KTaO3 -The New Kid on the Spintronics Block.

Long after the heady days of high-temperature superconductivity, the oxides came back into the limelight in 2004 with the discovery of the 2D electron gas (2DEG) in SrTiO3 (STO) and several heterostructures based on it. Not only do these materials exhibit interesting physics, but they have also opened up new vistas in oxide electronics and spintronics. However, much of the attention has recently shifted to KTaO3 (KTO), a material with all the "good" properties of STO (simple cubic structure, high mobility, etc.) but with the additional advantage of a much larger spin-orbit coupling. In this state-of-the-art review of the fascinating world of KTO, it is attempted to cover the remarkable progress made, particularly in the last five years. Certain unsolved issues are also indicated, while suggesting future research directions as well as potential applications. The range of physical phenomena associated with the 2DEG trapped at the interfaces of KTO-based heterostructures include spin polarization, superconductivity, quantum oscillations in the magnetoresistance, spin-polarized electron transport, persistent photocurrent, Rashba effect, topological Hall effect, and inverse Edelstein Effect. It is aimed to discuss, on a single platform, the various fabrication techniques, the exciting physical properties and future application possibilities of this family of materials.

A Reduction in Particle Size Generally Causes Body-Centered-Cubic Metals to Expand but Face-Centered-Cubic Metals to Contract.

From a careful analysis of existing data as well as new measurements, we show that the size dependence of the lattice parameters in metal nanoparticles with face-centered cubic (fcc) and body-centered cubic (bcc) symmetries display opposite trends: nanoparticles with fcc structure generally contract with decreasing particle size, while those with bcc structure expand. We present a microscopic explanation for this apparently puzzling behavior based on first-principles simulations. Our results, obtained from a comparison of density functional theory calculations with experimental data, indicate that the nanoparticles are capped by a surface monolayer of oxygen atoms, which is routinely detected by surface-sensitive techniques. The bcc- and fcc-based nanoparticles respond in contrasting fashion to the presence of the oxygen capping layer, and this dictates whether the corresponding lattice parameter would increase or decrease with size reduction. The metal-oxygen bonds at the surface, being shorter and stronger than typical metal-metal bonds, pull the surface metal atoms outward. This outward movement of surface atoms influences the core regions to a larger extent in the relatively open bcc geometry, producing a rather large overall expansion of the cluster, compared to the bulk. In case of fcc clusters, on the other hand, the outward movement of surface metal atoms does not percolate too far inside, resulting in either a smaller net expansion or contraction of the cluster depending on the extent of surface oxygen coverage. Our study therefore provides a convincing physicochemical basis for the correlation between the underlying geometry and the nature of change of the lattice parameters under size reduction.

Is There a Lower Size Limit for Superconductivity?

The ultimate lower size limit for superconducting order to exist is set by the "Anderson criterion"-arising from quantum confinement-that appears to be remarkably accurate and universal. We show that carefully grown, phase-pure, nanocrystalline bcc-Ta remains superconducting (with ordering temperature, TC ≈ 0.9 K) down to sizes 40% below the conventional estimate of the Anderson limit of 4.0 nm. Further, both the TC and the critical magnetic field exhibit an unusual, nonmonotonic size dependence, which we explain in terms of a complex interplay of quantum size effects, surface phonon softening, and lattice expansion. A quantitative estimation of TC within first-principles density functional theory shows that even a moderate lattice expansion allows superconductivity in Ta to persist down to sizes much lower than the conventional Anderson limit, which can be traced to anomalous softening of a phonon due to its coupling with electrons. This appears to indicate the possibility of bypassing the Anderson criterion by suitable crystal engineering and obtaining superconductivity at arbitrarily small sizes, an obviously exciting prospect for futuristic quantum technologies. We take a critical look at how the lattice expansion modifies the Anderson limit, an issue of fundamental interest to the study of nanoscale superconductivity.

Local structure, composition, and crystallization mechanism of a model two-phase "composite nanoglass".

