Nanohybrids of BCN-Fe1-xS for Sodium and Lithium Hybrid Ion Capacitors.

Hybrid ion capacitors (HIC) are receiving a lot of attention due to their potential to achieve high energy and power densities, but they remain insufficient. It is imperative to explore outstanding and environmentally benign electrode materials to achieve high-performing HIC systems. Here, a unique boron carbon nitride (BCN)-based HIC system that comprises a microporous BCN structure and Fe1-xS nanoparticle incorporated BCN nanosheets (BNF) as cathode and anode, respectively is reported. The BNF is prepared through a facile one-pot calcination process using dithiooxamide (DTO), boric acid, and iron source. In situ, crystal growth of Fe1-xS facilitates the formation of BCN structure through the creation of holes/defects in the polymeric structure. The first principle density functional (DFT) theory simulations demonstrate the structural and electronic properties of the hybrid of BCN and Fe1-xS as compelling anode materials for HIC applications. The DFT calculations reveal that both BCN and BNF structures have excellent metallic characters with Li+ storage capacities of 128.4 and 1021.38 mAh g-1 respectively. These findings are confirmed experimentally where the BCN-based HIC system delivers exceptional energy and power densities of 267.5 Wh kg-1/749.5 W kg-1 toward Li+ storage, which outweighs previous HIC performances and demonstrates favorable performance for Li+ and Na+ storages.

Incorporation of Bimetallic Sulfide with Carbon Nitride for Advanced Na-Ion Batteries.

Sodium-ion batteries (SIBs) have received tremendous attention owing to their low cost, high working voltages, and energy density. However, the design and development of highly efficient SIBs represent a great challenge. Here, a unique and reliable approach is reported to prepare carbon nitride (CN) hybridized with nickel iron sulfide (NFCN) using simple reaction between Ni-Fe layered double hydroxide and dithiooxamide. The characterization results demonstrate that the hybridization with optimal amount of CN induces local distortion in the crystal structure of the hybrid, which would benefit SIB performance. Systematic electrochemical studies with a half-cell configuration show that the present hybrid structure exhibits a promising reversible specific capacity of 348 mAh g-1 at 0.1 A g-1 after 100 cycles with good rate capability. Simulation result reveals that the iron atoms in nickel iron sulfide act as a primary active site to accommodate Na+ ions. At last, with a full cell configuration using NFCN and Na3 V2 (PO4 )2 O2 F as the anode and cathode, respectively, the specific capacity appears to be ≈95 mAh g-1 after 50 cycles at 0.1 A g-1 condition. This excellent performance of these hybrids can be attributed to the synergistic effect of the incorporated CN species and the high conductivity of nickel-iron sulfide.

Realization of High Magnetization in Artificially Designed Ni/NiO Layers through Exchange Coupling.

High-magnetization materials play crucial roles in various applications. However, the past few decades have witnessed a stagnation in the discovery of new materials with high magnetization. In this work, Ni/NiO nanocomposites are fabricated by depositing Ni and NiO thin layers alternately, followed by annealing at specific temperatures. Both the as-deposited samples and those annealed at 373 K exhibit low magnetization. However, the samples annealed at 473 K exhibit a significantly enhanced saturation magnetization exceeding 607 emu cm-3 at room temperature, surpassing that of pure Ni (480 emu cm-3 ). Material characterizations indicate that the composite comprises NiO nanoclusters of size 1-2 nm embedded in the Ni matrix. This nanoclustered NiO is primarily responsible for the high magnetization, as confirmed by density functional theory calculations. The calculations also indicate that the NiO clusters are ferromagnetically coupled with Ni, resulting in enhanced magnetization. This work demonstrates a new route toward developing artificial high-magnetization materials using the high magnetic moments of nanoclustered antiferromagnetic materials.

Classification of the Residues after High and Low Order Explosions Using Machine Learning Techniques on Fourier Transform Infrared (FTIR) Spectra.

Forensic science is a field that requires precise and reliable methods for the detection and analysis of evidence. One such method is Fourier Transform Infrared (FTIR) spectroscopy, which provides high sensitivity and selectivity in the detection of samples. In this study, the use of FTIR spectroscopy and statistical multivariate analysis to identify high explosive (HE) materials (C-4, TNT, and PETN) in the residues after high- and low-order explosions is demonstrated. Additionally, a detailed description of the data pre-treatment process and the use of various machine learning classification techniques to achieve successful identification is also provided. The best results were obtained with the hybrid LDA-PCA technique, which was implemented using the R environment, a code-driven open-source platform that promotes reproducibility and transparency.

