T. Venkatesan

Electronic phase separation at the LaAlO3/SrTiO3 interface

There are many electronic and magnetic properties exhibited by complex oxides. Electronic phase separation (EPS) is one of those, the presence of which can be linked to exotic behaviours, such as colossal magnetoresistance, metal-insulator transition and high-temperature superconductivity. A variety of new and unusual electronic phases at the interfaces between complex oxides, in particular between two non-magnetic insulators LaAlO(3) and SrTiO(3), have stimulated the oxide community. However, no EPS has been observed in this system despite a theoretical prediction. Here, we report an EPS state at the LaAlO(3)/SrTiO(3) interface, where the interface charges are separated into regions of a quasi-two-dimensional electron gas, a ferromagnetic phase, which persists above room temperature, and a (superconductor like) diamagnetic/paramagnetic phase below 60 K. The EPS is due to the selective occupancy (in the form of 2D-nanoscopic metallic droplets) of interface sub-bands of the nearly degenerate Ti orbital in the SrTiO(3). The observation of this EPS demonstrates the electronic and magnetic phenomena that can emerge at the interface between complex oxides mediated by the Ti orbital.

Niobium doped TiO2: Intrinsic transparent metallic anatase versus highly resistive rutile phase

We report on the structural, electrical, and optical properties of 5% niobium doped TiO2 thin films grown on various substrates by pulsed laser deposition. The epitaxial anatase Nb:TiO2 film on LaAlO3 is shown to be an intrinsic transparent metal and its metallic property arises from Nb substitution into Ti site as evidenced by the Rutherford backscattering channeling result. In contrast, the rutile Nb:TiO2 thin films show insulating behaviors with 2–3 orders higher room temperature electrical resistivity and ∼30 times lower mobility. A blueshift in the optical absorption edge is observed in both phases, though of differing magnitude.

Graphene Oxides as Tunable Broadband Nonlinear Optical Materials for Femtosecond Laser Pulses

Graphene oxide (GO) thin films on glass and plastic substrates were found to display interesting broadband nonlinear optical properties. We have investigated their optical limiting activity for femtosecond laser pulses at 800 and 400 nm, which could be tuned by controlling the extent of reduction. The as-prepared GO films were found to exhibit excellent broadband optical limiting behaviors, which were significantly enhanced upon partial reduction by using laser irradiation or chemical reduction methods. The laser-induced reduction of GO resulted in enhancement of effective two-photon absorption coefficient at 400 nm by up to ∼19 times and enhancement of effective two- and three-photon absorption coefficients at 800 nm by ∼12 and ∼14.5 times, respectively. The optical limiting thresholds of partially reduced GO films are much lower than those of various previously reported materials. Highly reduced GO films prepared by using the chemical method displayed strong saturable absorption behavior.

Magnetism in MoS2 induced by proton irradiation

Molybdenum disulphide, a diamagnetic layered dichalcogenide solid, is found to show magnetic ordering at room temperature when exposed to a 2 MeV proton beam. The temperature dependence of magnetization displays ferrimagnetic behavior with a Curie temperature of 895 K. A disorder mode corresponding to a zone-edge phonon and a Mo valence higher than +4 has been detected in the irradiated samples using Raman and x-ray photoelectron spectroscopy, respectively. The possible origins of long-range magnetic ordering in irradiated MoS2 samples are discussed.

Origin of the Two-Dimensional Electron Gas at LaAlO3=SrTiO3 Interfaces: The Role of Oxygen Vacancies and Electronic Reconstruction

The relative importance of atomic defects and electron transfer in explaining conductivity at the crystalline LaAlO3/SrTiO3 interface has been a topic of debate. Metallic interfaces with similar electronic properties produced by amorphous oxide overlayers on SrTiO3 have called in question the original polarization catastrophe model. We resolve the issue by a comprehensive comparison of (100)-oriented SrTiO3 substrates with crystalline and amorphous overlayers of LaAlO3 of different thicknesses prepared under different oxygen pressures. For both types of overlayers, there is a critical thickness for the appearance of conductivity, but its value is always 4 unit cells (around 1.6 nm) for the oxygen-annealed crystalline case, whereas in the amorphous case, the critical thickness could be varied in the range 0.5 to 6 nm according to the deposition conditions. Subsequent ion milling of the overlayer restores the insulating state for the oxygen-annealed crystalline heterostructures but not for the amorphous ones. Oxygen post-annealing removes the oxygen vacancies, and the interfaces become insulating in the amorphous case. However, the interfaces with a crystalline overlayer remain conducting with reduced carrier density. These results demonstrate that oxygen vacancies are the dominant source of mobile carriers when the LaAlO3 overlayer is amorphous, while both oxygen vacancies and polarization catastrophe contribute to the interface conductivity in unannealed crystalline LaAlO3/SrTiO3 heterostructures, and the polarization catastrophe alone accounts for the conductivity in oxygen-annealed crystalline LaAlO3/SrTiO3 heterostructures. Furthermore, we find that the crystallinity of the LaAlO3 layer is crucial for the polarization catastrophe mechanism in the case of crystalline LaAlO3 overlayers.