We report a detailed study of the local composition and structure of a model, bi-phasic nanoglass with nominal stoichiometry Cu55Nb45. Three dimensional atom probe data suggest a nanoscale-phase-separated glassy structure having well defined Cu-rich and Nb-rich regions with a characteristic length scale of ≈ 3 nm. However, extended x-ray absorption fine structure analysis indicates subtle differences in the local environments of Cu and Nb. While the Cu atoms displayed a strong tendency to cluster and negligible structural order beyond the first coordination shell, the Nb atoms had a larger fraction of unlike neighbors (higher chemical order) and a distinctly better-ordered structural environment (higher topological order). This provides the first experimental indication that metallic glass formation may occur due to frustration arising from the competition between chemical ordering and clustering. These observations are complemented by classical as well as ab initio molecular dynamics simulations. Our study indicates that these nanoscale phase-separated glasses are quite distinct from the single phase nanoglasses (studied by Gleiter and others) in the following three respects: (i) they contain at least two structurally and compositionally distinct, nanodispersed, glassy phases, (ii) these phases are separated by comparatively sharp inter-phase boundaries, and (iii) thermally induced crystallization occurs via a complex, multi-step mechanism. Such materials, therefore, appear to constitute a new class of disordered systems that may be called a composite nanoglass.

Structural phase transitions in trigonal Selenium induce the formation of a disordered phase.

Arguments based on the Mermin-Wagner theorem suggest that the quasi-1D trigonal phase of Se should be unstable against long wavelength perturbations. Consisting of parallel Se-Se chains, this essentially fragile solid undergoes a partial transition to a monoclinic structure (consisting of 8-membered rings) at low temperatures (≈50 K), and to a distorted trigonal phase at moderate pressures (≈3GPa). Experimental investigations on sub-millimeter-sized single crystals provide clear evidence that these transitions occur via a novel and counter-intuitive route. This involves the reversible formation of an intermediate, disordered structure that appears as a minority phase with increasing pressure as well as with decreasing temperature. The formation of the disordered state is indicated by: (a) a 'Boson-peak' that appears at low temperatures in the specific heat and resonance Raman data, and (b) a decrease in the intensity of Raman lines over a relatively narrow pressure range. We complement the experimental results with a phenomenological model that illustrates how a first order structural transition may lead to disorder. Interestingly, nanocrystals of trigonal Se do not undergo any structural transition in the parameter space studied; neither do they exhibit signs of disorder, further underlining the role of disorder in this type of structural transition.

Nano-welding and junction formation in hydrogen titanate nanowires by low-energy nitrogen ion irradiation.

Crystalline hydrogen titanate (H2Ti3O7) nanowires were irradiated with N(+) ions of different energies and fluences. Scanning electron microscopy reveals that at relatively lower fluence the nanowires are bent and start to adhere strongly to one another as well as to the silicon substrate. At higher fluence, the nanowires show large-scale welding and form a network of mainly 'X' and 'Y' junctions. Transmission electron microscopy and Raman scattering studies confirm a high degree of amorphization of the nanowire surface after irradiation. We suggest that while ion-irradiation induced defect formation and dangling bonds may lead to chemical bonding between nanowires, the large scale nano-welding and junction network formation can be ascribed to localized surface melting due to heat spike. Our results demonstrate that low energy ion irradiation with suitable choice of fluence may provide an attractive route to the formation and manipulation of large-area nanowire-based devices.

A review of finite size effects in quasi-zero dimensional superconductors.

