Momentum-Resolved Electronic Structures and Strong Electronic Correlations in Graphene-like Nitride Superconductors.

Although transition-metal nitrides have been widely applied for several decades, experimental investigations of their high-resolution electronic band structures are rare due to the lack of high-quality single-crystalline samples. Here, we report on the first momentum-resolved electronic band structures of titanium nitride (TiN) films, which are remarkable nitride superconductors. The measurements of the crystal structures and electrical transport properties confirmed the high quality of these films. More importantly, from a combination of high-resolution angle-resolved photoelectron spectroscopy and first-principles calculations, the extracted Coulomb interaction strength of TiN films can be as large as 8.5 eV, whereas resonant photoemission spectroscopy yields a value of 6.26 eV. These large values of Coulomb interaction strength indicate that superconducting TiN is a strongly correlated system. Our results uncover the unexpected electronic correlations in transition-metal nitrides, potentially providing a perspective not only to understand their emergent quantum states but also to develop their applications in quantum devices.

Li Salt Assisted Highly Flexible Carbonaceous Ni3N@polyimide Electrode for an Efficient Asymmetric Supercapacitor.

This work used a highly flexible, sustainable polyimide tape as a substrate to deposit ductile-natured carbonaceous Ni3N (C/Ni3N@polyimide) material for supercapacitor application. C/Ni3N was prepared using a co-sputtering technique, and this method also provided better adhesion of the electrode material over the substrate, which is helpful in improving bending performance. The ductile behavior of the sputter-grown electrode and the high flexibility of the polyimide tape provide ultimate flexibility to the C/Ni3N@polyimide-based supercapacitor. To achieve optimum electrochemical performance, a series of electrochemical tests were done in the presence of various electrolytes. Further, a flexible asymmetric supercapacitor (NC-FSC) (C/Ni3N//carbon@polyimide) was assembled by using C/Ni3N as a cathode and a carbon thin film as an anode, separated by a GF/C-glass microfiber soaked in optimized 1 M Li2SO4 aqueous electrolyte. The NC-FSC offers a capacitance of 324 mF cm-2 with a high areal energy density of 115.26 µWh cm-2 and a power density of 811 µW cm-2, with ideal bending performance.

Highly-Efficient and Robust Zn Anodes Enabled by Sub-1-µm Zincophilic CrN Coatings.

For exploring advanced Zn-ion batteries (ZIBs) with long lifespan and high Coulombic efficiency (CE), the critically important point is to limit the undesired Zn dendrite and parasitic reactions. Among the coating for electrode is a promising strategy, relying on the trade-off between its thickness and stability to achieve the ultra-stable Zn anodes in ZIBs. Herein, a submicron-thick (≈0.4 µm) zincophilic CrN coatings are fabricated by a facile and industry-compatible magnetron sputtering approach. It is exhilarating that the ultrathin and dense CrN coatings with strong adsorption ability for Zn2+ exhibit an impressive lifespan up to 3700 h with ≈100% CE at 1 mA cm-2. Along with the experiments and theoretical calculations, it is verified that the introduced CrN coatings cannot only effectively suppress the dendrite growth and notorious parasitic reactions, but also allow the uniform Zn deposition due to the reduced nucleation energy. Moreover, the as-assembled Zn@CrN‖MnO2 full cell delivers a high specific capacity of 171.1 mAh g-1 after 1000 cycles at 1 A g-1, much better than that of Zn‖MnO2 analog (97.8 mAh g-1). This work provides a facile strategy for scalable fabrication of ultrathin zincophilic coating to push forward the practical applications of ZIBs.

Sustaining Surface Lithiophilicity of Ultrathin Li-Alloy Coating Layers on Current Collector for Zero-Excess Li-Metal Batteries.

Zero-excess Li-metal batteries (ZE-LMBs) have emerged as the ultimate battery platform, offering an exceptionally high energy density. However, the absence of Li-hosting materials results in uncontrolled dendritic Li deposition on the Cu current collector, leading to chronic loss of Li inventory and severe electrolyte decomposition, limiting its full utilization upon cycling. This study presents the application of ultrathin (≈50 nm) coatings comprising six metallic layers (Cu, Ag, Au, Pt, W, and Fe) on Cu substrates in order to provide insights into the design of Li-depositing current collectors for stable ZE-LMB operation. In contrast to non-alloy Cu, W, and Fe coatings, Ag, Au, and Pt coatings can enhance surface lithiophilicity, effectively suppressing Li dendrite growth, thereby improving Li reversibility. Considering the distinct Li-alloying behaviors, particularly solid-solution and/or intermetallic phase formation, Pt-coated Cu current collectors maintain surface lithiophilicity over repeated Li plating/stripping cycles by preserving the original coating layer, thereby attaining better cycling performance of ZE-LMBs. This highlights the importance of selecting suitable Li-alloy metals to sustain surface lithiophilicity throughout cycling to regulate dendrite-less Li plating and improve the electrochemical stability of ZE-LMBs.