Switchable Ultrathin Quarter-wave Plate in Terahertz Using Active Phase-change Metasurface.

Metamaterials open up various exotic means to control electromagnetic waves and among them polarization manipulations with metamaterials have attracted intense attention. As of today, static responses of resonators in metamaterials lead to a narrow-band and single-function operation. Extension of the working frequency relies on multilayer metamaterials or different unit cells, which hinder the development of ultra-compact optical systems. In this work, we demonstrate a switchable ultrathin terahertz quarter-wave plate by hybridizing a phase change material, vanadium dioxide (VO2), with a metasurface. Before the phase transition, VO2 behaves as a semiconductor and the metasurface operates as a quarter-wave plate at 0.468 THz. After the transition to metal phase, the quarter-wave plate operates at 0.502 THz. At the corresponding operating frequencies, the metasurface converts a linearly polarized light into a circularly polarized light. This work reveals the feasibility to realize tunable/active and extremely low-profile polarization manipulation devices in the terahertz regime through the incorporation of such phase-change metasurfaces, enabling novel applications of ultrathin terahertz meta-devices.

Oxygen electrocatalysis on (001)-oriented manganese perovskite films: Mn valency and charge transfer at the nanoscale

We report that the oxygen reduction reaction (ORR) activities of (001)-oriented manganese perovskite films decrease from 10 to 1 nm by more than an order of magnitude, which can be attributed to the barrier associated with interfacial band bending that impedes electron transfer to the electrolyte, and reduction of Mn3+ due to charge transfer from the Nb:SrTiO3 substrate. Furthermore, we show by substitution in La1−x(Ca,Sr)xMnO3 that Mn3+, not Mn4+, is the active valence state for ORR.

Metal-insulator transition in SrTiO(3-x) thin films induced by frozen-out carriers.

Z. Q. Liu, D. P. Leusink, X. Wang, W. M. Lü, K. Gopinadhan, A. Annadi, Y. L. Zhao, X. H. Huang, S. W. Zeng, Z. Huang, A. Srivastava, S. Dhar, T. Venkatesan, and Ariando1,2∗ NUSNNI-Nanocore, Department of Physics, Department of Electrical and Computer Engineering, National University of Singapore, Singapore and Faculty of Science and Technology and MESA Institute for Nanotechnology, University of Twente, 7500 AE Enschede, The Netherlands (Dated: January 13, 2013)

Enhanced cytotoxicity to cancer cells by mitochondria-targeting MWCNTs containing platinum(IV) prodrug of cisplatin

Among the arsenal of nano-materials, carbon nanotubes (CNTs) are becoming more prominent due to favorable attributes including their unique shape, which promotes cellular-uptake, and large aspect-ratio that facilitates functionalization of bioactive molecules on their surface. In this study, multi-walled carbon nanotubes (MWCNTs) were functionalized with either mitochondrial-targeting fluorescent rhodamine-110 (MWCNT-Rho) or non-targeting fluorescein (MWCNT-Fluo). Despite structural similarities, MWCNT-Rho associated well with mitochondria (ca. 80% co-localization) in contrast to MWCNT-Fluo, which was poorly localized (ca. 21% co-localization). Additionally, MWCNT-Rho entrapping platinum(IV) pro-drug of cisplatin (PtBz) displayed enhanced potency (IC50 = 0.34 ± 0.07 μM) compared to a construct based on MWCNT-Fluo (IC50 ≥ 2.64 μM). Concurrently, preliminary in vitro toxicity evaluation revealed that empty MWCNT-Rho neither decreased cell viability significantly nor interfered with mitochondrial membrane-potential, while seemingly being partially expelled from cells. Due to its targeting capability and apparent lack of cytotoxicity, MWCNT-Rho complex was used to co-encapsulate PtBz and a chemo-potentiator, 3-bromopyruvate (BP), and the resulting MWCNT-Rho(PtBz+BP) construct demonstrated superior efficacy over PtBz free drug in several cancer cell lines tested. Importantly, a 2-fold decrease in mitochondrial potential was observed, implying that mitochondrial targeting of compounds indeed incurred additional intended damage to mitochondria.

Highly Active Epitaxial La(1-x)Sr(x)MnO3 Surfaces for the Oxygen Reduction Reaction: Role of Charge Transfer.

Most studies of oxide catalysts for the oxygen reduction reaction (ORR) use oxide powder, where the heterogeneity of exposed surfaces and the composite nature of electrodes limit fundamental understanding of the reaction mechanism. We present the ORR activity of epitaxially oriented La(1-x)Sr(x)MnO3 surfaces and investigate, by varying Sr substitution, the relationship between the role of charge transfer and catalytic activity in an alkaline environment. The activity is greatest for La(1-x)Sr(x)MnO3 with 33% Sr, containing mixed Mn(3+/4+), and the (110) and (111) orientations display comparable activities to that of the (001). Electrochemical measurements using the facile redox couple [Fe(CN)6](3-/4-) illustrate that increasing ORR activity trends with faster charge-transfer kinetics, indicating the importance of facile charge transfer at the oxide/water interface and mixed Mn valence in promoting ORR kinetics.