Quantum confinement and surface effects (SEs) dramatically modify most solid state phenomena as one approaches the nanometer scale, and superconductivity is no exception. Though we may expect significant modifications from bulk superconducting properties when the system dimensions become smaller than the characteristic length scales for bulk superconductors-such as the coherence length or the penetration depth-it is now established that there is a third length scale which ultimately determines the critical size at which Cooper pairing is destroyed. In quasi-zero-dimensional (0D) superconductors (e.g. nanocrystalline materials, isolated or embedded nanoparticles), one may define a critical particle diameter below which the mean energy level spacing arising from quantum confinement becomes equal to the bulk superconducting energy gap. The so-called Anderson criterion provides a remarkably accurate estimate of the limiting size for the destabilization of superconductivity in nanosystems. This review of size effects in quasi-0D superconductors is organized as follows. A general summary of size effects in nanostructured superconductors (section 1) is followed by a brief overview of their synthesis (section 2) and characterization using a variety of techniques (section 3). Section 4 reviews the size-evolution of important superconducting parameters-the transition temperature, critical fields and critical current-as the Anderson limit is approached from above. We then discuss the effect of thermodynamic fluctuations (section 5), which become significant in confined systems. Improvements in fabrication methods and the increasing feasibility of addressing individual nanoparticles using scanning probe techniques have lately opened up new directions in the study of nanoscale superconductivity. Section 6 reviews both experimental and theoretical aspects of the recently discovered phenomena of 'parity effect' and 'shell effect' that lead to a strong, non-monotonic size dependence of the superconducting energy gap and associated properties. Finally, we discuss in section 7 the properties of ordered heterostructures (bilayers and multilayers of alternating superconducting and normal phases) and disordered heterostructures (nanocomposites consisting of superconducting and normal phases), which are primarily controlled by the proximity effect.

The nature of the structural phase transition from the hexagonal (4H) phase to the cubic (3C) phase of silver.

The phase transition from the hexagonal 4H polytype of silver to the commonly known 3C (fcc) phase was studied in detail using x-ray diffraction, electron microscopy, differential scanning calorimetry and Raman spectroscopy. The phase transition is irreversible and accompanied by extensive microstructural changes and grain growth. Detailed scanning and isothermal calorimetric analysis suggests that it is an autocatalytic transformation. Though the calorimetric data suggest an exothermic first-order phase transition with an onset at 155.6 °C (for a heating rate of 2 K min(-1)) and a latent heat of 312.9 J g(-1), the microstructure and the electrical resistance appear to change gradually from much lower temperatures. The 4H phase shows a Raman active mode at 64.3 cm(-1) (at 4 K) that undergoes mode softening as the 4H → 3C transformation temperature is approached. A first-principles density functional theory calculation shows that the stacking fault energy of 4H-Ag increases monotonically with temperature. That 4H-Ag has a higher density of stacking faults than 3C-Ag, implies the metastability of the former at higher temperatures. Energetically, the 4H phase is intermediate between the hexagonal 2H phase and the 3C ground state, as indicated by the spontaneous transformation of the 2H to the 4H phase at -4 °C. Our data appear to indicate that the 4H-Ag phase is stabilized at reduced dimensions and thermally induced grain growth is probably responsible for triggering the irreversible transformation to cubic Ag.

A stable, quasi-2D modification of silver: optical, electronic, vibrational and mechanical properties, and first principles calculations.

We report the optical, electronic, vibrational and mechanical properties of a stable, anisotropic, hexagonal (4H) form of silver. First principles calculations based on density functional theory were used to simulate the phonon dispersion curves and electronic band structure of 4H-Ag. The phonon dispersion data at 0 K do not contain unstable phonon modes, thereby confirming that it is a locally stable structure. The Fermi surface of the 4H phase differs in a subtle way from that of the cubic phase. Experimental measurements indicate that, when compared to the commonly known face-centered cubic (3C) form of silver, the 4H-Ag form shows a 130-fold higher, strongly anisotropic, in-plane resistivity and a much lower optical reflectance with a pronounced surface plasmon contribution that imparts a distinctive golden hue to the material. Unlike common silver, the lower symmetry of the 4H-Ag structure allows it to be Raman active. Mechanically, 4H-Ag is harder, more brittle and less malleable. Overall, this novel, poorly metallic, anisotropic, darker and harder crystallographic modification of silver bears little resemblance to its conventional counterpart.

Multiferroic behavior in elemental selenium below 40 K: effect of electronic topology.

