Symposium Organizers
Kirk H. Bevan, McGill University
Sohrab Ismail-Beigi, Yale University
T. Zac Ward, Oak Ridge National Laboratory
Zhenyu Zhang, University of Science and Technology of China
Symposium Support
MDC Vacuum Products, LLC
NBM Design Inc.
Princeton Scientific Corp.
PVD Products
Quantum Design, Inc.
STAIB Instruments
SURFACE Systems amp; Technologies GmbH amp; Co. KG
P2: Strongly Correlated Thin Films II
Session Chairs
Monday PM, December 02, 2013
Hynes, Level 2, Room 201
2:30 AM - P2.01
Coherent X-Ray Scattering from Striped Serpentine Nanodomains in a Ferroelectric/Dielectric Superlattice
Qingteng Zhang 1 Pice Chen 1 Zhonghou Cai 2 Ross Harder 2 Sara Callori 3 Matthew Dawber 3 Paul Evans 1
1University of Wisconsin-Madison Madison USA2Argonne National Laboratory Argonne USA3Stony Brook University Stony Brook USA
Show AbstractFerroelectric thin films form striped polarization nanodomains in order to minimize the electrostatic energy. The boundaries of between domains have unique properties such as electromechanical clamping and electrical conductance and can also have crystallographic structures that are distinct from bulk materials. Experimental studies of the configuration and structure of the nanodomains of ultra-thin ferroelectric films in applied electric fields are challenging because the fabrication of top electrodes can destroy the domain pattern and the thinness of the ferroelectric layers leads to large leakage currents. Ferroelectric/dielectric superlattices, however, form nanodomains similar to ultra-thin ferroelectric films because the neighboring ferroelectric layers are weakly coupled due to the electrical isolation of the dielectric layers. The study of ferroelectric nanodomains in ferroelectric/dielectric superlattices, especially their spatial configuration and switching dynamics, provides insight into the structure and dynamics of a more general class of striped domains.
We have studied nanodomain structures in a PbTiO3/SrTiO3 superlattice using synchrotron coherent x-ray diffraction. The degree of transverse coherence of the x-ray probe is increased by illuminating the focusing optics through a narrow slit with a width matching the coherence length of the x-rays. The superlattice nanodomains produce speckle diffraction patterns which contain depend in detail on the arrangement and structure of the nanodomains. We have observed speckle scattering patterns using x-ray beams prepared with focusing optics based on Kirkpatrick-Baez mirrors and Fresnel zone plate. When the numerical aperture of the focusing optics is small, the spatial profile of the speckles is determined by the illumination function at far-field limit. However, when the numerical aperture is large, the spatial profile of the speckles is determined by the interference of the illumination functions and the angular width can be an order of magnitude smaller than the convergent angle of the focusing optics. The speckle visibility decreases with the increase of slit width and count time in both cases. The degree of correlation between speckle patterns decreases over time due to the drift of the experimental setup. A spatial map of the correlation coefficient indicates that there is no spatial correlation of the in-plane nanodomains, which agrees with the approximation of the coherence length calculated from the envelope of the speckle pattern.
2:45 AM - P2.02
Local Control of Magnetic Anisotropy in Permalloy Thin Films Coupled to Ferroelectric Domains of BaTiO3 Single Crystals
Sean Wu Fackler 1 Tieren Gao 1 Sang-Wook Cheong 2 Ichiro Takeuchi 1
1University of Maryland College Park USA2Rutgers, the State University of New Jersey Piscataway USA
Show AbstractWe are investigating the coupling between ferroelectric domains of BaTiO3 (BTO) single crystals and magnetic domains in permalloy (Py) thin films deposited on top of them. We reproducibly fabricate dense magnetic stripes near the transcritical state by controlling sputtering deposition parameters. The films display partial out-of-plane anisotropy which is clearly visible as dense stripe domains in magnetic force microscopy. The stripe domains are used as an indicator to investigate the local coupling behavior between Py thin films and BTO crystals. Piezoresponse force microscopy of the crystals shows clear presence and spatial modulation of a-c domains in BTO. When the Py/BTO crystals are annealed above the Curie temperature of BTO (130#9675;C) and cooled down, stripe domains in Py develop local anisotropy modulation consistent with distribution of a-c domains. In particular, there is a clear and abrupt change in deduced in-plane magnetic anisotropy in Py at the a-c domain boundary of BTO. Magnetic stripe period also changes at the a-c domain boundary which is accounted for by magnetoelastic energy. The detailed coupling behavior achieved under different conditions is described by micromagnetic models.
3:00 AM - *P2.03
Design of a Polar Metal with Highly Anisotropic Thermoelectric Properties
James Rondinelli 1
1Drexel University Philadelphia USA
Show AbstractThe metallic features in materials, which provide low-resistance channels for electrical conduction, lead to effective screening of local electric dipole moments. Itinerant electrons disfavor both their formation and cooperative ordering. Consequently, most metals with a finite density of states and partial band occupation exhibit centric (inversion symmetric) crystal structures. Despite this contraindication, noncentrosymmetric metals (NCSM) lacking inversion were proposed more than fifty years ago, with some examples discovered serendipitously later. Here we describe a design framework to alleviate the property disparities and accelerate NCSM discovery: The primary ingredient relies on the removal of inversion symmetry through displacements of atoms whose electronic degrees of freedom are decoupled from the states at the Fermi level. Density functional theory calculations validate our crystal-chemistry strategy, and predict a polar perovskite ruthenate to be metallic and robust to spin-orbit interactions. Motivated by recent suggestions that degenerately doped ferroelectrics exhibit advantageous thermoelectric responses, we show that the thermopower in this polar metal exhibits large anisotropy for particular doping regimes along the polar axis. Although the high-density of states is unfavorable for a high power factor, our results indicate highly functional NCSM could be tailored for targeted thermoelectric applications.
This work was performed in collaboration with Dr. Danilo Puggioni and sponsored by the U.S. Army Research Office under grant no. W911NF-12-1-0133.
3:30 AM - P2.04
Fast, Low Temperature Topotactic Valence State Reversal in Strontium Cobaltites
Hyoung Jeen Jeen 1 Woo Seok Choi 1 John W. Freeland 2 Dongwon Shin 1 Jun Hee Lee 3 Valentino R. Cooper 1 Michael D. Biegalski 4 Sung Seok A. Seo 5 Hiromichi Ohta 6 Matthew F. Chisholm 1 Karin M. Rabe 7 Ho Nyung Lee 1
1Oak Ridge National Laboratory Oak Ridge USA2Argonne National Laboratory Argonne USA3Princeton University Princeton USA4Oak Ridge National Laboratory Oak Ridge USA5University of Kentucky Lexington USA6Hokkaido University Sapporo Japan7Rutgers University Piscataway USA
Show AbstractFast, reversible redox reactions in solids at low temperatures without thermomechanical degradation are a promising strategy for the enhancement of the overall performance and lifetime of many energy and environmental technologies, including solid oxide fuel cells, batteries and catalytic converters. Despite many efforts to search for new materials and routes to overcome the technical challenges, the robust nature of the cation&’s oxidation state and the high thermodynamic barrier have hindered the realization of fast catalytic reactions and bulk diffusion at low temperatures. Here, we report a low-temperature topotactic phase transition in SrCoOx grown directly by pulsed laser epitaxy as one of two distinct crystalline phases, either the perovskite SrCoO3-δ or the brownmillerite SrCoO2.5. Based on real-time temperature dependent characterizations with x-ray diffraction and optical spectroscopy, we found that the two topotactic phases can be reversibly switched at a remarkably reduced temperature (200~300 oC) in a considerably short time (< 1 min) without destroying the parent framework. This phase reversal accompanies distinct electronic (metal vs. insulator) and magnetic (ferromagnetic and antiferromagnetic) transitions. Therefore, our results on low temperature topotactic valence state reversal provide valuable insight not only in understanding the structure-physical property relationship in multivalent oxides, but also for identifying new opportunities for technological applications, such as low temperature catalysts.
The work was supported by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division.
3:45 AM - P2.05
Crystallographic Orientation and Strain Dependence of Oxygen Vacancy Order and Electronic Transport at Cobaltite Interfaces
Shameek Bose 1 Manish Sharma 1 Maria A. Torija 1 Jaume Gazquez 2 3 Maria Varela 2 3 Valeria Lauter 4 Haile Ambaye 4 Richard J. Goyette 4 Michael R. Fitzsimmons 5 Josh Schmitt 1 Chris Leighton 1
1University of Minnesota Minneapolis USA2Oak Ridge National Laboratory Oak Ridge USA3Universidad Complutense de Madrid Madrid Spain4Oak Ridge National Laboratory Oak Ridge USA5Los Alamos National Laboratory Los Alamos USA
Show AbstractThin films and heterostructures of the perovskite cobaltites are of great interest, not only from the point of view of fundamental physics and materials science, but also for technological applications such as solid oxide fuel cells, gas membranes and multiferroics. Their properties are, however, severely deteriorated from the bulk, being dominated by the presence of interfacial “dead layers”. Working with the prototypical SrTiO3(001)/La1-xSrxCoO3 (LSCO) system, we recently discovered that this degradation in the magnetic and electronic transport at the interface is caused by nanoscopic magneto-electronic phase separation. This was shown to occur primarily due to accumulation of oxygen vacancies near the interface, driven by the fascinating interplay between the strain state and oxygen vacancy ordering [1, 2]. In the present work we show how this understanding allows for engineering of the interfacial magnetic and electronic transport properties via manipulation of this oxygen vacancy superstructure [3, 4]. Using reciprocal space mapping, we demonstrate the ability to control, via the vacancy ordering, the critical strain relaxation thickness by changing the sign of the strain (from tensile on SrTiO3 to compressive on LaAlO3) and crystallographic orientation ((001) vs. (110)). Furthermore, SQUID magnetometry, polarized neutron reflectometry (PNR) and magneto-transport confirm the concomitant mitigation of the interfacial degradation for LSCO films grown on LaAlO3(001) and SrTiO3(110), as compared to films grown on SrTiO3 (001). Finally, we provide cross sectional electron energy loss spectroscopy (EELS) data showing the preservation of both oxygen and hole carrier concentration at the LaAlO3(001)/LSCO and SrTiO3(110)/LSCO interfaces, strikingly different to the severely depleted SrTiO3(001)/LSCO interface Our work thus opens up a new route to tailor interfacial electronic transport and magnetic properties, thereby engineering complex oxide device performance.
Work supported by NSF and DOE (neutron scattering). Research at ORNL supported by U.S. DOE-BES, MS&E Division, at UCM by ERC Starting Investigator Award.
[1] Torija et al., Adv. Mater. 23, 2711 (2011)
[2] Gazquez et al., Nano Lett. 11, 973 (2011)
[3] Gazquez, Bose et al., APL Materials 1, 012105 (2013)
[4] Bose et al. (in preparation)
4:30 AM - P2.06
Engineering Nonlinear I-V Characteristics in Phase Separated Manganite Thin Films
Vijay Raj Singh 1 2 Anil Kumar Rajapitamahuni 1 2 Xia Hong 1 2
1University of Nebraska-Lincoln Lincoln USA2University of Nebraska-Lincoln Lincoln USA
Show AbstractWe have investigated the I-V characteristics of 5-10 nm La_0.7Ca_0.3MnO_3 (LCMO) and La_0.5Sr_0.5MnO_3 (LSMO) thin films grown epitaxial on (001) SrTiO_3 (STO), (001) LaAlO_3 (LAO) and (110) NdGaO_3 substrates via off-axis radio frequency magnetron sputtering. These films show high crystallinity and have RMS roughness of 2-3 Å. The LSMO films with thickness above 6 nm show metal-insulator transitions (MIT) at ~275K and exhibit linear I-V characteristics in the whole temperature range investigated (10 K to 350 K). As the film thickness approaches the electrically dead layer thickness, LSMO becomes totally insulating and exhibits a strong nonlinear behavior in I-V. In the LCMO films, we observe a strong correlation between the I-V characteristics and the MIT. Linear I-V dependence has been observed in the paramagnetic insulating phase and nonlinear I-V starts to develop below the MIT transition temperature (~150 K). We discuss the origin of our observations within the phase separation model and explore how to engineer the I-V characteristics in manganite thin films via film thickness, substrate strain, and an electric field effect through a neighboring ferroelectric gate.
We acknowledge the support from NSF Grant CAREER No. DMR-1148783, the Center for NanoFerroic Devices (CNFD) and the Nanoelectronics Research Initiative (NRI).
4:45 AM - P2.07
Nano-Confinement Steep Metal-Insulator Transition Driven by Temperature and Magnetic Field in Extremely Small (La,Pr,Ca)MnO3 Epitaxial Nanowall Prepared by 3D Nano-Template PLD
Hidekazu Tanaka 1 Yasushi Fujiwara 1 Azusa N. Hattori 1 Kohei Fujiwara 1
1Osaka University Ibaraki Japan
Show AbstractStrongly correlated electron materials exhibit rich and unique properties including colossal magnetoresistance (CMR) in manganite system and so on. Since the discovery of the intrinsic inhomogenence, nanoscale electronic phase separation is thought to play an important role in correlated electronic materials, and the interplay between the nanoscale electric phases lead to exotic properties. In (La,Pr,Ca)MnO3 /(LPCMO), the coexistence and competition between nano ferromagnetic metal phase and nano charge ordering insulator phase result in CMR effect [1]. By spatially confining materials to length scales smaller than the electronic nano phases, a huge effect, i.e., a steep MR change would emerge. Thus. it is possible to artificially design their behavior and expected to create drastic changes in magnetic and electric properties by capturing a single nano phase into nanostructure. For this purpose, we have developed 3D nano-template PLD technique [2, 3] to construct extremely small metal oxide nanostructures, and succeed to form LPCMO nanowall wire structures with 50 nm width. The LPCMO nanowall wire exhibited nano-confinement metal-insulator transition properties driven by both temperature and magnetic field. The drastic resistivity change of a single domain corresponds to the first-order insulator-metal transition of a single domain. For example, this nanowall wire sample showed a digital resistance change at 80 K while a film sample displays the gradual resistance change. Above 80 K, in addition to the insulator feature (negative temperature coefficient of resistance) the discrete drops in resistivity were observed. Very steep magnetoresistance change was also observed on LPCMO nanowall wire sample while smooth MR change appeared on thin film sample. We will also report a quantitative correlation between nano-spatial size and nano-confinement MIT properties and discuss the revealed a single phase dynamics in correlated oxide nano-structures.
[1] M. Uehara et al., Nature 399, 560 (1999)
[2] Y. Fujiwara, A. N. Hattori, K. Fujiwara and H. Tanaka, Jpn. J. Appl. Phys. 52 (2013)015001
[3] T. Kushizaki, K. Fujiwara, A. N. Hattori, T. Kanki and H. Tanaka, Nanotechnology 23 (2012) 485308
5:00 AM - P2.08
Direct Quantification of Charge Transfer at Oxide Interfaces Using Atomic-Resolution Electron Energy Loss Spectroscopy
Julia Mundy 1 Yasuyuki Hikita 2 Takeaki Hidaka 3 Takeaki Yajima 2 Takuya Higuchi 3 Harold Hwang 2 David Muller 1 Lena Kourkoutis 1
1Cornell University Ithaca USA2Stanford University Palo Alto USA3The University of Tokyo Kashiwa Japan
Show AbstractElectronic changes at polar interfaces between transition metal oxides offer the tantalizing possibility to stabilize novel ground states yet can also cause unintended reconstructions in thin films poised for next-generation devices. The very nature of these interfacial reconstructions should be qualitatively different for metallic and insulating films as the electrostatic boundary conditions and compensation mechanisms are distinct. Interfacial electronic charge transfers to equilibrate chemical potentials and balance interface charges are expected in a metal, and for insulators there is the possibility for either sustained internal electric fields or an interface dipole to cancel an otherwise growing electrostatic potential - the so-called ‘polar catastrophe&’ Here, we probe the charge distribution for manganite-titanate interfaces traversing the metal-to-insulator transition.
Using scanning transmission electron microscopy (STEM) in combination with electron energy loss spectroscopy (EELS), we measure the elemental concentration and valence of the cations at a series of La1-xSrxMnO3/SrTiO3 interfaces. We directly quantify both the charge transfer, manifest as valence changes on the interfacial manganese sites, as well as extrinsic defects such as cation interdiffusion and vacancies. We find an intrinsic interfacial electronic reconstruction in the insulating films (x le; 0.2), where the total charge measured quantitatively agrees with that needed to cancel the polar catastrophe. Surprisingly the width of the charge transferred region remains constant for the insulating films, despite differences in cation interdiffusion. As the manganite becomes metallic with increased hole-doping, the total charge build-up and its spatial range drop substantially consistent with screening lengths in metallic La0.7Sr0.3MnO3. Direct quantification of the intrinsic charge transfer and spatial width should lay the framework for devices harnessing these unique electronic phases.
5:15 AM - P2.09
The Influence of Non-Collinear Spin Structures on Magnetotransport in LaNiO3/La0.7Sr0.3MnO3 Superlattices
Jason D Hoffman 1 Brian J Kirby 2 Anand Bhattacharya 1 3
1Argonne National Laboratory Argonne USA2National Institute of Standards and Technology Gaithersburg USA3Argonne National Laboratory Argonne USA
Show AbstractThe interlayer exchange coupling between magnetic layers separated by non-magnetic spacers can give rise to new spin structures that are distinct from the bulk constituents. In this work, we investigate the non-collinear spin structures that arise in superlattices containing paramagnetic LaNiO3 and ferromagnetic La0.7Sr0.3MnO3. Using ozone-assisted molecular beam epitaxy, we have fabricated a series of (LaNiO3)n/(La0.7Sr0.3MnO3)9 superlattices where n is varied from 1 to 9 unit cells on (001) SrTiO3 and LSAT substrates. The total superlattice thickness is maintained at 60 nm by varying the number of superlattice repetitions. The magnetic structure of several superlattices was measured using polarized neutron reflectometry as a function of temperature and applied magnetic field. For low fields, we find the magnetization of neighboring La0.7Sr0.3MnO3 layers to be non-collinear due to an antiferromagnetic interlayer exchange coupling, which persists to temperatures above 250 K. In the low-field regime we observe positive magnetoresistance using in-plane transport, which competes with the negative magnetoresistance of La0.7Sr0.3MnO3 at high fields. We discuss underlying mechanisms for the observed effects and possible applications to oxide-based magnetoresistive devices.
