Alkali cation stabilization of defects in 2D MXenes at ambient and elevated temperatures.

Transition metal carbides have been adopted in energy storage, conversion, and extreme environment applications. Advancements in their 2D counterparts, known as MXenes, enable the design of unique structures at the ~1 nm thickness scale. Alkali cations have been essential in MXenes manufacturing processing, storage, and applications, however, exact interactions of these cations with MXenes are not fully understood. In this study, using Ti3C2Tx, Mo2TiC2Tx, and Mo2Ti2C3Tx MXenes, we present how transition metal vacancy sites are occupied by alkali cations, and their effect on MXene structure stabilization to control MXene's phase transition. We examine this behavior using in situ high-temperature x-ray diffraction and scanning transmission electron microscopy, ex situ techniques such as atomic-layer resolution secondary ion mass spectrometry, and density functional theory simulations. In MXenes, this represents an advance in fundamentals of cation interactions on their 2D basal planes for MXenes stabilization and applications. Broadly, this study demonstrates a potential new tool for ideal phase-property relationships of ceramics at the atomic scale.

Unraveling the composition of each atomic layer in the MXene/MAX phase structure - identification of oxycarbide, oxynitride, and oxycarbonitride subfamilies of MXenes.

MXenes, the largest known family of 2D materials, are known for their complicated structure consisting of many different elements. Their properties can be finely tuned by precise engineering of the composition of each atomic layer. Thus it is necessary to further develop the secondary ion mass spectrometry (SIMS) technique which can unambiguously identify each element with atomic precision. The newly established protocol of deconvolution and calibration of the SIMS data enables layer-by-layer characterization of MAX phase and MXene samples with ±1% accuracy. Such precision is particularly important for samples that consist of several different transition metals in their structure. This confirms that most MXenes contain a substantial amount of oxygen in the X layers, thus enabling the identification of oxycarbide, oxynitride, and oxycarbonitride subfamilies of these materials. It can also be applied for under- and over-etched samples and to determine the exact composition of termination layers. Generally, the SIMS technique may provide invaluable support in the synthesis and optimization of MAX phase and MXene studies.

TiO2/PDA Multilayer Nanocomposites with Exceptionally Sharp Large-Scale Interfaces and Nitrogen Doping Gradient.

The evolving field of photocatalysis requires the development of new functional materials, particularly those suitable for large-scale commercial systems. One particularly promising approach is the creation of hybrid organic/inorganic materials. Despite being extensively studied, materials such as polydopamine (PDA) and titanium oxide continue to show significant promise for use in such applications. Nitrogen-doped titanium oxide and free-standing PDA films obtained at the air/water interface are particularly interesting. This study introduces a straightforward and reproducible approach for synthesizing a novel class of large-scale multilayer nanocomposites. The method involves the alternate layering of high-quality materials at the air/water interface combined with precise atomic layer deposition techniques, resulting in a gradient nitrogen doping of titanium oxide layers with exceptionally sharp oxide/polymer interfaces. The analysis confirmed the presence of nitrogen in the interstitial and substitutional sites of the TiO2 lattice while maintaining the 2D-like structure of the PDA films. These chemical and structural characteristics translate into a reduction of the band gap by over 0.63 eV and an increase in the photogenerated current by over 60% compared with pure amorphous TiO2. Furthermore, the nanocomposites demonstrate excellent stability during the 1 h continuous photocurrent generation test.

Ultrafast optical properties of stoichiometric and non-stoichiometric refractory metal nitrides TiNx, ZrNx, and HfNx.

Refractory metal nitrides have recently gained attention in various fields of modern photonics due to their cheap and robust production technology, silicon-technology compatibility, high thermal and mechanical resistance, and competitive optical characteristics in comparison to typical plasmonic materials like gold and silver. In this work, we demonstrate that by varying the stoichiometry of sputtered nitride films, both static and ultrafast optical responses of refractory metal nitrides can efficiently be controlled. We further prove that the spectral changes in ultrafast transient response are directly related to the position of the epsilon-near-zero region. At the same time, the analysis of the temporal dynamics allows us to identify three time components: the "fast" femtosecond one, the "moderate" picosecond one, and the "slow" at the nanosecond time scale. We also find out that the non-stoichiometry does not significantly decrease the recovery time of the reflectance value. Our results show the strong electron-phonon coupling and reveal the importance of both the electron and lattice temperature-induced changes in the permittivity near the ENZ region and the thermal origin of the long tail in the transient optical response of refractory nitrides.

