Magnetotransport studies of Fe vacancy-ordered Fe4+δSe5 nanowires.

We studied the electrical transport of Fe4+δSe5 single-crystal nanowires exhibiting √5 × âˆš5 Fe-vacancy order and mixed valence of Fe. Fe4+δSe5 compound has been identified as the parent phase of FeSe superconductor. A first-order metal-insulator (MI) transition of transition temperature T MI ∼ 28 K is observed at zero magnetic fields (B). Colossal positive magnetoresistance emerges, resulting from the magnetic field-dependent MI transition. T MI demonstrates anisotropic magnetic field dependence with the preferred orientation along the c axis. At temperature T < ∼17 K, the state of near-magnetic field-independent resistance, which is due to spin polarized even at zero fields, preserves under magnetic fields up to B = 9 T. The Arrhenius law shift of the transition on the source-drain frequency dependence reveals that it is a nonoxide compound with the Verwey-like electronic correlation. The observation of the magnetic field-independent magnetoresistance at low temperature suggests it is in a charge-ordered state below T ∼ 17 K. The results of the field orientation measurements indicate that the spin-orbital coupling is crucial in √5 × âˆš5 Fe vacancy-ordered Fe4+δSe5 at low temperatures. Our findings provide valuable information to better understand the orbital nature and the interplay between the MI transition and superconductivity in FeSe-based materials.

Mode Dependency of Quantum Decoherence Studied via an Aharonov-Bohm Interferometer.

We investigate the dependence of decoherence on the mode number M in a multiple-mode Aharonov-Bohm (AB) interferometer. The design of the AB interferometer allows us to precisely determine M by the additivity rule of ballistic conductors; meanwhile, the decoherence rate is simultaneously deduced by the variance of the AB oscillation amplitude. The AB amplitude decreases and fluctuates with depopulating M. Moreover, the normalized amplitude exhibits a maximum at a specific M (∼9). Data analysis reveals that the charge-fluctuation-induced dephasing, which depends on the geometry and the charge relaxation resistance of the system, could play an essential role in the decoherence process. Our results suggest that the phase coherence, in principle, can be optimized using a deliberated design and pave one of the ways toward the engineering of quantum coherence.

Crystal phase-dependent nanophotonic resonances in InAs nanowire arrays.

Nanostructures have many material, electronic, and optical properties that are not found in bulk systems and that are relevant for technological applications. For example, nanowires realized from III-V semiconductors can be grown into a wurtzite crystal structure. This crystal structure does not naturally exist in bulk where these materials form the zinc-blende counterpart. Being able to concomitantly grow these nanowires in the zinc-blende and/or wurtzite crystal structure provides an important degree of control for the design and optimization of optoelectronic applications based on these semiconductor nanostructures. However, the refractive indices of this new crystallographic phase have so far not been elucidated. This shortcoming makes it impossible to predict and utilize the full potential of these new nanostructured materials for optoelectronics applications: a careful design and optimization of optical resonances by tuning the nanostructure geometry is needed to achieve optimal performance. Here, we report and analyze striking differences in the optical response of nanophotonic resonances in wurtzite and zinc-blende InAs nanowire arrays. Specifically, through reflectance measurements we find that the resonance can be tuned down to λ ≈ 380 nm in wurtzite nanowires by decreasing the nanowire diameter. In stark contrast, a similar tuning to below λ ≈ 500 nm is not possible in the zinc-blende nanowires. Furthermore, we find that the wurtzite nanowires can absorb twice as strongly as the zinc-blende nanowires. We attribute these strikingly large differences in resonant behavior to large differences between the refractive indices of the two crystallographic phases realized in these nanostructures. We anticipate our findings to be relevant for other III-V materials as well as for all material systems that manifest polytypism. Taken together, our results demonstrate crystal phase engineering as a potentially new design dimension for optoelectronics applications.

Large thermoelectric power factor enhancement observed in InAs nanowires.

We report the observation of a thermoelectric power factor in InAs nanowires that exceeds that predicted by a single-band bulk model by up to an order of magnitude at temperatures below about 20 K. We attribute this enhancement effect not to the long-predicted 1D subband effects but to quantum-dot-like states that form in electrostatically nonuniform nanowires as a result of interference between propagating states and 0D resonances.