5:30 AM - P2.10
Modulating Electronic Transport in the Rare-Earth Nickelates Using a Ferroelectric
Matthew Marshall 1 Andrei Malashevich 1 Ankit Disa 1 Hanghui Chen 1 2 Sohrab Ismail-Beigi 1 Fred Walker 1 Charles Ahn 1
1Yale University New Haven USA2Columbia University New York City USA
Show AbstractThe rare-earth perovskite nickelates (RNiO3) have a strong coupling between structure and electronic transport. The nickelates accommodate changes in the unit cell volume by elongating and shortening the in-plane Ni-O bond lengths and bending or flattening the in-plane Ni-O-Ni bond angles. Because transport in RNiO3 depends on these structural parameters, tuning the structural parameters affects electronic transport. The unit cell volume can be changed by applying pressure or by varying the radius of the rare earth ion. For instance, LaNiO3 is a paramagnetic metal in the bulk, while the other rare earth nickelates undergo a metal-insulator transition as the radius of the rare earth ion is changed. Structural parameters in the nickelates have been successfully tuned by layering in superlattices and with epitaxial strain. These are static effects; in order to dynamically tune electronic transport in RNiO3, we use the ferroelectric PbZr0.2TiO3 (PZT) to couple the polarization of the PZT to the electronic transport of RNiO3 films. Switching the polarization of the ferroelectric from up to down has a dramatic effect on electronic transport in the RNiO3, and can be understood within the context of charge and structure.
5:45 AM - P2.11
The Effect of Biaxial Strain on Octahedral Rotation in Rare-Earth Nickelate Superlattices
Patrick M. McBride 1 Cyrus E. Dreyer 1 Anderson Janotti 1 Chris G. Van de Walle 1
1University of California, Santa Barbara Santa Barbara USA
Show AbstractHeterostructures of complex oxides have attracted great attention for the interplay between structure, electronic, and magnetic properties, offering unique opportunities in device applications. Here we investigate the effects of epitaxial strain on the structural properties of LaNiO3. We perform first-principles calculations based on density functional theory to investigate the NiO6 octahedral tilts of strained LaNiO3 layers in LaNiO3/SrTiO3 superlattices. Recent experimental results suggest that octahedral connectivity at LaNiO3/SrTiO3 interfaces determines the local structure, but the effect of epitaxial strain on the LaNiO3 layers has remained unclear. We present quantitative results for the octahedral tilt angles as a function of both biaxial strain and distance from the substrate for LaNiO3 grown on SrTiO3 (001). Our results indicate that LaNiO3 exhibits vanishing octahedral tilt angles under certain strain conditions, a finding that holds important consequences for its electronic properties.
P1: Strongly Correlated Thin Films I
Session Chairs
Kirk H. Bevan
T. Zac Ward
Monday AM, December 02, 2013
Hynes, Level 2, Room 201
9:30 AM - P1.01
Creating Room Temperature Multifunctionality through BiFeO3/Manganite Perovskite Superlattices
Judith L. MacManus-Driscoll 1 Eun-Mi Choi 1 T. Fix 1 S. Singh 2 J. Xiong 2 J. X. Zhu 2 Z. Bi 2 M. Fitzsimmons 2 H. Wang 3 Quanxi Jia 2
1University of Cambridge Cambridge United Kingdom2LANL Los Alamos USA3Texas Aamp;M University College Station USA
Show AbstractUnderstanding interface in complex oxide heterostructure is scientifically and technologically important since interfaces and surfaces determine the physical properties through coupled competing order parameters (magnetic, charge, orbital, etc.). In this talk, we present two types of BiFeO3 related superlattice (SL) systems, BiFeO3/BiMnO3 (BFO/BMO) and La0.7Sr0.3MnO3/BiFeO3 (LSMO/BFO). The structure of SL-BFO/BMO films is equivalent to 90° rotated nanoscale checkerboard (NCB) BFO/BMO. The film properties are in remarkable agreement with the theoretical predictions of a TC = ~ 407 K for NCB-BFO/BMO. Our experimental results provide an explanation of the emergence of magnetism in complex oxide heterostructures and show how to create a room temperature multiferroic. In SL-LSMO/BFO, the BFO layer showed the magnetization of ~ 75 ± 25 kA/m at 10 K. By ab initio calculation based on the density functional theory, SL-LSMO/BFO has much larger interfacial ferromagnetism of > ~ 0.3 mu;B/Fe than the canted moment 0.03 mu;B/Fe in the bulk BiFeO3. SL-BFO/BMO showed a high magnetic transition temperature (TC ~ 400 K).
9:45 AM - P1.02
Probing Strain Modulated Electronic Structure in Mixed Phase Bismuth Ferrite
Jeffery Aguiar 1 Sundaram Sankar Krishnan 2 Quentin Ramasse 3 Dmitry Kepaptsoglou 2 Wen-I Liang 4 Nigel Browning 5 Ying-Hao Chu 4 Paul Munroe 2 Nagarajan Valanoor 2
1Los Alamos National Laboratory Los Alamos USA2University of New South Wales Syndey Australia3SuperSTEM Laboratory Daresbury United Kingdom4National Chiao Tung University Taiwan Taiwan5Pacific Northwest National Laboratory Richland USA
Show AbstractOxide heterostructures play an important role in the design of next generation functional information storage and electronic devices. Given the complexities of these oxide heterointerfaces, studying their structure and chemistry at the atomic scale and providing vital information relating to their valence and electronic structure is pivotal to explain the observed properties, such as their electromechanical behavior and related magnetic ordering. A combination of scanning transmission electron microscopy and density functional theory is used to probe mixed phase bismuth ferrite and reveals systematic changes in electronic structure across a phase boundary in the film.
Techniques such as X-ray absorption spectroscopy (XAS) and near-edge X-ray fine absorption spectra (NEXAFS) typically detect minute spectral changes, but not well suited to investigate atomic scale interfacial phenomena. Conversely, scanning transmission electron microscopy (STEM) and STEM-based electron energy loss spectroscopy (EELS) is one method that is able to provide the spatial distribution of electronic phenomena at nanostructured oxide interfaces with single atom and vacancy sensitivity. The unique combination of STEM and density functional theory (DFT) computations further provides valuable insight into the electronic structure controlling functional responses of oxide heterostructures. In order to address the effect of strain-induced configurations at the interface and beyond, however, a progressive study traversing the boundary layer is still lacking and must be conducted.
Here we combine aberration-corrected STEM with sub-Ångstrom resolution EELS and DFT methods to reveal strain modulated electronic structure and bonding perturbations in mixed phase bismuth ferrite thin films. In contrast to previous works, we focus on the incremental spectral transitions in the electronic signatures across the boundary layer to explain the interfacial electronic structure and the concomitant role of strain induced structure on the observed properties. High angle annular dark field (HAADF) and EELS chemical mapping is utilized to observe the atomic structure. Non-linear least squares (NLSS) spectral peak fitting and DFT further confirm these observed changes are attributed to changes in bonding environment surrounding the central iron cation and result in a change in electronic structure. Furthermore, DFT analyses suggest the same changes are attributed to a breakage in the structural symmetry across the boundary due to the simultaneous presence of increasing epitaxial strain and off axial symmetry in the T phase within the square-pyramidal oxygen cages. We expect the results presented to have a significant impact on the fundamental approach to and understanding of the effect of epitaxial strain on the resultant ferroelectric, piezoelectric coefficients, and complex phase equilibria in multiferroics.
10:00 AM - *P1.03
Coupling Magnetism to Electricity in Multiferroic Heterostructures
Ramamoorthy Ramesh 1 John T. Heron 2
1University of California, Berkeley Berkeley USA2Cornell University Ithaca USA
Show AbstractComplex perovskite oxides exhibit a rich spectrum of functional responses, including magnetism, ferroelectricity, highly correlated electron behavior, superconductivity, etc. The basic materials physics of such materials provide the ideal playground for interdisciplinary scientific exploration. Over the past decade we have been exploring the science of such materials (for example, colossal magnetoresistance, ferroelectricity, etc) in thin film form by creating epitaxial heterostructures and nanostructures. Among the large number of materials systems, there exists a small set of materials which exhibit multiple order parameters; these are known as multiferroics. Using our work in the field of ferroelectric(FE) and ferromagnetic oxides as the background, we are now exploring such materials, as epitaxial thin films as well as nanostructures. Specifically, we are studying the role of thin film growth, heteroepitaxy and processing on the basic properties as well as magnitude of the coupling between the order parameters. In our work we are exploring the switchability of the antiferromagnetic order using this coupling.
What is the importance of this work ? Antiferromagnets(AFM) are pervasive in the recording industry. They are used as exchange biasing layers in MTJ&’s etc. However, to date there has been no antiferomagnet that is electrically tunable. We believe that the multiferroic BiFeO3 is one compound where this can be observed at room temperature. The next step is to explore the coupling of a ferromagnet to this antiferromagnet through the exchange biasing concept. Ultimately, this will give us the opportunity to switch the magnetic state in a ferromagnet( and therefore the spin polarization direction) by simply applying an electric field to the underlying antiferromagnetic ferroelectric. In this talk, I will describe our progress to date on this exciting possibility.
10:30 AM - P1.04
Local Conductivity at Domain and Phase Boundaries in Supertetragonal BiFeO3 Thin Films
Saeedeh Farokhipoor 1 Christianne Beekman 2 Wolter Simons 2 Beatriz Noheda 1 Hans M. Christen 2
1Zernike Institute for Advance Materials, University of Groningen Groningen Netherlands2Materials Science and Technology Division, Oak Ridge National Laboratory Oak Ridge USA
Show AbstractIn recent years, engineering and characterization of domain walls has developed with a view to future nanoscale device applications. One of the pivotal physical properties of domain walls is enhanced conduction, which has been extensively studied in different types of oxides in the last few years. In ferroelastic materials the domain walls are known to attract oxygen vacancies [E.K.H Salje et al., ChemPhysChem. (2010)]. It has been pointed out [S. Farokhipoor & B. Noheda PRL (2011)] that in BiFeO3 the migration of oxygen vacancies to the walls can lower the electronic injection barrier at the interface with the metal and locally enhance conduction. Here we have investigated highly strained BiFeO3 thin films grown on LaAlO3 substrates [C. Beekman et al., Adv. Mater (2013)]. These films consist of a stripe-like coexistence of two polymorphs that are each different from BiFeO3&’s bulk phase, leading to an interesting strain landscape across the film. By investigating the local conduction at different types of domain walls and phase boundaries by means of scanning probe techniques, we find a clear correlation between the strain state, the oxygen vacancy concentration and the local conductivity.
10:45 AM - P1.05
Coupling between Electron Transport and Ferroelectric Polarization in Domain Engineered BiFeO3 Epitaxial Films
Linghan Ye 1 Alexandra Merkouriou 1 Jon Ihlefeld 2 Carolina Adamo 3 Darrell Schlom 3 Ramamoorthy Ramesh 4 Bryan D. Huey 1
1Institute of Material Sciences Storrs USA2Sandia National Laboratories Albuquerque USA3Cornell University Ithaca USA4University of California, Berkeley Berkeley USA
Show AbstractThe domain structure of ferroelectric and multiferroic materials can have a significant effect on electron transport properties. Piezo Force Microscopy allows unique investigations of such nanoscale effects, and can further be implemented to monitor domain switching dynamics. BiFeO3 thin films engineered with distinct strains and interfacial configurations are thereby shown to influence the ferroelectric domain distributions, with up to 50 mu;m of domain boundary per mu;m2. Coupling these results with conductive AFM, correlations between such domain configurations and through-film electron transport are comprehensively studied, identifying conditions for enhancing devices coupling ferroelectric polarization and conductivity. Characteristic switching processes are demonstrated for distinct specimen conditions as well, including nucleation times and growth velocities, domain wall densities at discrete steps during the switching process, and the distribution of 71°, 109°, and 180° initial and ultimate polarization reorientations. These results provide unique insight into the behavior of ferroelectric domains at the nanoscale for interfacial engineering of optimally performing electron transport devices.
11:30 AM - P1.06
Thickness-Dependent Paraelectric-Ferroelectric Phase Transition in La-Doped BiFeO3 Films on Si Substrates
Deyang Chen 1 2 Xiaohong Zhu 1 3 Christopher Tobias Nelson 1 4 Ya Gao 1 5 Claudy Rayan Serrao 1 Di Yi 1 James David Clarkson 1 Jian Liu 1 Ramamoorthy Ramesh 1 4
1University of Carlifornia, Berkeley Berkeley USA2South China University of Technology Guangzhou China3Sichuan University Chengdu China4Lawrence Berkeley National Laboratory Berkeley USA5Tinghua University Beijing China
Show AbstractChemical substitution is widely used to induce phase transition in BiFeO3 films. Our previous research discovered the phase transition from rhombohedral phase to orthorhombic phase through La doping in BiFeO3 films. Here we report a thickness-dependent paraelectric-ferroelectric phase transition in La-doped BiFeO3 films on Si substrates, opening up a new path to achieving phase transition. Epitaxial 20% La doping BiFeO3 films (LBFO20) with thickness of 10 to 100 nm were grown on (001) SrTiO3-buffered Si substrates with SRO as bottom electrodes (~20 nm) by pulsed laser deposition. X-ray Diffraction (XRD) results show the peak splitting in 60 and 100 nm LBFO20 films, but there are no peak splitting in 10 to 40 nm films, which demonstrates the paraelectric orthorhombic phase to ferroelectric rhombohedral phase transition. Piezoresponse force microscopy (PFM) and piezoelectric property measurement results are consistently with XRD data. Using PFM, we find that 100nm LBFO20 film cannot be switched with -15 V dc bias and 60nm film can be switched slightly, whereas LBFO20 films with thickness from 10 to 40 nm can be switched completely with -8 v dc bias, which further reveals the paraelectric-ferroelectric phase transition with decreasing thickness of films. Transmission electron microscopy (TEM) shows that lots of orthorhombic phase exists in 100 nm LBFO20 film, however, in 20 nm film, there is almost entirely made up of ferroelectric rhombohedral phase. Orthorhombic and rhombohedral phase boundary is also discovered in the films. In summary, our finding provides a new path to drive the paraelectric-ferroelectric phase transition and also offers a possible route to study morphotropic phase boundary (MPB).
11:45 AM - P1.07
Flexoelectric Effect in the Reversal of Self-Polarization and Associated Changes in the Electronic Functional Properties of BiFeO3 Thin Films
Byung Chul Jeon 1 2 Daesu Lee 1 2 Sangdon Bu 4 Mayng Hwan Lee 3 Sang Mo Yang 1 2 Seung Chul Chae 1 2 Tae Kwon Song 3 Jin-Seok Chung 5 Jong-Gul Yoon 6 Tae Won Noh 1 2
1Center for Functional Interfaces of Correlated Electron Systems, Institute for Basic Science (IBS) Seoul Republic of Korea2Department of Physics and Astronomy, Seoul National University Seoul Republic of Korea3School of Nano and Advanced Materials Engineering, Changwon National University Changwon Republic of Korea4Department of Physics, Chonbuk National University Jeonju Republic of Korea5Department of Physics, Soongsil University Seoul Republic of Korea6Department of Physics, University of Suwon Hwaseong Republic of Korea
Show AbstractFlexoelectric effect is the generation of an electric field by a strain gradient via electro-mechanical coupling. This effect was predicted theoretically by Kogan in 1964 and experimentally observed by Bursian and Zaikovskii in 1968. The phenomenon was given the name ‘flexoelectricity&’ by Indenbom et al. in 1981. However, there have been few studies on flexoelectric effects in solids. For bulk solids, it was believed that flexoelectric effects should be minimal. However, it was recently shown that the strain gradient in nano-structured materials and/or epitaxial oxide thin films could be 6 or 7 orders of magnitude larger than the corresponding bulk values. After this realization, there has been increased interest in this phenomenon. These electromechanical coupling effects have provided answers to many physical phenomena that could not be explained before.
In this presentation, we will address that fully strained BiFeO3 films are self-poled, having a down ward polarization; this indicated that the interfacial effect is dominant. In contrast, the relaxed films have upward self-polarization, indicating that the flexoelectric effect is dominant. Moreover, quantification of the flexoelectric fields are estimated, indicating that the flexoelectric field in relaxed BFO is higher about one order of magnitude, compared with that of the uniaxially strained BFO film. Interestingly enough, the two kinds of films also exhibit different unidirectional current flows, referred to as the diode effect. By understanding the self-poling mechanisms in BiFeO3 films, such as ferroelectric hysteresis and electronic transport characteristics, the configuration of the as-grown films can be optimized to allow full utilization of the ferroelectric functional device.
12:00 PM - *P1.08
Benchmarking Spintronic Devices Based on Magnetoelectric Oxides
Dmitri E. Nikonov 1 Ian A. Young 1 Sasikanth Manipatruni 1
1Intel Corp. Hillsboro USA
Show AbstractAs CMOS transistors are scaled towards atomistic sizes, the research is underway to find beyond-CMOS logic devices which would complement CMOS in futures computational circuits. Majority of currently considered logic gates include spintronic devices, i.e. ones involving ferromagnets. With the currently available switching methods based on passing current through these devices - spin torque and spin Hall effects - these gates are expected to switch with longer time and larger energy than comparable electronic gates. Recently, switching of magnetization by application of voltage was demonstrated via magnetoelectric effects relying on interfaces of ferromagnets with oxides. We simulate a variety of spintronic gates switched with both spin torque and magnetoelectric effects. Various cases of switching are considered, values of magnetoelectric coefficients necessary for switching are determined. We show that only magnetoelectric switching results in time and energy comparable to those of CMOS devices.
12:30 PM - P1.09
Different Polarization Dependence of Transient Current in Polycrystalline and Epitaxial Thin Pb(Zr,Ti)O3 Films
Liubov Delimova 1 Ekaterina Gushchina 2 Valentin Yuferev 1 Igor Grekhov 1
1Ioffe Institute of the RAS St. Petersburg Russian Federation2Ioffe Institute of the RAS St. Petersburg Russian Federation
Show AbstractConduction mechanisms in thin ferroelectric Pb(Zr,Ti)O3(PZT) films are controlled to a great extent by the film/electrode interfaces. In polycrystalline PZT films with heterophase grain boundaries coalescence of grain polarization charge and semiconducting grain boundaries can trigger such transport effects as intergrain photovoltaic effect [1] and clockwise current hysteresis [2].
We use direct current-voltage measurements and Scanning Spreading Resistance Microscopy to study transport characteristics of thin PZT films depending on its polarization. In direct current-voltage measurements a bias voltage is applied to the structure as a sequence of steps of the same amplitude and duration. The voltage rise rate is changed within the range of 1-0.001 V/s by variation of the step amplitude and duration. The current measurements are done in preliminary poled films.