Attenuating the Polysulfide Shuttle Mechanism by Separator Coating.

Lithium-sulfur batteries have a high energy density but lack cycle stability to reach market maturity. This is mainly due to the polysulfide shuttle mechanism, i. e., the leaching of active material from the cathode into the electrolyte and subsequent side reactions. We demonstrate how to attenuate the polysulfide shuttle by magnetron sputtering molybdenum oxysulfide, manganese oxide, and chromium oxide onto microporous polypropylene separators. The morphology of the amorphous coatings was analyzed by SEM and XRD. Electrochemical cyclization quantified how these coatings improved Coulombic efficiency and cycle stability. These tests were conducted in half cells. We compare the different performances of the different coatings with the known chemical and adsorption properties of the respective coating materials.

Structural phase transition and resistive switching properties of CuxO films during post-thermal annealing.

We studied the phase change and resistive switching characteristics of copper oxide (CuxO) films through post-thermal annealing. This investigation aimed to assess the material's potential for a variety of electrical devices, exploring its versatility in electronic applications. The CuxO films deposited by RF magnetron sputtering were annealed at 300, 500, and 700 °C in ambient air for 4 min by rapid thermal annealing (RTA) method, and then it was confirmed that the structural phase change from Cu2O to CuO occurred with increasing annealing temperature. Resistive random-access memory (ReRAM) devices with Au/CuxO/p+-Si structures were fabricated, and the ReRAM properties appeared in CuO-based devices, while Cu2O ReRAM devices did not exhibit resistive switching behavior. The CuO ReRAM device annealed at 500 °C showed the best properties, with a on/off ratio of 8 × 102, good switching endurance of ∼100 cycles, data retention for 104s, and stable uniformity in the cumulative probability distribution. This characteristic change could be explained by the difference in the grain size and density of defects between the Cu2O and CuO films. These results demonstrate that superior and stable resistive switching properties of RF-sputtered CuxO films can be obtained by low-temperature RTA.

Tuneable quantised conductance memory states in TiO2based resistive switching devices in crossbar geometry for high density memory applications.

The tunability and controllability of conductance quantization mediated multilevel resistive switching (RS) memory devices, fabricated in crossbar geometry can be a promising alternative for boosting storage density. Here, we report fabrication of Cu/TiO2/Pt based RS devices in 8 × 8 crossbar geometry, which showed reliable bipolar RS operations. The crossbar devices showed excellent spatial and temporal variability, time retention and low switching voltage (<1 V) and current (∼100µA). Furthermore, during the reset switching, highly repeatable and reliable integral and half-integral quantized conductance (QC) was observed. The observed QC phenomenon was attributed to the two dimensional confinement of electrons as lateral width of the conducting filament (CF) matches the fermi wavelength. The magnitude and number of the QC steps were found to increase from ∼2.5 to 12.5 and from 5 to 18, respectively by increasing the compliance current (IC) from 50 to 800µA which also increased the diameter of the CF from ∼1.2 to 3.3 nm. The enhancement in both number and magnitude of QC states was explained using electrochemical dissolution mechanism of CF of varying diameter. A thicker CF, formed at higherIC, undergoes a gradual rupture during reset process yielding a greater number of QC steps compared to a thinner CF. The realisation of QC states in the crossbar Cu/TiO2/Pt device as well asICmediated tunability of their magnitude and number may find applications in high-density resistive memory storage devices and neuromorphic computing.

Robust ZTO-reinforced Ag nanowire hybrid transparent conductive thin films with absorption-enhanced electromagnetic interference shielding property.