Advanced TiO2/Al2O3 Bilayer ALD Coatings for Improved Lithium-Rich Layered Oxide Electrodes.

Surface modification is a highly effective strategy for addressing issues in lithium-rich layered oxide (LLO) cathodes, including phase transformation, particle cracking, oxygen gas release, and transition-metal ion dissolution. Existing single-/double-layer coating strategies face drawbacks such as poor component contact and complexity. Herein, we present the results of a low-temperature atomic layer deposition (ALD) process for creating a TiO2/Al2O3 bilayer on composite cathodes made of AS200 (Li1.08Ni0.34Co0.08Mn0.5O2). Electrochemical analysis demonstrates that TiO2/Al2O3-coated LLO electrodes exhibit improved discharge capacities and enhanced capacity retention compared with uncoated samples. The TAA-5/AS200 bilayer-coated electrode, in particular, demonstrates exceptional capacity retention (∼90.4%) and a specific discharge capacity of 146 mAh g-1 after 100 cycles at 1C within the voltage range of 2.2 to 4.6 V. The coated electrodes also show reduced voltage decay, lower surface film resistance, and improved interfacial charge transfer resistances, contributing to enhanced stability. The ALD-deposited TiO2/Al2O3 bilayer coatings exhibit promising potential for advancing the electrochemical performance of lithium-rich layered oxide cathodes in lithium-ion batteries.

Colorful InAs nanowire arrays: from strong to weak absorption with geometrical tuning.

One-dimensional nanostructure arrays can show fascinatingly different, tunable optical response compared to bulk systems. Here we study theoretically and demonstrate experimentally how to engineer the reflection and absorption of light in epitaxially grown vertical arrays of InAs nanowires (NWs). A striking observation is optically visible colors of the array, which we show can be tuned depending on the geometrical parameters of the array. Specifically, larger diameter NW arrays absorb light more effectively out to a longer wavelength compared to smaller diameter arrays. Thus, controlling the diameter provides a way to tune the optically observable color of an array. We also find that arrays with a larger amount of InAs material reflect less light (or absorb more light) than arrays with less material. On the basis of these two trends, InAs NW arrays can be designed to absorb light either much more or much less efficiently than a thin film of an effective medium containing the same amount of InAs as the NW array. The tunable absorption and low area filling factor of the NW arrays compared to thin film bode well for III-V photovoltaics and photodetection.

A study on Ti-doped Fe3O4 anode for Li ion battery using machine learning, electrochemical and distribution function of relaxation times (DFRTs) analyses.

Among many transition-metal oxides, Fe3O4 anode based lithium ion batteries (LIBs) have been well-investigated because of their high energy and high capacity. Iron is known for elemental abundance and is relatively environmentally friendly as well contains with low toxicity. However, LIBs based on Fe3O4 suffer from particle aggregation during charge-discharge processes that affects the cycling performance. This study conjectures that iron agglomeration and material performance could be affected by dopant choice, and improvements are sought with Fe3O4 nanoparticles doped with 0.2% Ti. The electrochemical measurements show a stable specific capacity of 450 mAh g-1 at 0.1 C rate for at least 100 cycles in Ti doped Fe3O4. The stability in discharge capacity for Ti doped Fe3O4 is achieved, arising from good electronic conductivity and stability in microstructure and crystal structure, which has been further confirmed by density functional theory (DFT) calculation. Detailed distribution function of relaxation times (DFRTs) analyses based on the impedance spectra reveal two different types of Li ion transport phenomena, which are closely related with the electron density difference near the two Fe-sites. Detailed analyses on EIS measurements using DFRTs for Ti doped Fe3O4 indicate that improvement in interfacial charge transfer processes between electrode and Li metal along with an intermediate lithiated phase helps to enhance the electrochemical performance.

Vibrational and electrochemical studies of pectin-a candidate towards environmental friendly lithium-ion battery development.

