Atomic Electron Research Articles

Binary ZnS–ZnO films as an alternative buffer layer for solar cell applications

In this research, binary ZnS–ZnO films were fabricated by a two-step process, offering an alternative buffer layer solution for photovoltaic solar cell applications. ZnS films were attained through thermal evaporation, after which they were annealed in air at separate temperatures resulting in films containing both ZnS and ZnO phases. Structural, electrical, ellipsometric, optical, and surface properties were examined in detail to elucidate their applicability as a buffer layer in photovoltaic applications. X-ray diffraction patterns revealed that the films exhibit cubic ZnS and hexagonal ZnO crystal structures, wherein crystallite size is augmented with higher annealing temperatures. ZnS films exhibited a needle-shaped surface morphology, as confirmed through atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) images. Annealing caused noteworthy modifications on the surfaces of the films. Additionally, absorption spectra denote two distinct absorption regions forming as a result of the annealing process, possibly indicating the emergence of ZnS and ZnO phases. Photoluminescence analyses demonstrate that binary ZnS–ZnO films exhibit greater emission intensities than single-phase ZnS films. Additionally, the annealing process caused the electrical resistivity of films to reduce from 1.28 × 105 to 3.84 × 101 Ω cm. These results suggest that binary ZnS–ZnO films produced via annealing can be considered as promising buffer layers in potential photovoltaic solar cell applications.

Intergranular corrosion of Ni-30Cr in high-temperature hydrogenated water after removing surface passivating film

High-resolution transmission electron microscopy and atom probe tomography are used to characterize the initial passivation and subsequent intergranular corrosion of degraded grain boundaries in a model Ni-30Cr alloy exposed to 360 °C hydrogenated water. Upon initial exposure for 1000 h, the alloy surface directly above the grain boundary forms a thin passivating film of Cr2O3, protecting the underlying grain boundary from intergranular corrosion. However, the metal grain boundary experiences severe Cr depletion and grain boundary migration during this initial exposure. To understand how Cr depletion affects further corrosion, the local protective film was sputtered away using a glancing angle focused ion beam. Upon further exposure, the surface fails to repassivate, and intergranular corrosion is observed through the Cr-depleted region. Through this combination of high-resolution microscopy and localized passive film removal, we show that, although high-Cr alloys are resistant to intergranular attack and stress corrosion cracking, degradation-induced changes in the underlying metal at grain boundaries make the material more susceptible once the initial passive film is breached.

Transmission electron microscopy study of the radiation-induced amorphization in the Cr-W-C ternary M23C6

To provide mechanistic insight into the phase stability of M23C6 under irradiation, bulk M23C6 (Cr-W-C system) specimens with a W concentration range of 0–12 at.% were first subjected to helium ion irradiation and then investigated by systematic TEM/STEM observation. The atomic resolution electron microscopy analysis revealed that the preferential occupation site of the W atom is the 8c site, and the 48 h site is also occupied when the W concentration is >7 at.%. The atomic arrangement of the M23C6 particle in F82H steel is similar to that of the specimen of 1 W (3 at.% W), and the chemical formula of the M23C6 particle in F82H steel is described as Cr13Fe9W1C6. Radiation-induced amorphization was strongly related to the W concentration in the bulk M23C6, and amorphization was observed only at W concentrations of ∼12 at.% under the present irradiation condition. Line analysis of HAADF and its FFT images confirmed the chemical disordering associated with W atoms, which appears to increase with increasing W concentration. Based on these results, the mechanism of radiation-induced amorphization appears to be different between bulk M23C6 and the M23C6 particles. Specifically, the amorphization of bulk M23C6 is mainly influenced by the addition of a high concentration of W, while the synergistic effects of elements including Cr, Fe, and W are attributed to RIA in fine M23C6 particles. Moreover, the energetic change associated with the W/Fe atom exchange in the M23C6 system is estimated to explain the occurrence of chemical disordering and its resultant amorphization behavior, which provides a new viewpoint to achieve a deeper understanding of the mechanisms behind radiation-induced amorphization. Secondary abstractThe chemical composition of M23C6 particles in F82H steel and the hypothesis of its radiation-induced amorphization mechanism was proposed by HREM observation of He-irradiated M23C6 ingots.