The both experimental techniques, we use to study the polycrystalline (111) textured 100-nm-thick PZT film deposited on PbTiO3/Ir/SiO2/Si substrate and epitaxial (001) oriented 210-nm-thick PZT film deposited on SrRuO3/SrTiO3 substrate, revealed the same results at micro and nanoscale ranges. A current response from PZT film to applied bias contains a long relaxation component, which is shown to depend on voltage rise rate and the polarization direction. However the current dependence on the polarization is found to be completely different for the polycrystalline and epitaxial films. The current of polycrystalline film is much larger when the bias is directed against the polarization, which can be associated with screening of polarization charge by traps charge on grain boundaries with bias variation [2]. While the current of epitaxial films is larger if the bias direction coincides with the polarization, which cannot be explained by ferroelectric switching. We consider the measured current of the epitaxial film as the transient current caused by hole&’s capture at or electron&’s emission from traps level. The electron&’s emission probability is controlled by the impurity potential, which becomes asymmetrical in the presence of spontaneous polarization: the probability of electron's emission in the polarization direction is larger than that against the polarization. Since the electron moves again the external bias, the more favorable condition for quick electron emission and the current relaxation takes place when the bias is directed against the polarization. Therefore, the larger current value measured when the bias and polarization directions are coincides reflects the slower emission of electron and slower current relaxation. The clockwise current hysteresis is observed at any preliminary polarization of the both polycrystalline and epitaxial films. The model, which allows us to estimate characteristics of the transient current, is proposed.
[1] IEEE-TUFFC 58, pp. 2252-2258 (2011).
[2] MRS Proc. 1292, mrsf10-1292-k03-31(2011).
12:45 PM - P1.10
Room Temperature Negative Capacitance in Ferroelectric-Dielectric Heterostructure
Weiwei Gao 1 Asif Khan 1 Jayakanth Ravichandran 2 Long You 1 Chun Wing Yeung 1 Chenming Hu 1 Ramamoorthy Ramesh 3 4 5 Sayeef Salahuddin 1
1University of California, Berkeley Berkeley USA2University of California, Berkeley Berkeley USA3University of California, Berkeley Berkeley USA4University of California, Berkeley Berkeley USA5Lawrence Berkeley National Laboratory Berkeley USA
Show AbstractAs a novel physical concept, Ferroelectric (FE) negative capacitance (NC) can be effectively utilized to reduce the sub-threshold swing (SS) of ultra-low power MOSFET applications below the fundamental physical limit of 60 mV/decade [1]. According to Salahuddin et al., the negative capacitance state of a ferroelectric capacitor is an unstable non-equilibrium state and can be effectively stabilized under static conditions if it is placed in series with dielectric capacitor. Recently, the experimental demonstrations of ferroelectric negative capacitance phenomenon have been reported by several research groups [2, 3]. However, the negative capacitance effect is only observed in a certain high temperature range, which closely depends on the Curie temperature of ferroelectric materials. In order to be compatible with MOSFET applications, it is necessary to look for proper ferroelectric materials, which can provide negative capacitance effect at the MOSFET operating temperature. In this talk, we will introduce the room temperature negative capacitance effect in LaAlO3/Ba0.8Sr0.2TiO3 (LAO/BSTO) superlattice heterostructure.
The artificial superlattices, [(LAO)m/(BSTO)n]11 (m=6, 12, and 18; n=18, 12, and 6) were grown on the SrRuO3-covered (001)-SrTiO3 (STO), (110)-GdScO3 (GSO) and (110)-DyScO3 (DSO) substrates by Laser-Molecular Beam Epitaxy technique. During the deposition, the substrate temperature was kept at 750 °C for the (LAO)m/(BSTO)n superlattice, 700 °C for the SrRuO3 and the oxygen pressure at 50 mTorr. The capacitance of superlattices were measured by 4194A Impedance/Gain-Phase Analyzer with frequency up to 1 MHz at room temperature. These superlattices show an enhanced capacitance compared to single dielectric LAO film of the same thickness equal to the total thickness in the superlattice. This means that the capacitance of the superlattice has gone up, rather than going down, even after adding additional layers to LAO and thereby increasing the total thickness of the overall capacitance. This is the first observation of room temperature negative capacitance effect in ferroelectric/dielectric heterostructures at room temperature. The effect of lattice strain, FE thickness etc. on the negative capacitance will be discussed in this talk.
Symposium Organizers
Kirk H. Bevan, McGill University
Sohrab Ismail-Beigi, Yale University
T. Zac Ward, Oak Ridge National Laboratory
Zhenyu Zhang, University of Science and Technology of China
Symposium Support
MDC Vacuum Products, LLC
NBM Design Inc.
Princeton Scientific Corp.
PVD Products
Quantum Design, Inc.
STAIB Instruments
SURFACE Systems amp; Technologies GmbH amp; Co. KG
P4: Emergent Oxide Interface Devices II
Session Chairs
Kirk H. Bevan
Joachim Maier
Tuesday PM, December 03, 2013
Hynes, Level 2, Room 201
2:30 AM - P4.01
Investigation of Halogen Ions on Tunnel Oxide for Improving Reliability of NAND Flash Memory
Jiyul Park 1 Dae-Hee Kim 1 Byungduck Jo 1 Daehwan Yun 1 Pyung Hwa Kim 1 Milim Park 1 Byoungjun Park 1 Myeongwon Lee 1 Yong Seok Suh 1 Seongjo Park 1 Myoungkwan Cho 1 Kunok Ahn 1 Jinwoong Kim 1
1SK Hynix Cheongju Republic of Korea
Show AbstractRecently, solid-state drives based on NAND flash memory have been a interest in replacement of hard-disk drives due to their high speed data transmission, low power, and high reliability. The reliability including endurance and retention characteristics of NAND flash memory cells is degraded as shrinking the gate pitch size of NAND flash memory cells. Sicne a few of trap sites located in tunnel oxide can affect to the reliability of NAND flash memory in the shrunk technology [1], it is a very critical challenge to improve the quality of tunnel oxide and its interface. Many studies have been reported, such as increasing the quality of tunnel oxide, inter-poly dielectric as well as inter-layer dielectrics [2,3]. Also, the effect of halogen ions on the tunnel oxide has been studied, which is ion implantion into the p-type gate [4]. In this paper, halogen ions are incorporated into tunnel oxide with the implantation process through inter-layer dielectric which is deposited on the formed cell structure for protecting cells against moisture, hydrogen, and defects. To diffuse the halogen ions upto tunnel oxide and cure the inter-layer dielectric, the samples are annealed. Interface-trap charge (ΔVit), direct-current current-voltage (DCIV), and charge-to-breakdown (QBD) methods are used to characterize electrical properties. It is found that the quality of tunnel oxide and interface is enhanced with the concentration of ions, which is due to the reduction of the number of trap sites caused by diffusion through the inter-layer dielectric. It is shown that the reliability characteristics after program/erase cycles and retention at high temperature are improved with the implant dose. In conclusion, the reliability of NAND flash memory can be improved with the decrease of the number of defects in dielectrics of its cells by halogen ions.
References
[1] J.D. Lee et al., Proc. IRPS , 497 (2003)
[2] S.Y. Wang et al., Solid-State Electron., 50, 1171 (2006).
[3] C.H. Liu et al., Proc. VLSI Tech., 35 (2009).
[4] C.C. Chen et al., Electrochem. Solid-State Lett., 3, 290 (2000)
2:45 AM - P4.02
Building Realistic Models of High-K Oxide/Semiconductor Interfaces
Tiziana Musso 1 Teemu Hynninen 1 2 Adam Foster 1
1Aalto University Helsinki Finland2Tampere University of Technology Tampere Finland
Show AbstractIn this work, we use the Charge-Optimized Many-Body potential (COMB), an empirical potential parameterized for Si/SiO2 [1,2] and Hf/HfO2 systems [3], with the aim of modeling novel semiconductor/oxide interfaces with realistic features of interface structure. The COMB potential is particularly well suited to model interfaces because it is a variable charge potential that allows charges to dynamically evolve during the simulation. The modified COMB potential has been implemented within Pysic [4], an ASE (Atomic Simulation Environment) calculator in an object-based Python environment.
Building on the framework of the COMB potential developed by Shan et al. [2] (used in LAMMPS [5]), we have modified the same in order to obtain more realistic results. The implemented potential has been tested on Si3Oy (y = 1-6) and HfOn (n = 2-6) clusters. Further, ab-initio results from the VASP code [6], and classical results from LAMMPS and Pysic codes for optimized silica and hafnia bulk phases have been compared.
After suitable testing, we model the Si/SiO2/HfO2 interface. Considering that a layer of silica is always formed between adjacent Si and HfO2 slabs, molecular dynamics simulations of the Si/SiO2 interface have been carried out, and the results have been compared with earlier ReaxFF studies [7]. Finally, we prepare a series of Si/SiO2/HfO2 interfaces and filter them to find characteristic representations of real interfaces. These key interfaces are further studied at the first principles level, looking at their electronic structure and the possible role of defects in electron transport across the interface.
[1] J. Yu et al, Physical Review B 75, 085311 (2007)
[2] Tzu-Ray Shan et al, Physical Review B 82, 235302 (2010)
[3] Tzu-Ray Shan et al, Physical Review B 81, 125328 (2010)
[4] http://butler.cc.tut.fi/~hynnine5/programs/pysic/doc/index.html
[5] S. Plimpton, J Comp Phys 117, 1-19 (1995)
[6] G. Kresse and J. Hafner, Physical Review B, 47-558 (1993)
[7] van Duin et al, The Journal of Physical Chemistry A 105, 9396-9409 (2001)
3:00 AM - *P4.03
Characterization and Modeling of the Conduction and Switching Mechanisms of HfOx Based RRAM
Shimeng Yu 1 H.-S. Philip Wong 2
1Arizona State University Tempe USA2Stanford University Stanford USA
Show AbstractOxide based resistive switching memory (RRAM) is one of the promising candidates for future non-volatile memory application due to its simple structure, low switching voltage (<3 V), fast switching speed (<10 ns), excellent scalability (<10 nm), and great compatibility with the CMOS process technology. The development of the RRAM technology involves key challenges such as the unclear physics of resistive switching in oxides, relatively poor uniformity, and large variability of the switching parameters. This talk gives an overview of efforts to address these issues through experiments and modeling.
The physical mechanism of resistive switching is generally attributed to the conductive filament (made up of oxygen vacancies) formation and rupture in the oxide due to field assisted oxygen ion migration. As a model system for device physics study, HfOx based RRAM devices were fabricated and characterized. To identify the electron conduction mechanism, various electrical characterization techniques such as I-V measurements at various temperatures, low-frequency noise measurements, and AC conductance measurements were employed. It was suggested that the trap-assisted-tunneling is the dominant conduction mechanism. In order to explore the oxygen ion migration dynamics, pulse switching measurements were performed. An exponential voltage-time relationship was found between the switching time and the applied voltage. To obtain a first-order understanding of the variability of resistive switching, a Kinetic Monte Carlo (KMC) numerical simulator was developed. The generation/recombination/migration probabilities of oxygen vacancies and oxygen ions were calculated, and the conductive filament configuration was updated stochastically according to those probabilities. The KMC simulation can reproduce many experimental observations in the DC I-V sweep, pulse switching, endurance cycling, and retention baking, etc. The tail bits in the resistance distribution are attributed to the oxygen vacancy left over in the gap region due to a competition between the oxygen vacancy generation and recombination. To enable circuit and system development using RRAM, a compact device model was developed. The compact model, implemented in MATLAB, HSPICE, and Verilog-A, which can be employed in many commonly available circuit simulators using the SPICE engine.
3:30 AM - P4.04
Improvement of Reliability Characteristics by Controlling Grain Size and Shape of the Floating Gate Using Rapid Thermal Oxidation Technique in Sub-20 nm NAND Flash Memory
Jo Byungduck 1 Park Byoungjun 1 Kim Dae-Hee 1 Park Jiyul 1 Lee Jeahoon 1 Park Seongjo 1 Cho Myoungkwan 1 Ahn Kun-ok 1 Kim Jinwoong 1
1SK Hynix Cheongju Republic of Korea
Show AbstractAs the NAND flash memory cell is scaling down into sub-20 nm technologies, the reliability characteristics such as endurance and retention of NAND flash memory cells are dramatically degraded. Especially, in NAND flash memory cell, properties of floating gate (FG) as a charge storage node are the critical factors in reliability. Up to now, grain size of poly-silicon, carbon-doped FG and the dopant type of FG have been studied to enhance reliability of NAND cells [1,2]. In this paper, we will show rapid thermal oxidation (RTO) effect on poly-silicon as used FG for improving endurance characteristics. The varied RTO process temperature and time after the deposition of poly-silicon are investigated to modify a physical structure of FG and their electrical properties of poly-silicon. When the RTO process is skipped or the sample is annealed at low temperature (compared with reference samples), the shape of the upper FG becomes narrow. Furthermore, the height of FG is lower and the grain size of poly-silicon is smaller. We can confirm these results from TEM and AFM images. For the comparison of reliability between the samples, threshold voltage (Vth) distribution of cells before and after program/erase (P/E) cycles is measured. The sample annealed with lower RTO temperature exhibits better program disturbance characteristic and narrower width of Vth distribution. These results indicate that the small grain size of poly-silicon disperses the electric field between FG and inter-poly dielectrics, which reduces generation of interfacial and oxide trap sites during P/E cycles. Also, increased on-current through the strings and reduction of interference between cells lead narrow Vth distribution. In conclusion, high reliability of NAND Flash can be achieved with the proposed RTO technique in sub-20 nm technology.
References
[1] A. T. Voutsas et al., J. Electrochem. Soc., 140, 282 (1993).
[2] J. Pu et al., IEEE Electron Dev. Lett., 29, 688 (2008).
3:45 AM - P4.05
Polarization Control of the Schottky Barrier at a Metal/N-Type-Ferroelectric Interface
Xiaohui Liu 1 Yong Wang 2 John Burton 1 Evgeny Tsymbal 1
1Department of Physics and Astronomy amp; Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln Lincoln USA2Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory Richland USA
Show AbstractWhile ferroelectric materials are normally considered as insulators, semiconducting ferroelectrics have been known for a long time to exhibit bistable conduction characteristics.[1] With the advent of modern growth techniques for complex oxide heterostuctures, devices can now be fabricated which exhibit polarization controlled charge transport and switchable photovoltaic effects, as observed in semiconducting BiFeO3.[2] In addition, recent experimental and theoretical studies found that ferroelectric polar displacements persist in BaTiO3, a prototypical oxide ferroelectric, even up to quite high levels of electron doping.[3,4] The co-existence of the ferroelectric phase with conductivity opens the door to new functionalities which may provide a unique route for novel device applications. Using first-principles methods and electrostatic modeling we explore the effect that the switchable polarization of electron-doped BaTiO3 (n-BaTiO3) has on the electronic properties at the SrRuO3/n-BaTiO3 (001) interface. Ferroelectric polarization controls the accumulation and depletion of electron charge at the interface, and the associated bending of the n-BTO conduction band determines the transport regime across the interface. We find that the interface exhibits a wide Schottky tunnel barrier for one polarization orientation, whereas an Ohmic-like contact is present for the opposite polarization orientation, leading to a large change in interface resistance associated with polarization reversal. Calculations reveal a large (five orders of magnitude) change in the interface resistance as a result of polarization switching, making the polarization control of interface transport regimes a fascinating prospect for potential device applications.
[1] V. Fridkin, Ferroelectric semiconductors (Consultants Bureau: New York, 1980) 318pp.
[2] A. Q. Jiang, C. Wang, K. J. Jin, X. B. Liu, J. F. Scott, C. S. Hwang, T. A. Tang, H. B. Lu, and G. Z. Yang, Advanced Mater. 23, 1277 (2011).
[3] T. Kolodiazhnyi, M. Tachibana, H. Kawaji, J. Hwang, and E. Takayama-Muromachi, Phys. Rev. Lett. 104, 147602 (2010).
[4] Y. Wang, X. Liu, J. D. Burton, S. S. Jaswal, and E. Y. Tsymbal, Phys. Rev. Lett. 109, 247601 (2012).
4:30 AM - P4.06
Correlated Electron Membrane Transistors with Ionic Liquid Gates
Jai Sim 1 You Zhou 1 Shriram Ramanathan 1
1Harvard University Cambridge USA
Show AbstractThere is growing interest in understanding unexpected properties arising at oxide interfaces, whether due to new physics arising from many body effects or simply chemical composition change-driven phenomena. In this context, a liquid-oxide interface is interesting to probe band bending effects (electrostatic) and chemical diffusion (such as by ionic species injection) driven resistance modulation. Electric double layer transistors (EDLTs) are well suited to study these competing effects. Vanadium oxide (VO2) is of contemporary interest as a model material to investigate correlated electron phenomena, metal insulator phase transition mechanisms, and as well as for potential applications in switching devices. Membranes of such oxides allow studies on electronic transport in confined structures, and enable measurements in chemical potential gradients. We demonstrate a robust lithographic patterning method to fabricate self-supported sub-50nm VO2 membranes that undergo a phase transition. Utilizing such self-supported membranes, we directly observed shift in metal-insulator transition temperature arising from stress relaxation and consistent opening of the hysteresis. Electric double layer transistors were then fabricated with the membranes and compared to thin film devices on nitride substrates. The ionic liquid allowed reversible modulation of channel resistance and distinguishing bulk process from the surface effects. From the shift in the metal-insulator transition temperature, the carrier density doped through electrolyte gating is estimated to be 1*10^20 cm^-3. Hydrogen annealing studies showed little difference in resistivity between the film and the membrane indicating rapid diffusion of hydrogen in the vanadium oxide rutile lattice, consistent with previous observations. We will present a detailed discussion on interpretation of transistor response that includes electrostatic, electrochemical and chemical effects, all of which can modulate the resistance of a phase change correlated oxide.
4:45 AM - P4.07
Rewritable Metal-Insulator Transition in Vanadium Dioxide Using Ultraviolet Radiation
Lu Guo 1 Greg Stone 1 Venkatraman Gopalan 1 Haitian Zhang 1 Roman Engel-Herbert 1 Eugene Freeman 2 Nikhil Shukla 2 Suman Datta 2 June H. Lee 6 Hanjong Paik 4 5 Darrell G Schlom 4 5 Thomas Fitzgibbons 3 John V. Badding 3
1Penn State University State College USA2Penn State University State College USA3Penn State University State College USA4Cornell University Ithaca USA5Kavli Institute at Cornell for Nanoscale Science Ithaca USA6Argonne National Laboratory Argonne USA
Show AbstractWe demonstrate light induced modification of the metal-insulator transition in single crystalline VO2 ultrathin films (2-15nm) grown on (001) TiO2 substrates using molecular beam epitaxy. These films exhibit a metal insulator transition (MIT) from a metallic phase with a rutile structure to a monoclinic insulating phase at 278K. This temperature is well below the bulk transition temperature of 340K due to strain from the substrate lattice mismatch with the VO2 structure. Exposure to 257 nm wavelength UV light at 0.94W/cm2 power density suppresses the MIT causing the films to remain metallic to temperatures as low as 150K. Various thermal annealing experiments aimed at recovering the MIT transition will be presented. The ability to write, erase, and reconfigure metallic regions within an insulating VO2 film presents a flexible and powerful means to build electronic circuits using correlated oxides.