The quasi-one-dimensional, chiral crystal structure of Selenium has fascinating implications: we report simultaneous magnetic and ferroelectric order in single crystalline Se microtubes below ≈40 K. This is accompanied by a structural transition involving a partial fragmentation of the infinite chains without losing overall crystalline order. Raman spectral data indicate a coupling of magnons with phonons and electric field, while the dielectric constant shows a strong dependence on magnetic field. Our first-principles theoretical analysis reveals that this unexpected multiferroic behavior originates from Selenium being a weak topological insulator. It thus exhibits stable electronic states at its surface, and magnetism emerges from their spin polarization. Consequently, the broken two-fold rotational symmetry permits switchable polarization along its helical axis. We explain the observed magnetoelectric couplings using a Landau theory based on the coupling of phonons with spin and electric field. Our work opens up a new class of topological surface-multiferroics with chiral bulk structure.

Controlled clustering in metal nanorod arrays leads to strongly enhanced field emission characteristics.

We show that controlled clustering in electrochemically grown silver nanorods results in up to 50% enhancement in their field emission performance. Larger cluster size and nanorod length lead to a lower turn-on electric field, a higher current density and a larger enhancement factor. However, beyond a critical length (≈30 µm), the nanorods begin to form disordered ridges instead of well separated conical clusters and the field emission performance proceeds to deteriorate. With the help of finite element modelling, we show that a larger cluster size indeed leads to an enhanced electric field at the cluster edges, effectively reducing screening effects and thereby enhancing the field emission performance. Though our present work pertains to silver nanorods, a similar clustering of nanorods is observed in many types of electrochemically grown nanorods, and even in carbon nanotubes and Si nanowires grown by other techniques. Hence, we expect this study to have general applicability in the design of better nanorod-based field emitters.

Conjugation of cytochrome c with hydrogen titanate nanotubes: novel conformational state with implications for apoptosis.

We show that hydrogen titanate (H(2)Ti(3)O(7)) nanotubes form strongly associated reversible nano-bio-conjugates with the vital respiratory protein, cytochrome c. Resonance Raman spectroscopy along with direct electrochemical studies indicate that in this nano-bio-conjugate, cytochrome c exists in an equilibrium of two conformational states with distinctly different formal redox potentials and coordination geometries of the heme center. The nanotube-conjugated cytochrome c also showed enhanced peroxidase activity similar to the membrane-bound protein that is believed to be an apoptosis initiator. This suggests that such a nanotube-cytochrome c conjugate may be a good candidate for cancer therapy applications.

Novel hexagonal polytypes of silver: growth, characterization and first-principles calculations.

We report a study of the relative effects of dimensional and kinetic constraints on the stabilization of metastable, polytypic forms of metallic silver. We show that the hexagonal 4H polytype (hitherto observed only in size-constrained systems) can be produced in the form of bulk thin films by suitably slowing down the growth kinetics. Further, using extremely slow growth conditions, we have been successful in depositing a novel, two-dimensional, metastable polytype (2H) of silver, which is highly reactive (easily oxidized) and has a density 23% lower than normal silver. First-principles calculations based on density functional theory confirm that the 4H structure is relatively stable. However, local stability analysis via a determination of the phonon dispersion of the 2H structure reveals that it is only marginally stable with an energy surface that is rather flat or weakly varying with respect to many of the modes. This makes a large contribution to the configurational entropy and is probably the reason for the metastability of the observed 2H polytype with an unusually large lattice constant along the c-direction.

Growth of aligned ZnO nanorod arrays from an aqueous solution: effect of additives and substrates.

We report a simple, versatile, low cost fabrication technique for synthesizing nanorod arrays whose architecture is suited for many applications spanning the nanometer to micrometer range. Specifically, we have covered the range of nanorod diameter from 50 to 1200 nm. From a detailed study of the growth parameters involved in the synthesis of the ZnO nanorod arrays from an aqueous solution, we report, in particular, the effects of varying the capping agent, substrate and substrate-seeding. We find that seeding the substrate and selecting the appropriate capping agent play the most crucial roles in the alignment of nanorod arrays. Our study on the use of different precursor materials and varied substrates for the growth of ZnO nanorod arrays should lead to an enhanced understanding of the controllable growth of ZnO crystals and nanostructures.

Lattice size induced moment formation on isolated Fe atoms in nanocrystalline Nb.