In vitro and in ovo photodynamic efficacy of nebulized curcumin-loaded tetraether lipid liposomes prepared by DC as stable drug delivery system

Lung cancer is one of the most common causes of high mortality worldwide. Current treatment strategies, e.g., surgery, radiotherapy, chemotherapy, and immunotherapy, insufficiently affect the overall outcome. In this study, we used curcumin as a natural photosensitizer in photodynamic therapy and encapsulated it in liposomes consisting of stabilizing tetraether lipids aiming for a pulmonary drug delivery system against lung cancer. The liposomes with either hydrolyzed glycerol-dialkyl-glycerol tetraether (hGDGT) in different ratios or hydrolyzed glycerol-dialkyl-nonitol tetraether (hGDNT) were prepared by dual centrifugation (DC), an innovative method for liposome preparation. The liposomes’ physicochemical characteristics before and after nebulization and other nebulization characteristics confirmed their suitability. Morphological characterization using atomic force and transmission electron microscopy showed proper vesicular structures indicative of liposomes. Qualitative and quantitative uptake of the curcumin-loaded liposomes in lung adenocarcinoma (A549) cells was visualized and proven. Phototoxic effects of the liposomes were detected on A549 cells, showing decreased cell viability. The generation of reactive oxygen species required for PDT and disruption of mitochondrial membrane potential were confirmed. Moreover, the chorioallantoic membrane (CAM) model was used to further evaluate biocompatibility and photodynamic efficacy in a 3D cell culture context. Photodynamic efficacy was assessed by PET/CT after nebulization of the liposomes onto the xenografted tumors on the CAM with subsequent irradiation. The physicochemical properties and the efficacy of tetraether lipid liposomes encapsulating curcumin, especially liposomes containing hGDNT, in 2D and 3D cell cultures seem promising for future PDT usage against lung cancer.

Establishing Ohmic Contact of a Radial Compressed CNT Bundle with High Work Function Metal.

Establishing low-resistance ohmic contact is critical for developing electronic devices based on traditional silicon and new low-dimensional materials. Due to unprecedented electronic and mechanical properties, the one-dimensional carbon nanotubes (CNTs) have been used as source/drain, gate, or tunnel to fabricate transistors. However, the mechanism causing low-resistance ohmic contact is not clear yet. Here, the hybrid atomic force microscopy-scanning electron microscopy (AFM-SEM) instrument was developed to establish lower-resistance ohmic contact between a radial compressed deformed multiwalled CNT bundle and high work function metal (platinum and gold). The radial compression structure under strong van der Waals attraction was in situ characterized through the SEM image to obtain the diameter and width and through AFM to get height and to perform nanoindentation, indicating that Pt has the smaller radial compression deformation. Molecular dynamics simulations exhibit that compared to Pt, a wider ribbon-like graphene layer formed when the radial compressed CNTs contacted with Au. The bond forming and electron orbital overlapping between C atoms of deformed CNTs and the high work function metal atom is beneficial for good electrical contact.

Cr5.7Si2.3P8N24-A Chromium(+IV) Nitridosilicate Phosphate with Amphibole-Type Structure.

The first nitridic analog of an amphibole mineral, the quaternary nitridosilicate phosphate Cr5.7Si2.3P8N24 was synthesized under high-pressure high-temperature conditions at 1400 °C and 12 GPa from the binary nitrides Cr2N, Si3N4 and P3N5, using NH4N3 and NH4F as additional nitrogen source and mineralizing agent, respectively. The crystal structure was elucidated by single-crystal X-ray diffraction with microfocused synchrotron radiation (C2/m, a=9.6002(19), b=17.107(3), c=4.8530(10) Å, β=109.65(3)°). The elemental composition was analyzed by energy dispersive X-ray spectroscopy. The structure consists of vertex-sharing PN4-tetrahedra forming zweier double chains and edge-sharing (Si,Cr)-centered octahedra forming separated ribbons. Atomic resolution scanning transmission electron microscopy shows ordered Si and Cr sites next to a disordered Si/Cr site. Optical spectroscopy indicates a band gap of 2.1 eV. Susceptibility measurements show paramagnetic behavior and support the oxidation state Cr+IV, which is confirmed by EPR. The comprehensive analysis expands the field of Cr-N chemistry and provides access to a nitride analog of one of the most prevalent silicate structures.