Insights into the physical and chemical properties of struvite crystal surfaces in terms of the effectiveness of bacterial adhesion.

In this paper, we present the results of research on the physicochemical properties of two selected faces of the struvite crystal, which is the main component of infectious urinary stones. Two main faces, (001) and ([Formula: see text]), ending the c-axis, were selected for the study. These faces are not related by symmetry relations, which means, among other things, that they should have a different atomic structure, which was confirmed experimentally. In addition, the studies show that the tested surfaces have hydrophilic properties, however, the ([Formula: see text]) face is more hydrophilic compared to the (001) face. The physicochemical properties of the crystal as a whole, as well as the physicochemical properties of these faces influence the magnitude of adhesion. The adhesive force in both water and artificial urine is greater for face ([Formula: see text]) compared to face (001). The assessment of the adhesion of Proteus mirabilis bacteria in artificial urine also shows that the adhesion is greater for face ([Formula: see text]) than for face (001). The adhesion of bacteria to the examined faces of the struvite crystal, and in particular the increased adhesion of bacteria to the face ([Formula: see text]), may be the first stage of biofilm formation, which may result in a high rate of recurrence of infectious urinary stones after treatment.

Development of Quaternary InAlGaN Barrier Layer for High Electron Mobility Transistor Structures.

A quaternary lattice matched InAlGaN barrier layer with am indium content of 16.5 ± 0.2% and thickness of 9 nm was developed for high electron mobility transistor structures using the metalorganic chemical-vapor deposition method. The structural, morphological, optical and electrical properties of the layer were investigated planning realization of microwave power and terahertz plasmonic devices. The measured X-ray diffraction and modeled band diagram characteristics revealed the structural parameters of the grown In0.165Al0.775Ga0.06N/Al0.6Ga0.4N/GaN heterostructure, explaining the origin of barrier photoluminescence peak position at 3.98 eV with the linewidth of 0.2 eV and the expected red-shift of 0.4 eV only. The thermally stable density of the two-dimension electron gas at the depth of 10.5 nm was experimentally confirmed to be 1.2 × 1013 cm-2 (1.6 × 1013 cm-2 in theory) with the low-field mobility values of 1590 cm2/(V·s) and 8830 cm2/(V·s) at the temperatures of 300 K and 77 K, respectively.

Titanium Nitride as a Plasmonic Material from Near-Ultraviolet to Very-Long-Wavelength Infrared Range.

Titanium nitride is a well-known conductive ceramic material that has recently experienced resumed attention because of its plasmonic properties comparable to metallic gold and silver. Thus, TiN is an attractive alternative for modern and future photonic applications that require compatibility with the Complementary Metal-Oxide-Semiconductor (CMOS) technology or improved resistance to temperatures or radiation. This work demonstrates that polycrystalline TiNx films sputtered on silicon at room temperature can exhibit plasmonic properties continuously from 400 nm up to 30 µm. The films' composition, expressed as nitrogen to titanium ratio x and determined in the Secondary Ion Mass Spectroscopy (SIMS) experiment to be in the range of 0.84 to 1.21, is essential for optimizing the plasmonic properties. In the visible range, the dielectric function renders the interband optical transitions. For wavelengths longer than 800 nm, the optical properties of TiNx are well described by the Drude model modified by an additional Lorentz term, which has to be included for part of the samples. The ab initio calculations support the experimental results both in the visible and infra-red ranges; particularly, the existence of a very low energy optical transition is predicted. Some other minor features in the dielectric function observed for the longest wavelengths are suspected to be of phonon origin.

Mechanisms of Ohmic Contact Formation of Ti/Al-Based Metal Stacks on p-Doped 4H-SiC.

Ohmic contacts on p-doped 4H-SiC are essential for the fabrication of a wide range of power electron devices. Despite the fact that Ti/Al based ohmic contacts are routinely used for ohmic contacts on p-doped 4H-SiC, the underlying contact formation mechanisms are still not fully understood. TLM structures were fabricated, measured and analyzed to get a better understanding of the formation mechanism. SIMS analyses at the Ti3SiC2-SiC interface have shown a significant increase of the surface near Al concentration. By using numerical simulation it is shown that this additional surface near Al concentration is essential for the ohmic contact formation.

