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Transition metal selenides (TMS) have excellent research prospects and significant attention in supercapacitors (SCs) owing to their high electrical conductivity, superior electrochemical activity and excellent structural stability. However, the commercial utilization of TMS remains challenge due to their elaborate synthesis. Present study designed a hierarchical cobalt selenide (CoSe2) nanowire array on Ni-foam to serve as a positive electrode for asymmetric SCs (ASCs). The nanowires-like morphology of CoSe2 was highly advantageous for SCs, as it offered enhanced electrical conductivity, plenty of surface sites, and short ion diffusion. The as-obtained, CoSe2 nanowire electrode demonstrated outstanding electrochemical features, with an areal capacity of 1.08 mAh cm−2 at 3 mA cm−2, high-rate performance (69.5 % at 50 mA cm−2), as well as outstanding stability after 10,000 cycles. The iron titanium nitride@nitrogen-doped graphene (Fe-TiN@NG) was prepared as a negative electrode to construct the ASCs cell. The obtained ASCs cell illustrated an energy density of 91.8 W h kg−1 at a power density of 281.4 W kg−1 and capacity retention of 94.6% over 10,000 cycles. The overall results provide a more efficient strategy to develop redox-ambitious active materials with a high capacity for advanced energy-storage systems.

Atomic-scale precision epitaxy of perovskite oxide superlattices provides unique opportunities for controlling the correlated electronic structures, activating effective control knobs for intriguing functionalities including electromagnetic, thermoelectric, and electrocatalytic behaviors. In this study, we investigated the close interplay between the atomic and electronic structures of correlated superlattices synthesized by atomic-scale precision epitaxy. In particular, we employ superlattices composed of correlated magnetic SrRuO3 (SRO) and quantum paraelectric SrTiO3 (STO) layers. In those superlattices, RuO6 octahedral distortion is systematically controlled from 167 to 175 degrees depending on the thickness of the STO layers, also affecting the TiO6 octahedral distortion within the STO layer. Customized octahedral distortion within SRO/STO superlattices in turn modifies the electronic structures of both the Ti and Ru compounds, observed by X-ray absorption spectroscopy. Our results identify the close correlation between atomic lattice and electronic structures enabled by the facile controllability of atomic-scale epitaxy, which would be useful for designing future correlated oxide devices., 14 pages

We synthesized a series of slightly erbium-substituted yttrium iron garnets (Er:YIG), Y

The electronic structure of an atomic-layer-deposited MoS2 monolayer on SiO2 was investigated using X-ray absorption spectroscopy (XAS) and synchrotron X-ray photoelectron spectroscopy (XPS). The angle-dependent evolution of the XAS spectra and the photon-energy-dependent evolution of the XPS spectra were analyzed in detail using an ab-initio electronic structure simulation. Although similar to the theoretical spectra of an ideal free-standing MoS2 ML, the experimental spectra exhibit features that are distinct from those of an ideal ML, which can be interpreted as a consequence of S-O van der Waals (vdW) interactions. The strong consensus among the experimental and theoretical spectra suggests that the vdW interactions between MoS2 and adjacent SiO2 layers can influence the electronic structure of the system, manifesting a substantial electronic interaction at the MoS2-SiO2 interface.

We examined the chemical and local structural properties of oxidized TiN/ZnS and TiN/ZnO thin films using X-ray absorption spectroscopy (XAS). The composite films were oxidized by post-deposition annealing (PDA) under various oxygen partial pressures (P(O2)). The results of the X-ray absorption near-edge structure (XANES) analyses showed that the S and N vaporized, and a zinc titanate (ZnTiO3)-like phase formed when annealed under the oxygen ambiance. An ab initio XANES simulation as well as the extended X-ray absorption fine structure (EXAFS) analysis further resolved the local structures of ZnTiO3-like phase into high symmetry structures such as ilmenite-like or perovskite-like local structure; for instance, the local structure of TiN/ZnS films annealed with P(O2) = 2 Torr could be described as a mixture of 50% ilmenite ZnTiO3 + 30% perovskite ZnTiO3 + 20% wurtzite ZnO local structures. The formation of ZnTiO3-like local structure is also subject to the temperature during the PDA or the choice of bottom layers (ZnS or ZnO). The temperature of the TiN/ZnS-to-ZnTiO3 local structural phase transformation, was estimated to be 500–600 °C at P(O2) = 2 Torr, and ZnO as bottom layer apparently expedited such local structural evolution by supplying oxygen to TiN.