Cr5.7Si2.3P8N24—A Chromium(+IV) Nitridosilicate Phosphate with Amphibole‐Type Structure

AbstractThe first nitridic analog of an amphibole mineral, the quaternary nitridosilicate phosphate Cr5.7Si2.3P8N24 was synthesized under high‐pressure high‐temperature conditions at 1400 °C and 12 GPa from the binary nitrides Cr2N, Si3N4 and P3N5, using NH4N3 and NH4F as additional nitrogen source and mineralizing agent, respectively. The crystal structure was elucidated by single‐crystal X‐ray diffraction with microfocused synchrotron radiation (C2/m, a=9.6002(19), b=17.107(3), c=4.8530(10) Å, β=109.65(3)°). The elemental composition was analyzed by energy dispersive X‐ray spectroscopy. The structure consists of vertex‐sharing PN4‐tetrahedra forming zweier double chains and edge‐sharing (Si,Cr)‐centered octahedra forming separated ribbons. Atomic resolution scanning transmission electron microscopy shows ordered Si and Cr sites next to a disordered Si/Cr site. Optical spectroscopy indicates a band gap of 2.1 eV. Susceptibility measurements show paramagnetic behavior and support the oxidation state Cr+IV, which is confirmed by EPR. The comprehensive analysis expands the field of Cr−N chemistry and provides access to a nitride analog of one of the most prevalent silicate structures.

Scanning transmission electron microscopy and atom probe tomography analysis of non-stoichiometry long-period-stacking-ordered structures in Mg-Ni-Y/Sm alloys

The long-period-stacking-ordered (LPSO) structure affects the mechanical, corrosion and hydrolysis properties of Mg alloys. The current work employs high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) and atom probe tomography (APT) to investigate the structural and local chemical information of LPSO phases formed in Mg-Ni-Y/Sm ternary alloys after extended isothermal annealing. Depending on the alloying elements and their concentrations, Mg-Ni-Y/Sm develops a two-phase LPSO + α-Mg structure in which the LPSO phase contains defects, hybrid LPSO structure, and Mg insertions. HAADF-STEM and APT indicate non-stoichiometric LPSO with incomplete Ni6(Y/Sm)8 clusters. In addition, the APT quantitatively determines the local composition of LPSO and confirms the presence of Ni within the Mg bonding layers. These results provide insight into a better understanding of the structure and hydrolysis properties of LPSO-Mg alloys.

Characterization and modeling of plasma sheath in 2.45 GHz hydrogen ECR ion sources

In this article, we present a multi-fluid numerical model developed for application on electron cyclotron resonance ion sources (ECRIS). The 1D-model is matured to compute the density of the ion species in the plasma sheath in the presence of an inhomogeneous magnetic field of a 2.45 GHz ECRIS. The multi-fluid model in cylindrical coordinates is focused on solving the continuity and momentum equations of hydrogen plasma particles to characterize their sheath properties. In addition, 28 important processes, including volume and surface collisions, have been included in the COMSOL Multiphysics package to simulate the ECR plasma. We study the elementary processes containing electron–atom, electron–molecule, atom–molecule, molecule–molecule, and particle–wall interactions. Then, the results of the model and the simulation of a 2D-hydrogen plasma are reported, and future perspectives are discussed throughout the paper.