Pectin polymers are considered for lithium-ion battery electrodes. To understand the performance of pectin as an applied buffer layer, the electrical, magnetic, and optical properties of pectin films are investigated. This work describes a methodology for creating pectin films, including both pristine pectin and Fe-doped pectin, which are optically translucent, and explores their potential for lithium-ion battery application. The transmission response is found extended in optimally Fe-doped pectin, and prominent modes for cation bonding are identified. Fe doping enhances the conductivity observed in electrochemical impedance spectroscopy, and from the magnetic response of pectin evidence for Fe3+ is identified. The Li-ion half-cell prepared with pectin as binder for anode materials such as graphite shows stable charge capacity over long cycle life, and with slightly higher specific capacity compare with the cell prepared using polyvinylidene fluoride (PVDF) as binder. A novel enhanced charging specific capacity at a high C-rate is observed in cells with pectin binder, suggesting that within a certain rate (∼5 C), pectin has higher capacity at faster charge rates. The pectin system is found as a viable base material for organic-inorganic synthesis studies.

Switching currents limited by single phase slips in one-dimensional superconducting Al nanowires.

An aluminum nanowire switches from superconducting to normal as the current is increased in an upsweep. The switching current (I(s)) averaged over upsweeps approximately follows the depairing critical current (I(c)) but falls below it. Fluctuations in I(s) exhibit three distinct regions of behaviors and are nonmonotonic in temperature: saturation well below the critical temperature T(c), an increase as T(2/3) at intermediate temperatures, and a rapid decrease close to T(c). Heat dissipation analysis indicates that a single phase slip is able to trigger switching at low and intermediate temperatures, whereby the T(2/3) dependence arises from the thermal activation of a phase slip, while saturation at low temperatures provides striking evidence that the phase slips by macroscopic quantum tunneling.

Superconductivity in the PbO-type structure alpha-FeSe.

The recent discovery of superconductivity with relatively high transition temperature (Tc) in the layered iron-based quaternary oxypnictides La[O(1-x)F(x)] FeAs by Kamihara et al. [Kamihara Y, Watanabe T, Hirano M, Hosono H (2008) Iron-based layered superconductor La[O1-xFx] FeAs (x = 0.05-0.12) with Tc = 26 K. J Am Chem Soc 130:3296-3297.] was a real surprise and has generated tremendous interest. Although superconductivity exists in alloy that contains the element Fe, LaOMPn (with M = Fe, Ni; and Pn = P and As) is the first system where Fe plays the key role to the occurrence of superconductivity. LaOMPn has a layered crystal structure with an Fe-based plane. It is quite natural to search whether there exists other Fe based planar compounds that exhibit superconductivity. Here, we report the observation of superconductivity with zero-resistance transition temperature at 8 K in the PbO-type alpha-FeSe compound. A key observation is that the clean superconducting phase exists only in those samples prepared with intentional Se deficiency. FeSe, compared with LaOFeAs, is less toxic and much easier to handle. What is truly striking is that this compound has the same, perhaps simpler, planar crystal sublattice as the layered oxypnictides. Therefore, this result provides an opportunity to better understand the underlying mechanism of superconductivity in this class of unconventional superconductors.

Computation of distribution of relaxation times by Tikhonov regularization for Li ion batteries: usage of L-curve method.

In this paper, the distribution of relaxation times (DRTs) functions are calculated numerically in Matlab for synthetic impedance data from single parallel [Formula: see text] circuit and two parallel [Formula: see text] circuits connected in series, experimental impedance data from supercapacitors and α-LiFeO2 anode based Li ion batteries. The quality of the impedance data is checked with the Kramers-Krönig (KK) relations. The DRTs are calculated within the KK compatible regime for all the systems using Tikhonov regularization (TR) method. Here we use a fast and simple L-curve method to estimate the TR parameter (λ) for regularization of the Fredholm integral equations of first kind in impedance. Estimation of the regularization parameters are performed effectively from the offset of the global corner of the L-curve rather than simply using the global corner. The physical significances of DRT peaks are also discussed by calculating the effective resistances and capacitances coupled with peak fitting program. For instance, two peaks in the DRTs justify the electrical double layer capacitance and ion diffusion phenomena for supercapacitors in low to intermediate frequencies respectively. Moreover, the surface film effect, Li/electrolyte and electrode/electrolyte charge transfer related processes are identified for α-LiFeO2 anode based Li-ion batteries. This estimation of the offset of the global corner extends the L-curve approach coupled with the Tikhonov regularization in the field of electrochemistry and can also be applied in similar process detection methods.

