Pre-deposition substrate etching by metal ion bombardment is an efficient and fast cleaning method that ensures improved chemical and topological substrate surface modification. Here, we study the effects of metal ion mass and kinetic energy on etching of industrially-relevant cemented carbide (WC) substrate as well as on adhesion at the Ti0.50Al0.50N/WC interface. Cr+ or W+ ion fluxes are generated by high-power impulse magnetron sputtering (HiPIMS), while their kinetic energy E-kin is tuned by applying negative substrate bias voltage synchronously with the metal ion-rich portion of the flux. The time evolution of ion fluxes at the substrate plane is studied with energy- and time-resolved ion mass spectrometry. The threshold substrate bias voltage required to initiate substrate etching is in the 900-1000 V range for both Cr+ and W+ fluxes. Moreover, we show that the adhesion strength of Ti0.50Al0.50N coatings correlates with E-kin. For E-kin < 900 eV, Cr or W interlayers are grown and no significant improvement in the adhesion strength is observed. Contrary, for E-kin > 900 eV, effective substrate etching with energetic metal ions significantly improves the adhesion strength: we demonstrate an increase of 76-79 % after etching with metal ions as compared to the untreated substrate.

In this study, a simple thermal reduction process is used to synthesize a rGO-Ca2Fe2O5 (rGO-CFO) nanocomposite, with the morphological and optical characteristics of the CFO nanomaterial being modified by the rGO incorporation. The interface between rGO nanosheets and CFO nanoparticles facilitates efficient charge separation and resulting transfer of photogenerated charge carriers across the rGO nanosheets, demonstrated from photoluminescence and Mott-Schottky tests. Compared to CFO (2.1 eV), rGO-CFO has a reduced band gap energy of 1.9 eV. As synthesized nanocomposites were initially optimized and utilized for photodegradation of organic effluent Methylene blue (MB). An addition of 5 wt% rGO to the CFO demonstrated an improved photodegradation efficiency (97%) compared to bare CFO (72%). An active species trapping experiment was used to assess the MB photodegradation mechanism. The results demonstrate that hydroxyl radicals and holes are the major active species involved in photodegradation. The optimized composition (5rGO-CFO) was further tested for degradation of Bisphenol-A and Tetracycline (antibiotic). Altogether, these investigations show that the rGO-CFO is a highly efficient photocatalyst that can be used to remediate emerging contaminants in sunlight.

Single-crystal CrB₂/TiB₂ diboride superlattices with well-defined layers are promising candidates for neutron optics. However, excess B in sputter-deposited TiB_y using a single TiB₂ target deteriorates the structural quality of CrB_x/TiB_y (0001) superlattices. We study the influence of co-sputtering of TiB₂ + Ti on the stoichiometry and crystalline quality of 300-nm-thick TiB_y single layers and CrB_x/TiB_y (0001) superlattices on Al₂O₃(0001) substrates grown by DC magnetron sputter epitaxy at growth-temperatures T_S ranging from 600 to 900 °C. By controlling the relative applied powers to the TiB₂ and Ti magnetrons, y could be reduced from 3.3 to 0.9. TiB_2.3 grown at 750 °C exhibited epitaxial domains about 10x larger than non-co-sputtered films. Close-to-stoichiometry CrB_1.7/TiB_2.3 superlattices with modulation periods Λ = 6 nm grown at 750 °C showed the highest single crystal quality and best layer definition. TiB_2.3 layers display rough top interfaces indicating kinetically limited growth while CrB_1.7 forms flat and abrupt top interfaces indicating epitaxial growth with high adatom mobility.

Hafnium diboride (HfB2) is a promising candidate as a seed layer for GaN growth on Si substrates due to its excellent lattice and thermal coefficients matching with both materials. This work investigates the epitaxial growth of AlB2-type non-stoichiometric HfB2 (HfB(2+delta )with -0.1 < delta < 0.6) thin films on Si(111) using magnetron co-sputtering. We demonstrated that the process temperature significantly affected the surface roughness (R-RMS similar to 0.5-4 nm), film composition, and the nucleation of secondary impurity phases. Films deposited between 700 and 900 degrees C exhibit epitaxial growth on the Si substrate with a well-defined relationship of ( 0001 ) (HfB 2) & Vert; ( 111 ) (Si )and [ 11 2 <overline> 0 ] (HfB 2) & Vert; [ 1 1 <overline> 0 ] (Si). Detailed x-ray diffraction and scanning transmission electron microscopy analyses reveal that impurity phases detected at high temperatures are primarily carbon-rich phases, identified as HfCx or HfCxBy. Interestingly, this secondary phase's crystal orientation follows the orientation of its surroundings. The different findings in terms of contamination (C and O) and deposition temperature offer valuable insights for further growth optimizing of high-quality epitaxial HfB2 thin films on Si(111) for future GaN-on-Si integration.

Near-stoichiometric chromium diboride films were subject to in situ annealing inside a scanning transmission electron microscope to access the thermal behavior of the film and embedded structural planar defects. Independent of films' stoichiometry, the planar defects were unaffected by the applied heat treatments. On the contrary, the interfaces between the boron-rich tissue phase and the CrB2 phase were reshaped in the overstoichometric CrB2 film. At high temperatures, diffusion of contact metal species (platinum) from the focused ion beam sample preparation was triggered, with subsequent migration onto the sample. This resulted in the formation of metal-rich regions as directly observed and characterized at the atomic level. We determined that platinum did not react with the diboride structure but is accommodated by various defects present in the film.

Rhombohedral boron carbide, often referred to as r-B4C, is a potential material for applications in optoelectronic and thermoelectric devices. From fundamental thin film growth and characterization, we investigate the film-substrate interface between the r-B4C films grown on 4H-SiC (000 (1) over bar) (C-face) and 4H-SiC (0001) (Si-face) during chemical vapor deposition (CVD) to find the origin for epitaxial growth solely observed on the C-face. We used high-resolution (scanning) transmission electron microscopy and electron energy loss spectroscopy to show that there is no surface roughness or additional carbon-based interlayer formation for either substrate. Based on Raman spectroscopy analysis, we also argue that carbon accumulation on the surface hinders the growth of continued epitaxial r-B4C in CVD.