A New Spin-Correlated Plasmon in Novel Highly Oriented Single-Crystalline Gold Quantum Dots.

A concept of spin plasmon, a collective mode of spin-density, in strongly correlated electron systems has been proposed since the 1930s. It is expected to bridge between spintronics and plasmonics by strongly confining the photon energy in the subwavelength scale within single magnetic-domain to enable further miniaturizing devices. However, spin plasmon in strongly correlated electron systems is yet to be realized. Herein, we present a new spin correlated-plasmon at room temperature in novel Mott-like insulating highly oriented single-crystalline gold quantum-dots (HOSG-QDs). Interestingly, the spin correlated-plasmon is tunable from the infrared to visible, accompanied by spectral weight transfer yielding a large quantum absorption midgap state, disappearance of low-energy Drude response, and transparency. Supported with theoretical calculations, it occurs due to an interplay of surprisingly strong electron-electron correlations, s-p hybridization and quantum confinement in the s band. The first demonstration of the high sensitivity of spin correlated-plasmon in surface-enhanced Raman spectroscopy is also presented.

Unusual Hole and Electron Midgap States and Orbital Reconstructions Induced Huge Ferroelectric Tunneling Electroresistance in BaTiO3/SrTiO3.

Oxide heterostructures have attracted a lot of interest because of their rich exotic phenomena and potential applications. Recently, a greatly enhanced tunneling electroresistance (TER) of ferroelectric tunnel junctions (FTJs) has been realized in such heterostructures. However, our understanding on the electronic structure of resistance response with polarization reversal and the origin of huge TER is still lacking. Here, we report on electronic structures, particularly at the interface and surface, and the control of the spontaneous polarization of BaTiO3 films by changing the termination of a SrTiO3 substrate. Interestingly, unusual electron and hole midgap states are concurrently formed and accompanied by orbital reconstructions, which determine the ferroelectric polarization orientation in the BaTiO3/SrTiO3. Such unusual midgap states, which yield a strong electronic screening effect, reduce the ferroelectric barrier width and height, and pin the ferroelectric polarization, lead to a dramatic enhancement of the TER effect. The midgap states are also observed in BaTiO3 films on electron-doped Nb/SrTiO3 revealing its universality. Our result provides new insight into the origin of the huge TER effect and opens a new route for designing ferroelectric tunnel junction-based devices with huge TER through interface engineering.

Microporous Carbon Nitride (C3 N5.4 ) with Tetrazine based Molecular Structure for Efficient Adsorption of CO2 and Water.

Mesoporous carbon nitrides with C3 N5 and C3 N6 stoichiometries created a new momentum in the field of organic metal-free semiconductors owing to their unique band structures and high basicity. Here, we report on the preparation of a novel graphitic microporous carbon nitride with a tetrazine based chemical structure and the composition of C3 N5.4 using ultra-stable Y zeolite as the template and aminoguanidine hydrochloride, a high nitrogen-containing molecule, as the CN precursor. Spectroscopic characterization and density functional theory calculations reveal that the prepared material exhibits a new molecular structure, which comprises two tetrazines and one triazine rings in the unit cell and is thermodynamically stable. The resultant carbon nitride shows an outstanding surface area of 130.4 m2 g-1 and demonstrates excellent CO2 adsorption per unit surface area of 47.54 µmol m-2 , which is due to the existence of abundant free NH2 groups, basic sites and microporosity. The material also exhibits highly selective sensing over water molecules (151.1 mmol g-1 ) and aliphatic hydrocarbons due to its unique microporous structure with a high amount of hydrophilic nitrogen moieties and recognizing ability towards small molecules.

Broad Range FTIR Spectroscopy and Multivariate Statistics for High Energetic Materials Discrimination.