Capacitive deionization (CDI) technology is currently considered a potential candidate for brackish water desalination. In this study, we designed iron oxide nanoparticle-incorporated activated carbon (AC/Fe2O3) via a facile and cost-effective hydrothermal process. The as-synthesized material was characterized using several techniques and tested as electrodes in CDI applications. We found that the distinctive properties of the AC/Fe2O3 electrode, i.e., high wettability, high surface area, unique structural morphology, and high conductivity, resulted in promising CDI performance. The electrosorptive capacity of the AC/Fe2O3 nanocomposite reached 6.76 mg g−1 in the CDI process, with a high specific capacitance of 1157.5 F g−1 at 10 mV s−1 in a 1 M NaCl electrolyte. This study confirms the potential use of AC/Fe2O3 nanocomposites as viable electrode materials in CDI and other electrochemical applications.

Over the last two decades, the capacitive deionization (CDI) technique has been developed into a high performance, low-cost, and environmental-friendly desalination technology. The development of novel advanced nanostructures via the hybridization of diverse carbon materials to improve the performance of CDI technology has attracted considerable attention. In this study, the combination of graphene hydrogel and ZrO2-doped TiO2 nanofibers as efficient dopants into activated carbon (AC), has been achieved through a simple electrospinning technique followed by a post annealing process. The strong interactions between the graphene hydrogel, nanofibers and AC were found to enhance the wettability as well as the electrical conductivity of the AC. The morphology and electrochemical performance of the as-synthesized composite were characterized by field-emission scanning electron microscopy (FE-SEM), Transmission electron microscopy (TEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). What’s more, the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and synchrotron X-ray absorption structures (XAS) are performed to investigate the atomic and electronic structure of titania and zirconia in order to understand their phase stability. We observed the appearance of anatase structure of titania and cubic structure of zirconia after doping the AC and graphene hydrogel with the nanofibers. The water contact angle of the composite was examined and found to be less than 3°. The introduced nanocomposite showed high electrosorption capacity of 9.34 mg g−1 at the initial solution conductivity of ∼100 μS cm−1, which is much higher compared to the other surveyed materials; these results should be attributed to its significant hydrophilicity, high specific capacitance, and reduced charge transfer resistance.

Grafting nanotechnology on thermoelectric materials leads to significant advances in their performance. Creation of structural defects including nano-inclusion and interfaces via nanostructuring ac...

The electronic structure of an atomic-layer-deposited MoS

The chemical and magnetic states of Fe/Fe2O3 thin films prepared by e-beam evaporation were investigated by using element-specific techniques, X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). It was clearly shown that the Fe layers are oxidized to form an antiferromagnetic (AFM) FeOx, while the bottom oxide remained a weak ferromagnet (wFM) (α+γ)-type Fe2O3. Dependences of the peak intensities and lineshapes on the Fe thickness and measurement geometry further demonstrate that FeOx layers reside mostly at the interface realizing an FM (Fe)/AFM (FeOx)/wFM (Fe2O3), whilst the spin directions lie in the sample plane for all the samples. The self-stabilized intermediate oxide can act as a physical barrier for spins to be injected into the wFM oxide, implying a substantial influence on tailoring the spin tunneling efficiency for spintronics application.

Bonding geometry engineering of metal-oxygen octahedra is a facile way of tailoring various functional properties of transition metal oxides. Several approaches, including epitaxial strain, thickness, and stoichiometry control, have been proposed to efficiently tune the rotation and tilting of the octahedra, but these approaches are inevitably accompanied by unnecessary structural modifications such as changes in thin-film lattice parameters. In this study, we propose a method to selectively engineer the octahedral bonding geometries, while maintaining other parameters that might implicitly influence the functional properties. A concept of octahedral tilt propagation engineering has been developed using atomically designed SrRuO3/SrTiO3 superlattices. In particular, the propagation of RuO6 octahedral tilting within the SrRuO3 layers having identical thicknesses was systematically controlled by varying the thickness of adjacent SrTiO3 layers. This led to a substantial modification in the electromagnetic properties of the SrRuO3 layer, significantly enhancing the magnetic moment of Ru. Our approach provides a method to selectively manipulate the bonding geometry of strongly correlated oxides, thereby enabling a better understanding and greater controllability of their functional properties., 27 pages, 4 figures, 6 supplementary figures