Boron nitride (BN) is a promising 2D material as well as a potential wide-bandgap semiconductor. Chemical vapor deposition (CVD) is commonly used to deposit single layers or thin films of BN, but the deposition process is insufficiently understood at an atomic scale. the CVD of BN is studied using two boron precursors, the organoboranes, triethylborane, and trimethylborane. Using high resolution (scanning) transmission electron microscopy and electron energy loss spectroscopy, this study shows that hexagonal-BN (h-BN) nucleates and grows epitaxially for approximate to 4 nm before it either polytype transforms to rhombohedral-BN (r-BN), turns to less ordered turbostratic-BN or is terminated by a layer of amorphous carbon. this study proposes that the carbon in the organoboranes deposits on the epitaxially growing h-BN surface and this either leads to the polytype transition to r-BN, the transition to less ordered BN growth, or complete surface poisoning with carbon terminating BN growth. These results question the use of organoboranes in CVD of epitaxial BN films, and the polytype stability of h-BN growing on graphene. The influence of carbon toward epitaxial h-BN growth is examined using high-resolution microscopy. For most of the film, carbon induced a polytype transition from h-BN to local r-BN to turbostatic-BN ending epitaxial growth. In some localized BN structures, carbon is absent, here the epitaxial film growth is sustained to higher thickness with a uniform polytype transition from h-BN to r-BN. image

The hardness and fracture toughness of high-temperature wear-resistant transition metal aluminum nitride multilayer films depend largely on the constituting layer ' s structure, compositional modulation, morphology, and interface coherency. We present a study on 1-micron thick multilayered films consisting of stacked layers of TiN and Zr 0.37 Al 0.63 N 1.09 , each layer being 10 nm thick. The films were grown using ion-assisted reactive magnetron sputtering on MgO(001) and Si(001) at substrate temperatures ranging from ambient to 900 degrees C. By increasing growth temperature, we found that the ZrAlN layers transition from near amorphous to nanocrystalline wurtzite to decomposed c-ZrN and w-AlN domains. Concurrently, the TiN layers exhibit strong fiber texture, polycrystallinity, and epitaxial growth carried by the ZrN domains. Both hardness and fracture stress, evaluated by nanoindentation and micromechanical tests, increase with temperature from H=24 GPa M g O , 23 GPa Si to 36 GPa M g O , 30 GPa Si , and sigma F Si = 6.1-7.7 GPa, respectively. An improved fracture toughness of K IC =2.4-2.8 MPa root m is related to different toughening mechanisms for the various microstructures. The difference in hardness between the substrates is related to compressive stress due to the deposition conditions and thermal contraction. The superior fracture stress is attributed to dense multilayers, free from macroscopic defects due to ion-assisted growth. After being deposited at 200 degrees C, the multilayers remained thermally stable when vacuum annealed for 15 hours at 900 degrees C, with no significant change in phase composition or hardness. The improved hardness, toughness, and temperature stability of the otherwise brittle nitrides are promising for industrial applications.

Intercalated layered materials offer distinctive properties and serve as precursors for important two-dimensional (2D) materials. However, intercalation of non-van der Waals structures, which can expand the family of 2D materials, is difficult. We report a structural editing protocol for layered carbides (MAX phases) and their 2D derivatives (MXenes). Gap-opening and species-intercalating stages were respectively mediated by chemical scissors and intercalants, which created a large family of MAX phases with unconventional elements and structures, as well as MXenes with versatile terminals. The removal of terminals in MXenes with metal scissors and then the stitching of 2D carbide nanosheets with atom intercalation leads to the reconstruction of MAX phases and a family of metal-intercalated 2D carbides, both of which may drive advances in fields ranging from energy to printed electronics.

Out-of-plane chemically ordered transitionmetal boride(o-MAB) phases, Ta4M & DPRIME;SiB2 (M & DPRIME; = V, Cr), and a structurally equivalent disordered solidsolution MAB phase, Ta4MoSiB2, are synthesized.DFT calculations are used to examine the dynamic stability, elasticproperties, and electronic density states of the MAB phases. We report on the synthesis of computationally predictedout-of-planechemically ordered transition metal borides labeled o-MAB phases, Ta4M & DPRIME;SiB2 (M & DPRIME; =V, Cr), and a structurally equivalent disordered solid solution MABphase Ta4MoSiB2. The boride phases were preparedusing solid-state reaction sintering of the constituting elements.High-resolution scanning transmission electron microscopy along withRietveld refinement of the powder-X-ray diffraction patterns revealedthat the synthesized o-MAB phases Ta4CrSiB2 (98 wt % purity) and Ta4VSiB2 (81 wt% purity) possess chemical ordering with Ta preferentially residingin the 16l position and Cr and V in the 4c position, whereas Ta4MoSiB2 (46wt % purity) was concluded to form a disordered solid solution. Densityfunctional theory (DFT) calculations were used to investigate thedynamic stability, elastic properties, and electronic density statesfor the MAB phases, confirming the stability and suggesting the boridesbased on Cr and Mo to be stiffer than those based on V and Nb.

Traditional age hardening mechanisms in refractory ceramics consist of precipitation of fine particles. These processes are vital for widespread wear-resistant coating applications. Here, we report novel Guinier-Preston zone hardening, previously only known to operate in soft light-metal alloys, taking place in refractory ceramics like multicomponent nitrides. The added superhardening, discovered in thin films of Ti-Al-W-N upon high temperature annealing, comes from the formation of atomic-plane-thick W disks populating {111} planes of the cubic matrix, as observed by atomically resolved high resolution scanning transmission electron microscopy and corroborated by ab initio calculations and molecular dynamics simulations. Guinier-Preston zone hardening concurrent with spinodal decomposition is projected to exist in a range of other ceramic solid solutions and thus provides a new approach for the development of advanced materials with outstanding mechanical properties and higher operational temperature range for the future demanding applications.

c-TiAlN/h-Cr2N multilayer thin films, with modulation period lambda of 10 nm, 20 nm, and 30 nm and different Cr2N/lambda thickness ratios (25 %, 50 % and 75 %), were deposited on c-plane sapphire using reactive DC magnetron sputtering. All multilayers exhibited preferred orientation [Cr2N(0001)/ TiAlN(111)](x), regardless of the modulation period and thickness ratios. X-ray diffraction f-scans revealed an influence of the Cr2N layer thickness on the overall orientation quality of the multilayer, where the thicker the Cr2N layer the higher orientation quality. Atomically resolved high-angle annular dark-field scanning transmission electron microscopy revealed well defined and homogeneous atom stacking in the Cr2N layers. In contrast, the cubic TiAlN layer was found to be composed of coherent cubic AlN-rich and TiN-rich regions. Additionally, the TiAlN layers were found with a higher density of grain boundaries compared to the Cr2N layers. Mechanical properties evaluation revealed that the film with a 20 nm period and 75 % Cr2N thickness ratio exhibited the highest hardness of 27.11 +/- 0.72 GPa and an reduced elastic modulus of 349.1 +/- 6.84 GPa. The hardness increased as the thickness of Cr2N increased, until reaching 10 nm, after which it remained at a high level (similar to 25 GPa).