3D Depth Profile Reconstruction of Segregated Impurities using Secondary Ion Mass Spectrometry.

The presented protocol combines excellent detection limits (1 ppm to 1 ppb) using secondary ion mass spectrometry (SIMS) with reasonable spatial resolution (~1 µm). Furthermore, it describes how to obtain realistic three-dimensional (3D) distributions of segregated impurities/dopants in solid state materials. Direct 3D depth profile reconstruction is often difficult to achieve due to SIMS-related measurement artifacts. Presented here is a method to identify and solve this challenge. Three major issues are discussed, including the i) nonuniformity of the detector being compensated by flat-field correction; ii) vacuum background contribution (parasitic oxygen counts from residual gases present in the analysis chamber) being estimated and subtracted; and iii) performance of all steps within a stable timespan of the primary ion source. Wet chemical etching is used to reveal the position and types of dislocation in a material, then the SIMS result is superimposed on images obtained via scanning electron microscopy (SEM). Thus, the position of agglomerated impurities can be related to the position of certain defects. The method is fast and does not require sophisticated sample preparation stage; however, it requires a high-quality, stable ion source, and the entire measurement must be performed quickly to avoid deterioration of the primary beam parameters.

Magnetic Domains without Domain Walls: A Unique Effect of He

We show that it is possible to engineer magnetic multidomain configurations without domain walls in a prototypical rare-earth-transition-metal ferrimagnet using keV He^{+} ion bombardment. We additionally show that these patterns display a particularly stable magnetic configuration due to a deep minimum in the energy of the system caused by flux closure and a corresponding reduction of the magnetostatic energy without an increase in energy by exchange and anisotropy terms across the walls. This occurs because light-ion bombardment affects an element's relative contribution to the properties of the ferrimagnet differently. Therefore, it is possible to control the relative contribution from each magnetic subsystem. The selection of material and the use of light-ion bombardment allow us to engineer domain patterns in continuous magnetic films, which open a way to fabricate them in a much smaller scale than currently possible. Our Letter emphasizes that the right criterion to determine the presence or absence of a domain wall is whether there is a rotation of the spin for each sublattice and that changes of the direction of effective magnetization alone do not constitute an appropriate criterion.

Growth of highly oriented MoS2via an intercalation process in the graphene/SiC(0001) system.

A method of growing highly oriented MoS2 is presented. First, a Mo film is deposited on a graphene/SiC(0001) substrate and the subsequent annealing of it at 750 °C leads to intercalation of Mo underneath the graphene layer, which is confirmed by secondary ion mass spectrometry (SIMS) measurements. Formation of highly oriented MoS2 layers is then achieved by sulfurization of the graphene/Mo/SiC system using H2S gas. X-ray diffraction reveals that the MoS2 layers are highly oriented and parallel to the underlying SiC substrate surface. Further SIMS experiments reveal that the intercalation process occurs via the atomic step edges of SiC and Mo and S atoms gradually diffuse along SiC atomic terraces leading to the creation of the MoS2 layer. This observation can be explained by a mechanism of highly oriented growth of MoS2: nucleation of the crystalline MoS2 phase occurs underneath the graphene planes covering the flat parts of SiC steps and Mo and S atoms create crystallization fronts moving along terraces.

Three dimensional localization of unintentional oxygen impurities in gallium nitride.

Further development of gallium nitride (GaN) based optoelectronic devices requires in-depth understanding of the defects present in GaN grown on a sapphire substrate. In this work, we present three dimensional secondary ion mass spectrometry (SIMS) detection of oxygen. Distribution of these impurities is not homogeneous and the vast majority of oxygen atoms are agglomerated along pillar-shaped structures. Defect-selective etching and scanning electron microscopy imaging complement SIMS results and reveal that oxygen is predominantly present along the cores of screw and mixed dislocations, which proves their high tendency to be decorated by oxygen. A negligible amount of oxygen can be found within the bulk of the material and along the edge dislocations.

Damage-induced voltage alteration (DIVA) contrast in SEM images of ion-irradiated semiconductors.