The development of high-performance electrode materials is the main factor in improving the efficiency of the capacitive deionization (CDI) process. Activated carbon is the most extensively used electrode material because of its excellent physicochemical properties and low cost; however, its desalination application has been largely limited owing to its poor wettability. In this study, we prepared a ZnO nanoparticle-incorporated activated carbon/graphene hydrogel composite via ultrasonication and freeze-drying, followed by a hydrothermal treatment. As the hydrophilicity, electrical conductivity, and electrosorptive capacity were improved owing to the presence of the graphene hydrogel and ZnO nanoparticles, the as-fabricated nanocomposite showed excellent specific capacitance (746.5F g−1 at 10 mV s−1), salt removal efficiency (83.65%), and electrosorptive capacity (9.95 mg g−1). Thus, the nanocomposite design devised in this study has potential in realizing the practical CDI applications of activated carbon.

The direction of ferroelectric polarization is prescribed by the symmetry of the crystal structure. Therefore, rotation of the polarization direction is largely limited, despite the opportunity it offers in understanding important dielectric phenomena such as piezoelectric response near the morphotropic phase boundaries and practical applications such as ferroelectric memory. In this study, we report the observation of continuous rotation of ferroelectric polarization in order-disorder type LiNbO3 thin films. The spontaneous polarization could be tilted from an out-of-plane to an in-plane direction in the thin film by controlling the Li vacancy concentration within the hexagonal lattice framework. Partial inclusion of monoclinic-like phase is attributed to the breaking of macroscopic inversion symmetry along different directions and the emergence of ferroelectric polarization along the in-plane direction., 38 pages, 12 figures

The direction of ferroelectric polarization is prescribed by the symmetry of the crystal structure. Therefore, rotation of the polarization direction is largely limited, despite the opportunity it offers in understanding important dielectric phenomena such as piezoelectric response near the morphotropic phase boundaries and practical applications such as ferroelectric memory. In this study, we report the observation of continuous rotation of ferroelectric polarization in order-disorder-type LiNbO

The chemical and nanostructural changes of TiN/SnO2 composite films during post-deposition annealing (PDA) was investigated by scanning electron microscopy, transmission electron microscopy, and X-ray absorption spectroscopy. It was found that during annealing in an oxygen-rich environment, TiN is converted to TiO2 and diffuses into the SnO2 region along grain boundaries to form a SnO2/TiO2 oxide nanocomposite. In addition, rupture of the Si substrate in contact with the nanocomposite was clearly observed. The nanostructural changes and rupture of the Si surface were found to depend on the oxygen partial pressure during PDA, indicating that thermal oxidation can induce abrupt chemical and structural reconstruction in the composite films.

The electronic structure of an amorphous SnO (a-SnO) thin film was examined by using spectroscopic methods including tender and soft x-ray absorption spectroscopies (XAS) and spectroscopic ellipsometry (SE). XAS at the Sn L1−, L3−, and O K-edges revealed that in a-SnO, the Sn 5px/y orbital states, which comprise the conduction band minimum (CBM), are broadened significantly compared to the case of crystalline SnO, whereas the hybridized Sn 5spz-O 2p states above the CBM are persistent. A lowering of the 5px/y states at the CBM by −0.4 eV and a reduction of the indirect bandgap were also observed. These orbital-dependent evolutions upon amorphization were caused by weakened interlayer couplings in the disordered quasi-2-dimensional semiconductor. However, the functionality of a-SnO as a p-type semiconductor would not be degraded significantly because the isotropic Sn 5s orbital states dominate in the valence band states.