The objective of this work was to measure infrared spectra of high explosive materials (HE) in wide spectral range in order to acquire information for their complete characterization and find out the regions that are the most discriminatory for each material. Four HEs were measured by means of Fourier Transform Infrared (FTIR) spectroscopy in a very broad range (from near- via mid- to far-IR). Obtained spectra were subsequently evaluated using multivariate statistical methods for dimension reduction and results grouping. Clustering was assessed in terms of compactness and stability in order to distinguish which region or regions are most suitable for the identification based on spectral signature. Based on outcomes of visualization method (silhouette plot) used to compare results of implemented chemometric methods (HCA, PAM, and PCA) done on FTIR spectra collected for four high explosive materials (PETN, C-4, RDX, and TNT) within all regions, it seems that the mid-IR region is the most informative for the distinction among analyzed HE materials based on substance spectral signatures. However, it is worth noticing that also the near-IR region can be used for good differentiation.

Detection of High-Explosive Materials within Fingerprints by Means of Optical-Photothermal Infrared Spectromicroscopy.

As we live under a constant threat of global terrorism, the effective detection of highly energetic materials is one of the critical procedures needed at a variety of locations, including airports, border checkpoints, and entrances to high-security buildings. In this work, the application of optical-photothermal infrared (O-PTIR) spectromicroscopy for the detection of highly explosive materials within fingerprints is described. High-explosive (HE) materials (e.g., PETN, RDX, C-4, or TNT) were used to prepare contaminated fingerprints. These were subsequently deposited on various objects, including microscopic glass slides, a table, a mug, etc. Samples deposited on glass slides were directly sent for analyses; for other samples, adhesive tapes were used to lift off fingermarks. In cases of difficulty in locating fingerprints, additional powders were used to enhance their visibility. Experiments were performed with a mIRage IR microscope working in a noncontact, far-field reflection mode, offering submicron IR spectroscopy and imaging. Fast imaging (several characteristic absorbances were selected for every substance of interest) was used to locate "suspicious" particles among various residues present in fingerprints. Subsequently, spectra were collected for those particles. Reflection mode O-PTIR spectra taken from powdered and nonenhanced fingerprints were of comparable quality to transmission mode FTIR spectra collected for pure HEs. On the basis of the performed experiments, we consider O-PTIR spectromicroscopy to open a new avenue for the nondestructive, efficient, and reliable analysis of exogenous substances deposited within fingerprints. The real significance of O-PTIR is in its ability to deliver high-quality, spatially resolved FTIR transmission-like spectra below the diffraction limit of infrared wavelengths, doing so in an easy-to-use reflection (far-field) mode. Collected spectra are also searchable and interpretable in both commercial and institutional IR databases without mathematical modeling.

Optical constants and absorption properties of Te and TeO thin films in the 13-14†nm spectral range.

Undesired mask-induced effects caused by thick absorber layers in EUV photomasks reduce the quality of the projected patterns at the wafer stage in EUV photolithography scanners. New materials with better absorption properties than the state-of-the-art absorbers, TaN and TaBN, are required to mitigate these effects. In this work, we investigated the optical properties (δ and k) of Te and TeO films in the 13-14 nm range, and the absorption properties of these two materials at 13.5 nm. δ and k are obtained through fitting experimental values of reflectivity versus angle of incidence in the EUV range. We follow a methodology which combines different characterization techniques (X-ray reflectivity, EUV reflectivity, and X-ray photoemission spectroscopy) to reduce the number of free parameters in models and hence, increase the reliability of the optical constants obtained. At 13.5 nm, we obtain δ=0.03120, k = 0.07338 for Te, and δ=0.04099, k = 0.06555 for TeO. To experimentally verify the absorption properties of these materials, different thicknesses of Te and TeO films are cast on top of a state-of-the-art mask-quality EUV multilayer with 66.7% reflectivity at 13.5 nm. We found that a reflectivity of ∼0.7% can be attained with either 32.4 nm of Te, or 34.7 nm of TeO, greatly surpassing the absorption properties of TaN and TaBN. The morphology and surface roughness of the Te and TeO films deposited on the multilayer are also investigated.

Methodological approach for trace and essential elements assessment in prostate tissue by SRIXE method.