Localized electronic reconfiguration at CoNi-BTC-MOFs to accelerate oxygen evolution reaction

To efficiently control oxygen evolution reaction (OER) at electrocatalysts holds enormous promise for large-scale production of clean energy, but faces the scarcity of practical regulation strategies due to underexplored catalytic mechanism. Herein, a facile and feasible strategy is developed involving metal-metal super-exchange interaction to manipulate the electronic state configuration of catalysts, and the as-synthesized Ni-doped Co-1,3,5-benzenetricarboxylic acid Metal-Organic Frameworks (MOFs) only require an overpotential as low as 260 mV to reach a large current of 200 mA cm−2, which is much lower than 400 mV for the commercial RuO2 catalyst. The introduced Ni atoms lead to more broadly occupied states and d-band center close to the Fermi energy level for the spin-polarization of the electrons in Co atoms, thus decreasing the orbital occupancy to facilitate the adsorption/desorption of the reaction intermediates and lowering the rate-determining step barrier to accelerate OER. Our findings have an important paradigm role in the design of electrocatalysts with high performance for oxygen evolution reaction.

Surface activation of Hastalex by vacuum argon plasma for cytocompatibility enhancement

Here, we present surface analysis and biocompatibility evaluation of novel composite material based on graphene oxide traded as Hastalex. First, the surface morphology and elemental analysis of the pristine material were examined by atomic force and scanning electron microscopies, and by energy-dispersive and X-ray photoelectron spectroscopies, respectively. The Hastalex surface was then modified by plasma (3 and 8 W with exposure times up to 240 s), the impact of which on the material surface wettability and morphology was further evaluated. In addition, the material aging was studied at room and elevated temperatures. Significant changes in surface roughness, morphology, and area were detected at the nanometer scale after plasma exposure. An increase in oxygen content due to the plasma exposure was observed both for 3 and 8 W. The plasma treatment had an outstanding effect on the cytocompatibility of Hastalex foil treated at both input powers of 3 and 8 W. The cell number of human MRC-5 fibroblasts on Hastalex foils exposed to plasma increased significantly compared to pristine Hastalex and even to tissue culture polystyrene. The plasma exposure also affected the fibroblasts’ cell growth and shape.

Atomic single-molecule imaging by the confinement methods in advanced microscopy

Atomic single-molecule imaging has drawn extensive attention for exploring different behaviors and properties of small molecules. However, current techniques still face challenges, due to the thermal activity and beam sensitivity of small molecules. Recently, ångström-level spatial resolution for single molecules was successfully demonstrated using different imaging methods, including scanning tunneling microscopy, atomic force microscopy, cryogenic and transmission electron microscopy. In this perspective, we focus on different confinement strategies in these single-molecule imaging techniques, and summarize the recent studies of the structures and behaviors of single molecules. Especially, a new concept of spatial confinement at room temperature has been achieved by using microporous materials, such as zeolites, which has made it possible to fix and visualize the configurations of single molecule inside channels. In outlook, we describe what progress we can make along such a confinement strategy, and what new perspectives and discoveries we may find beyond our imagination.

Method for in situ polypyrrole coating, and the example of its use for functionalization of polyurethane anisotropic electrospun mats

The in situ coating of polymer substrate with polypyrrole, described herein with detailed know-how, represents a novel technique of surface functionalization. The choice of oxidizing agent and the polymerization time both affect the properties of the thin polypyrrole layer. The specific conductivity, free surface energy, thickness, topography, and FTIR spectra of polypyrrole layer were determined. The conductive coatings were further used to functionalize both isotropic and anisotropic electrospun polyurethane nanofibrous mats to show their applicability and study the bioactive effect of both the anisotropy and conductivity together. The morphology of composites was studied by means of atomic force microscopy and scanning electron microscopy. A complex cytocompatibility study was performed, including determining cytotoxicity by optical and fluorescence microscopy, the advanced qualification of cell morphology by cell-image analysis, and a study of stem cell behavior. The results clearly showed the significant impact of substrate modification on cells, especially on fibroblasts while the embryonic stem cells were less affected. This study shows not only the effective way to prepare a thin conducting layer based on polypyrrole but also demonstrates its importance for the fabrication of smart biomaterials.

Transferable Hirshfeld atom model for rapid evaluation of aspherical atomic form factors.