5:00 AM - P4.08
Electric-Field Control of Transport Properties in VO2 Nanowires with Side Gates via Air Gap
Teruo Kanki 1 Tsubasa Sasaki 1 Hidekazu Tanaka 1
1Osaka Univ. Ibaraki Japan
Show AbstractStrongly correlated electron systems are of much interest for the development of highly sensitive sensors and phase change memories that use the Mott transition driven by external forces. Especially vanadium dioxide (VO2) is a promising material to lead to realization of their devices because of drastic change of conductive properties with several orders of magnitude by temperature and an electric field. Recently, electric-double-layer transistor based on VO2 channel is attracting attention in the huge changes of resistance by the electric-filed [1,2].
In this research, we focus on a side-gate-type field-effect transistor (SG-FET) via air gap with VO2 nano-wire channel and tried to modulate channel resistance by an electric field under various kinds of gas atmospheres (air, N2 and etchellip;).
VO2 thin films were prepared by a pulsed laser deposition technique. In patterning of the SG-FET, we applied a nanoimprint lithography technique and successfully obtained over 60 devices at a time with high controllability of size, shape and position in a large area (4 mm x 4 mm).
When a gate voltage (Vg) was applied to a VO2 channel from both sides across air gap with 200 nm in width, the resistance drastically decreased at Vg=100 V and recovered at Vg=-100 V in air, exhibiting memory effect, while the resistance remained unchanged in N2 atmosphere. It is considered that the change of resistance is caused by a redox reaction. In this meeting, we will report the detail experimental results and their analysis.
This work was supported by JSPS KAKENHI Grant Numbers 21676001 and 25286058
[1] M. Nakano et al, Nature 487 (2012) 459. [2] J. Jeong et al, Science 339 (2013) 1402.
5:15 AM - P4.09
Interfacial Capacitance between an Fe3O4 Film and a Nb:SrTiO3 Substrate
Ryota Takahashi 1 Yasuo Cho 2 Mikk Lippmaa 1
1Institute for Solid State Physics Kashiwa Japan2Research Institute of Electrical Communication Sendai Japan
Show AbstractMagnetite (Fe3O4) is a prototype multiferroic material with both spontaneous magnetization and dielectric polarization. Below the well-known metal-insulator (Verwey) transition at 120 K, a reg-ular arrangement of the B-site Fe2+ and Fe3+ ions in an inverse spinel structure results in a charge-ordering pattern with an alternation of short and long Fe-Fe bonds. The coexistence of bond-centered and charge-centered charge ordering induces an electronic polarization along the monoclinic b-axis [1]. Recently, we have demonstrated pyroelectric detection of a spontaneous polarization in Fe3O4 films grown on Nb:SrTiO3 substrates below the Verwey transition point [2]. Moreover, quasi-static pyroelectric measurements of Pd/Fe3O4/Nb:SrTiO3 junctions revealed a very large effective pyroelec-tric coefficient of 735 nC/cm2K at 60 K. This value is comparable to the well-known large pyroelec-tric coefficient of Pb(Sc,Ta)O3 films, 600 nC/cm2K, and much larger than the 20 nC/cm2K coefficient of PbTiO3/MgO films. Such a large pyroelectric coefficient may be related to the interface between the Fe3O4 film and a semiconducting Nb:SrTiO3 substrate that was used as a bottom electrode. We have therefore investigated the interfacial capacitance of Fe3O4/Nb:SrTiO3 junctions below the Ver-wey transition point.
Fe3O4 films were grown on Nb:SrTiO3(001) substrates by pulsed laser deposition [3]. Typical Fe3O4 film thicknesses were 13 to 546 nm. For the electric contacts, 100-nm-thick Pd top electrodes were deposited on the Fe3O4 film surface by e-beam evaporation. The polar state was characterized by measuring the pyroelectric response and by scanning nonlinear dielectric microscopy (SNDM). The capacitance value was measured by using an LCR meter as a function of temperature and frequency. The temperature dependence of capacitance for all samples presented strong dielectric dispersion be-tween 20 and 50 K. Above 60 K, the capacitance value was constant and not dependent on the Fe3O4 film thickness, even though the capacitance value should be inversely proportional to the film thick-ness. This indicates that the measurements are affected by interfacial capacitance due to the formation of a depletion layer between the Fe3O4 film and the Nb:SrTiO3(001) substrate. A large interfacial ca-pacitance is expected to enhance the effective pyroelectric response of Pd/Fe3O4/Nb:SrTiO3 junctions.
[1] J. Brink et al, J. Phys.: Condens. Mater. 20, 424217 (2008)
[2] R. Takahashi et al. Physical Review B, 86, 144105 (2012))
[3] R. Takahashi et al. Crystal Growth & Design 12, 2679-2683 (2012)
5:30 AM - P4.10
Effect of Interface Structure on Schottky Barrier Height in SrRuO3/SrTiO3 Heterojunctions
Vemulavada Sampath Kumar 1
1Indian Institute of Technology Hyderabd Hyderabad India
Show AbstractComplex oxide heterostructures are highly promising for technological applications as they offer novel device concepts and functionalities. One of the fundamental parameters that influence the characteristics of the metal/oxide heterostructure is the Schottky barrier formed at the interface. The Schottky barrier height (SBH) is strongly influenced by the atomic structure of the metal/oxide interface and is of fundamental interest as an intrinsic property of the system. The SrRuO3/SrTiO3(001) heterostructure is a prototypical system to study SBH at the oxide metal/dielectric interface. In recent years, the SrRuO3 (SRO) has attracted a lot of attention as an electrode material for ultrathin ferroelectric films. Using ab-initio calculations, we have studied the p-type SBH and its dependence on the interface structure in SRO/STO heterostructure. In addition, we have estimated the p-SBH using semi-empirical Metal-Induced-Gap-States (MIGS) model. In particular we have considered three types of interfaces: RuO2/SrO/TiO2, RuO2/BaO/TiO2 and MnO2/SrO/TiO2. The ab-initio estimate of p-SBH comes out to be 1.27, 1.33 and 0.78 eV for RuO2/SrO/TiO2, RuO2/BaO/TiO2 and MnO2/SrO/TiO2 interfaces respectively. We find that semi-empirical MIGS model overestimate the p-SBH by ~2 eV. We have also studied the workfunctions of SRO surfaces with different terminations. The workfunction of SRO(001) surface with RuO2 termination is larger by 2.42 eV than that with SrO termination. The calculated value of SRO(001) surface workfunction with RuO2 termination is 5.0 eV and is in close agreement with the experimental value of 5.2 eV. We have also tested the validity of a recently proposed generic relation between the metal work function and the Young&’s modulus, in case of SRO.
5:45 AM - P4.11
BiFeO3 Domain Wall Energies and Structures: A Combined Experimental and Density Functional Theory +U Study
Yi Wang 1 Chris Nelson 2 Benjamin Winchester 1 Alexander Melville 3 Shunli Shang 1 Zi-Kui Liu 1 Darrell Schlom 3 4 Xiaoqing Pan 2 Long-Qing Chen 1
1The Pennsylvania State University University Park USA2The University of Michigan Ann Arbor USA3Cornell University Ithaca USA4Kavli Institute at Cornell For Nanoscale Science Ithaca USA
Show AbstractWe determined the atomic structures and energies of 109°, 180° and 71° domain walls in BiFeO3, combining density functional theory +U calculations and aberration-corrected transmission electron microscopy images. Both the calculation and the measurement show that across the domain walls the Fe sublattice is relatively uniform and the Bi sublattice shows a substantial shift, implying that the change in polarization is due to the shift of the Bi sublattice. The oxygen octahedral rotation changes across the three types of walls correspond to the thicknesses obtained by analyzing the atomic displacement distributions from both the density functional theory +U calculations and HAADF images. The calculated wall energies (γ) follow the sequence γ109 < γ180 < γ71 for the 109°, 180°, and 71° walls. We attribute the high 71° wall energy to an opposite tilting rotation of the oxygen octahedra and the low 109° wall energy to the opposite twisting rotation of the oxygen octahedra across the domain walls. [Phys. Rev. Lett. (accepted June 2013)].
P3: Emergent Oxide Interface Devices I
Session Chairs
Kirk H. Bevan
Dmitri Nikonov
Tuesday AM, December 03, 2013
Hynes, Level 2, Room 201
9:30 AM - P3.01
Effect of Preparation of TiN Electrode on the Switching Behavior of TiN/HfOx/TiN Structures for Resistive RAM
Katrina A Morgan 1 Ruomeng Huang 1 Stuart Pearce 1 Le Zhong 2 Liudi Jiang 2 C. H. (Kees) De Groot 1
1University of Southampton Southampton United Kingdom2University of Southampton Southampton United Kingdom
Show AbstractThe impact of the quality of TiN electrodes on the switching characteristics of HfOx-based resistive random access memory (ReRAM) devices is investigated in this work. It is shown that by changing the method of preparation of the top TiN electrode, the Ron/Roff ratio of the device is altered by up to three orders of magnitude.
Two types of TiN/HfOx/TiN devices have been fabricated where the top 200nm TiN electrode has been deposited by two different sputtering methods. For one device, the top TiN electrode was deposited by reactive sputtering, using a titanium target in a nitrogen environment. For the other device, the top TiN electrode was deposited by non-reactive sputtering, using a titanium nitride target. XRD, EDX and electrical measurements show the TiN layer, deposited in a nitrogen environment, is single-phase stoichiometric TiN and has a sheet resistance of 6Omega;/square. The other TiN layer, deposited by a titanium nitride target, contains oxygen and has a sheet resistance of 505Omega;/square. This indicates that this TiN layer readily reacts with oxygen in the HfOx layer beneath, forming a TiOxNy layer between the top electrode and the insulator.
The device with the stoichiometric titanium nitride layer results in bipolar switching, with a Ron/Roff ratio <5. The device with an oxygen titanium nitride layer results in unipolar switching, with a Ron/Roff ratio of 10^4. The larger Ron/Roff ratio in this device supports the theory of oxygen vacancies leading to the formation of conductive filaments. It is likely that the formation of the TiOxNy layer causes oxygen vacancies to be created in the HfOx layer, aiding the switching of the device, leading to an increase in the Ron/Roff ratio. In the other device, reaction between the stoichiometric TiN and the HfOx layer beneath is minimal, resulting in low concentration of oxygen vacancies in the HfOx layer and therefore leads to a smaller Ron/Roff ratio. These results show that an oxygen layer between the top electrode and insulator is advantageous for resistive memory applications.
9:45 AM - P3.02
Abnormal Effect of Oxygen Vacancies and Two Hysteresis Curves in Oxide-Based Semiconductors
Jae Sung Lee 1 Shin Buhm Lee 2 Byungnam Kahng 2 Tae Won Noh 2
1Korea Institute for Advanced Study Seoul Republic of Korea2Seoul National University Seoul Republic of Korea
Show AbstractSemiconductors with mobile dopants (SMDs), which are distinct from conventional semiconductors, exhibit a unique physical property; they demonstrate memristive hysteretic current-voltage curves. Memristive behaviour, theoretically proposed in 1971 and experimentally realised in 2008, refers to the dependence of a semiconductor&’s resistance on the history of the applied current flow and its internal state. The fundamental peculiarity of an SMD memristive hysteresis curve is that it exhibits two oppositely rotating directions, whose origin is still debatable. In this presentation, we introduce an SMD model to describe the electronic-barrier modulation due to the motion of mobile dopants in oxide semiconductor under an electric field. We will show that oxygen vacancy migration near the Schottky-interface region induces abnormal modulation of the electronic barrier; low (high) density of dopants near a metal-semiconductor interface lead to high (low) conductance, while the conventional ionic and electronic models predict the reverse behaviours. From this observation, we will show that the two directions of the hysteresis I-V curve originate from the spatial inhomogeneity of the mobile dopant distribution in the SMD.
10:00 AM - *P3.03
Thermodynamics of Heterostructures and Equilibrium Charge Carrier Distribution at Oxide Interfaces
Joachim Maier 1
1MPI for Solid State Research Stuttgart Germany
Show AbstractThe equilibrium charge carrier distribution at abrupt contacts is considered by not only allowing electrons but also cations or anions to be mobile, the control parameters being partial pressures, temperature and doping content [1]. This leads to the generalized ther-modynamic picture involving mixed conductors. A variety of interfacially dominated sys-tems (composites, nanoceramics, heterolayered systems) are treated and experimental evidence is given for the significance of ionic redistribution: ion transport along CaF2/BaF2 heterolayers [2], coupling of ion and electron redistribution at LiF/TiO2 con-tacts [3], generalized point defect chemistry in nanocrystalline SrTiO3 [4], the space charge storage in Li2O/Ru composites [5].
The significance of “nano-ionics” as basic discipline underlying these phenomena will be highlighted as far as emergent electron transport properties at complex oxide interfaces are concerned.
References
[1] J. Maier, Progress in Solid State Chemistry 23, 171-263 (1995); Nature Materials 4, 805-815 (2005).
[2] N. Sata, K. Eberman, K. Eberl, and J. Maier, Nature 408, 946-949 (2000); X. X. Guo and J.Maier, Ad-vanced Materials 21, 2619-2631 (2009).
[3] C. L. Li, L. Gu, X. X. Guo, D. Samuelis, K. Tang, and J. Maier, Nano Letters 12, 1241-1246 (2012).
[4] P. Lupetin, G. Gregori, and J. Maier, Angewandte Chemie International Edition 49, 10123-10126 (2010).
[5] J. Maier, Angewandte Chemie International Edition 52, 4998-5026 (2013).
10:30 AM - P3.04
Control of Magnetotransport Properties of Zinc Ferrite Thin Films via Reversible Electrochemical Reactions
Kohei Fujiwara 1 Takashi Ichimura 1 Tatsuya Hori 1 Hidekazu Tanaka 1
1Osaka University Ibaraki Japan
Show AbstractThe electrical control of magnetism using a field-effect transistor structure is currently an area of active research in spintronics. Recent progress in gating technology that uses high-k dielectrics, ferroelectric insulators, and electrolytes, has made it possible to change the magnetic properties of various ferromagnetic materials including 3d metals and oxides. The field effect using an ionic liquid has been considered very powerful because of the extremely high-density charge carrier accumulation [1-3]. Very recently, along with carrier doping, oxygen diffusion was found to be induced by the large electric field created at the interface between the oxide surface and ionic liquid [4]. This provides us an additional degree of freedom to control material&’s properties via electrochemical reactions. Here we report the electrochemical control of electrical and magnetic properties of spinel zinc ferrite (ZnxFe3minus;xO4) at room temperature.
Epitaxial thin films of Zn0.5Fe2.5O4 were grown on MgO(001) substrates by pulsed-laser deposition [5]. The film was patterned into a Hall bar geometry by photolithography and Ar ion milling. An ionic liquid, DEME-TFSI, was then dropped such that the Zn0.5Fe2.5O4 channel and Au gate electrode form an electric-double-layer capacitor. The device exhibited n-type behavior; the application of a positive gate bias VG increased the drain current ID (conductivity). A large hysteresis observed in the ID-VG curve is similar to those of VO2 devices for which oxygen diffusion by ionic-liquid gating was first reported. Further support to the presence of electrochemical reactions was obtained from the VG polarity dependence of the initial ID-VG curve. The application of a positive VG was found to be necessary to trigger the hysteresis and conductivity modulation. We speculate that the extraction of oxygen ions at the Zn0.5Fe2.5O4 surface occurs when negatively biased. The tendency of the change in conductivity against the variation in the oxygen nonstoichiometry was well reproduced by transport measurements using the films grown under various oxygen pressures. Utilizing this gate-induced bistable zero-bias states, we controlled the magnetoresistance of Zn0.5Fe2.5O4.
[1] M. Weisheit et al., Science 315, 349 (2007).
[2] Y. Yamada et al., Science 332, 1065 (2011).
[3] K. Shimamura et al., Appl. Phys. Lett. 100, 122402 (2012).
[4] J. Jeong et al., Science 339, 1402 (2013).
[5] T. Ichimura et al., Jpn. J. Appl. Phys. 52, 068002 (2013).
10:45 AM - P3.05
Transport Properties of LiTi2O4 Superconducting Spinel Oxide Thin Films
Shingo Maruyama 1 Jin Kui 2 Shintaro Yasui 1 Richard Andrew Suchoski 1 Jongmoon Shin 1 Richard L. Greene 2 Ichiro Takeuchi 1
1University of Maryland College Park USA2University of Maryland College Park USA
Show AbstractLiTi2O4 has attracted much attention as the only known oxide superconductor with a spinel structure. We are investigating the transport properties of expitaxially grown LiTi2O4 thin films on MgAl2O4 substrates using pulsed laser deposition. Since Li can easily evaporate during the deposition process, we use Li excess Li4Ti5O12 as a target and deposit films in vacuum [1]. LiTi2O4 films grown on (111) and (100) MgAl2O4 substrates showed superconducting transition temperatures at asymp;12 K, consistent with previous reports [1,2]. Transport properties including tunneling and the Hall effect have been measured. We will also discuss the thickness dependence of the transport properties and the electrostatic gating effect using an ionic liquid as the gate material. This work is supported by AFOSR. Ref. [1] Kumatani et al., Appl. Phys. Lett. 101, 123103 (2012). [2] Chopdekar et al., Physica C 469, 1885 (2009).