The compositional evolution of TiN/SnS2 thin films exposed to post-deposition annealing (PDA) at various O2 pressures (P(O2) = 0, 0.1, 1, 2 and 5 Torr) was examined using X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy and transmission electron microscopy. All the results of the analyses showed that the PDA oxidized the hetero-structured films to form SnO2+TiO2 nanocomposites throughout the film, driving out sulfur ions. The chemical and microstructural evolution according to the oxidation was confirmed by TEM and the energy-dispersive spectroscopy analyses. The XAS analysis particularly showed that with increasing P(O2), the composition of the nanocomposites changed and the microstructure of the titania in the nanocomposites evolved from an anatase to a rutile structure gradually. The conduction band structure also changed in accordance with this microstructural evolution. Electrical measurements on devices with the oxidized SnS2/TiN heterostructure and additional thick TiN metal electrode, further showed that the contact resistance decreased dramatically after the PDA. This implies that the formation of SnO2+TiO2 at the interface between semiconducting SnS2 and metallic TiN can be an effective way to improve the metal-semiconductor contacts.

The electronic structure of the Sn-added p-type SnO thin film was examined using x-ray absorption spectroscopy (XAS). Sn was intentionally added to a pristine SnO film, and the film was annealed to form p-type SnO. Sn L1- and L3-edge XAS was used to examine the oxidation states of the Sn-added p-type SnO. Compared to the case of the reference SnO, the spectrum of the Sn-added SnO (after annealing) partly contained the lineshape for SnO2, suggesting that the oxidation of Sn + SnO was progressed such that the film became preferably SnO2 + SnO rather than Sn + SnO2. O K-edge XAS, x-ray photoelectron spectroscopy (XPS), and spectroscopic ellipsometry (SE) were also used to scrutinize the electronic structure. The direct bandgap of the annealed film was estimated to be ~3.6 eV, consistent with the reported SnO2 bandgap, while that of the as-deposited Sn-added SnO was

The local bonding structures of GexTe1-x (x = 0.5, 0.6, and 0.7) films prepared through atomic layer deposition (ALD) with Ge(N(Si(CH3)3)2)2 and ((CH3)3Si)2Te precursors were investigated using Ge K-edge X-ray absorption spectroscopy (XAS). The results of the X-ray absorption fine structure analyses show that for all of the compositions, the as-grown films were amorphous with a tetrahedral Ge coordination of a mixture of Ge-Te and Ge-Ge bonds but without any signature of Ge-GeTe decomposition. The compositional evolution in the valence band electronic structures probed through X-ray photoelectron spectroscopy suggests a substantial chemical influence of additional Ge on the nonstoichiometric GeTe. This implies that the ALD process can stabilize Ge-abundant bonding networks like -Te-Ge-Ge-Te- in amorphous GeTe. Meanwhile, the XAS results on the Ge-rich films that had undergone post-deposition annealing at 350 °C show that the parts of the crystalline Ge-rich GeTe became separated into Ge crystallites and rhombohedral GeTe in accordance with the bulk phase diagram, whereas the disordered GeTe domains still remained, consistent with the observations of transmission electron microscopy and Raman spectroscopy. Therefore, amorphousness in GeTe may be essential for the nonsegregated Ge-rich phases and the low growth temperature of the ALD enables the achievement of the structurally metastable phases.

We investigated the electronic structures of ultrathin SrRuO3 (SRO) films with n = 1, 2, 3, 4, and 8 monolayers (MLs) on SrTiO3 substrates using O K-edge X-ray absorption spectroscopy (XAS). The intensities of the low-energy features reflect the strengths of the Ru 4d-O 2p orbital hybridization. The Ru 4d orbital state evolves with the increasing SRO thickness, exhibiting a crossover at approximately n = 2. For thick SRO films (n ≥ 3), this constitutes a metallic band, while for the 1 or 2 ML film, the band features shift to a higher energy to form a bandgap (> 0.2 eV), reflecting the emergent insulating nature. The polarization dependence of the peak intensities further shows that in the metallic films (n ≥ 3), Ru t2g - O 2p hybridizations are strong and anisotropic with stronger (weaker) equatorial (apical) hybridizations, possibly owing to compressive strain effects from the SrTiO3 substrate, while in thinner films (n ≤ 2), the hybridization effects become weak and rather isotropic because of the localization of Ru 4d orbitals. Thus, the evolution of anisotropic hybridizations in SRO films in the vicinity of the thickness-driven metal-insulator transition was substantiated.