Tarapada Sarkar

Electron Transport at the TiO2 Surfaces of Rutile, Anatase, and Strontium Titanate: The Influence of Orbital Corrugation

The two-dimensional electron gas in SrTiO3 created by an overlayer of amorphous LaAlO3 is compared with those at the TiO2-terminated surfaces of rutile and anatase. Differences in conductivity are explained in terms of the limiting Ti-O-Ti bond angles (orbital corrugation), band dispersion, and polaron formation. At 300 K, the sheet conductivity and mobility of anatase exceed those for SrTiO3 or rutile by one or two orders of magnitude, respectively. The electrons in rutile become localized below 25 K.

Unexpected observation of spatially separated Kondo scattering and ferromagnetism in Ta alloyed anatase TiO2 thin films.

We report the observation of spatially separated Kondo scattering and ferromagnetism in anatase Ta0.06Ti0.94O2 thin films as a function of thickness (10–200 nm). The Kondo behavior observed in thicker films is suppressed on decreasing thickness and vanishes below ~25 nm. In 200 nm film, transport data could be fitted to a renormalization group theory for Kondo scattering though the carrier density in this system is lower by two orders of magnitude, the magnetic entity concentration is larger by a similar magnitude and there is strong electronic correlation compared to a conventional system such as Cu with magnetic impurities. However, ferromagnetism is observed at all thicknesses with magnetic moment per unit thickness decreasing beyond 10 nm film thickness. The simultaneous presence of Kondo and ferromagnetism is explained by the spatial variation of defects from the interface to surface which results in a dominantly ferromagnetic region closer to substrate-film interface while the Kondo scattering is dominant near the surface and decreasing towards the interface. This material system enables us to study the effect of neighboring presence of two competing magnetic phenomena and the possibility for tuning them.

The effect of oxygen vacancies on water wettability of transition metal based SrTiO3 and rare-earth based Lu2O3

Understanding the structural, physical and chemical properties of the surface and interfaces of different metal-oxides and their possible applications in photo-catalysis and biology is a very important emerging research field. Motivated in this direction, this article would enable understanding of how different fluids, particularly water, interact with oxide surfaces. We have studied the water contact angle of 3d transition metal oxide thin films of SrTiO3, and of 4f rare-earth oxide thin films of Lu2O3. These metal oxides were grown using pulsed laser deposition and they are atomically flat and with known orientation and explicitly characterized for their structure and composition. Further study was done on the effects of oxygen vacancies on the water contact angle of the 3d and 4f oxides. For 3d SrTiO3 oxide with oxygen vacancies, we have observed an increase in hydroxylation with consequent increase of wettability which is in line with the previous reports whereas an interesting opposite trend was seen in the case of rare-earth Lu2O3 oxide. Density functional theory simulations of water interaction on the above mentioned systems have also been presented to further substantiate our experimental findings.

Fermi surface reconstruction and anomalous low-temperature resistivity in electron-doped La2−xCexCuO4

We report ab-plane Hall Effect and magnetoresistivity measurements on La2-xCexCuO4 thin films as a function of doping for magnetic fields up to 14T and temperatures down to 1.8K. A dramatic change in the low temperature (1.8 K) normal state Hall coefficient is found near a doping Ce=0.14. This, along with a nonlinear Hall resistance as a function of magnetic field, suggests that the Fermi surface reconstructs at a critical doping of Ce= 0.14. A competing antiferromagnetic phase is the likely cause of this Fermi surface reconstruction. Low temperature linear-in-T resistivity is found at Ce=0.14, but anomalously, also at higher doping. We compare our data with similar behavior found in hole-doped cuprates at a doping where the pseudogap ends

Effect of Nb and Ta substitution on donor electron transport and ultrafast carrier dynamics in anatase TiO2 thin films

Ta and Nb substituted TiO2 are important transparent conducting oxides that have potential for applications in photovoltaics, photocatalysis, and water splitting/CO2 sequestration. In addition to donating electrons, what are the effects of Nb and Ta substitution? Here we observe strong experimental evidence that Ta and Nb substitution induces large and small polarons in anatase TiO2 epitaxial thin films. The degenerate donor electrons (from both Nb and Ta) show a high temperature T3 dependence on electrical resistivity, which confirms the presence of large polarons, along with room temperature metallic transport. This is further confirmed by the enhancement in the electron effective mass, which was estimated from thermopower measurements. Femtosecond transient absorption (fs-TA) reveals the life time of the Ti-t2g and eg levels and the separation of these levels are consistent with the X-ray absorption spectroscopy (XAS) measurement. In addition, fs-TA reveals the presence of small polarons with a life time substantially >1 ns, which arises from defect levels and is a consequence of Ta and Nb substitution. X-ray photoelectron spectroscopy (XPS) provides evidence of Ti3+, which may be identified as the defects responsible for the small polarons. These long-lived small polarons may provide a way to minimize recombination dynamics in TiO2-based electrodes for photo-excited devices.

Compensated thermal conductivity of metallically conductive Ta-doped TiO2

Electrical and thermal conductivities of epitaxial, high-quality Ta-doped TiO2 (Ta:TiO2) thin films were experimentally investigated in the temperature range of 35–375 K. Structurally identified as the anatase phase, degenerate Ta doping leads to high electrical conductivity in TiO2, reaching >105 (Ω-m)−1 at 5 at. % of Ta, making it a potential candidate for indium-free transparent conducting oxides. In stark contrast, Ta doping suppresses the thermal conductivity of TiO2 via strong phonon-impurity scattering imposed by the Ta dopant which has a high mass contrast with Ti that it substitutes. For instance, the near-peak value shows a >50% reduction, from 9.0 down to 4.4 W/m-K, at just 2 at. % doping at 100 K. Interestingly, further Ta doping beyond 2 at. % no longer reduces the measured total thermal conductivity, which is attributed to a high electronic contribution to thermal conduction that compensates the alloy-scattering loss, as well as possibly the renormalization of phonon dispersion relation in the heavy doping regime originating from doping-induced lattice stiffening. As a result, at high Ta doping, TiO2 exhibits high electrical conductivity without much degradation of thermal conductivity. For example, near room temperature, 5 at. % Ta doped TiO2 shows over 3 orders of magnitude enhancement in electrical conductivity from undoped TiO2, but with only less than 10% reduction in thermal conductivity. The metallic Ta:TiO2 maintaining reasonable good thermal conductivity might find application in energy devices where good conduction to both charge and heat is needed.

Magnetic Modes in Rare Earth Perovskites: A Magnetic-Field-Dependent Inelastic Light Scattering study

Here, we report the presence of defect-related states with magnetic degrees of freedom in crystals of LaAlO3 and several other rare-earth based perovskite oxides using inelastic light scattering (Raman spectroscopy) at low temperatures in applied magnetic fields of up to 9 T. Some of these states are at about 140 meV above the valence band maximum while others are mid-gap states at about 2.3 eV. No magnetic impurity could be detected in LaAlO3 by Proton-Induced X-ray Emission Spectroscopy. We, therefore, attribute the angular momentum-like states in LaAlO3 to cationic/anionic vacancies or anti-site defects. Comparison with the other rare earth perovskites leads to the empirical rule that the magnetic-field-sensitive transitions require planes of heavy elements (e.g. lanthanum) and oxygen without any other light cations in the same plane. These magnetic degrees of freedom in rare earth perovskites with useful dielectric properties may be tunable by appropriate defect engineering for magneto-optic applications.