Studies of single crystal artificial superlattices (SLs) of transition-metal (TM) diborides, which is instru- mental to understand hardening mechanisms at nanoscale, is lacking. Here, CrBx/TiBy (0001) diboride SLs [x,y E 1.7-3.3] are grown epitaxially on Al2O3(0001) substrates by direct-current magnetron sputter epitaxy. Growth conditions for obtaining well-defined SLs with good interface quality are found at 4 mTorr Ar pressure and 600 degrees C. 1 -mu m-thick SL films deposited with modulation periods A between 1 and 10 nm, and A=6 nm SLs with TiBy-to-A layer thickness ratios F ranging from 0.2 to 0.8 are studied. SLs with A=6 nm and F in the range of 0.2-0.4, with a near stoichiometric B/TM ratio, exhibit the high- est structural quality. The effects of F and stoichiometries (B/TM ratio) on the distribution of B in the SL structures are discussed. By increasing the relative thickness of TiBy, the crystalline quality of SLs starts to deteriorate due to B segregation in over-stoichiometric TiBy, resulting in narrow epitaxial SL columnar growth with structurally-distorted B-rich boundaries. Moreover, increasing the relative thickness of under-stoichiometric CrBx enhances the SL quality and hinders formation of B-rich boundaries. The SLs are found to exhibit hardness values in the range of 29-34 GPa.(c) 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

We report the synthesis of three out-of-plane chemically ordered quaternary transition metal borides (o-MAB phases) of the chemical formula M4CrSiB2 (M = Mo, W, Nb). The addition of these phases to the recently discovered o-MAB phase Ti4MoSiB2 shows that this is indeed a new family of chemically ordered atomic laminates. Furthermore, our results expand the attainable chemistry of the traditional M5SiB2 MAB phases to also include Cr. The crystal structure and chemical ordering of the produced materials were investigated using high-resolution scanning transmission electron microscopy and X-ray diffraction by applying Rietveld refinement. Additionally, calculations based on density functional theory were performed to investigate the Cr preference for occupying the minority 4c Wyckoff site, thereby inducing chemical order.

Synthesis of high-entropy sublattice nitride (HESN) coatings by magnetron sputtering is typically done using custom-made alloyed targets with specific elemental compositions. This approach is expensive, requires long delivery times, and offers very limited flexibility to adjust the film composition. Here, we demonstrate a new method to grow HESN films, which relies on elemental targets arranged in the multicathode configuration with substrates rotating during deposition. TiVNbMoWN films are grown at a temperature of similar to 520(degrees)C using Ti, V, Nb, and Mo targets operating in the direct current magnetron sputtering mode, while the W target, operated by high power impulse magnetron sputtering (HiPIMS), provides a source of heavy ions. The energy of the metal ions EW+ is controlled in the range from 80 to 620 eV by varying the amplitude of the substrate bias pulses V-s, synchronized with the metal-ion-rich phase of HiPIMS pulses. We demonstrate that W(+ )irradiation provides dynamic recoil mixing of the film-forming components in the near-surface atomic layers. For EW+ >= 320 eV the multilayer formation phenomena, inherent for this deposition geometry, are suppressed and, hence, compositionally uniform HESN films are obtained, as confirmed by the microstructural and elemental analysis.(c) 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license(http://creativecommons.org/licenses/by/4.0/)

The development of abundant, cheap, and highly active catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is important for hydrogen production. Nanolaminate ternary transition metal carbides (MAX phases) and their derived two-dimensional transition metal carbides (MXenes) have attracted considerable interest for electrocatalyst applications. Herein, four new MAX@MXene core-shell structures (Ta2CoC@ Ta2CTx, Ta2NiC@Ta2CTx, Nb2CoC@Nb2CTx, and Nb2NiC@Nb2CTx), in which the core region is Co/Ni-MAX phases while the edge region is MXenes, have been prepared. Under alkaline electrolyte conditions, the Ta2CoC@Ta2CTx core-shell structure showed an overpotential of 239 mV and excellent stability during the HER with MXenes as the active sites. For the OER, the Ta2CoC@Ta2CTx core- shell structure showed an overpotential of 373 mV and a small Tafel plot (56 mV dec-1), which maintained a bulk crystalline structure and generated Co-based oxyhydroxides that formed by surface reconstruction as active sites. Considering rich chemical compositions and structures of MAX phases, this work provides a new strategy for designing multifunctional electrocatalysts and also paves the way for further development of MAX phase-based materials for clean energy applications.

Metastable super-saturated Zr1_xAlxN alloys tend to phase separate into the equilibrium cubic (c) ZrN and wurtzite (w) AlN due to a deep miscibility gap. Transformation is shown here to follow distinctly different paths depending on if Zr1_xAlxN (x = 0.3 and 0.6) is sputter deposited as a single layer or multi-layered with TiN, and further varied by post-deposition annealing. Using in situ high-energy synchrotron wide-angle X-ray scattering and analytical transmission electron microscopy, surface segregation effects are compared to secondary phase transformations occurring in as-deposited layers during thermal annealing up to 1000 degrees C. For the primary phase transformation from the vapor phase, w-AlN nucleates and an AlN-ZrN labyrinthine structure evolves at elevated deposition temperature with semi-coherent interfaces over several nanometers, where the higher Al content narrows the structure in both single and multilayers. Transformation in thinner alloy layers is governed by epitaxial forces which stabilize single-phase c-Zr0.4Al0.6N, which enables c-Zr0.4Al0.6N/TiN superlattice growth at temperatures as low as 350 degrees C. Regardless of the decomposition route, the formation of c-AlN is impeded and w-AlN instantaneously forms during transformation. In contrast, isostructural decomposition into w-AlN and w-Zr (Al)N occurs in w-Zr0.4Al0.6N alloys during annealing.

The recent discovery of chemical ordering in quaternary borides offers new ways of exploring properties and functionalities of these laminated phases. Here, we have synthesized and investigated chemical ordering of the laminated Mo4MnSiB2 (T2) phase, thereby introducing a magnetic element into the family of materials coined o-MAB phases. By X-ray diffraction and scanning transmission electron microscopy, we provide evidence for out-of-plane chemical ordering of Mo and Mn, with Mo occupying the 16l site and Mn preferentially residing in the 4c site. Mn and B constitute quasi-two-dimensional layers in the laminated material. We have therefore also studied the magnetic properties by magnetometry, and no sign of long-range magnetic order is observed. An initial assessment of the magnetic ordering has been further studied by density functional theory (DFT) calculations, and while we find an antiferromagnetic configuration to be the most stable one, ferromagnetic ordering is very close in energy.