OBJECTIVE: The goal of this contribution is to present and familiarize the medical community with the method for the assessment of trace and essentials elements in prostate tissue sections. MATERIALS AND METHODS: X-ray fluorescence based technique(namely Synchrotron Induced X-ray Emission (SRIXE)) is described in terms of methodology, sample preparation and the evaluation of the recorded results (spectral data sets). Materials for the samples were collected from the patients underwent radical prostatectomy due to Adenocarcinoma prostatae. Specimens were freeze-dried, cut by microtome (to the thickness of 15 µm), one slice was placed on Mylar foil (for SRIXE measurements) and adjacent one on microscopic glass (for histopathological assessment). RESULTS: Results presented here show the usability of SRIXE method for the evaluation of concentration of trace and essential elements in prostate tissue sections with the spatial resolution better than 15 microns. DISCUSSION: Histopathological analysis of samples, which is only focused on morphological features, is unable to reveal information about changes in biochemical signature of tissues affected by the illness. SRIXE is a powerful and promising technique to analyse even very low concentrations oat the cellular level without any labelling or separating procedures. Obtained results may be correlated with classic histopathological assessment allowing for drawing conclusions on the changes in certain elements concentrations with the progression of disease. Moreover, mentioned in this work analysis, can be performed for any type of biological tissues.

Oxygen Passivation Mediated Tunability of Trion and Excitons in MoS_{2}.

Using wide spectral range in situ spectroscopic ellipsometry with systematic ultrahigh vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS_{2} isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A (1.92 eV) and B (2.02 eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure. This tunability of the excitonic effects is likely due to passivation and reemergence of the gap states in the band structure during oxygen adsorption and desorption, respectively, as indicated by ab initio density functional theory calculation results. This Letter unravels and emphasizes the important role of adsorbed oxygen in the optical spectra and many-body interactions of MoS_{2}.

Coexistence of Midgap Antiferromagnetic and Mott States in Undoped, Hole- and Electron-Doped Ambipolar Cuprates.

We report the first observation of the coexistence of a distinct midgap state and a Mott state in undoped and their evolution in electron and hole-doped ambipolar Y_{0.38}La_{0.62}(Ba_{0.82}La_{0.18})_{2}Cu_{3}O_{y} films using spectroscopic ellipsometry and x-ray absorption spectroscopies at the O K and Cu L_{3,2} edges. Supported by theoretical calculations, the midgap state is shown to originate from antiferromagnetic correlation. Surprisingly, while the magnetic state collapses and its correlation strength weakens with dopings, the Mott state in contrast moves toward a higher energy and its correlation strength increases. Our result provides important clues to the mechanism of electronic correlation strengths and superconductivity in cuprates.

Electronic defect states at the LaAlO3/SrTiO3 heterointerface revealed by O K-edge X-ray absorption spectroscopy.

Interfaces of two dissimilar complex oxides exhibit exotic physical properties that are absent in their parent compounds. Of particular interest is insulating LaAlO3 films on an insulating SrTiO3 substrate, where transport measurements have shown a metal-insulator transition as a function of LaAlO3 thickness. Their origin has become the subject of intense research, yet a unifying consensus remains elusive. Here, we report evidence for the electronic reconstruction in both insulating and conducting LaAlO3/SrTiO3 heterointerfaces revealed by O K-edge X-ray absorption spectroscopy. For the insulating samples, the O K-edge XAS spectrum exhibits features characteristic of electronically active point defects identified as noninteger valence states of Ti. For conducting samples, a new shape-resonance at ∼540.5 eV, characteristic of molecular-like oxygen (empty O-2p band), is observed. This implies that the concentration of electronic defects has increased in proportion with LaAlO3 thickness. For larger defect concentrations, the electronic defect states are no longer localized at the Ti orbitals and exhibit pronounced O 2p-O 2p character. Our results demonstrate that, above a critical thickness, the delocalization of O 2p electronic states can be linked to the presence of oxygen vacancies and is responsible for the enhancement of conductivity at the oxide heterointerfaces.

XAFCA: a new XAFS beamline for catalysis research.

A new X-ray absorption fine-structure (XAFS) spectroscopy beamline for fundamental and applied catalysis research, called XAFCA, has been built by the Institute of Chemical and Engineering Sciences, and the Singapore Synchrotron Light Source. XAFCA covers the photon energy range from 1.2 to 12.8 keV, making use of two sets of monochromator crystals, an Si (111) crystal for the range from 2.1 to 12.8 keV and a KTiOPO4 crystal [KTP (011)] for the range between 1.2 and 2.8 keV. Experiments can be carried out in the temperature range from 4.2 to 1000 K and pressures up to 30 bar for catalysis research. A safety system has been incorporated, allowing the use of flammable and toxic gases such as H2 and CO.

Pre-processing of Fourier transform infrared spectra by means of multivariate analysis implemented in the R environment.