11:30 AM - P3.06
Structure and Oxygen Control of Physical Properties of the SrRuO3 Film Surface
Alexander Tselev 1 P. Ganesh 1 Liang Qiao 1 Wolter Siemons 1 Zheng Gai 1 Michael D. Biegalski 1 Arthur P. Baddorf 1 Sergei V. Kalinin 1
1Oak Ridge National Laboratory Knoxville USA
Show AbstractOxide thin films and heterostructures have become one of the focal points of physical research in the last 20 years, with a large number of novel phenomena associated with oxide structures. It is well-established, that oxygen stoichiometry strongly affects oxide properties. In this context, oxygen-controlled properties of oxide surfaces are of special interest. In particular, surfaces are the key intermediate step during film growth that influences the structure and properties of interfaces in hetersotructures. High cationic and oxygen lability on surfaces can lead to multivariant adatom reconstructions. Furthermore, oxygen-related surface electrochemistry was shown to be directly influencing physical processes in bulk of thin films with effects on such phenomena as ferroelectric phase stability or metal-insulator phase transitions. In turn, oxygen evolution and reduction reactions at the surfaces are key processes in operation of energy conversion devices, catalysts, oxygen sensors and pumps, and other functional systems. In this work, we explored coupling between oxygen behavior and physical functionality on the surface of SrRuO3 (SRO), one of the most studied oxide materials with perovskite structure, using few nanometer thick films of SRO epitaxially grown by pulsed laser deposition (PLD) on (001)SrTiO3 substrates. We have for the first time succeeded in atomic-resolution scanning tunneling microscopy (STM) imaging of as-deposited SRO films grown at conditions, which are normally used for deposition of SRO electrode layers in complex oxide functional heterostructures. The STM images showed atomic patterns on the film surfaces, which were not reported before. Depending on growth/annealing conditions, zigzag and rectangular linear structures were observed and identified as formed by oxygen adatoms. Further, we performed a detailed in situ and ex situ experimental investigation of surfaces of SRO thin films using a combination of x-ray and ultraviolet photoelectron spectroscopy (PES), magnetometry, and magnetotransport measurements. Ab-initio DFT modeling revealed a link between the patterns of adsorbed oxygen atoms and the electronic and magnetic properties of the topmost atomic layer. DFT showed relatively large adsorption energies of oxygen in the observed surface structures indicating their stability at deposition temperature. The modeling predicted that oxygen adatoms possess frustrated local spin moments with possible spin-glass behavior of the surface covered by adsorbed oxygen due to random ferromagnetic/antiferromagnetic coupling between spins of oxygen adatoms and spins of the underlying SRO. In turn, the pristine SrO-terminated surface is half-metallic, which is of a strong interest for realization of spintronic devices. This research was sponsored by the DMSE, BES, U.S. DOE (AT, WS, SVK). Research at the ORNL's CNMS was sponsored by the Division of Scientific User Facilities, U.S. DOE.
11:45 AM - P3.07
Lift-off Patterning of Oxide Interfaces with High Mobility 2DEG
Nirupam Banerjee 1 M. Huijben 1 G. Koster 1 G. Rijnders 1
1University of Twente Enschede Netherlands
Show AbstractExistence of two dimensional electron gas (2DEG) with high mobility at the atomically engineered interface between two wide band-gap perovskite insulators, SrTiO3 (STO) and LaAlO3 (LAO) has stimulated research interests to utilize these functional oxide interfaces in key electronic devices such as high mobility electron transistors (HMET). Although excellent interfacial transport properties were manifested, structuring these delicate heterointerfaces without damaging the substrate STO single crystal has remained elusive which is essential for their integration with other device components. Physical etching processes employing “top-down” patterning approach were unsuitable since they induce substrate conductivity through creation of oxygen vacancies.
We demonstrate development of a novel procedure for fabricating patterned functional interfaces based on an epitaxial-lift-off technique without utilizing any physical etching process. Devices incorporating precisely patterned interfaces of LAO-STO were fabricated and temperature dependent magneto transport properties were investigated. High-quality interface properties were found to be conserved in the patterned devices structures promoting future studies of low-dimensional confinement on high mobility interface conductivity as well as interfacial magnetism. In addition the pathway is shown to be capable of fabricating precise structures of other functional perovskites like ferroelectric PZT with dimensions down to nano-scale.
12:00 PM - *P3.08
Monolithically Integrated Circuits from Functional Oxides
Jochen Mannhart 1 Rainer Jany 2 Christoph Richter 2 Carsten Woltmann 1 Georg Pfanzelt 1 Benjamin Foerg 2 Marcus Rommel 1 Thomas Reindl 1 Ulrike Waizmann 1 Juergen Weis 1 Julia Mundy 3 David Muller 3 4 Hans Boschker 1
1Max Planck Institute Stuttgart Germany2Augsburg University Augsburg Germany3Cornell University Ithaca USA4Kavli Institute at Cornell for Nanoscale Science Ithaca USA
Show AbstractThe rich array of conventional and exotic electronic properties that can be generated by oxide heterostructures are of great potential value for device applications. Particularly promising are the d-electron or f-electron-based mobile electron systems at interfaces in complex oxides. However, the actual physical implementation of functional complex oxide heterostructures is challenged by a higher defect density than is characteristic for semiconductor multilayers. Indeed, only single transistors bare of any circuit functionality have been realized from complex oxides. In the presentation we report that oxide electronic devices can be more defect-tolerant than semiconducting devices are.
We have fabricated robust oxide NMOS circuits and demonstrate LaAlO3-SrTiO3 chips with hundreds of thousands transistors. Providing the capability to process the signals of functional oxide devices such as sensors directly on oxide chips, these results illustrate the practicability and the potential of oxide electronics.
12:30 PM - P3.09
Nanoscale Charge Transport Characteristics at Perovskite Interfaces - A Holistic Perspective
Ramsey Kraya 1 Laura Kraya 2
1Johns Hopkins University Baltimore USA2Princeton University Princeton USA
Show AbstractHere we investigate how charge transport properties scale down to the nanoscale regime, comparing the properties to standard semiconductor materials and providing a perspective on what it means to device manufacturing. Strontium titanate - the prototypical oxide material - has been widely studied for applications in thermoelectrics, nanoelectronics, catalysis, and other uses. We investigated how charge transport is effected at interfaces to stronitium titanate under a wide range of conditions - by varying contact size, interface shape, dopant concentration, surface structures and in various combinations and relate the the results to experiments utilizing standard semiconducting materials such as silicon and gallium arsenide. Also, the results of the analysis have wide ranging implications, especially for ferroelectric perovskite materials and serves as the basis for understanding and controlling switching effects - both polarization and oxygen migration based switching.
12:45 PM - P3.10
Low Temperature Transport of LaAlO3/SrTiO3-Based Nanodevices
Daniela Stornaiuolo 1 Stefano Gariglio 1 Alexandre Famp;#234;te 1 Danfeng Li 1 Nuno J.G. Couto 1 2 Alberto F. Morpurgo 1 2 Jean-Marc Triscone 1
1University of Geneva Geneva Switzerland2University of Geneva Geneva Switzerland
Show AbstractThe two-dimensional electron gas (2DEG) at the interface between LaAlO3 and SrTiO3 (LAO/STO) displays a variety of electronic properties, including superconductivity, magnetism and Rashba spin-orbit interaction, and offers the possibility to control some of them using electric field effect. These features make it one of the most interesting multifunctional materials in oxide electronics.
Using a patterning technique based on electron beam lithography, we realized nanodevices with various geometries, which enable us to investigate different aspects of the physics of the LAO/STO system, both in the normal and in the superconducting regime.
Nanobridges with width down to 200 nm display superconducting properties that can be tuned by an electric field effect [1]. By optimizing the design of the nanostructure and the field effect geometry, we can achieve large tunability with low gate voltages, allowing the exploration of a wider range of dopings.
In these devices, we also studied the evolution in temperature and doping of the spin-orbit interaction, to map its relation with the superconducting state.
[1] D. Stornaiuolo et al., Applied Physics Letters, 101, 222601 (2012)
Symposium Organizers
Kirk H. Bevan, McGill University
Sohrab Ismail-Beigi, Yale University
T. Zac Ward, Oak Ridge National Laboratory
Zhenyu Zhang, University of Science and Technology of China
Symposium Support
MDC Vacuum Products, LLC
NBM Design Inc.
Princeton Scientific Corp.
PVD Products
Quantum Design, Inc.
STAIB Instruments
SURFACE Systems amp; Technologies GmbH amp; Co. KG
P6: Emergent Oxide 2DEG Properties II
Session Chairs
T. Zac Ward
Atsushi Tsukazaki
Wednesday PM, December 04, 2013
Hynes, Level 2, Room 201
2:30 AM - P6.01
Influence of SrTiO3 Surface Preparation Methods on the Transport Properties of LaAlO3/SrTiO3 Interfaces
John G. Connell 1 Oleksandr B. Korneta 1 John Nichols 1 S. S. Ambrose Seo 1
1University of Kentucky Lexington USA
Show AbstractLaAlO3/SrTiO3 interfaces are known to display various intriguing properties such as metallic, insulating, superconducting, and magnetic properties at low temperatures depending on their growth conditions. Here we show that the transport properties of the interfaces are also affected by substrate surface-preparation methods. Using the deionized-water leaching method [1] and the commonly-used buffered hydrofluoric acid (BHF)-etching method, we have prepared atomically-flat, TiO2-terminated SrTiO3 (001) substrates. We have then grown epitaxial LaAlO3 thin-films of various thicknesses using pulsed laser deposition. Electrical transport measurements show that the surface preparation has little effect on the transport properties of metallic samples with ns > 1014 cm-2. However, less metallic samples with ns < 1013 cm-2 show clear changes in their transport properties depending on the chemical etching methods. Our results suggest that the substrate preparation method is critical to the interfacial-transport properties.
[1] J. G. Connell, B. J. Isaac, G. B. Ekanayake, D. R. Strachan, and S. S. A. Seo, Appl. Phys. Lett., 101, 251607, (2012).
2:45 AM - P6.02
First-Principles Studies of the Two-Dimensional Electron Gas at the Interface between Two Polar Materials
Tula R Paudel 1 Evgeny Y Tsymbal 1
1University of Nebraska, Lincoln Lincoln USA
Show AbstractFollowing the discovery of the two-dimensional electron gas (2DEG) at the interface between polar LaAlO3 (LAO) and non-polar SrTiO3 (STO) grown in the [001] direction, many similar heterostructures with ever interesting physical properties have been proposed and investigated. Here using the first-principles theory, we explore the emergence of the 2DEG at the interface between two polar materials—a large material group—and thus broaden the field for designing highly conducing interfaces. We consider a model LAO-STO heterostructure stacked in the [111] direction. In the [111] direction both free standing LAO and STO are polar with alternatively charged planes-(LaO3)3- and (Al)3+ in the former and (SrO3)4 and (Ti)4+ in later with inevitable surface reconstruction. However, when LAO is deposited on STO, the reconstruction is partially relieved leading to a perfect Ti/LaO3 interface and n-type conductivity. We describe this phenomenon in terms of a modified polar catastrophe model predicting the critical thickness of the LAO layer of eight (LaO3-Al) bilayers. From the calculated electronic band structure we predict conductivity asymmetry between in-plane [1-10] and [11 -2] directions. Our findings are consistent with the experiment performed by S.S. Ryu, C.W. Bark, T. Hernandez, Hua Zhou, D.D. Fong, Y. Zhang, J. Podkaminer, X.Q. Pan, M.S. Rzchowski, and C.B. Eom.
3:00 AM - *P6.03
Giant Photovoltaic Effects Driven by Residual Polar Field within Unit-Cell-Scale LaAlO3 Films on SrTiO3
Changgan Zeng 1
1University of Science and Technology of China Hefei China
Show AbstractFor polar/nonpolar heterostructures, Maxwell&’s theory dictates that the electric potential in the polar components will increase divergently with the film thickness. For LaAlO3/SrTiO3, a conceptually intriguing route, termed charge reconstruction, has been proposed to avert such “polar catastrophe”. The existence of a polar potential in LaAlO3 is a prerequisite for the validity of the charge reconstruction picture, yet to date, its direct measurement remains a major challenge. Here we establish unambiguously the existence of the residual polar potential in ultrathin LaAlO3 films on SrTiO3, using a novel photovoltaic device design as an effective probe. The measured lower bound of the residual polar potential is 1.0 V. Such a direct observation of the giant residual polar potential within the unit-cell-scale LaAlO3 films amounts to a definitive experimental evidence for the charge reconstruction picture, and also points to new technological significance of oxide heterostructures in photovoltaic and sensing devices with atomic-scale control.
3:30 AM - P6.04
Scanning Tunneling Spectroscopic Study of LaAlO3/SrTiO3 Heterostructures
Taro Hitosugi 1 2 Katsuya Iwaya 1 Ryota Shimizu 1 Takeo Ohsawa 1 Susumu Shiraki 1
1Tohoku Univ. Sendai Japan2JST-PRESTO Tokyo Japan
Show AbstractTransition-metal oxides display a variety of functionalities at their surfaces and interfaces, which have been induced by structural and electronic modifications. However, the origins of the functionalities are still in debate. To understand the origins of such phenomena and to further explore intriguing functionalities, it is important to elucidate, at the atomic level, their electronic structures and how those heterogeneous interfaces are formed.
We report direct visualizations of initial growth nature of sub-unit cell SrTiO3 (STO) and LaAlO3 (LAO) films formed on the top of atomically-ordered STO(001)-(radic;13×radic;13)-R33.7° substrate surfaces [1] using a scanning tunneling microscopy/spectroscopy (STM/STS) combined with pulsed laser deposition (PLD).[2] The STO(001)-(radic;13×radic;13)-R33.7° surface [3] is used as an excellent template in terms of atomic-scale structures and surface composition revealed by STM and x-ray photoelectron spectroscopy, respectively.
The STM/STS imaging of sub-UC LAO islands revealed that a TiOx layer of the STO substrate has transferred to the topmost surface of the LAO layer, indicating that the TiOx layer can be viewed as a graphene-like one unit-cell TiOx sheet. [4] This structure can be regarded as a new oxide nanomaterial.
Further, we intentionally tune the atomic-scale surface structure of STO homoepitaxial thin film, and directly image surface electronic states of STO by using STS. We present the first-time, real-space observation of different symmetry constraints of STO surface electrons, controlled by both temperature and surface-defect concentrations.
These findings on the atomic-scale nature of perovskite surfaces lead to preparation of higher-quality thin films and surfaces/interfaces exhibiting novel electronic and magnetic properties.
[1] R. Shimizu, T. Hitosugi et al., Appl. Phys. Lett. 100, 263106 (2012).
[2] K. Iwaya, R. Shimizu, T. Hashizume, T. Hitosugi, Rev. Sci. Instrum. 82, 083702 (2011).
[2] R. Shimizu, T. Hitosugi et al., ACS Nano, 5, 7967 (2011).
[4] Ohsawa et al., submitted.
3:45 AM - P6.05
High Mobility Conduction at (110) and (111) LaAlO3/SrTiO3 Interfaces
Gervasi Herranz 1 Mateusz Scigaj 1 Nico Dix 1 Jaume Gazquez 1 Maria Varela 2 3 Florencio Sanchez 1 Josep Fontcuberta 1
1Institut de Ciencia de Materials de Barcelona - CSIC Bellaterra Spain2Oak Ridge National Laboratory Oak Ridge USA3Universidad Complutense de Madrid Madrid Spain
Show AbstractThe two-dimensional electron gas (2DEG) confined at the interface between oxide band-insulators as LaAlO3 and SrTiO3 is of the highest interest. Until recently, the observation of the 2DEG has been restricted to the interface between TiO2-terminated SrTiO3(001) substrates and epitaxial LaAlO3 films. Surprisingly, a 2DEG has also been found when amorphous films of several oxides are deposited on TiO2-terminated SrTiO3(001) substrates. In all these cases, only the neutral TiO2 surface of SrTiO3(001) has been shown to be conductive. Here we show that this restriction can be surpassed. Properly treated (110) and (111) oriented SrTiO3 substrates were used to deposit LaAlO3 films by pulsed laser deposition assisted by reflection high energy electron diffraction (RHEED). In spite of the high energy of (110) and (111) surfaces of perovskites the films can be grown by a layer-by-layer mechanism, thus permitting flat interface and perfect control of the number of unit cells deposited. Remarkably, (110) and (111) LaAlO3/SrTiO3 interfaces are conducting. High-resolution transmission electron microscopy characterization of (110) samples shows atomically sharp interfaces with no observation of (001)-faceting. Moreover we show that amorphous interfaces do not form exclusively on the neutral TiO2-terminated SrTiO3(001) surface: conducting (110) interfaces with amorphous LaAlO3, SrTiO3 and YSZ can also be prepared. Remarkably for all these interfaces, whatever epitaxial or amorphous, a critical thickness is found below which the samples are insulating, although the number of LaAlO3 unit cells required to trigger the insulator-to-metal transition is dependent on the orientation. These findings open a new perspective both for materials research and for elucidating the ultimate microscopic mechanism of carrier doping.
Electron microscopy work at ORNL was supported by the U.S. Department of Energy (DOE), Basic Energy Sciences (BES), Materials Sciences and Engineering Division.
4:30 AM - P6.06
Stoichiometry Dependence and Thermal Stability of NdGaO3/SrTiO3 Heterostructures
Felix Gunkel 1 2 Katharina Skaja 1 2 Andrey Shkabko 1 2 Regina Dittmann 1 2 Susanne Hoffmann-Eifert 1 2 Rainer Waser 1 2
1Forschungszentrum Juelich Juelich Germany2RWTH Aachen Aachen Germany
Show AbstractThe formation of a highly conducting interface between the two nominal band gap insulators lanthanum aluminate (LaAlO3 , LAO) and strontium titanate (SrTiO3, STO) has been subject to many recent studies. Being a promising oxide heterostructure system to emulate and exceed the properties of semiconductor interface devices, substantial advances in the fabrication and understanding of oxide systems are likely to provide intriguing implications for physics as well as for technology.
The fundamental question, how the electrical conductivity can be induced at oxide interfaces, is still under controversial discussion. In order to understand whether the underlying LAO/STO interface reconstruction can be regarded as a universal effect at oxide interfaces between polar and non-polar perovskite materials, it is essential to find alternative perovskite systems next to LAO/STO which also form a conducting interface.
This contribution provides a detailed analysis of the structural and electrical properties of neodymium gallate/strontium titanate (NdGaO3 /SrTiO3 , NGO/STO) heterostructures exhibiting similar interface conductivity as the LAO/STO system.
As will be shown, the cation stoichiometry of NGO thin films can be tuned over a wide range by the variation of the PLD growth temperature. A detailed investigation of the electrical transport in NGO/STO heterostructures grown at various deposition temperatures reveals an interesting correlation between the NGO cation stoichiometry and the NGO/STO interface conductivity. Moreover, the NGO/STO system is characterized in terms of a defect chemistry model. An enhanced analysis of the defect structure of the NGO/STO interface is provided by in situ conductance measurements under high temperature oxygen equilibrium. At the same time, the high temperature experiment reveals a transition from metallic to insulating behavior at elevated temperatures. This thermal instability of the interface reconstruction is attributed to a preferential evaporation of gallium.
From the growth experiments as well as from the high temperature treatment, we were able to identify the importance of the B-site cation, namely gallium, for the existence of metallic conductivity at the NGO/STO interface. This provides insight into the conduction mechanism at the NGO/STO interface and rules out an Nd-ion implantation scenario as possible origin of the high electron concentration [1].
[1] F. Gunkel et al., Appl. Phys. Lett. 102, 071601 (2013).