The ion-irradiation damage effects in semiconductors were directly visualized by means of scanning electron microscopy at low beam acceleration voltages (low-kV SEM). The Al0.55Ga0.45As (p-type and n-type) epitaxial layers grown over GaAs substrates were irradiated with energetic He+ ions with fluencies ranging from 8e12 to 8e13 cm-2 and studied in cross-sectional view after cleavage. Secondary electron images collected at low energy (0.5 - 1 keV) of primary electrons show strong contrast related to the local differences in the material resistivity resulting from the ion-induced damage. The main aim of the paper is to present, for the first time, the interpretation of the mechanism of SEM image contrast formation, which has been referred to as Damage-Induced Voltage Alteration (DIVA) contrast and is based on the charging effect in SEM. The unrivalled advantage of this imaging technique is the possibility of immediate two-dimensional visualization of damage effects without complex sample preparation.

Destructive role of oxygen in growth of molybdenum disulfide determined by secondary ion mass spectrometry.

The application of secondary ion mass spectrometry (SIMS) in investigation and comparison of molybdenum disulfide (MoS2) films grown on SiO2, Al2O3 and BN substrates is presented. SIMS measurements of the MoS2/substrate interface reveals oxygen out-diffusion from the substrates containing oxygen and the formation of an amorphous MoOS layer in addition to MoS2. The total area of MoS2 domains covering the substrate is directly related to the type of substrate. For SiO2, small triangular domains of MoS2 separated by amorphous MoOS material are observed. For Al2O3, the sizes of the MoS2 domains are drastically improved due to the higher stability of sapphire. For a BN substrate, SIMS measurements reveal a uniform MoS2 coverage over the whole 2-inch wafer. These results show the destructive role of oxygen released from substrates such as SiO2 or Al2O3 during the growth process of MoS2. The fast and cheap growth process on a non-oxide substrate allows large wafer-scale uniform molybdenum disulfide material to be obtained, which is promising for device fabrication.

Crystallisation Phenomena of In2O3:H Films.

The crystallisation of sputter-deposited, amorphous In2O3:H films was investigated. The influence of deposition and crystallisation parameters onto crystallinity and electron hall mobility was explored. Significant precipitation of metallic indium was discovered in the crystallised films by electron energy loss spectroscopy. Melting of metallic indium at ~160 °C was suggested to promote primary crystallisation of the amorphous In2O3:H films. The presence of hydroxyl was ascribed to be responsible for the recrystallization and grain growth accompanying the inter-grain In-O-In bounding. Metallic indium was suggested to provide an excess of free electrons in as-deposited In2O3 and In2O3:H films. According to the ultraviolet photoelectron spectroscopy, the work function of In2O3:H increased during crystallisation from 4 eV to 4.4 eV, which corresponds to the oxidation process. Furthermore, transparency simultaneously increased in the infraredspectral region. Water was queried to oxidise metallic indium in UHV at higher temperature as compared to oxygen in ambient air. Secondary ion mass-spectroscopy results revealed that the former process takes place mostly within the top ~50 nm. The optical band gap of In2O3:H increased by about 0.2 eV during annealing, indicating a doping effect. This was considered as a likely intra-grain phenomenon caused by both (In°)O•• and (OH-)O• point defects. The inconsistencies in understanding of In2O3:H crystallisation, which existed in the literature so far, were considered and explained by the multiplicity and disequilibrium of the processes running simultaneously.

A-Crater-within-a-Crater Approach for Secondary Ion Mass Spectrometry Evaluation of the Quality of Interfaces of Multilayer Devices.

Further development and optimization of modern optoelectronic devices requires fast and reliable procedures that may evaluate the quality of interfaces. For thick multilayer devices, mixing effect may significantly prevent proper interpretation of secondary ion mass spectrometry depth profiles especially if a region of interest is located far from the sample surface. In this work, we present how to overcome this problem with a so-called a-crater-within-a-crater approach. In this notion, a high energetic primary ion beam is used to rapidly remove most of the material forming a large crater. Then, the energy is significantly reduced and a new smaller crater is formed at the bottom of the previous one. Close to the region of interest, the impact energy is decreased to 150 eV and thus an interface can be analyzed with minimal mixing effect and thus its quality can be adequately assessed. Usefulness of this approach is tested on an epitaxial structure of a triple-junction solar cell and reliable information about the structure imperfection has been obtained: p and n dopants in the tunnel junction overlapped, deteriorating the operation of the device.

Oxygen out-diffusion and compositional changes in zinc oxide during ytterbium ions bombardment.