Technological advances have accelerated the pursuit of transparent conducting thin films (TCFs) with superior mechanical properties, durability, efficient optoelectrical performance and substrate compatibility as a pivotal focus in the realm of flexible transparent electronics. Against this background, this work investigates the fabrication of multilayer silver nanowire (AgNW) thin films reinforced by zinc tin oxide (ZTO) thin film encapsulation on polycarbonate substrates by a combination of sputtering and spin-coating techniques. An investigation of the influence of AgNW percolation networks on the optoelectrical properties of ZTO/AgNW/ZTO hybrid thin films was carried out. The impact of ZTO protective layers on the enhancement of electrical properties, adhesivity, flexibility and environmental stability of the multilayer TCF was elucidated. Additionally, to explore the compatibility of the fabricated TCF in integrated device and stealth applications, its electromagnetic interference shielding properties were investigated. The hybrid TCF showed 99.47% EMI shielding efficiency with an absorption-dominant EMI shielding effectiveness of 22.7 dB in the x-band region.

Construction of Co-ZIF-derived CoS2@Cu hollow heterogeneous nanotube array for the detection of hydrazine in environmental water samples.

As a neurotoxin, it is necessary to establish a low cost, stable and sensitive method for the quantitative detection of hydrazine. Using Co-ZIF (zeolite imidazole framework) nanorods as precursor, CoS2 hollow nanotube array heterogeneous structure loaded with Cu nanoparticles were prepared on carbon cloth (CC) by etching, calcination and plasma magnetron sputtering (CoS2@Cu HNTA/CC). As a self-supporting electrode, its hollow heterogeneous structure provides a large area of electron transfer channel for the oxidation of the food pollutant hydrazine. In addition, bimetallic synergies and in situ N doping regulated the electronic structure of CoS2@Cu HNTA/CC, and thus significantly improved the electrical conductivity and catalytic activity. As an efficient hydrazine sensor with a wide linear range of 1 µM L-1-10 mM (1 µM-1 mM and 1 mM-10 mM), its sensitivity and the limit of detection are 7996 µA mM-1 cm-2, 3772 µA mM-1 cm-2 and 0.276 µM (S/N = 3), respectively. This study provides a new strategy for the construction of MOFs (Metal Organic Framework)-derived bimetallic composites and their application in electrochemical sensing.

A comprehensive calibration of integrated magnetron sputtering and plasma enhanced chemical vapor deposition for rare-earth doped thin films.

A new integrated deposition system taking advantage of magnetron sputtering and electron cyclotron-plasma enhanced chemical vapour deposition (IMS ECR-PECVD) is presented that mitigates the drawbacks of each fabrication system. This tailor-made system provides users with highly homogeneous and pure thin films with less undesired hydrogen and well-controlled rare-earth concentration compared to existing methods of rare-earth doping, such as metalorganic powders, sputtering, and ion implantation. We established the first comprehensive report on the deposition parameters of argon flow and sputtering power to achieve desired rare-earth concentrations in a wide composition range of terbium (Tb) doped-silicon oxide (Tb:SiOx) matrices including silicon-rich (x < 2), oxygen-rich (x > 2), and stoichiometric silicon oxide (x = 2). The deposition parameters to fabricate crystalline structure (Tb2Si2O7) in oxygen-rich samples are reported where Tb ions are optically active. IMS ECR-PECVD pushes the solubility limit of the rare-earth dopant in silicon films to 17 at.% for the desired future nanophotonic devices. Supplementary Information: The online version contains supplementary material available at 10.1557/s43578-023-01207-2.

The thermal stability and degradation mechanism of Cu/Mo nanomultilayers.

The microstructural evolution of Cu/Mo nanomultilayers upon annealing was investigated by X-ray diffraction and transmission electron microscopy. The isothermal annealing process in the temperature ranges of 300-850°C was conducted to understand the thermal behavior of the sample and follow the transformation into a nanocomposite. Annealing at 600°C led to the initiation of grain grooving in the investigated nanomultilayer, and it degraded into a spheroidized nanocomposite structure at 800°C. The sample kept the as-deposited Cu {111}//Mo{110} fiber texture up to 850°C. The residual stress was investigated to explain microstructure changes. The activation energy of degradation kinetics of Cu/Mo nanomultilayers was determined to understand the rate-determining mechanism for the degradation of nanolaminate structures.

This study investigates the microstructural evolution of Cu/Mo nanomultilayers during vacuum annealing up to 85°C and provides important insights into their thermal stability and degradation mechanisms for development and application.

Conductive single-phase SrMoO3 epitaxial films synthesized in pure Ar ambience via plasma-assisted radio frequency sputtering.