Pre-processing of Fourier transform infrared (FTIR) spectra is typically the first and crucial step in data analysis. Very often hyperspectral datasets include the regions characterized by the spectra of very low intensity, for example two-dimensional (2D) maps where the areas with only support materials (like mylar foil) are present. In that case segmentation of the complete dataset is required before subsequent evaluation. The method proposed in this contribution is based on a multivariate approach (hierarchical cluster analysis), and shows its superiority when compared to the standard method of cutting-off by using only the mean spectral intensity. Both techniques were implemented and their performance was tested in the R statistical environment - open-source platform - that is a favourable solution if the repeatability and transparency are the key aspects.

Performance assessment and beamline diagnostics based on evaluation of temporal information from infrared spectral datasets by means of R Environment for statistical analysis.

Assessment of the performance and up-to-date diagnostics of scientific equipment is one of the key components in contemporary laboratories. Most reliable checks are performed by real test experiments while varying the experimental conditions (typically, in the case of infrared spectroscopic measurements, the size of the beam aperture, the duration of the experiment, the spectral range, the scanner velocity, etc.). On the other hand, the stability of the instrument response in time is another key element of the great value. Source stability (or easy predictable temporal changes, similar to those observed in the case of synchrotron radiation-based sources working in non top-up mode), detector stability (especially in the case of liquid nitrogen- or liquid helium-cooled detectors) should be monitored. In these cases, recorded datasets (spectra) include additional variables such as time stamp when a particular spectrum was recorded (in the case of time trial experiments). A favorable approach in evaluating these data is building hyperspectral object that consist of all spectra and all additional parameters at which these spectra were recorded. Taking into account that these datasets could be considerably large in size, there is a need for the tools for semiautomatic data evaluation and information extraction. A comprehensive R archive network--the open-source R Environment--with its flexibility and growing potential, fits these requirements nicely. In this paper, examples of practical implementation of methods available in R for real-life Fourier transform infrared (FTIR) spectroscopic data problems are presented. However, this approach could easily be adopted to many various laboratory scenarios with other spectroscopic techniques.

Defect Engineering and Emission Tuning of Wide-Bandgap MAPbCl3 Perovskite.

Lead-chloride perovskites are promising candidates for optoelectronic applications, such as visible-blind UV photodetection. It remains unclear how the deep defects in this wide-bandgap material impact the carrier recombination dynamics. In this work, we study the defect properties of MAPbCl3 (MA = CH3NH3) based on photoluminescence (PL) measurements. Our investigations show that apart from the intrinsic emission, four sub-bandgap emissions emerge, which are very likely to originate from the radiative recombination of excitons bound to several intrinsic vacancy and interstitial defects. The intensity of various emission features can be tuned by adjusting the type and ratio of precursors used during synthesis. Our study not only provides important insights into the defect property and carrier recombination mechanism in this class of material but also demonstrates efficient strategies for defect passivation and engineering, paving the way for further development of lead-chloride perovskite-based optoelectronic devices.

Robust Superconductivity in Infinite-Layer Nickelates.

The recent discovery of nickelate superconductivity represents an important step toward understanding the four-decade mastery of unconventional high-temperature superconductivity. However, the synthesis of the infinite-layer nickelate superconductors shows great challenges. Particularly, surface capping layers are usually unitized to facilitate the sample synthesis. This leads to an important question whether nickelate superconductors with d9 configuration and ultralow valence of Ni1+ are in metastable state and whether nickelate superconductivity can be robust? In this work, a series of redox cycling experiments are performed across the phase transition between perovskite Nd0.8Sr0.2NiO3 and infinite-layer Nd0.8Sr0.2NiO2. The infinite-layer Nd0.8Sr0.2NiO2 is quite robust in the redox environment and can survive the cycling experiments with unchanged crystallographic quality. However, as the cycling number goes on, the perovskite Nd0.8Sr0.2NiO3 shows structural degradation, suggesting stability of nickelate superconductivity is not restricted by the ultralow valence of Ni1+, but by the quality of its perovskite precursor. The observed robustness of infinite-layer Nd0.8Sr0.2NiO2 up to ten redox cycles further indicates that if an ideal high-quality perovskite precursor can be obtained, infinite-layer nickelate superconductivity can be very stable and sustainable under environmental conditions. This work provides important implications for potential device applications for nickelate superconductors.