4:45 AM - P6.07
Using a Multiferroic to Gate the 2D E-Gas at LaAlO3/SrTiO3 Interface
Christian Mix 1 Frank Demuth 1 Mathias Klaeui 1 Gerhard Jakob 1
1University of Mainz Mainz Germany
Show AbstractMaterial systems dominated by interface effects provide promising chances to investigate new physical properties. A wide range of new physical effects can only be found in multilayered oxide thin film structures. The combination of a multiferroic to manipulate the transport properties of a conductive interface opens a path to an effective and ultrathin field effect device. We investigate the multiferroic material BiFeO3 in order to use it as a ferroelectric gate electrode for the quasi two dimensional electron gas (2DEG) at the LaAlO3/SrTiO3 interface. The oxide thin films are prepared by Pulsed Laser Deposition in a controlled oxygen gas atmosphere. The ferroelectric properties of the BiFeO3 layers are characterized by Piezo-Force Microscopy (PFM). In addition PFM is utilized to switch the polarization of the BiFeO3 layer in out-of-plane direction by the use of the 2DEG as a back electrode. The transport properties of the 2DEG at the interface are strongly affected by an electric field in out-of-plane direction. This experiment was performed with gate electrodes on the backside of the substrate. The conductivity of the 2DEG is significantly modified by the existence of a multiferroic BiFeO3 top layer even in the unpoled state. As a first step to device fabrication and to make use of the PFM to manipulate the conductivity of the 2DEG the samples were microstructured by the use of an amorphous mask technique. Resistivity data of a microstructured line of the 2DEG is analyzed in correspondence to the area of the BiFeO3 polarized in the two possible out-of-plane polarizations of BiFeO3.
P5: Emergent Oxide 2DEG Properties I
Session Chairs
Sohrab Ismail-Beigi
Jochen Mannhart
Wednesday AM, December 04, 2013
Hynes, Level 2, Room 201
9:45 AM - P5.02
In Situ Control of Atomic Stacking during the Growth of Perovskite Interfaces
Bruce A. Davidson 1 Aleksandr Yu. Petrov 1 Haichao Xu 2
1CNR-IOM Trieste Italy2Fudan University Shanghai China
Show AbstractThe fabrication of atomically-abrupt perovskite interfaces has usually depended on careful preparation prior to growth (i.e., in the preparation of substrates with unique surface termination) and extensive analysis afterwards (i.e., TEM-EELS and/or SXRD analysis of the chemical and crystallographic structure of the interface). We demonstrate a new in situ method to identify and control the surface termination and interface stacking during growth, based on careful use of reflection high-energy electron diffraction (RHEED), that significantly improves the atomic design of perovskite interfaces [1]. This technique requires independent supply of A- and B-site cations during deposition, achieved by shuttering the elemental sources in reactive molecular beam epitaxy (MBE) growth [2]. Rather than using oscillations of the specular spot to count the deposition of single ABO3 molecular layers, detailed information on surface termination and layer inversion can be extracted from diffracted beam (DB) oscillations and rocking curves [3]. The utility of this approach derives from the observation that the DB oscillations during shuttered deposition show a common phenomenology across many perovskite families for the full range of B-site valence between 3+ and 4+ and under different strain states; we will demonstrate this from data taken during the growth of titanate, manganite and ferrite films [4]. Conversely, RHEED rocking curves (RCs) are performed without deposition, and unique diffracted-beam RCs can be correlated with different surface terminations deduced from DB oscillations or other methods. Together, these advances in RHEED technique allow us to precisely prepare one perovskite surface before the deposition of an interface, resulting in the elimination of cation intermixing and anomalous lattice dilations that have previously been observed. This approach has also yielded magnetic tunnel junctions with record tunneling magnetoresistance [5].
[1] A. Yu. Petrov, X. Torrelles, A. Verna, H. Xu, A. Cossaro, M. Pedio, J. Garcia-Barriocanal, G. R. Castro and B. A. Davidson, Adv. Mater. (in press).
[2] J. H. Haeni, C. D. Theis and D. G. Schlom, J. Electroceram. 4, 385 (2000).
[3] T. Hikita, T. Hanada, M. Kudo and M. Kawai, Surf. Sci. 287-288, 377 (1993).
[4] A. Yu. Petrov, H. Xu and B. A. Davidson, in preparation.
[5] R. Werner, A. Yu. Petrov, L. Alvarez Miño, R. Kleiner, D. Koelle and B. A. Davidson, Appl. Phys. Lett. 98, 162505 (2011).
10:00 AM - *P5.03
High Mobility 2D Transport in Well-Regulated ZnO Based Wurtzite Heterostructures
Atsushi Tsukazaki 1 2
1Institute for Materials Research, Tohoku University Sendai Japan2PRESTO-JST Tokyo Japan
Show AbstractSpontaneous polarization in wurtzite crystal structure is one of dominant origins for the accumulation of two-dimensional electron gas (2DEG), which is applicable for the transparent field effect transistor. We have shown that MgZnO/ZnO interfaces generate high-mobility 2DEG due to the mismatch in electric polarization of constituent piezoelectric materials [1]. The electron mobility is now approaching to 1 million cm2V-1s-1 with using distilled pure ozone as oxygen source in molecular-beam epitaxy [2]. Compared with well-studied GaAs heterostrucutres, strong correlated 2D transport phenomena are pronounced in ZnO heterostructures due to large effective mass of electron (0.3 m0) in ZnO [3,4]. In addition, 3D transition metals can be doped nearby the heterointerface with keeping high mobility above 10,000 cm2V-1s-1. Such a variety of choices of cation in wurtzite oxide heterostructures is quite unique to generate 2D electrons, which gives new opportunity to find interesting transport phenomena. The talk will cover the materials aspect and quantum transport as well as fractional quantum Hall effect at low temperatures.
This work has been carried out under the collaboration with Prof. M. Kawasaki group in Univ. of Tokyo.
[1] A. Tsukazaki et al., Science 315, 1388 (2007). [2] J. Falson et al., Appl. Phys. Express 4, 091101 (2011). [3] A. Tsukazaki et al., Phys. Rev. B 78, 233308 (2008). Nature Materials 9, 889 (2010). [4] Y. Kozuka et al., Phys. Rev. B 85, 075302 (2012).
10:30 AM - P5.04
Mechanism to Generate a Two-Dimensional Electron Gas at the Surface of the Charge-Ordered Semiconductor BaBiO3
Veronica Vildosola 1 Francisco Guller 1 2 Ana Maria Llois 1 2
1Centro Atamp;#243;mico Constituyentes San Martin Argentina2Facultad de Ciencias Exactas y Naturales -UBA Buenos Aires Argentina
Show AbstractWe will talk about a new physical mechanism to generate a two-dimensional electron gas, namely, the breaking of charge ordering at the surface of a charge ordered semiconductor due to the incomplete oxygen environment of the surface ions. The emergence of the 2D gas is independent of the presence of oxygen vacancies or polar discontinuities; this is a self-doping effect. This mechanism might apply to many charge ordered systems, in particular, we will discuss the case of BaBiO3(001). In bulk, this material is a prototype of a “forbidden valence” compound in which the formal "metallic" Bi(4+) is skipped exhibiting a charge disproportionated Bi(3+)- Bi(5+) ordered structure. At room temperature, this charge disproportionation together with the breathing distortions gives rise to a Peierls semiconductor with monoclinic crystal structure. At higher temperatures (T$>$ 750K) or upon doping, it turns cubic and metallic. Interestingly, doped BaBiO3 was one of the first non-cuprates high-Tc superconductors discovered. The outer layer of the Bi-terminated simulated surface turns more cubic-like and metallic while the inner layers remain in the insulating monoclinic state. On the other hand, the metallization does not occur for the Ba termination, a fact that makes this system appealing for nanostructuring. Finally, this finding sets another possible route for future exploration: the potential scenario of 2D superconductivity at the BaBiO3 surface.
10:45 AM - P5.05
MBE Growth and Electronic Transport Study of NdTiO3/SrTiO3 Heterostructures
Peng Xu 1 Bharat Jalan 1
1University of Minnesota Minneapolis USA
Show AbstractUltra thin Mott insulators at the brink of insulator-to-metal transition, and the interfaces between a Mott insulator and a band insulator have received much attention due the remarkable physics they exhibit such as interface-stabilized ground states (two-dimensional (2D) electron gases, 2D superconductivity, Mott metal-insulator transition (MIT), ferromagnetism), which do not exist in the bulk. Remarkably rare-earth titanates (RTiO3, where R is a rare-earth element), a Mott insulator display a rich magnetic phase diagram with an incompletely understood crossover from antiferromagnetic to ferromagnetic ordering of Ti3+ spins as a function of tolerance factor [1]. Doping with ions such as Sr results in suppression of magnetic order and insulator-metal transitions. Here we focus on the hybrid molecular beam epitaxy (MBE) growth, using co-deposition, of NdTiO3, a 0.8 eV Mott gap antiferromagnetic insulator with a 100 K ordering temperature. Hybrid MBE approach employs titanium tetra isopropoxide (TTIP) as a titanium source, and solid elemental source for Nd (using high temperature effusion cell). No additional oxygen was supplied during growth as TTIP also supplies oxygen.
In this presentation, we will present a detailed structural and electrical characterization of oxide heterostructures formed of a ultra thin (~1 - 5 nm) NdTiO3 films, sandwiched between SrTiO3(001) grown on (La0.3Sr0.7)(Al0.65Ta0.35)O3(001) (LSAT) and SrTiO3(001) substrates using the hybrid MBE technique. High-resolution x-ray diffraction (HRXRD) of ~1.3 nm (from grazing-incidence x-ray reflectivity) NdTiO3 films grown on LSAT (001) with a ~3 nm SrTiO3 buffer, and a ~3 nm capping layer, confirmed phase pure, epitaxial, NdTiO3 films in the (110) orientation on LSAT(001). HRXRD revealed that all the NdTiO3 films remain under compressive strain on LSAT(001) with an out-of-plane lattice parameter (as a sensitive probe to stoichiometry and relaxation) of 3.99 Å for nearly stoichiometric films, which further decreases with increasing Ti/Nd beam flux ratio. Atomic force microscopy confirmed atomically smooth film surfaces with root mean square roughness of ~ 0.1 nm. Resistivity and Hall measurements on ~3 nm STO/~1.3 nm NdTiO3/~3 nm STO/LSAT(001) heterostructure, reveal room temperature resistivity of 3 x 104 Omega;/sq, n-type carriers at a remarkably high concentration of ~1.1 × 1014 cm-2, and a Hall mobility of about ~2 cm2V-1s-1. We will discuss these results in the context of extremely high-density 2DEGs formation at the polar/nonpolar NdTiO3(Ti3+)/SrTiO3(Ti4+) interfaces. Finally, temperature dependent transport and magnetotransport studies will be described in detail as a function of NdTiO3 thickness, and will be related to the influence of cation non-stoichiometry, strain and growth rates of NdTiO3 films grown on different substrates.
[1] Y. Okimoto et.al., Phys. Rev. B., 51, 9561, 1995
11:30 AM - P5.06
Enhancing Electronic Reconstruction at a Complex Oxide-Interface
Daesung Park 1 James Mudd 1 Marc Walker 1 Aleksander Krupski 1 Sean McMitchell 1 Chris McConville 1
1University of Warwick Coventry United Kingdom
Show AbstractTwo-dimensional (2D) conducting interface between two complex oxides with perovskite structures, e. g. LaAlO3 (LAO) and single-terminated SrTiO3 (STO), has been paid a great deal of attention for the advancement of novel oxide-optoelectronics. [Nature 427, 423 (2004)] The nature of this interface between two band insulators has been under much debate to explain the origin of the observed interface conductivity based on intrinsic and extrinsic mechanisms (electronic reconstruction, oxygen deficiency, and intermixing phase). In the interest of this study, the intentional control of the Ti valence electrons (3+/4+) is explored by incorporating an extremely light element (e.g. boron, B) in to the LAO lattice forming La(BxAl1-x)O with the intention of enhancing the quantity of 2DEG at the heterointerface. Furthermore, the electrostatic potential can be modulated with the enhancement of polarization mainly arising from built-in strain. In order to investigate those effects, LBAO films have been grown on TiO2-terminated STO (001) substrate as a function of B concentration (x = 0, 0.02, 0.05, 0.1, and 0.2) using pulsed laser deposition (PLD) in oxygen-rich ambient (to avoid extrinsic oxygen defects near the interface region). The electronic structure of the modulated interfaces has been characterized for changes in the valence band edge using monochromatic x-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS) and scanning tunneling spectroscopy (STS). In addition, temperature dependent Hall-effect measurements have also been carried out to examine the variation of sheet resistance with different B distribution across the interface region. We demonstrate here control of the interface conductivity depending on critical thickness and B concentration.
Presenting author: [email protected]
Corresponding author: [email protected]
11:45 AM - P5.07
Extreme Carrier Concentrations and Metallic Conduction in Thin LaTiO3 Films
Ke Zou 1 Fred Walker 1 Charles Ahn 1
1Yale University New Haven USA
Show AbstractEmergent electronic properties in oxide heterostructures formed by Mott insulators and band insulators, such as superconductivity and magnetism, have attracted significant research interest. In this talk, we report precise atomic layer growth of a Mott insulator LaTiO3 on a conventional band insulator (LaAlO3)0.3(Sr2AITaO6)0.7 by molecular beam epitaxy. Because of the lattice mismatch, thin LaTiO3 films have an in-plane compressive strain of ~2.5%. Extremely high carrier concentrations of sim;1015/cm2 and metallic conduction have been observed in LaTiO3 films that are only a few nm thick. We discuss the thickness dependence of the electronic properties and explore possible applications of these heterostructures.
12:00 PM - *P5.08
Band Gap Engineering of SrTiO3 and Related Double Perovskites from First Principles
Jeffrey B. Neaton 1
1Lawrence Berkely National Laboratory Berkeley USA
Show AbstractThe ability to tune the electronic structure of perovskite oxides is of significant interest in areas ranging from superconductivity to thermoelectricity to solar energy conversion. For example, SrTiO3 (STO) has been long explored in solar water splitting applications due to its favorable flat-band potentials and stability against degradation in water. However, its indirect optical gap of 3.2 eV is too large for efficient light harvesting in the solar spectrum. In this talk, I will describe theoretical calculations, based on first-principles density functional theory and many-body perturbation theory, demonstrating how epitaxial strain can be used to significantly reduce the band gap of STO. Additionally, we introduce a new class of related, as-yet unmade V5+ and Cr6+ double perovskite compounds with low band gaps spanning much of the visible spectrum. Finally, we explore the effects of oxygen vacancies and epitaxial layering on the structure and electronic properties of (SrTiO3)n(SrFeO3-x)1 superlattices, showing that for small n, the band gaps of these systems can be reduced below that of STO. For each of these systems, our results will be thoroughly discussed in the context of contemporary experiments.
12:30 PM - P5.09
A Two-Dimensional Electron Gas in Modulation Doped SrTiO3
Adam Paul Kajdos 1 Daniel Ouellette 2 Tyler Cain 1 Susanne Stemmer 1
1UC Santa Barbara Santa Barbara USA2UC Santa Barbara Santa Barbara USA
Show AbstractTwo-dimensional electron gases (2DEGs) in complex oxide heterostructures command
considerable interest by exhibiting phenomena arising from strong electron correlations, such as
superconductivity and magnetism. Most studies have so far focused on 2DEGs at polar/nonpolar
interfaces between nonpolar SrTiO3 and polar LaAlO3, GdTiO3, or LaTiO3, where mobile charge carriers are generated by a polar discontinuity. This leads to large carrier densities, on the order of 3×1014 cm-2, which are fixed by the density of surface unit cells at the interface. An alternative method for creating a 2DEG is modulation doping, which was originally developed for III-V heterostructures with great success but has not yet been applied to complex oxides. This approach utilizes a doped larger-band-gap semiconductor to transfer mobile charge carriers to an undoped, smaller-band-gap semiconductor, where the charge carrier mobility is higher due to the absence of ionized dopants.
We present a 2DEG in SrTiO3 created via modulation doping by interfacing undoped SrTiO3 with a larger-band-gap material, SrTi1-xZrxO3, which is doped n-type. All layers were grown using hybrid molecular beam epitaxy. The growth of SrTi1-xZrxO3 was realized with the addition of a metalorganic precursor for Zr, zirconium tert-butoxide, leading to stoichiometric films that could be doped with La without losing mobile charge carriers to defect-related trapping. In-situ reflection high-energy electron diffraction (RHEED) patterns for all SrTi1-xZrxO3 films are streaky and exhibit intensity oscillations with time, indicating layer-by-layer growth of
atomically smooth films. X-ray diffraction (XRD) 2theta;-omega; scans in the vicinity of the SrTiO3 (002) reflection show a single, separate (002) peak for SrTi1-xZrxO3 films and clearly defined Laue oscillations.
Magnetoresistance measurements of modulation doped heterostructures at temperatures
down to 0.45 K and magnetic fields up to 14 T indicate that electrons are transferred into the
SrTiO3, and a 2DEG is formed. Tilting experiments show that Shubnikov-de Haas oscillations depend only on the perpendicular magnetic field, confirming the two-dimensional confinement of carriers in the SrTiO3. Experimental Shubnikov-de Haas oscillations are compared with calculations, and discrepancies are discussed. Using a multicarrier model for the Hall coefficient, we argue that all mobile charge carriers in the SrTiO3 give rise to magnetoresistance oscillations, in contrast to prior studies of 2DEGs in SrTiO3, where up to 60-95% of mobile charge carriers do not give rise to oscillations
12:45 PM - P5.10
Electronic Transport in Quasi-2D Electron Gases with Extreme Carrier Concentration
Craig Eaton 1 Jarrett A Moyer 2 Roman Engel-Herbert 1
1The Pennsylvania State University University Park USA2University of Illinois at Urbana-Champaign Urbana USA
Show AbstractOxide heterostructures have attracted a lot of attention due to the wealth of phenomena emerging at the interfaces. Recent efforts have been devoted to two-dimensional electron gases (2DEG) forming as a result of an electronic reconstruction originated by the polar discontinuity at polar oxide interfaces. Besides LaAlO3-SrTiO3 [1] interfaces, the existence of a 2DEG has been demonstrated on LaTiO3-SrTiO3 [2], LaVO3-SrTiO3 [3], LaGaO3-SrTiO3 [4], GdTiO3-SrTiO3 [5] and NdGaO3-SrTiO3 [6]. In all cases the sheet carrier concentrations of 2DEGs formed at these interfaces were below the upper limit of 3.5×1014 cm-2 in correspondence to the ideal value of 1/2 electron per unit cell to compensate the polar discontinuity. Exceeding these sheet carrier concentrations to study electronic transport phenomena in 2DEGs with extreme carrier concentrations requires another approach that overcomes this intrinsic limit.