The cubic perovskite SrMoO3 with a paramagnetic ground state and remarkably low room-temperature resistivity has been considered as a suitable candidate for the new-era oxide-based technology. However, the difficulty of preparing single-phase SrMoO3 thin films by hydrogen-free sputtering has hindered their practical use, especially due to the formation of thermodynamically favorable SrMoO4 impurity. In this work, we developed a radio frequency sputtering technology enabling the reduction reaction and achieved conductive epitaxial SrMoO3 films with pure phase from a SrMoO4 target in a hydrogen-free, pure argon environment. We demonstrated the significance of controlling the target-to-substrate distance (TSD) on the synthesis of SrMoO3; the film resistivity drastically changes from 1.46 × 105 µΩ·cm to 250 µΩ·cm by adjusting the TSD. Cross-sectional microstructural analyses demonstrated that films with the lowest resistivity, deposited for TSD = 2.5 cm, possess a single-phase SrMoO3 with an epitaxial perovskite structure. The formation mechanism of the conductive single-phase SrMoO3 films can be attributed to the plasma-assisted growth process by tuning the TSD. Temperature-dependent resistivity and Hall effect studies revealed metal-like conducting properties for low-resistive SrMoO3 films, while the high-resistive ones displayed semiconductor-like behavior. Our approach makes hydrogen-free, reliable and cost-efficient scalable deposition of SrMoO3 films possible, which may open up promising prospects for a wide range of future applications of oxide materials.

For the first time, we developed a plasma-assisted RF sputtering technology enabling the reduction reaction for the synthesis of single-phase conductive SrMoO₃ epitaxial films from insulating SrMoO₄ in pure-argon atmosphere.

Highly Localized Optical Field Enhancement at Neon Ion Sputtered Tungsten Nanotips.

We present laser-driven rescattering of electrons at a nanometric protrusion (nanotip), which is fabricated with an in situ neon ion sputtering technique applied to a tungsten needle tip. Electron energy spectra obtained before and after the sputtering show rescattering features, such as a plateau and high-energy cutoff. Extracting the optical near-field enhancement in both cases, we observe a strong increase of more than 2-fold for the nanotip. Accompanying finite-difference time-domain (FDTD) simulations show a good match with the experimentally extracted near-field strengths. Additionally, high electric field localization for the nanotip is found. The combination of transmission electron microscope imaging of such nanotips and the determination of the near-field enhancement by electron rescattering represent a full characterization of the electric near-field of these intriguing electron emitters. Ultimately, nanotips as small as single nanometers can be produced, which is of utmost interest for electron diffraction experiments and low-emittance electron sources.

Tungsten Molecular Species in Deuterium Plasmas in Contact with Sputtered W Surfaces.

We show that in plasmas generated in deuterium in the presence of sputtered W surfaces, various molecular tungsten species are formed, whose chemical composition depends on the presence of gaseous impurities, namely, nitrogen, oxygen, and hydrogen. A magnetron discharge was used for plasma sustaining, and the species were investigated by mass spectrometry and optical emission spectroscopy. The identified tungsten-containing molecules are described by the chemical formula WOxNyDzHt, where x = 0-4, y = 0-3, z = 0-3, t = 0-5. Presumptively, even higher mass tungsten molecular species are present in plasma, which were not detected because of the limitation of the spectrometer measurement range to 300 amu. The presence of these molecules will likely impact the W particle balance and dust formation mechanisms in fusion plasmas.

Charge-State-Enhanced Ion Sputtering of Metallic Gold Nanoislands.

Experimental results on the charge-state-dependent sputtering of metallic gold nanoislands are presented. Irradiations with slow highly charged ions of metallic targets were previously considered to show no charge state dependent effects on ion-induced material modification, since these materials possess enough free electrons to dissipate the deposited potential energy before electron-phonon coupling can set in. By reducing the size of the target material down to the nanometer regime and thus enabling a geometric energy confinement, a possibility is demonstrated to erode metallic surfaces by charge state related effects in contrast to regular kinetic sputtering.

High Thermoelectric Performance of Non-Stoichiometric and Oriented GeTe Thin Films.