Oxygen release and out-diffusion in zinc oxide crystals during heavy ions bombardment has been suggested by many experimental techniques. In this work we have employed secondary ion mass spectrometry to study ZnO implanted with ytterbium ions. Our measurements confirm formation of an oxygen-depleted layer and oxygen out-diffusion and agglomeration at the surface. Moreover, an average compositional change in a heavily damaged near-surface region can also be monitored. This reproducible measurement procedure with subnanometer depth resolution allows to localize precisely these altered layers at the depth of 14-28 nm (oxygen-depleted layer) and 9 nm (maximum of the amorphized region). Such precise measurements may prove to be valuable for further characterization of ion beam induced defects in wide bandgap compound semiconductors and optimization of optoelectronic devices based on these materials.

Oxygen-induced high diffusion rate of magnesium dopants in GaN/AlGaN based UV LED heterostructures.

Further development of GaN/AlGaN based optoelectronic devices requires optimization of the p-type material growth process. In particular, uncontrolled diffusion of Mg dopants may decrease the performance of a device. Thus it is meaningful to study the behavior of Mg and the origins of its diffusion in detail. In this work we have employed secondary ion mass spectrometry to study the diffusion of magnesium in GaN/AlGaN structures. We show that magnesium has a strong tendency to form Mg-H complexes which immobilize Mg atoms and restrain their diffusion. However, these complexes are not present in samples post-growth annealed in an oxygen atmosphere or Al-rich AlGaN structures which naturally have a high oxygen concentration. In these samples, more Mg atoms are free to diffuse and thus the average diffusion length is considerably larger than for a sample annealed in an inert atmosphere.

Formation of a highly doped ultra-thin amorphous carbon layer by ion bombardment of graphene.

Ion bombardment of graphene leads to the formation of defects which may be used to tune properties of the graphene based devices. In this work, however, we present that the presence of the graphene layer on a surface of a sample has a significant impact on the ion bombardment process: broken sp2 bonds react with the incoming ions and trap them close to the surface of the sample, preventing a standard ion implantation. For an ion bombardment with a low impact energy and significant dose (in the range of 1014 atoms cm-2) an amorphization of the graphene layer is observed but at the same time, most of the incoming ions do not penetrate the sample but stop at the surface, thus forming a highly doped ultra-thin amorphous carbon layer. The effect may be used to create thin layers containing desired atoms if no other technique is available. This approach is particularly useful for secondary ion mass spectrometry where a high concentration of Cs at the surface of a sample significantly enhances the negative ionization probability, allowing it to reach better detection limits.

Self-organized multi-layered graphene-boron-doped diamond hybrid nanowalls for high-performance electron emission devices.

Carbon nanomaterials such as nanotubes, nanoflakes/nanowalls, and graphene have been used as electron sources due to their superior field electron emission (FEE) characteristics. However, these materials show poor stability and short lifetimes, which prevent their use in practical device applications. The aim of this study was to find an innovative nanomaterial possessing both high robustness and reliable FEE behavior. Herein, a hybrid structure of self-organized multi-layered graphene (MLG)-boron doped diamond (BDD) nanowall materials with superior FEE characteristics was successfully synthesized using a microwave plasma enhanced chemical vapor deposition process. Transmission electron microscopy reveals that the as-prepared carbon clusters have a uniform, dense, and sharp nanowall morphology with sp3 diamond cores encased by an sp2 MLG shell. Detailed nanoscale investigations conducted using peak force-controlled tunneling atomic force microscopy show that each of the core-shell structured carbon cluster fields emits electrons equally well. The MLG-BDD nanowall materials show a low turn-on field of 2.4 V µm-1, a high emission current density of 4.2 mA cm-2 at an applied field of 4.0 V µm-1, a large field enhancement factor of 4500, and prominently high lifetime stability (lasting for 700 min), which demonstrate the superiority of these materials over other hybrid nanostructured materials. The potential of these MLG-BDD hybrid nanowall materials in practical device applications was further illustrated by the plasma illumination behavior of a microplasma device with these materials as the cathode, where a low threshold voltage of 330 V (low threshold field of 330 V mm-1) and long plasma stability of 358 min were demonstrated. The fabrication of these hybrid nanowalls is straight forward and thereby opens up a pathway for the advancement of next-generation cathode materials for high brightness electron emission and microplasma-based display devices.