Here we present the growth of SrTiO3/SrVO3/SrTiO3 heterostructures on (La0.3Sr0.7)(Al0.65Ta0.35)O3 [LSAT] substrates by hybrid molecular beam epitaxy, where strontium was supplied using a conventional effusion cell and transition metals titanium and vanadium from the metal-organic precursor titanium-isopropoxide and vanadium oxi-tri-isopropoxide, respectively. Here, the interfaces between SrTiO3 and SrVO3 are non-polar and carrier confinement in the correlated metal SrVO3 (d1 configuration, 1 electron per unit cell) is achieved using insulating SrTiO3 as barrier. Growth challenges associated with the differences of the self-regulated growth window of SrTiO3 and optimal growth conditions for SrVO3 to ensure stoichiometry of both oxide thin films as well as sequential growth by hybrid MBE using different metalorganic precursor sources is discussed. We report the structural quality determined by X-ray diffraction and temperature dependent transport properties attained for a series of SrTiO3/SrVO3/SrTiO3 heterostructures with SrVO3 thicknesses ranging from 30nm down to 1nm. Whereas in the thick film limit very low resistivities of around 2×10-6 ohm-cm were achieved at low temperature one order of magnitude decrease in the conductivity was found for SrVO3 of around 10 nm thickness. The trends will be discussed in terms of stoichiometry, interface scattering and band width reduction through dimensional confinement.
Financial support was provided by ONR through Grant No. N00014-11-1-0665 and the National Science Foundation through the Penn State MRSEC program DMR-0820404.
[1] A. Ohtomo, and H.Y. Hwang, Nature 427, 423 (2004).
[2] A. Ohtomo, D. A. Muller, J. L. Grazul, and H.Y. Hwang, Nature 419, 378 (2002).
[3] Y. Hotta, T. Susaki, H.Y. Hwang, Phys. Rev. Lett. 99, 236805 (2007).
[4] P. Perna, D. Maccariello, M. Radovic, et.al., Appl. Phys. Lett. 97, 152111 (2007).
[5] P. Moetakef, J.Y. Zhang, A. Kozhanov, et. al. Appl. Phys. Lett. 98, 112110 (2011).
[6] U.S. di Uccio, C. Aruta, C. Cantoni, et.al. e-print arXiv:1206.5083v1.
Symposium Organizers
Kirk H. Bevan, McGill University
Sohrab Ismail-Beigi, Yale University
T. Zac Ward, Oak Ridge National Laboratory
Zhenyu Zhang, University of Science and Technology of China
Symposium Support
MDC Vacuum Products, LLC
NBM Design Inc.
Princeton Scientific Corp.
PVD Products
Quantum Design, Inc.
STAIB Instruments
SURFACE Systems amp; Technologies GmbH amp; Co. KG
P8: Strongly Correlated Thin Films III
Session Chairs
Kirk H. Bevan
Changgan Zeng
Thursday PM, December 05, 2013
Hynes, Level 2, Room 201
2:30 AM - P8.01
Polarons in Perovskitic Oxides: Bulk vs Surface
Paul Erhart 1 Andreas Klein 2
1Chalmers University of Technology Gothenburg Sweden2Technische Universitamp;#228;t Darmstadt Darmstadt Germany
Show AbstractSelf-trapping of charge carriers is a well-known phenomenon in various halides. It has also been discussed with respect to several wide band gap oxides. Such polaronic carriers are formed when an electronic state couples to the lattice. For large coupling the self-trapped carrier is strongly localized and the lattice distortion is confined to a small volume. These so-called "small" polarons usually migrate via hopping mechanisms and their occurrence has therefore a significant impact on the electronic transport properties.
We have investigated the formation and electronic structure of both self-trapped holes and electrons in several perovskitic oxides. To this end we have carried out density functional theory calculations and ab-initio molecular dynamics simulations based on a combination of conventional exchange-correlation functionals and local potentials as well as hybrid exchange-correlation functionals. We demonstrate that in the bulk self-trapping of holes is typically rather weak compared to e.g., the alkali halides. The self-trapped hole is centered on just one oxygen ion and associated with rather small lattice distortions. At the surface the geometric constraints are relaxed and as a result self-trapping is considerably stronger. We have identified the atomic and electronic structure as well as the energetics of self-trapped carriers at the surfaces of several oxides. Based on this information we have identified generic trends and features. The implications of surface charge trapping for the interpretation of recent experimental results will be discussed.
2:45 AM - P8.02
The Strain Effect of Orbital Polarization in Nickelate Superlattices
Hyowon Park 1 2 Andrew J Millis 2 Chris A Marianetti 1
1Columbia University New York USA2Columbia University New York USA
Show AbstractWe study the orbital polarization in nickelate superlattices due to strain effects of substrates using density functional and dynamical mean field theory methods.
Superlattices consist of four unit-cell layers of metallic LaNiO3 and four unit-cell insulating layers of LaAlO3 for the compressive strain or GdScO3 for the tensile strain.
We show that the strain effect alone produces the Jahn-Teller distortion of the Ni-O octahedra and thereby the orbital polarizations are also pronounced.
Consistent with the recent x-ray absorption and resonant reflectivity experimental data, the compressive strain and the tensile strain have the different signs of orbital polarizations and the 3z2-r2 orbital is more occupied in the inner layers of four Ni layers which is realized by the rearrangement of the apical oxygen atoms.
3:00 AM - *P8.03
Computing the Phase Stability of Rare-Earth Nickelates via DFT+DMFT
Chris Marianetti 1 Hyowon Park 1 Andrew Millis 1
1Columbia University New York USA
Show AbstractComputing the total energy of strongly correlated electron systems is necessary for predicting the behavior at oxide interfaces. Density functional theory (DFT) is known to qualitatively break down when describing certain aspects of transition metal-oxides, including both electronic and structural features. These deficiencies can be remedied with a dual variable theory which combines DFT and the dynamical mean-field theory (ie. DFT+DMFT). Here we use DFT+DMFT to calculate the total energy of the various rare earth nickelates as a function of pressure and temperature. The inclusion of full charge self-consistency within a plane-wave basis, in addition to numerically exact solution of the DMFT impurity problem, yields some of the most complex total energy DFT+DMFT calculations that have been achieved to date. We show that DFT+DMFT produces the correct experimental ground states of the various rare-earth nickelates, namely the bond-length disproportionated structures for rare-earth elements with sizes smaller than La. The rare-earth element versus pressure phase diagram of the metal-insulator transition and the structural transition reveals that DFT+DMFT correctly captures the qualitative features of the experimental phase diagram. Applications to various oxide interfaces are also discussed.
3:30 AM - P8.04
Structural Origin of Ferromagnetism at Insulating Interfaces between LaMnO3 and SrTiO3
Hans M. Christen 1 Hyun Sik Kim 1 2 Manuel Roldan 1 Maria Varela 1 Mike Biegalski 1 Wolter Siemons 1 Ho Nyung Lee 1 Haile Ambaye 1 Valeria Lauter 1 Arturas Vailinois 3 Shuai Dong 4 Elbio Dagotto 1 4
1Oak Ridge National Laboratory Oak Ridge USA2Micron Technology, Inc. Boise USA3Stanford University Stanford USA4University of Tennessee Knoxville USA
Show AbstractThe emergence of interfacial properties in complex oxides, such as magnetic order or electronic conduction, provides an exciting path to the creation of novel functional materials, as well as a platform to test our predictions of such materials&’ behaviors. Here we report the formation of a ferromagnetic and insulating interface between paramagnetic SrTiO3 and antiferromagnetic LaMnO3 in pulsed-laser-deposition grown superlattices, with a magnetization of > 2.5 mu;B/Mn within a region of ~3 unit cells from the interface. Data will be shown from a broad range of measurements, including SQUID magnetometry on systematically varied superlattices, polarized neutron reflectometry to show the precise location of the ordered magnetic moments, extended x-ray absorption fine structure (EXAFS) to probe in-plane and out-of-plane Mn-O-Mn bond lengths and angles, electron transport that demonstrates the insulating nature of the interfaces, and scanning transmission electron microscopy (STEM). In particular, annular bright field STEM is capable of accurately detecting the positions of oxygen atoms, and shows the coherence of octahedral tilts, while local electron energy loss spectroscopy (EELS) indicates the absence of charge transfer between neighboring Mn and Ti ions. In combination, these experiments demonstrate that the coherence of structural distortions (i.e., octahedral tilt patterns) in LaMnO3/SrTiO3 superlattices leads to structurally induced ferromagnetism, clearly distinct from the behavior of mixed-valent manganites. These observations are important in the interpretation of interfacial effects in any perovskite heterostructure.
Research supported by the U.S. Department of Energy (DOE), Basic Energy Sciences (BES), Materials Sciences and Engineering Division, and performed in part at ORNL&’s Spallation Neutron Source (SNS) and Center for Nanophase Materials Sciences (CNMS), as well as at SLAC&’s Stanford Synchrotron Radiation Lightsource (SSRL), which are also sponsored by DOE-BES. M.R. is supported by the European Research Council Starting Investigator Award program.
4:30 AM - P8.06
Achieving Orbital Polarization in Nickelate Heterostructures
Ankit S Disa 1 Divine P Kumah 1 Andrei Malashevich 1 Hanghui Chen 1 Sohrab Ismail-Beigi 1 Fred J Walker 1 Charles H Ahn 1 2
1Yale University New Haven USA2Yale University New Haven USA
Show AbstractIn transition metal oxides, orbital polarization can enhance correlation effects, leading to anisotropic conductivity and novel magnetic orderings. Furthermore, many theoretical models posit that orbital polarization in cuprates may be crucial to the emergence of high-temperature superconductivity. Thus, there has been recent interest in developing systematic control over orbital polarization in correlated oxide systems. Here, we present a method to achieve large orbital polarizations in perovskite nickelates using artificial superlattices. From both experimental measurements and ab initio claculations comparing the atomic and electronic structure of bulk, thin film, and heterostructured nickelates, we elucidate the role of structural distortions in breaking orbital degeneracy. From these results, we propose a novel three-dimensional nickelate superlattice that demonstrates significant orbital symmetry breaking. The resulting electronic structure resembles that of the parent cuprate compounds and may lead to the emergence of unique electronic phases in nickelates.
4:45 AM - P8.07
Current Conduction around Nanodomain Inversion Dot in Lithium Tantalate Single Crystal Studied by Using C-AFM and SNDM
Yasuo Cho 1
1Tohoku University Sendai Japan
Show AbstractConduction at domain walls has attracted much interest recently among researchers in the field of ferroelectric materials due to anticipation of applications for future nanosized electronic devices. Conduction in the domain walls of BiFeO3 thin film[1], Pb(Zr0.2Ti0.8)O3 thin film[2] and thick LiNbO3 single crystal with super-bandgap light illumination [3] has been reported, and the potential for device applications that exploit these conducting features has been discussed. These experiments were conducted using conductive atomic force microscopy (C-AFM) and piezoresponse force microscopy (PFM). C-AFM measures the local current flow and PFM reveals the domain structures of samples. Although the aim of these studies is nanoscale electronics applications, the sizes of the measured domains were on the micrometer scale and the detected domain wall thickness and width of the current passage were also larger than 50 nm. As only one exception, Maksymovych et al. have reported that, in Pb(Zr0.2Ti0.8)O3 thin film, nanodomain shows metallic conductance without temperature dependence, while the conductivity of extended (large-) domain walls is thermally activated.[4] However, in the paper, the relationship between precisely (and actually) measured the dimension of domain and conduction current has not been revealed. Therefore, the domain wall conduction behavior has been still ambiguous for smaller domain sizes, such as that in the order of a few tens of nanometers. Therefore, we need the more experimental data for many kinds of ferroelectric materials to make deeper discussions. Moreover, although LiTaO3 is one of the most industrially utilized ferroelectric materials, domain wall conduction of LiTaO3 has been not been reported.
In this study, we investigate the current conduction related to nanodomain dots formed in congruent LiTaO3 single crystal thin films with the thickness of 51nm using C-AFM combined with scananing nonliear dielectric microscopy (SNDM). For relatively large nanodomain dots (ca. 100 nm diameter), a weak flowing current was detected at the domain wall under application of +0.5 V dc voltage to the sample. However, for smaller nanodomain dot sizes (<40 nm), the current flows over the entire area of the nanodomain dot (and not at the domain wall). Moreover, a nanodot area (15nm diameter) with an unusually stronger SNDM signal than that of the original surface was observed, where the current flow was relatively large. Finally, Schottky-like rectifying current flow was observed in a nanodomain inversion dot and the behavior was not related to the dot size.
This is the first report on current conduction around nanodomain inversion dots in a LiTaO3 single crystal thin film.
[1] J. Seidel , et al., Nat. Mater., 8, pp. 229 - 234 (2009)
[2] J. Guyonnet et al., Adv. Mater., 23, pp. 5377-5382 (2011)
[3] M. Schröder et al., Adv. Funct. Mater., 22, pp.3936-3944 (2012)
[4] P. Maksymovych et al., Nano Lett., 12, pp209-2013 (2011)
5:00 AM - P8.08
Engineering Correlation Effects via Artificially Designed Oxide Superlattices
Hanghui Chen 1 2 Chris Marianetti 2 Andrew Millis 1
1Columbia University New York USA2Columbia University New York USA
Show AbstractAb initio calculations are used to predict that a superlattice composed of layers of LaTiO3 and LaNiO3 alternating along the [001] direction is a S=1 Mott insulator with large magnetic moments on the Ni sites, negligible moments on the Ti sites and a charge transfer gap set by the energy difference between Ni-d and Ti-d states, distinct from conventional Mott insulators. Correlation effects are enhanced on the Ni sites via filling the oxygen p states and reducing the Ni-O-Ni bond angle. Small hole (electron) doping of the superlattice leads to a two-dimensional single-band situation with holes (electrons) residing on Ni d_{x^2-y^2} (Ti d_{xy}) orbital and coupled to antiferromagnetically correlated spins in the NiO2 layer.
5:15 AM - P8.09
Surface Structure, Screening Effects, and Electronic States of LaNiO3 Thin Films from First Principles
Andrei Malashevich 1 Sohrab Ismail-Beigi 1
1Yale University New Haven USA
Show AbstractAmong bulk perovskite rare-earth nickelates, lanthanum nickelate (LaNiO3), which has the largest rare-earth ion, is the only member that remains a paramagnetic metal down to the lowest temperatures. This is in contrast to the remaining nickelates that have antiferromagnetic ground states and display a metal-insulator transition (MIT) as a function of temperature. Nevertheless, a thickness-dependent MIT has been observed in thin films of nickelates and specifically in LaNiO3. This is of significant interest as heterostructures of LaNiO3 have been proposed to emulate the electronic properties of high-temperature cuprate superconductors which has spurred a great deal of recent activity in the field. The majority of studies have focused on nickelates in bulk and superlattice form with fewer studies on thin films.
We describe first-principles results based on density-functional theory for (001)-oriented LaNiO3 thin films. We analyze the relation between their atomic-scale structure and electronic states as well as the thickness dependence of these properties. This includes structural distortions near the surface as well as at the interface with the substrate (e.g., polar displacements or NiO6 octahedral rotations and tilts). A number of these distortions are associated with the fact that, based on formal charge counting, the stoichiometric (001) films are polar. We will describe how screening via combined ionic relaxation and electronic redistribution operates in the near-surface region.
5:30 AM - P8.10
Origins of the Insulator-Metal Transition in SmNiO3 Epitaxial Thin Films
Rafael Jaramillo 1 Sieu D Ha 2 Shriram Ramanathan 2
1MIT Cambridge USA2Harvard University Cambridge USA
Show AbstractThe rare-earth nickelates (RNiO3) are appealing candidates for the growing number of proposed applications of functional layers in oxide electronics. RNiO3 are also a testing ground for our understanding of strongly interacting electrons on the verge of localization. RNiO3 feature an insulator-metal transition (IMT, at TIM) that varies from 0 to 600 K. TIM and the electronic correlation in the metal phase can be tuned by cation substitution, epitaxial strain, or dimensionality control. A physical explanation of the electronic phase diagram remains elusive.
We report an infrared spectroscopic study of the electronic structure of SmNiO3 epitaxial thin films. By measuring with fine temperature steps across TIM we track the evolution of spectral features associated with the metallic and insulating phases. Furthermore, by varying oxygen content we observe how the metallic phase adjusts to chemical disorder.
We find that the interaction between lattice distortions and the Ni-O bond covalence is responsible for the IMT in SmNiO3. This interaction nimbly shifts spectral weight (SW) over the large energy scale established by the Ni-O orbital interaction, as observed experimentally at TIM both here and elsewhere. The changes in atomic configuration that are responsible for the SW shift are identified as breathing and bending modes that are well defined phonons for T < TIM, but merge into the coherent electronic response for T > TIM. The bandgap for T < TIM merges into a Holstein side-band for T > TIM, identifying SmNiO3 as a polaronic conductor (but not a polaronic insulator). Our results support the emerging experimental consensus on the crystal structure of all RNiO3 for T < TIM by experimentally connecting particular lattice distortions to the electronic structure [1]. We also find support in new theories of RNiO3 that emphasize the role played by Ni-O covalence and local atomic configuration [2, 3]. Our results also draw striking connections between electron-phonon coupling and bad metal conductivity observed in some complex electron oxides including the cuprates and the manganites.
[1] Alonso et al. Phys. Rev. B 87, 18411 (2013).
[2] Park, Millis and Marianetti, Phys. Rev. Lett. 109, 156402 (2012).
[3] Lau and Millis, Phys. Rev. Lett. 110, 126404 (2013).
5:45 AM - P8.11
Resonant X-Ray Studies of NdNiO3 Heterostructures
Divine P Kumah 1 Ankit Disa 1 Joseph H Ngai 1 Hanghui Chen 1 Sohrab Ismail-Beigi 1 Fred Walker 1 Charles H Ahn 1
1Yale University New Haven USA
Show AbstractCorrelated complex oxide systems exhibit interesting spin, charge, and orbital degrees of freedom that are strongly coupled to their atomic-scale structure. This link is important for the rare earth nickelates, which exhibit first order metal-insulator transitions, antiferromagnetism, and charge ordering. Using a combination of resonant synchrotron diffraction, x-ray absorption spectroscopy, and first principles theoretical calculations, we study the coupling between atomic-scale structural distortions and the electronic and magnetic phase transitions in strained NdNiO3 thin films and NdNiO3/NdAlO3 superlattices grown using molecular beam epitaxy. Temperature dependent studies of the atomic and electronic structure are used to understand the effects of doping and dimensionality in controlling charge disproportionation at the metal-insulator transition in NdNiO3 heterostructures.