Photoconduction (PC) properties were investigated for ternary indium aluminium nitride (InxAl1-xN) nanorods (NRs) with different indium compositions (x) from 0.35 to 0.68, as grown by direct-current reactive magnetron sputter epitaxy. Cross-sectional scanning transmission electron microscopy (STEM) reveals single-crystal quality of the vertically aligned InxAl1-xN NRs. Single-rod photodetector devices with good ohmic contacts were fabricated using the focused-ion-beam technique (FIB), where the In-rich In0.68Al0.32N NR exhibits an optimal photocurrent responsivity of 1400 A W-1 and photoconductive gain of 3300. A transition from a positive photoresponse to a negative photoresponse was observed, while increasing the In composition x from 0.35 to 0.57. The negative PC was further enhanced by increasing x to 0.68. A model based on the coexistence and competition of deep electron trap states and recombination centers was proposed to explain the interesting composition-dependent PC in these ternary III-nitride 1D nanostructures.

Zirconium diboride (ZrB2) films have been deposited by direct current magnetron sputtering (DCMS) from a ZrB2 compound target on Al2O3 (0001) substrates held at 600, 700, 800, and 900 degrees C, and with two different axial magnetic field strengths, 34 and 104 G, generated using a coil surrounding the substrate. Plasma probe measurements show an increase of the ion fluxes on floating-potential substrates of the two different configurations by a factor of 2.8 for 104 G compared to 34 G, while the ion energy remained relatively constant at approximate to 12 eV. Time-of-flight elastic recoil detection analysis (ToF-ERDA) show that films deposited with a magnetic field of 34 G are highly overstoichiometric with B/Zr ratios approximate to 2.4, while films deposited with 104 G exhibit a B/Zr ratios approximate to 2.1. The levels of oxygen and carbon in the films are below 1 at. % irrespective of growth conditions. X-ray diffraction (XRD) 0/20 scans, complemented by pole figure measurements, reveal that all deposited films are 0001-oriented. XRD 0/20 scans of the 000t peak intensities and co (rocking-curve) widths show increased ZrB2 crystal quality with increasing temperature for both magnetic field strengths. Minimum electrical resistivity of approximate to 100 p omega cm is achieved for an axial magnetic field of 104 G, independent of temperature.

CaMnO3 is a perovskite with attractive magnetic and thermoelectric properties. CaMnO3 films are usually grown by pulsed laser deposition or radio frequency magnetron sputtering from ceramic targets. Herein, epitaxial growth of CaMnO3-y (002) films on a (112 over bar 0)-oriented LaAlO3 substrate using pulsed direct current reactive magnetron sputtering is demonstrated, which is more suitable for industrial scale depositions. The CaMnO3-y shows growth with a small in-plane tilt of <approximate to 0.2 degrees toward the (200) plane of CaMnO3-y and the (1 over bar 104) with respect to the LaAlO3 (112 over bar 0) substrate. X-ray photoelectron spectroscopy of the electronic core levels shows an oxygen deficiency described by CaMnO2.58 that yields a lower Seebeck coefficient and a higher electrical resistivity when compared to stoichiometric CaMnO3. The LaAlO3 (112 over bar 0) substrate promotes tensile-strained growth of single crystals. Scanning transmission electron microscopy and electron energy loss spectroscopy reveal antiphase boundaries composed of Ca on Mn sites along and , forming stacking faults.

High-entropy (HE) ceramics, by analogy with HE metallic alloys, are an emerging family of multielemental solid solutions. These materials offer a large compositional space, with a corresponding large range of properties. Here, we report the experimental realization of a 3D HE MAX phase, Ti1,0V0.7Cr0.05Nb1.0Ta1.0AlC3, and a corresponding 2D HE MXene in the form of freestanding flakes of average composition Ti1.1V0.7CrxNb1.0Ta0.6C3Tz (T-z = -F, -O, -OH), as produced by selective removal of AI from the HE MAX phase in aqueous hydrofluoric acid (HF). Initial tests on HE MXene "paper" electrodes show their high potential as electrode materials in supercapacitors through volumetric and gravimetric capacitances of 1688 F/cm(3) and 490 F/g, respectively, originating from a combination of diffusion- and surface-controlled charge storage processes. The introduction of the HE concept into the field of 2D materials suggests a wealth of future 2D materials and applications.

InxGa1-x N is a strategically important material for electronic devices given its tunable bandgap, modulated by the In/Ga ratio. However, current applications are hindered by defects caused by strain relaxation and phase separation in the material. Here, we demonstrate growth of homogeneous InxGa1-x N films with 0.3 < x < 0.8 up to similar to 30 nm using atomic layer deposition (ALD) with a supercycle approach, switching between InN and GaN deposition. The composition is uniform along and across the films, without signs of In segregation. The InxGa1-x N films show higher In-content than the value predicted by the supercycle model. A more pronounced reduction of GPC(InN) than GPC(GaN) during the growth processes of InN and GaN bilayers is concluded based on our analysis. The intermixing between InN and GaN bilayers is suggested to explain the enhanced overall In-content. Our results show the advantage of ALD to prepare high-quality InxGa1-x N films, particularly with high In-content, which is difficult to achieve with other growth methods.

The crystal reorganization of the IrMn thin film was observed by the in situ thermal annealing in the X-ray diffraction (XRD) and electron energy loss spectroscopy. From room temperature to 700 degrees C, the in situ annealing measurements identify the different Mn diffusion effects in three temperature ranges. First, between room temperature and 300 degrees C, the XRD profiles show the reorganization of Mn atoms from interstitials to IrMn lattice points. Second, between 300 and 400 degrees C, we observed the diffusion of Mn atoms from the IrMn thin film to the surface, causing the atomic Mn/Ir ratio to drop from 10 to 7. The MnO appeared on the film surface in this temperature range. Third, from 400 to 700 degrees C, the O content in the IrMn thin film increases to 8%, while the Mn/ Ir ratio continuously decreases from 7 to 5. The scanning transmission electron microscopy images also show that the crystal structure of IrMn thin film completely degrades to another structure.

Planar defect structures appearing in transition metal diboride (TMB2) thin films, grown by different magnetron sputtering-deposition approaches over a wide compositional and elemental range, were systematically investi-gated. Atomically resolved scanning transmission electron microscopy (STEM) imaging, electron energy loss spec-troscopy (EELS) elemental mapping, and first principles calculations have been applied to elucidate the atomic structures of the observed defects. Two distinct types of antiphase boundary (APB) defects reside on the {1(1) over bar 00} planes. These defects are without (named APB-1) or with (APB-2) local deviation from stoichiometry. APB-2 de-fects, in turn, appear in different variants. It is found that APB-2 defects are governed by the films composition, while APB-1 defects are endemic. The characteristic structures, interconnections, and circumstances leading to the formation of these APB-defects, together with their formation energies, are presented.