The increasing demand for micro-thermoelectric coolers and generators promotes the research on thermoelectric (TE) thin films. As a promising medium-temperature TE material, GeTe has attracted wide attention recently. However, the thermoelectric performance of thin-film GeTe remains inferior. Herein, oriented GeTe films with excessive Ge are obtained by magnetron co-sputtering technique, which can not only reduce the carrier concentration but also increase the carrier mobility, maintaining the high electrical conductivity of GeTe. Furthermore, higher structural symmetry and grain boundary scattering enhance the Seebeck coefficient of oriented GeTe films. As a result, the power factor (PF) value can reach as high as 2848 µW m-1 K-2 at room temperature and increase to 5263 µW m-1 K-2 at 600 K. Furthermore, a TE device with the Ge-rich GeTe thin film is fabricated and the maximum output power density (power per unit area) reaches 0.3 W cm-2 at ΔT = 250 K. This work demonstrates that the stoichiometry and orientation modulations are effective strategies to improve the thermoelectric performance of GeTe thin films.

An Unusual Microdomain Factor Controls Interaction of Organic Halides with the Palladium Phase and Influences Catalytic Activity in the Mizoroki-Heck Reaction.

In this work, using a combination of scanning and transmission electron microscopy (SEM and TEM), the transformations of palladium-containing species in imidazolium ionic liquids in reaction mixtures of the Mizoroki-Heck reaction and in related organic media are studied to understand a challenging question of the relative reactivity of organic halides as key substrates in modern catalytic technologies. The microscopy technique detects the formation of a stable nanosized palladium phase under the action of an aryl (Ar) halide capable of forming microcompartments in an ionic liquid. For the first time, the correlation between the reactivity of the aryl halide and the microdomain structure is observed: Ar-I (well-developed microdomains) > Ar-Br (microphase present) > Ar-Cl (minor amount of microphase). Previously, it is assumed that molecular level factors, namely, carbon-halogen bond strength and the ease of bond breakage, are the sole factors determining the reactivity of aryl halides in catalytic transformations. The present work reports a new factor connected with the nature of the organic substrates used and their ability to form a microdomain structure and concentrate metallic species, highlighting the importance of considering both the molecular and microscale properties of the reaction mixtures.

X-ray mirrors with sub-nanometre figure errors obtained by differential deposition of thin WSi2 films.

Differential deposition by DC magnetron sputtering was applied to correct for figure errors of X-ray mirrors to be deployed on low-emittance synchrotron beamlines. During the deposition process, the mirrors were moved in front of a beam-defining aperture and the required velocity profile was calculated using a deconvolution algorithm. The surface figure was characterized using conventional off-line visible-light metrology instrumentation (long trace profiler and Fizeau interferometer) before and after the deposition. WSi2 was revealed to be a promising candidate material since it conserves the initial substrate surface roughness and limits the film stress to acceptable levels. On a 300 mm-long flat Si mirror the average height errors were reduced by a factor of 20 down to 0.2 nm root mean square. This result shows the suitability of WSi2 for differential deposition. Potential promising applications include the upgrade of affordable, average-quality substrates to the standards of modern synchrotron beamlines.

Gas Flow Sputtering of Pt/C Films and their Performance in Electrocatalytic Hydrogen Evolution Reaction.

A single step deposition technique of Pt/C films for electrocatalytic applications is presented. The hollow cathode gas flow sputtering (GFS) method allows a catalyst production within few minutes without further steps. The herein presented films consist of small Pt nanocrystals (2-5 nm) deposited in a matrix of nanocrystalline carbon. The films show a low and stable overpotential under acidic conditions in the hydrogen evolution reaction (HER). Relatively low Pt-mass activity (<1 mA/µgPt ) is attributed to the yet too high Pt-content in the films. Another issue discovered in this work is a non-graphitic state of carbon resulting in its high resistivity. Still, the GFS deposition technique providing by nature high deposition rates and a substance-to-material yield of 80-90 % is advantageous than other sputtering techniques and especially chemical methods in that sense. This technique is scalable to areas in the range of square meters and thus represents an attractive way to efficiently produce large-scale cathode coatings for industrial electrolysers.

Magnetron sputtering onto nonionic surfactant for 1-step preparation of metal nanoparticles without additional chemical reagents.

Plasma-based sputtering onto liquids (SoL) is a straightforward approach for synthesizing small metal nanoparticles (NPs) without additional stabilizing reagents. In this work, nonionic surfactant Triton X-100 was used for the first time as a host liquid for the SoL process and the production of colloidal solutions of gold, silver and copper NPs was demonstrated. The average diameter of spherical Au NPs lies in the range from 2.6 to 5.5 nm depending on the conditions. The approach presented here opens the pathway to the production of concentrated dispersions of metal NPs of high purity that can be dispersed in water for future usage, therefore extending further the reach of this synthesis pathway.