Electrochemical Performance of Orthorhombic CsPbI3 Perovskite in Li-Ion Batteries.

A facile solution process was employed to prepare CsPbI3 as an anode material for Li-ion batteries. Rietveld refinement of the X-ray data confirms the orthorhombic phase of CsPbI3 at room temperature. As obtained from bond valence calculations, strained bonds between Pb and I are identified within PbI6 octahedral units. Morphological study shows that the as-prepared δ-CsPbI3 forms a nanorod-like structure. The XPS analysis confirm the presence of Cs (3d, 4d), Pb (4d, 4f, 5d) and I (3p, 3d, 4d). The lithiation process involves both intercalation and conversion reactions, as confirmed by cyclic voltammetry (CV) and first-principles calculations. Impedance spectroscopy coupled with the distribution function of relaxation times identifies charge transfer processes due to Li metal foil and anode/electrolyte interfaces. An initial discharge capacity of 151 mAhg-1 is found to continuously increase to reach a maximum of ~275 mAhg-1 at 65 cycles, while it drops to ~240 mAhg-1 at 75 cycles and then slowly decreases to 235 mAhg-1 at 100 cycles. Considering the performance and structural integrity during electrochemical performance, δ-CsPbI3 is a promising material for future Li-ion battery (LIB) application.

High pressure superconductivity in iron-based layered compounds studied using designer diamonds.

High pressure superconductivity in iron-based superconductor FeSe(0.5)Te(0.5) has been studied up to 15 GPa and 10 K using an eight probe designer diamond anvil in a diamond anvil cell device. Four probe electrical resistance measurements show the onset of superconductivity (T(c)) at 14 K at ambient pressure with T(c) increasing with increasing pressure to 19 K at a pressure of 3.6 GPa. At higher pressures beyond 3.6 GPa, T(c) decreases and extrapolation suggests non-superconducting behavior above 10 GPa. The loss of superconductivity coincides with the pressure induced disordering of the Fe(SeTe)(4) tetrahedra reported at 11 GPa in x-ray diffraction studies at ambient temperature.

Mobile metallic domain walls in an all-in-all-out magnetic insulator.

Magnetic domain walls are boundaries between regions with different configurations of the same magnetic order. In a magnetic insulator, where the magnetic order is tied to its bulk insulating property, it has been postulated that electrical properties are drastically different along the domain walls, where the order is inevitably disturbed. Here we report the discovery of highly conductive magnetic domain walls in a magnetic insulator, Nd2Ir2O7, that has an unusual all-in-all-out magnetic order, via transport and spatially resolved microwave impedance microscopy. The domain walls have a virtually temperature-independent sheet resistance of ~1 kilohm per square, show smooth morphology with no preferred orientation, are free from pinning by disorders, and have strong thermal and magnetic field responses that agree with expectations for all-in-all-out magnetic order.

Spatially resolved Hall effect measurement in a single semiconductor nanowire.

Efficient light-emitting diodes and photovoltaic energy-harvesting devices are expected to play an important role in the continued efforts towards sustainable global power consumption. Semiconductor nanowires are promising candidates as the active components of both light-emitting diodes and photovoltaic cells, primarily due to the added freedom in device design offered by the nanowire geometry. However, for nanowire-based components to move past the proof-of-concept stage and be implemented in production-grade devices, it is necessary to precisely quantify and control fundamental material properties such as doping and carrier mobility. Unfortunately, the nanoscale geometry that makes nanowires interesting for applications also makes them inherently difficult to characterize. Here, we report a method to carry out Hall measurements on single core-shell nanowires. Our technique allows spatially resolved and quantitative determination of the carrier concentration and mobility of the nanowire shell. As Hall measurements have previously been completely unavailable for nanowires, the experimental platform presented here should facilitate the implementation of nanowires in advanced practical devices.