We systematically study the oxidation properties of sputter-deposited TiB2.5 coatings up to 700 °C. Oxide-scale thickness dox increases linearly with time ta for 300, 400, 500, and 700 °C, while an oxidation-protective behavior occurs with dox=250∙ta0.2 at 600 °C. Oxide-layer’s structure changes from amorphous to rutile/anatase-TiO2 at temperatures ≥ 500 °C. Abnormally low oxidation rate at 600 °C is attributed to a highly dense columnar TiO2-sublayer growing near oxide/film interface with a top-amorphous thin layer, suppressing oxygen diffusion. A model is proposed to explain the oxide-scale evolution at 600 °C. Decreasing heating rate to 1.0 °C/min plays a noticeable role in the TiB2.5 oxidation.

Direct-current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS) were used to deposit understoichiometric Ti(1-x)Al(x)B(2-y )diboride coatings by sputtering from a segmented TiB2-AlB2 target using Ar and Kr as sputtering gas. For films with a fixed Al/(Ti + Al) ratio of x = 0.1 (Ti0.9Al0.1B2-y), the B content was varied with y & ISIN; (0.1, 0.6 and 0.7). For films with a fixed y = 0.7 (Ti1-xAlxB1.3), the Al content was varied with x & ISIN; (0.1, 0.4 and 0.7). Evaluation of the mechanical properties of the Ti1-xAlxB1.3 samples showed a reduction in both hardness and elastic modulus with increasing Al concentration, while the Ti0.9Al0.1B2-y samples showed a hardness increase with decreasing B content. Thus, Ti0.9Al0.1B1.3 films exhibited a superior hardness of 46.2 +/- 1.1 GPa and an elastic modulus of 523 & PLUSMN; 7 GPa, compared to the values for Ti0.9Al0.1B1.4 and Ti0.9Al0.1B1.9, showing a hardness of 44 +/- 1 GPa and 36 +/- 1 GPa, and an elastic modulus of 569 +/- 7 GPa and 493 +/- 6 GPa, respectively. The oxidation behavior of the mechanically most promising Ti0.9Al0.1B2-y sample series was investigated through air-annealing at 600 C for durations from 1 h to 10 h. All films formed a mixed non-conformal Al2O3-TiO2 oxide scale which acts as an inward and outward diffusion barrier, significantly reducing the oxidation rate compared to TiBz films, which form an oxide scale consisting of porous TiO2. The thinnest oxide scale after 10 h was found in the B-deficient samples, Ti0.9Al0.1B1.3 and Ti0.9Al0.1B1.4, at ~200 nm, which is significantly below that for Ti0.9Al0.1B1.9 at 320 nm. The enhanced oxidation resistance of highly understoichiometric films is due to the elimination of the B-rich tissue phase that is present at the grain boundaries for higher B content, where the latter has been shown to enhance the rate of oxidation in borides.

Solid-state precipitation can be used to tailor material properties, ranging from ferromagnets and catalysts to mechanical strengthening and energy storage. Thermoelectric properties can be modified by precipitation to enhance phonon scattering while retaining charge-carrier transmission. Here, unconventional Janus-type nanoprecipitates are uncovered in Mg3Sb1.5Bi0.5 formed by side-by-side Bi- and Ge-rich appendages, in contrast to separate nanoprecipitate formation. These Janus nanoprecipitates result from local comelting of Bi and Ge during sintering, enabling an amorphous-like lattice thermal conductivity. A precipitate size effect on phonon scattering is observed due to the balance between alloy-disorder and nanoprecipitate scattering. The thermoelectric figure-of-merit ZT reaches 0.6 near room temperature and 1.6 at 773 K. The Janus nanoprecipitation can be introduced into other materials and may act as a general property-tailoring mechanism.

Titanium boride, TiBx, thin films were grown by direct current magnetron co-sputtering from a compound TiB2 target and a Ti target at an Ar pressure of 2.2 mTorr (0.3 Pa) and substrate temperature of 450 ?degrees C. While keeping the power of the TiB2 target constant at 250 W, and by varying the power on the Ti target, P-Ti, between 0 and 100 W, the B/Ti ratio in the film could be continuously and controllably varied from 1.2 to 2.8, with close-tostoichiometric diboride films achieved for P-Ti = 50 W. This was done without altering the deposition pressure, which is otherwise the main modulator for the composition of magnetron sputtered TiBx diboride thin films. The film structure and properties of the as-deposited films were compared to those after vacuum-annealing for 2 h at 1100 ?degrees C. As-deposited films consisted of small (?50 nm) randomly oriented TiB2 crystallites, interspersed in an amorphous, sometimes porous tissue phase. Upon annealing, some of the tissue phase crystallized, but the diboride average grain size did not change noticeably. The near-stoichiometric film had the lowest resistivity, 122 mu omega cm, after annealing. Although this film had growth-induced porosity, an interconnected network of elongated crystallites provides a path for conduction. All films exhibited high hardness, in the 25-30 GPa range, where the highest value of similar to 32 GPa was obtained for the most Ti-rich film after annealing. This film had the highest density and was nano-crystalline, where dislocation propagation is interrupted by the off-stoichiometric grain boundaries.

Recently, we presented a family of in-plane chemically ordered transition metal borides of the general formula (M-2/3M-1/3")(2)AlB2. Here, we investigate incorporation of magnetic rare earth (RE) elements into this structure by synthesis and analysis of Mo4/3RE2/3AlB2, where RE = Ho, Tb, and Er. The crystal structure is verified by X-ray diffraction and scanning transmission electron microscopy, while the composition is derived from energy dispersive X-ray analysis. Through magnetization measurements, we also show that Mo4/3Ho2/3AlB2 orders antiferromagnetically below 9 K. We suggest that (M-2/3M-1/3")(2)AlB2 could potentially be a versatile platform for new magnetic materials, in 3D as well as 2D. [GARPHICS] IMPACT STATEMENT This paper introduces magnetic elements to i-MAB phases family with a formula of Mo4/3RE2/3AlB2 (RE = Ho, Er, and Tb), which opens a venue for further exploration of chemically ordered magnetic materials.