Form factors based on aspherical models of atomic electron density have brought great improvement in the accuracies of hydrogen atom parameters derived from X-ray crystal structure refinement. Today, two main groups of such models are available, the banks of transferable atomic densities parametrized using the Hansen-Coppens multipole model which allows for rapid evaluation of atomic form factors and Hirshfeld atom refinement (HAR)-related methods which are usually more accurate but also slower. In this work, a model that combines the ideas utilized in the two approaches is tested. It uses atomic electron densities based on Hirshfeld partitions of electron densities, which are precalculated and stored in a databank. This model was also applied during the refinement of the structures of five small molecules. A comparison of the resulting hydrogen atom parameters with those derived from neutron diffraction data indicates that they are more accurate than those obtained with the Hansen-Coppens based databank, and only slightly less accurate than those obtained with a version of HAR that neglects the crystal environment. The advantage of using HAR becomes more noticeable when the effects of the environment are included. To speed up calculations, atomic densities were represented by multipole expansion with spherical harmonics up to l = 7, which used numerical radial functions (a different approach to that applied in the Hansen-Coppens model). Calculations of atomic form factors for the small protein crambin (at 0.73 Å resolution) took only 68 s using 12 CPU cores.

Phase Transformation Temperature Prediction in Steels via Machine Learning.

The phase transformation temperature plays an important role in the design, production and heat treatment process of steels. In the present work, an improved version of the gradient-boosting method LightGBM has been utilized to study the influencing factors of the four phase transformation temperatures, namely Ac1, Ac3, the martensite transformation start (MS) temperature and the bainitic transformation start (BS) temperature. The effects of the alloying element were discussed in detail by comparing their influencing mechanisms on different phase transformation temperatures. The training accuracy was significantly improved by further introducing appropriate features related to atomic parameters. The melting temperature and coefficient of linear thermal expansion of the pure metals corresponding to the alloying elements, atomic Waber-Cromer pseudopotential radii and valence electron number were the top four among the eighteen atomic parameters used to improve the trained model performance. The training and prediction processes were analyzed using a partial dependence plot (PDP) and Shapley additive explanation (SHAP) methods to reveal the relationships between the features and phase transformation temperature.

A Quantum Mechanical Treatment of Electron Broadening in Strong Magnetic Fields. II. Large Enhancements due to Exchange Interactions

We present a quantum treatment of atom–electron collisions in magnetic fields, demonstrating the significant importance of including the effect of exchange that arises from two interacting electrons. We find strange behaviors that are not encountered in collisions without a magnetic field. In high magnetic fields, exchange can lead to orders of magnitude enhancements of collision cross sections. Additionally, the elastic collision cross sections that involve the ground state become comparable to those involving excited states, and states with large orbits have the largest contribution to the collisions. We anticipate significant changes to spectral line broadening in neutron star surfaces and atmospheres.

Strengthen oriented poly (L-lactic acid) monofilaments via mechanical training

Polymer materials have found extensive applications in the clinical and medical domains due to their exceptional biocompatibility and biodegradability. Compared to metallic counterparts, polymers, particularly Poly (L-lactic acid) (PLLA), are more suitable for fabricating biodegradable stents. As a viscoelastic material, PLLA monofilaments exhibit a creep phenomenon under sustained tensile stress. This study explores the use of creep to enhance the mechanical attributes of PLLA monofilaments. By subjecting the highly oriented monofilaments to controlled, constant force stretching, we achieved notable improvements in their mechanical characteristics. The results, as confirmed by tensile testing and dynamic mechanical analysis, revealed a remarkable 67 % increase in total elongation and over a 20 % rise in storage modulus post-mechanical training. Further microscopic analyses, including Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM), revealed enhanced spacing and cavity formation. These mechanical advancements are attributed to the unraveling and a more orderly arrangement of molecular chains in the amorphous regions. This investigation offers a promising approach for augmenting the mechanical properties of PLLA monofilaments, potentially benefiting their application in biomedical engineering.

