect Ventures in the form of Discovery Translation Fund. Y.L. and T.J.F. also appreciate support from the ARC Future Fellowships program. The DFT calculations performed in this work were undertaken using the NCI National Facility in Canberra, Australia, which is supported by the Australian Commonwealth Government. The authors acknowledge AMMRF facilities.
The authors declare no competing financial interests.
About this article
Cite this article
Hu, W., Liu, Y., Withers, R. et al. Electron-pinned defect-dipoles for high-performance colossal permittivity materials. Nature Mater 12, 821–826 (2013). https://doi.org/10.1038/nmat3691
This article is cited by
Microwave-assisted molybdenum-nickel alloy for efficient water electrolysis under large current density through spillover and Fe doping
Nano Research (2022)
Thickness-dependent structural, optical and dielectric properties of pulsed laser deposited Nb-doped SrTiO3 thin films
Journal of Materials Science: Materials in Electronics (2022)
Journal of Materials Science: Materials in Electronics (2022)
Bulletin of Materials Science (2022)
Journal of the Korean Physical Society (2022)