We recently showed that sputter-deposited Zr_1-xTa_xB_y thin films have hexagonal AlB₂-type columnar nanostructure in which column boundaries are B-rich for x < 0.2, while Ta-rich for x ≥ 0.2. As-deposited layers with x ≥ 0.2 exhibit higher hardness and, simultaneously, enhanced toughness. Here, we study the mechanical properties of ZrB_2.4, Zr_0.8Ta_0.2B_1.8, and Zr_0.7Ta_0.3B_1.5 films annealed in Ar atmosphere as a function of annealing temperature T_a up to 1200 °C. In-situ and ex-situ nanoindentation analyses reveal that all films undergo age hardening up to T_a = 800 °C, with the highest hardness achieved for Zr_0.8Ta_0.2B_1.8 (45.5±1.0 GPa). The age hardening, which occurs without any phase separation or decomposition, can be explained by point-defect recovery that enhances chemical bond density. Although hardness decreases at T_a > 800 °C due mainly to recrystallization, column coarsening, and planar defect annihilation, all layers show hardness values above 34 GPa over the entire T_a range.

Extensive research has been invested in two-dimensional (2D) materials, typically synthesized by exfoliation of van der Waals solids. One exception is MXenes, derived from the etching of constituent layers in transition metal carbides and nitrides. We report the experimental realization of boridene in the form of single-layer 2D molybdenum boride sheets with ordered metal vacancies, Mo4/3B2-xTz (where T-z is fluorine, oxygen, or hydroxide surface terminations), produced by selective etching of aluminum and yttrium or scandium atoms from 3D in-plane chemically ordered (Mo2/3Y1/3)(2)AlB2 and (Mo2/3Sc1/3)(2)AlB2 in aqueous hydrofluoric acid. The discovery of a 2D transition metal boride suggests a wealth of future 2D materials that can be obtained through the chemical exfoliation of laminated compounds.

This review celebrates the width and depth of electron microscopy methods and how these have enabled massive research efforts on MXenes. MXenes constitute a powerful recent addition to 2-dimensional materials, derived from their parent family of nanolaminated materials known as MAX phases. Owing to their rich chemistry, MXenes exhibit properties that have revolutionized ranges of applications, including energy storage, electromagnetic interference shielding, water filtering, sensors, and catalysis. Few other methods have been more essential in MXene research and development of corresponding applications, compared with electron microscopy, which enables structural and chemical identification at the atomic scale. In the following, the electron microscopy methods that have been applied to MXene and MAX phase precursor research are presented together with research examples and are discussed with respect to advantages and challenges.

Gallium nitride (GaN) is the main component of modern-day high electron mobility transistors due to its favorable electronic properties. As electronic devices become smaller with more complex surface architecture, the ability to deposit high-quality GaN films at low temperatures is required. Herein, we report a new highly volatile Ga(III) triazenide precursor and demonstrate its ability to deposit high-quality epitaxial GaN by atomic layer deposition (ALD). This new Ga(III) triazenide, the first hexacoordinated Ga-N bonded precursor used in a vapor deposition process, was easily synthesized and purified by either sublimation or recrystallisation. Thermogravimetric analysis showed single-step volatilization with an onset temperature of 155 degrees C and negligible residual mass. Three temperature intervals with self-limiting growth were observed when depositing GaN films. The GaN films grown in the second growth interval at 350 degrees C were epitaxial on 4H-SiC without an AlN seed layer and found to have a near stoichiometric Ga/N ratio with very low levels of impurities. In addition, electron microstructure analysis showed a smooth film surface and a sharp interface between the substrate and film. The band gap of these films was 3.41 eV with the Fermi level at 1.90 eV, showing that the GaN films were unintentionally n-type-doped. This new triazenide precursor enables ALD of GaN for semiconductor applications and provides a new Ga(III) precursor for future deposition processes.

Transition-metal diboride thin films, which have high melting points, excellent hardness, and good chemical and thermal conductivity, severely suffer from rapid oxidation in air. Here, we explore the influence of varying B content and resulting nanostructure change on the oxidation properties of TiBx thin films, with x = 1.43, 2.20, and 2.70. Results show that all as-deposited layers have columnar structure. The column boundaries of asdeposited TiB2.20 and TiB2.20 films grown by direct current magnetron sputtering (DCMS) are B-rich, while the as-deposited TiB1.43 films grown by high-power impulse magnetron sputtering (HiPIMS) show no apparent grain boundary phases and contain Ti-rich planar defects. The oxidation rate of TiBL43 air-annealed at 400 degrees C up to 48 h is significantly lower than that of TiB2.20 and TiB2.20 films. The oxidation rate of TiB1.43, TiB2.20, and TiB2.20 films was measured at 2.9 +/- 1.5, 7.1 +/- 1.0, and 20.0 +/- 5.0 nm/h, respectively, with no spallation of even as thick oxide scales as 0.5 mu m in any of the films. The improved oxidation resistance can be explained by the absence of B-rich tissue phase at the column boundaries of understoichiometric TiBx films, a phase that interlaces the nanocolumnar TiB2 structures in the corresponding overstoichiometric films. An easy oxidation pathway is thus eliminated.

We present an ALD approach to metastable In1-xGaxN with 0.1 &lt; x &lt; 0.5 based on solid In- and Ga-precursors that were co-sublimed into the deposition chamber in one pulse. A near In0.5Ga0.5N film with a bandgap value of 1.94 eV was achieved on a Si(100) substrate. Epitaxial In1-xGaxN(0002) was successfully grown directly on the 4H-SiC(0001) substrate.

Chrome-based anodization and sealing combined is a cost-effective solution for developing good corrosion protective coatings on aluminum (Al) and its alloys. The toxicity of hexavalent chromium, however, requires new, sustainable, environmentally friendly, and efficient chromate-free sealing procedures. Herein, a combination of cerium (Ce) sealing and hydrothermal sealing (HTS) is employed to improve the corrosion resistance of the commonly used alloy AA2024-T3 anodized by tartaric sulfuric acid (TSA). The morphologies and components of the resulting surfaces are systematically studied. Characterization technologies such as SEM, TEM, EDX, XRD, and XPS demonstrate the in-situ growth of Ce oxide nanoparticles all through the porous structures of the anodic coating and closing of the pores by additional HTS treatment. The results from the standardized corrosion test (ASTM B895) demonstrate an improved corrosion resistance obtained by the utilized chrome-free process.

Exploratory theoretical predictions in uncharted structural and compositional space are integral to materials discoveries. Inspired by M5SiB2 (T2) phases, the finding of a family of laminated quaternary metal borides, M M-4 SiB2, with out-of-plane chemical order is reported here. 11 chemically ordered phases as well as 40 solid solutions, introducing four elements previously not observed in these borides are predicted. The predictions are experimentally verified for Ti4MoSiB2, establishing Ti as part of the T2 boride compositional space. Chemical exfoliation of Ti4MoSiB2 and select removal of Si and MoB2 sub-layers is validated by derivation of a 2D material, TiOxCly, of high yield and in the form of delaminated sheets. These sheets have an experimentally determined direct band gap of approximate to 4.1 eV, and display characteristics suitable for supercapacitor applications. The results take the concept of chemical exfoliation beyond currently available 2D materials, and expands the envelope of 3D and 2D candidates, and their applications.