Measurements of the local susceptibility and 3d spin relaxation rate for single Fe impurities embedded in a nanocrystalline Nb host indicates the emergence of a local moment on Fe at and below a critical size of 11 nm. Our ab initio electronic structure calculations show that the moment formation occurs due to Stoner enhancement arising from a size dependent lattice expansion and a consequent shift in the Fermi level. We also show that a size-induced positive host spin polarization of the Nb-4d band electrons strongly influences the fluctuation rate of the Fe moment.

Optimization of the morphology of ZnO nanorods grown by an electrochemical process.

Zinc oxide nanorods were synthesized by a direct electrodeposition technique on indium tin oxide plates. The effect of a systematic variation of the deposition potential and the inter-electrode distance on the morphology of ZnO nanorods was investigated. X-ray diffraction studies indicated that the nanorods are highly c-axis oriented. The diameter of the nanorods depends mainly on the deposition potential and the electrode separation. Our detailed study of the synthesis-morphology correlations provide the optimal electrochemical conditions required for oriented ZnO nanorods with minimum diameter.

Competing effects of surface phonon softening and quantum size effects on the superconducting properties of nanostructured Pb.

The superconducting transition temperature (T(C)) in nanostructured Pb decreases from 7.24 to 6.4 K as the particle size is reduced from 65 to 7 nm, below which superconductivity is lost rather abruptly. In contrast, there is a large enhancement in the upper critical field (H(C2)) in the same size regime. We explore the origin of the unusual robustness of T(C) over such a large particle size range in nanostructured Pb by measuring the temperature dependence of the superconducting energy gap in planar tunnel junctions of Al/Al(2)O(3)/nano-Pb. We show that below 22 nm, the electron-phonon coupling strength increases monotonically with decreasing particle size, and almost exactly compensates for the quantum size effect, which is expected to suppress T(C).

The influence of nanoscale phase separation and devitrification on the electrical transport properties of amorphous Cu-Nb alloy thin films.

The formation of amorphous phases in immiscible alloys with a large positive enthalpy of mixing is thermodynamically unfavorable. Co-sputter deposited Cu-Nb films exhibit a nanoscale phase separation into Cu-rich and Nb-rich amorphous regions. They show relatively high room temperature resistivity, a negative temperature coefficient of resistance (TCR), and an incomplete superconducting transition with onset at 3.7 K. Annealing the nanophase-separated amorphous films at 200 °C results in the nucleation of fcc Cu-rich nanocrystals within an Nb-rich amorphous matrix. This film exhibits multiple resistance steps, eventually showing a sharp drop with (T(C))(onset) = 3.7 K. Annealing at 350 °C leads to complete devitrification via the formation of large bcc Nb-rich grains encapsulating the existing fcc Cu nanocrystals. These films show low room temperature resistivity, positive TCR, and a sharp superconducting transition with onset at 5.2 K. The electrical transport and superconducting behavior appear to be consistent with a two-stage crystallization process.

Universal, geometry-driven hydrophobic behaviour of bare metal nanowire clusters.

A parallel array of isolated metal nanowires is expected to be hydrophilic. We show, however, that a clustering of such nanowires brought about by vacuum drying produces a 'dual-scale roughness' and confers a strongly hydrophobic property to the surface. The mean size of the nanowire clusters as well as the contact angle are both found to be related to the wire length, and the critical wire length above which the surface becomes hydrophobic is ≈10 µm. Surface roughness is generally known to enhance water-repellent properties, but this is the first report of roughness-induced hydrophobicity on a bare (uncoated) metallic surface.

Ultra-low breakdown voltage and origin of 1/f(2) noise in metallic nanorod arrays.

The application of a dc voltage to an array of copper nanorods causes field evaporation of atoms from the tips, resulting in their progressive sharpening and a further increase in the local field. The process is self-limited by the build-up of space charge on the nanorod tips. From an analysis of the conductance noise recorded across the nanorod array, we show that the conduction mechanism bears a strong analogy with the stick-slip problem in sliding friction. The in situ sharpening results in an unprecedented lowering of the breakdown voltage of air by over 90%, as compared to plane parallel electrodes.