Synergistic incorporation of Ti3C2Tx with sulfonated poly(phenylene oxide) membranes: Unravelling multifaceted advancements in physicochemical, electrochemical, and antibacterial domains for enhanced electrodialytic desalination

This study delves into the solution-phase incorporation of Ti3C2Tx nanosheets into sulfonated poly(phenylene oxide) (SPPO) to prevail the conventional challenge of distant ionic channels in membranes. A series of membranes incorporating MXene (Ti3C2Tx nanosheets) at varying weight percentages (1 wt%, 2 wt%, and 5 wt%) underwent meticulous scrutiny of their physicochemical and electrochemical attributes. Among this series, MXe-02 emerged as particularly noteworthy, showing remarkable water sorption (WS= 43.8%), ion exchange capacity (IEC: 1.65 ± 0.05 meqg−1), and ionic conductivity (IC: 2.83×10−2 S cm−1), coupled with minimal dimensional change of 8.57% compared to its pristine counterpart, SPPO-B (WS=35.70%, IEC: 1.03±0.05 meqg−1, IC: 1.98×10–2 S cm−1). Advanced analytical techniques such as atomic force microscopy (AFM) and field emission-scanning electron microscopy (FE-SEM) provided insights into hydrophilic-hydrophobic phase separation, ionic domain clustering, and membrane surface attributes pivotal for enhancing electrochemical properties. Beyond optimal concentrations (>2 wt%), a significant composite-agglomeration effect hindered further advancements in physicochemical and electrochemical aspects, as verified by zeta potential measurements. The optimized MXe-02 membrane boasted a notable transport number of 0.89 with a substantial limiting current density (Ilim = 45 mA cm−2), offering a wide window for swift electrodialytic desalination. Moreover, MXe-02 membranes demonstrated an energy consumption of 0.98 kWh kg−1 and 93.52% energy efficiency, affirming their efficacy for brackish water desalination. Antibacterial properties were evaluated against Escherichia coli and Staphylococcus aureus, revealing MXe-02 and MXe-05's distinct zones of inhibition against S. aureus, highlighting their excellent antibacterial efficacy against Gram-positive bacteria. This comprehensive study shows the intricate interplay of MXene-incorporated membranes, offering valuable insights for advancing electrochemical and antibacterial performance in water desalination.

A Novel Non-Fullerene D-A Interface with Two Asymmetrical Electron Acceptors Facilitates Charge and Energy Transfer for Effective Carbon Dioxide Reduction.

Converting carbon dioxide (CO2) into high-value chemicals using solar energy remains a formidable challenge. In this study, the CSC@PM6:IDT6CN-M:IDT8CN-M non-fullerene small-molecule organic semiconductor is designed with highly efficient electron donor-acceptor (D-A) interface for photocatalytic reduction of CO2. Atomic Force Microscope and Transmission Electron Microscope images confirmed the formation of an interpenetrating fibrillar network after combination of donor and acceptor. The CO yield from the CSC@PM6:IDT6CN-M:IDT8CN-M reached 1346µmolg-1h-1, surpassing those of numerous reported inorganic photocatalysts. The D-A structure effectively facilitated charge separation to enable electrons transfer from the PM6 to IDT6CN-M:IDT8CN-M. Meanwhile, attributing to the dipole moments of the strong intermolecular interactions between IDT6CN-M and IDT8CN-M, the intermolecular forces are enhanced, and laminar stacking and π-π stacking are strengthened, thereby reinforcing energy transfer between acceptor molecules and significantly enhanced charge separation. Moreover, the strong internal electric field in the D-A interface enhanced the excited state lifetime of PM6:IDT6CN-M:IDT8CN-M. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis demonstrated that carboxylate (COOH*) is the predominant intermediate during CO2 reduction, and possible pathways of CO2 reduction to CO are deduced. This study presents a novel approach for designing materials with D-A interface to achieve high photocatalytic activity.

ERCS24: An updated version of the ERCS08 program for calculations of the cross sections for atomic electron removal based on the ECPSSR theory and its variants

ERCS24: An updated version of the ERCS08 program for calculations of the cross sections for atomic electron removal based on the ECPSSR theory and its variants