Epitaxial rhombohedral boron nitride (r-BN) films were deposited on ZrB2(0001)/4H-SiC(0001) by chemical vapor deposition at 1485 degrees C from the reaction of triethylboron and ammonia and with a minute amount of silane (SiH4). X-ray diffraction (XRD) w-scans yield the epitaxial relationships of r-BN(0001) k ZrB2(0001) out-of-plane and r-BN[11-20] k ZrB2[11-20] in-plane. Cross-sectional transmission electron microscopy (TEM) micrographs showed that epitaxial growth of r-BN films prevails to similar to 10 nm. Both XRD and TEM demonstrate the formation of carbon- and nitrogen-containing cubic inclusions at the ZrB2 surface. Quantitative analysis from x-ray photoelectron spectroscopy of the r-BN films shows B/N ratios between 1.30 and 1.20 and an O content of 3-4 at. %. Plan-view scanning electron microscopy images reveal a surface morphology where an amorphous material comprising B, C, and N is surrounding the epitaxial twinned r-BN crystals.

Several ternary phases are known in the Mo-Fe-B system. Previous ab initio calculations have predicted that they should exhibit a tempting mix of mechanical and magnetic properties. In this study, we have deposited Mo-Fe-B films with a Fe-content varying from 0-37 at.% using non-reactive DC (direct current) magnetron sputtering. The phase composition, microstructure, and mechanical properties were investigated using X-ray diffraction, scanning transmission electron microscopy, and nanoindentation measurements. Films deposited at 300 degrees C and with &gt;7 at.% Fe are nanocomposites consisting of two amorphous phases: a metal-rich phase and a metal-deficient phase. Hardness and elastic modulus were reduced with increasing Fe-content from similar to 29 to similar to 19 GPa and similar to 526 to similar to 353 GPa, respectively. These values result in H-3/E-2 ratios of 0.089-0.052 GPa, thereby indicating brittle behaviour of the films. Also, no indication of crystalline ternary phases was observed at temperatures up to 600 degrees C, suggesting that higher temperatures are required for such films to form.

CrB x thin films with 1.90 &lt; x &lt; 2.08 have been deposited by direct-current magnetron sputtering (DCMS) from a stoichiometric CrB 2 target at 5 and 20 mTorr (0.67 and 2.67 Pa) Ar pressure onto sapphire (0 0 01) substrates. All films, irrespective of deposition conditions, exhibit a (0 0 01) texture. Attesting to the achievement of close-to-stoichiometric composition, epitaxial film growth is observed at 900 ?C, while film growth at 500 ?C yields (0001) fiber texture. Film composition does not depend on substrate temperature but exhibits slightly reduced B content with increasing pressure for samples deposited at 900 ?C. Excess B in the overstoichiometric epitaxial CrB 2.08 films segregates to form B-rich inclusions. Understoichiometry in CrB 1.90 films is accommodated by Cr-rich stacking faults on { 1 1? 00 } prismatic planes. ? 2021 The Author(s). Published by Elsevier Ltd on behalf of Acta Materialia Inc. This is an open access article under the CC BY license ( http://creativecommons.org/licenses/by/4.0/ )

Herein, we synthesize fully dense, bulk, predominantly single-phase, polycrystalline samples of the layered ternary transition metal borides Mn5SiB2 and Fe5SiB2 by reactively hot-pressing Mn, Fe, FeB, Si, and B powders. The atomic structures were imaged using high-resolution scanning transmission electron mi-croscopy and revealed high-crystal quality. Elongated striped defects, confined below the nanometer in width, were observed. Selected area electron diffraction further accentuates the high-crystal quality by discrete spots of pattern, that is expected from a tetragonal crystal structure along the [001] zone axis. With Vickers hardness values of 12.1 +/- 0.4 GPa, and 12.7 +/- 0.1 GPa, for Mn5SiB2 and Fe5SiB2 respectively, these borides are relatively soft. The room temperature electrical resistivities were 1.5 +/- 0.1 and 1.2 +/- 0.1 mu Omega m, for Mn5SiB2 and Fe5SiB2, respectively. The binding energies of the Mn, Fe and Si measured by X-ray photoelectron spectroscopy bolster the idea that the bonds are quite metallic in character. Density functional theory (DFT) calculations confirm that the ground states of both compounds are ferromagnetic as observed experimentally. We also use DFT to predict the elastic and electronic properties. In both compounds, the density of states at the Fermi level are dominated by the d-orbitals of the transition metals. Neither material was readily machinable with conventional tooling, but is so with sharp cobalt steel bits or electro-discharge machining (EDM). (C) 2021 Elsevier B.V. All rights reserved.

A vacancy-ordered MXene, Mo1.33CTz, obtained from the selective etching of Al and Sc from the parent i-MAX phase (Mo2/3Sc1/3)(2)AlC has previously shown excellent properties for supercapacitor applications. Attempts to synthesize the same MXene from another precursor, (Mo2/3Y1/3)(2)AlC, have not been able to match its forerunner. Herein, we show that the use of an AlY2.3 alloy instead of elemental Al and Y for the synthesis of (Mo2/3Y1/3)(2)AlC i-MAX, results in a close to 70% increase in sample purity due to the suppression of the main secondary phase, Mo3Al2C. Furthermore, through a modified etching procedure, we obtain a Mo1.33CTz MXene of high structural quality and improve the yield by a factor of 6 compared to our previous efforts. Free-standing films show high volumetric (1308 F cm(-3)) and gravimetric (436 F g(-1)) capacitances and a high stability (98% retention) at the level of, or even beyond, those reported for the Mo1.33CTz MXene produced from the Sc-based i-MAX. These results are of importance for the realization of high quality MXenes through use of more abundant elements (Y vs. Sc), while also reducing waste (impurity) material and facilitating the synthesis of a high-performance material for applications.

A fast, convenient, and easy to perform method for preparing plan-view transmission electron microscopy (TEM) specimens of brittle materials is proposed. The method is ideal for thin films/coatings and based on obtaining wedge-shape geometries of the samples via conventional cutting and cleaving followed by gentle focused ion beam (FIB) milling to electron transparency. It enables multiple parallel windows for depth sectioning of the samples and facilitates FIB lift-out procedure. The method has been successfully applied for preparing high-quality plan-view TEM samples for a range of films deposited on Si, SiC, and Al2O3 which significantly enhances throughput and reduces time at the FIB. The method further offers high success rate even for the novice, stable handling and reproducibility, which greatly widens the application of advanced plan-view TEM studies in material science.