P7: Emergent Oxide 2DEG Properties III
Session Chairs
Thursday AM, December 05, 2013
Hynes, Level 2, Room 201
9:30 AM - P7.01
Synthesis of Artificial LaAlO3/SrTiO3 Interfaces by Pulsed-Laser Deposition: Towards Functional Superlattices
Stefano Gariglio 1 Danfeng Li 1 Alexandre Fete 1 Daniela Stornaiuolo 1 Claudia Cancellieri 1 Jean-Marc Triscone 1
1University of Geneva Geneva Switzerland
Show AbstractThe recent discovery of a two-dimensional electron gas (2DEG) formed at the interface between the two band insulators LaAlO3 and SrTiO3 [1] has generated significant interest because of its intriguing electronic properties [2], tunable superconductivity and rich phase diagram [3]. This interface naturally provides a versatile system to artificially build stacks of multiple 2D superconductors that would allow coupled 2D superconducting layers to be studied. Experimental efforts have been made to realize such superlattices. However, clear signatures in transport measurements of multiple parallel 2DEGs are still missing. One main obstacle is to preserve metallic behavior of the interface with LaAlO3 grown on an artificial SrTiO3 film [4]. Here, we grow SrTiO3 of different thicknesses under different growth conditions to demonstrate that the surface-termination and the film quality both appear to be essential to preserve the 2DEG. Our findings suggest that by controlling the top surface termination of the SrTiO3 layers and optimizing the SrTiO3 growth conditions, the 2DEG can be maintained, offering an approach to realize “genuine” LaAlO3/SrTiO3 multilayers.
[1] A. Ohtomo, H. Y. Hwang, Nature 427, 423 (2004).
[2] J. Mannhart, D. G. Schlom, Science 327, 1607 (2010).
[3] A. D. Caviglia et al., Nature 456, 624 (2008).
[4] C. W. Bark et al., PNAS 108, 4720 (2011).
9:45 AM - P7.02
Angular Dependence of Magnetoresistance in SrTiO3 Quantum Wells
Clayton Adam Jackson 1 Susanne Stemmer 1
1University of California, Santa Barbara Santa Barbara USA
Show AbstractSrTiO3 is a band insulator that is ubiquitous in oxide electronics, while GdTiO3 and SmTiO3 are ferrimagnetic and antiferromagnetic Mott insulators, respectively. SrTiO3/GdTiO3} and SrTiO3}/SmTiO3 interfaces show two-dimensional electron gases (2DEGs) with charge densities on the order of 3x1014 cm-2 per interface. Due to the staggered band alignment, the carriers reside in the SrTiO3. These 2DEGs exhibit many unique properties, including correlation effects, superconductivity and ferromagnetism. In this presentation, we will report on the angular dependence of the magnetoresistance in GdTiO3}/SrTiO3/GdTiO3 and SmTiO3/SrTiO3}/SmTiO3 extreme-carrier-density (6x1014 cm-2) quantum well structures. Both longitudinal and transverse magnetoresistance in GdTiO3/SrTiO3/GdTiO3 are hysteretic, while no hysteresis is found down to 2 K for SmTiO3/SrTiO3/SmTiO3. This supports the notion that the magnetism of the 2DEG is a proximity effect induced by the ferrimagnetic GdTiO3}. Negative magnetoresistance is found in both types of samples, and is discussed in the context of coupling of the 2DEGs with the ferrimagnetic and antiferromagnetic insulators.
We report on detailed studies of the relationship between the transverse and longitudinal magnetoresistance and the angles between current and magnetic field in-plane and between the plane of the film and magnetic field, respectively, in the GdTiO3/SrTiO3/GdTiO3 system. The data are analyzed in the context of spin Hall magnetoresistance and anisotropic magnetoresistance, respectively. Spin Hall magnetoresistance is a proximity effect induced at the interface between a conductor and an insulating ferromagnet. The observed effect in the GdTiO3/SrTiO3/GdTiO3 system is several orders of magnitude larger than documented observations of spin Hall magnetoresistance, as much as 0.25% in the longitudinal and 20% in the transverse orientations. We discuss the magnitude of this effect in terms of the quantum well geometry of the structure, the parallel magnetization in the two layers, and spin-orbit coupling in the SrTiO3.
10:00 AM - *P7.03
Magnetic Materials Based on Defects, Interfaces and O2p Holes
George A. Sawatzky 1
1University of British Columbia Vancouver Canada
Show AbstractIdeas based on theory and some experiments will be presented regarding possible new magnetic materials based on extended and point defects (1), interface engineering (2), anion substitution in oxides and hole and electron doping of oxides. The concentration will be on rather ionic oxides mostly not involving conventional magnetic elements. Special attention will also be placed on surface and interface effects involving polar surfaces as well as on the role of doped holes in O2p in charge transfer gap oxides. O2p holes play an extremely important role in the magnetism and superconductivity of oxides and new results will be presented regarding the ferromagnetic exchange coupling they introduce in transition metal oxides(3) and the interplay between transport properties, magnetic order and the general phase diagrams of materials involving O2p holes either in the so called self doped case of stochiometric oxides or in chemically substituted systems and cation or anion vacancies.
1. I. S. Elfimov, S. Yunoki, and G. A. Sawatzky PRL 89, 216403, (2002)
2. N. Pavlenko, T. Kopp, E.Y. Tsymbal, G.A. Sawatzky, J. Mannhart PRB 85, 020407, (2012)
3. Bayo Lau, Mona Berciu and George A. Sawatzky, PRL 106, 036401 (2011)
4. Berciu and G. A. Sawatzky, PRB 79, 195116 (2009)
10:30 AM - P7.04
Probing High-Density Two-Dimensional Electron Gases at Oxide Interfaces via Resonant Tunneling
Santosh Raghavan 1 S. James Allen 2 Susanne Stemmer 1
1University of California Santa Barbara USA2University of California Santa Barbara USA
Show AbstractThe realization of two dimensional electron gases (2DEG) at complex oxide interfaces such as SrTiO3/LaAlO3 and SrTiO3/GdTiO3 has led to the observation of novel phenomena such as superconductivity and ferromagnetism at these interfaces. A complete understanding of the complex transport phenomena at these oxide interfaces remains a challenge. Shubnikov de-Haas experiments and theoretical modeling of these interfaces show that multiple electronic subbands are involved in the transport and are primarily derived from the Ti-3d t2g states. In this presentation, we demonstrate the use of resonant tunneling to study the subband structure of high electron density 2DEGs with ~ 3×10^14 cm^-2 of mobile charge at the interface between two insulating materials, the band insulator SrTiO3 and the Mott insulator GdTiO3, respectively. We present the out-of-plane current-voltage (I-V) characteristics of SrTiO3/GdTiO3/SrTiO3 junctions fabricated from high quality molecular beam epitaxy (MBE) grown thin films. Here, the GdTiO3 serves at a tunnel barrier between the two 2DEGs that form at each SrTiO3/GdTiO3 interface. Temperature-dependent I-V measurements exhibit evidence of resonant tunneling between the two slightly asymmetric and spatially separated 2DEGs. We will demonstrate the use of dI/dV and d2I/dV2 profiles to understand the subband characteristics and to determine the subband spacing of the 2DEGs at these interfaces. We show that the subband properties estimated from our tunnel experiments are in excellent agreement with the results from recent DFT and tight-binding models of these interfaces published in the literature, indicating the presence of a low lying dxy sub-band which carries the highest amount of carriers, separated substantially in energy from higher lying dxz,yz states, followed by a large number of closely spaced higher energy levels. The subband spacing of the two asymmetric 2DEGs is used to show experimental evidence of the effect of charge carrier density on the confinement. We will show that the presence of compressive strain in our oxide heterostructures further confines the dxy subband and leads to further separation from the dxz,yz states. We discuss the importance of spin-orbit coupling at these interfaces which leads to mixing between the xy,yz and xz character of the t2g-orbitals and its implications in the interpretation of our results. We will also discuss the temperature-dependence of the results.
10:45 AM - P7.05
The Origin of Conductivity at SrTiO3/LaAlO3 Interface: Polar Catastrophe Model, Interfacial Cation Anti-Site Defects or Surface O Vacancies
Liping Yu 1 2 Alex Zunger 1
1University of Colorado at Boulder Boulder USA2National Renewable Energy Laboratory Golden USA
Show AbstractThe physical mechanisms responsible for the formation of a two-dimensional electron gas (2DEG) at the SrTiO3/LaAlO3 interface are still under intensive debate. The three leading scenarios are (i) ionization of the LAO valence band (“electronic reconstruction” via the polar catastrophe), (ii) transfer of charge from oxygen vacancies at LAO surface to the STO/LAO interface, or (iii) ionization of interfacial cation anti site defects ( “atomic reconstruction”). In this talk, we present hybrid functional electronic structure calculations of the formation enthalpies and defect ionization energies of various defects at the STO/LAO interface as well as at the LAO vacuum-surface. We address the points on (1) what causes the 2DEG at the interface (2) Why the observed interface carrier density is always one order smaller than that expected from pure electronic reconstruction model within polar catastrophe scenario? In particular, the role and coupling of the current three mechanisms in accounting for the formation of the 2DEG phenomena will be discussed. (This work is supported by the DOE Energy Frontier Research Center "Center for Inverse Design.")
11:30 AM - P7.06
Comparative Analysis of 2-Dimensional Electron Gases in Polar-Nonpolar Oxide Interfaces
Fabio Miletto Granozio 1 4 Carmela Aruta 1 Emiliano Di Gennaro 4 1 Alessandro Gadaleta 5 2 Amit Khare 1 Daniele Marre 5 2 Davide Massarotti 4 1 Ilaria Pallecchi 2 5 Muhammad Riaz 4 1 Umberto Scotti di Uccio 4 1 Francesco Tafuri 6 1 Claudia Cantoni 3
1CNR-SPIN Napoli Napoli Italy2CNR-SPIN Genova Genova Italy3Oak Ridge National Laboratory Oak Ridge USA4Universitamp;#224; Federico II di Napoli Napoli Italy5Universitamp;#224; di Genova Genova Italy6Seconda Universitamp;#224; di Napoli Aversa Italy
Show AbstractThe properties of the 2-dimensional electron gases (2DEGs) found at LaAlO3/SrTiO3, LaGaO3/SrTiO3 [1] and NdGaO3/SrTiO3 [2,3] interfaces are addressed and compared. In order to minimize the presence of oxygen vacancies, high oxygen pressure conditions (10-1 mbars [4]) for our pulsed laser deposition process are explored. Interfaces based on the respective amorphous counterparts, prepared according to [5], are also investigated. While in crystalline samples the formation of the 2DEG is attributed to the electronic reconstruction mechanism, conductivity in amorphous interfaces is attributed to the presence of oxygen vacancies.
Our investigations is based on a wide number of complementary techniques, including: variable temperature magneto-transport properties performed down to the superconducting/magnetic state; persistent photoconductivity effects, both under UV and visible light; a STEM/EELS analysis of the Ti3+ density profiles and of the polar distortions [6]; a number of advanced spectroscopic techniques, applied both in tabletop experiments and at synchrotron facilities.
All the investigated epitaxial polar-nonpolar interfaces exhibit a remarkably similar response under the application of our diversified set of investigation tools. Preliminary data about the complex pattern of experimental results emerging from the comparison of crystalline and amorphous interfaces are also discussed.
[1] P. Perna et., Appl. Phys. Lett. 97, 259901, (2010)
[2] C. Aruta et al., Appl. Phys. Lett.101, 031602 (2012)
[3] U. Scotti di Uccio et al, arXiv:1206.5083v1
[4] E. Di Gennaro et al, submitted to Adv. Opt. Mat.
[5] Y. Chen et al., Nano Lett. 11, 3774 (2011)
[6] C. Cantoni et al., Adv. Mater. 24, 3952 (2012)
11:45 AM - P7.07
Symmetry-Lowering in Extreme Electron Density SrTiO3 Quantum Wells
Jack Zhang 1 Jinwoo Hwang 1 Santosh Raghavan 1 Susanne Stemmer 1
1University of California Santa Barbara Santa Barbara USA
Show AbstractStrong electron correlations are responsible for a wealth of properties that exist in the perovskite materials, such as superconductivity and Mott metal-insulator transitions. In this presentation, we discuss the role of extreme electron densities in driving a structural transition in narrow SrTiO3 quantum wells, in the context of short-range Coulomb interactions.
SrTiO3 has the ideal cubic structure and no electrons in the d-band. When interfaced with rare earth titanates (such as GdTiO3), a high-density (~3×1014 cm-2) two-dimensional electron gas (2DEG) is formed, which resides in the d-bands of SrTiO3. By growing SrTiO3 quantum wells sandwiched between GdTiO3 layers, the 3D electron density in the SrTiO3 can be controlled by varying the SrTiO3 thickness to extreme electron densities not achievable by conventional doping. This allows for the study of the effects of extreme electron densities in a model system where strong correlations are not present in the bulk.
Using atomic resolution scanning transmission electron microscopy, we measure cation displacements in SrTiO3 quantum wells grown between GdTiO3 and SmTiO3. Such displacements are absent in bulk SrTiO3, but are present in the orthorhombic space group (Pbnm) of the interfacing rare earth titanate. These displacements are caused by cations rearranging to their local anion environment, a result of the large oxygen octahedral tilts in the orthorhombic structure. By characterizing the cation displacements as the angle formed between three successive cations, we show that SrTiO3 quantum wells below 2 unit cells undergo a distortion to an orthorhombic-like structure, while those above 2 unit cells remain bulk-like, at the precise thickness that a metal-insulator transition occurs in transport measurements for the GdTiO3/SrTiO3/GdTiO3 system. We show that the symmetry change is not a result of interfacial coupling (the structural changes necessary to maintain oxygen connectivity is accommodated in the GdTiO3), nor a result of interfacial roughness (from intensity measurements, as well as characterization of identifiable intermixed layers). SrTiO3 quantum wells interfaced with SmTiO3 (which have smaller octahedral tilts) show smaller cation displacements, and a metal-insulator transition was not observed. Our observations provide convincing evidence for a strong electron correlation driven effect, demonstrates the success of recent efforts in creating an artificial Mott insulator in a material that was originally a band insulator, and supports recent density functional theory that octahedral rotations are critical in promoting an insulating state.
12:00 PM - *P7.08
First-Principles Simulations of Exciton Dissociation at ZnO/Polymer Interface
Guangfen Wu 1 Zi Li 1 Gang Lu 1
1California State University Northridge Northridge USA
Show AbstractEfficient exciton dissociation at the donor/acceptor interface is crucial in high-performance organic-inorganic hybrid solar cells. Using first-principles simulations with van del Waals dispersion corrections, we have studied exciton dissociation dynamics at P3HT/ZnO donor/acceptor interface. We find that the incorporation of the dispersion correction plays an important role in predicting reliable interfacial structures. The time-dependent density functional theory (with a range-separated exchange-correlation functional) as well as non-adiabatic ab initio molecular dynamics are used to simulate the dynamics of exciton dissociation at the oxide/polymer interface, including both interfacial charge-transfer (CT) excitons, intra- and inter-molecular excitons at P3HT. We find that the charge separation depends on the energy difference and wave-function overlap between the CT and intramolecular excitons. The phonon modes responsible for exciton dissociation are identified. While both intramolecular and intermolecular excitons contribute to the interfacial charge separation, the former play a much more prominent role. The intramolecular exciton states adiabatically couple to the CT exciton states, while the intermolecular excitons can also relax to the low-lying intramolecular exciton states. We predict that lowering the CT exciton energy by introducing interfacial modifiers or increasing the donor exciton energy with more disordered P3HT molecules are two possible means to enhance exciton dissociation at P3HT/ZnO interface.
The work was supported by the NSF and ONR.
12:30 PM - P7.09
Interfacial Charge Ordering in (LaMnO3)2n / (SrMnO3)n Superlattices
Victor Pardo 1 Antia S. Botana 1 Jose Luis Lado 1 Daniel Baldomir 1
1Universidade Santiago de Compostela Santiago de Compostela Spain
Show AbstractRecently it has been reported that the manganite superlattices (LaMnO3)2n / (SrMnO3)n show a metal-insulator transition for n > 3. Here, based on ab initio calculations, we show that a possible mechanism to explain why the interfaces become insulating at that particular thickness is an electronic reconstruction phenomenon at the interface. When n becomes sufficiently large to have two bulk-like LaMnO3 and SrMnO3 insulating blocks separated by an interface, the mixed-valent Mn cations at the interface find it energetically favorable to form a charge-ordered layer rather than a metallic Mn(3.5+) layer. This Mn(3+) / Mn(4+) charge ordered checkerboard pattern leads to a gap opening at the Fermi level for multilayers with n > 3 where this pattern can be sustained.
We will show how for n < 3 the interface is always metallic and compare this results with other oxide superstructures and other systems where charge ordering occurs and place this work in the context of other interfacial electronic reconstruction phenomena that have been shown recently in various oxide materials.
12:45 PM - P7.10
Oxygen Chemical Diffusion across Epitaxial Oxide Interfaces: A Mixed Electronic Ionic Semiconductor Model
Jaume Roqueta 1 Alexandra Apostolidis 1 Julienne Chaigneau 1 Roberto Moreno 1 James Zapata 1 Monica Burriel 2 Jose Santiso 1 3
1Institut Catala de Nanociencia i Nanotecnologia (ICN2) Bellaterra Spain2Imperial College of London London United Kingdom3Consejo Superior de Investigaciones Cientamp;#237;ficas (CSIC) Bellaterra Spain
Show AbstractIn this work we describe a formalism to qualitatively understand chemical diffusion across epitaxial interfaces based on expanding charge transport equations of standard semiconductors to simultaneously include electron-hole and ionic interstitials-vacancy carriers. The incorporation of oxide defects as a second kind of mobile carriers with its corresponding band structure (or energy levels) is found to explain basic defect chemistry of these materials. Moreover, by referring electronic and ionic energy levels to a common vacuum level enables us to picture the epitaxial junctions as a combined electronic and ionic band diagram problem. We performed numerical integration of the transport equations to simulate the flow of electronic-ionic carriers between film and substrate when the film is exposed to sudden changes in oxygen gas partial pressures. We also provide band diagrams which are in correspondence with simulations. We found that this model is able to reproduce a variety of experimental results of the electric conductivity relaxation measurements on epitaxial films of La2NiO4 on NdGaO3 and SrTiO3 single crystal substrates when exposed to high temperatures and varying oxygen partial pressures. Since thin epitaxial oxide films and multilayers are generally deposited at high temperatures, where oxide defects mobility might become non negligible, we believe that this model can be of a wider interest to determine the role of oxide ionic defects and electronic charge transfer across interfaces, which may be essential to control their multifunctional properties.