The atomic structure and local composition of high quality epitaxial substoichiometric titanium diboride (TiB1.9) thin film, deposited by unbalanced magnetron sputtering, were studied using analytical high-resolution scanning transmission electron microscopy, density functional theory, and image simulations. The unpaired Ti is pinpointed to inclusion of Ti-based stacking faults within a few atomic layers, which terminates the {1 (1) over bar 00} prismatic planes of the crystal structure and attributed to the absence of B between Ti planes that locally relaxes the structure. This mechanism allows the line compound to accommodate off-stoichiometry and remain a line compound between defects. The planar defects are embedded in otherwise stoichiometric TiB2 and are delineated by insertion of dislocations. An accompanied decrease in Ti-Ti bond lengths along and across the faults is observed. (c) 2020ActaMaterialiaInc. PublishedbyElsevierLtd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)

Indium nitride (InN) is a highly promising material for high frequency electronics given its low bandgap and high electron mobility. The development of InN-based devices is hampered by the limitations in depositing very thin InN films of high quality. We demonstrate growth of high-structural-quality nanometer thin InN films on 4H-SiC by atomic layer deposition (ALD). High resolution x-ray diffraction and transmission electron microscopy show epitaxial growth and an atomically sharp interface between InN and 4H-SiC. The InN film is fully relaxed already after a few atomic layers and shows a very smooth morphology where the low surface roughness (0.14nm) is found to reproduce sub-nanometer surface features of the substrate. Raman measurements show an asymmetric broadening caused by grains in the InN film. Our results show the potential of ALD to prepare high-quality nanometer-thin InN films for subsequent formation of heterojunctions.

Low temperature deposition of high-quality epitaxial GaN is crucial for its integration in electronic applications. Chemical vapor deposition at approximately 800 °C using SiC with an AlN buffer layer or nitridized sapphire as substrate is used to facilitate the GaN growth. Here, we present a low temperature atomic layer deposition (ALD) process using tris(dimethylamido)gallium(III) with NH3 plasma. The ALD process shows self-limiting behaviour between 130–250 °C with a growth rate of 1.4 Å per cycle. The GaN films produced were crystalline on Si (100) at all deposition temperatures with a near stochiometric Ga/N ratio with low carbon and oxygen impurities. When GaN was deposited on 4H-SiC, the films grew epitaxially without the need for an AlN buffer layer, which has never been reported before. The bandgap of the GaN films was measured to be ∼3.42 eV and the Fermi level showed that the GaN was unintentionally n-type doped. This study shows the potential of ALD for GaN-based electronic devices.

Selective-area grown, catalyst-free GaN nanorod (NR) arrays grown on Si substrates have been realized using liquid-target reactive magnetron sputter epitaxy (MSE). Focused ion beam lithography (FIBL) was applied to pattern Si substrates with TiN(x)masks. A liquid Ga target was sputtered in a mixture gas of Ar and N-2, ranging the N(2)partial pressure (P-N) ratio from 100% to 50%. The growth of NRs shows a strong correlation withP(N)on the selectivity, coalescence, and growth rate of NRs in both radial and axial directions. The growth rate of NRs formed inside the nanoholes increases monotonically withP(N). TheP(N)ratio between 80% and 90% was found to render both a high growth rate and high selectivity. When theP(N)ratio was below 80%, multiple NRs were formed in the nanoholes. For aP(N)ratio higher than 90%, parasitic NRs were grown on the mask. An observed dependence of growth behavior upon theP(N)ratio is attributed to a change in the effective Ga/N ratio on the substrate surface, as an effect of impinging reactive species, surface diffusivity, and residence time of adatoms. The mechanism of NR growth control was further investigated by studying the effect of nanoholes array pitch and growth temperature. The surface diffusion and the direct impingement of adatoms were found to be the dominant factors affecting the lateral and axial growth rates of NR, respectively, which were well elucidated by the collection area model.

Tuning and tailoring of surface terminating functional species hold the key to unlock unprecedented properties for a wide range of applications of the largest 2D family known as MXenes. However, a few routes for surface tailoring are explored and little is known about the extent to which the terminating species can saturate the MXene surfaces. Among available terminations, atomic oxygen is of interest for electrochemical energy storage, hydrogen evolution reaction, photocatalysis, etc. However, controlled oxidation of the surfaces is not trivial due to the favored formation of oxides. In the present contribution, single sheets of Ti3C2Tx MXene, inherently terminated by F and O, are defluorinated by heating in vacuum and subsequentially exposed to O-2 gas at temperatures up to 450 degrees C in situ, in an environmental transmission electron microscope. Results include exclusive termination by O on the MXene surfaces and eventual supersaturation (x amp;gt; 2) with a retained MXene sheet structure. Upon extended O exposure, the MXene structure transforms into TiO2 and desorbs surface bound H2O and CO2 reaction products. These results are fundamental for understanding the oxidation, the presence of water on MXene surfaces, and the degradation of MXenes, and pave way for further tailoring of MXene surfaces.

Refractory transition-metal diborides (TMB2) are candidates for extreme environments due to melting points above 3000 degrees C, excellent hardness, good chemical stability, and thermal and electrical conductivity. However, they typically suffer from rapid high-temperature oxidation. Here, we study the effect of Al addition on the oxidation properties of sputter-deposited TiB2-rich Ti1-xAlxBy thin films and demonstrate that alloying the films with Al significantly increases the oxidation resistance with a slight decrease in hardness. TiB2.4 layers are deposited by dc magnetron sputtering (DCMS) from a TiB2 target, while Ti1-xAlxBy alloy films are grown by hybrid high-power impulse and dc magnetron co-sputtering (Al-HiPIMS/TiB2-DCMS). All as-deposited films exhibit columnar structure. The column boundaries of TiB2.4 are B-rich, while Ti0.68Al0.32B1.35 alloys have Ti-rich columns surrounded by a Ti(1-x)Al(x)By tissue phase which is predominantly Al rich. Air-annealing TiB2.4 at temperatures above 500 degrees C leads to the formation of oxide scales that do not contain B and mostly consist of a rutile-TiO2 (s) phase. The resulting oxidation products are highly porous due to the evaporation of B2O3 (g) phase as well as the coarsening of TiO2 crystallites. This poor oxidation resistance is significantly improved by alloying with Al. While air-annealing at 800 degrees C for 0.5 h results in the formation of an similar to 1900-nm oxide scale on TiB2.4, the thickness of the scale formed on the Ti0.68Al0.32B1.35 alloys is similar to 470 nm. The enhanced oxidation resistance is attributed to the formation of a dense, protective Al-containing oxide scale that considerably decreases the oxygen diffusion rate by suppressing the oxide-crystallites coarsening. (C) 2020 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.