Dense, single-phase, hard, and stress-free Ti0.32Al0.63W0.05N films grown by magnetron sputtering with dramatically reduced energy consumption.

The quest for lowering energy consumption during thin film growth, as by magnetron sputtering, becomes of particular importance in view of sustainable development goals. A recently proposed solution combining high power impulse and direct current magnetron sputtering (HiPIMS/DCMS) relies on the use of heavy metal-ion irradiation, instead of conventionally employed resistive heating, to provide sufficient adatom mobility, in order to obtain high-quality dense films. The major fraction of process energy is used at the sputtering sources rather than for heating the entire vacuum vessel. The present study aims to investigate the W+ densification effects as a function of increasing Al content in (Ti1-yAly)1-xWxN films covering the entire range up to the practical solubility limits (y ~ 0.67). Layers with high Al content are attractive to industrial applications as the high temperature oxidation resistance increases with increasing Al concentration. The challenge is, however, to avoid precipitation of the hexagonal wurtzite AlN phase, which is softer. We report here that (Ti1-yAly)1-xWxN layers with y = 0.66 and x = 0.05 grown by a combination of W-HiPIMS and TiAl-DCMS with the substrate bias Vs synchronized to the W+-rich fluxes (to provide mobility in the absence of substrate heating) possess single-phase NaCl-structure, as confirmed by XRD and SAED patterns. The evidence provided by XTEM images and the residual oxygen content obtained from ERDA analyses reveals that the alloy films are dense without discernable porosity. The nanoindentation hardness is comparable to that of TiAlN films grown at 400-500 °C, while the residual stresses are very low. We established that the adatom mobility due to the heavy ion W+ irradiation (in place of resistive heating) enables the growth of high-quality coatings at substrate temperatures not exceeding 130 °C provided that the W+ momentum transfer per deposited metal atom is sufficiently high. The benefit of this novel film growth approach is not only the reduction of the process energy consumption by 83%, but also the possibility to coat temperature-sensitive substrates.

The same chemical state of carbon gives rise to two peaks in X-ray photoelectron spectroscopy.

Chemical state analysis in X-ray photoelectron spectroscopy (XPS) relies on assigning well-defined binding energy values to core level electrons originating from atoms in particular bonding configurations. Here, we present direct evidence for the violation of this paradigm. It is shown that the C 1s peak due to C-C/C-H bonded atoms from adventitious carbon (AdC) layers accumulating on Al and Au foils splits into two distinctly different contributions, as a result of vacuum level alignment at the AdC/foil interface. The phenomenon is observed while simultaneously recording the spectrum from two metal foils in electric contact with each other. This finding exposes fundamental problems with the reliability of reported XPS data as C 1s peak of AdC is routinely used for binding energy scale referencing. The use of adventitious carbon in XPS should thus be discontinued as it leads to nonsense results. Consequently, ISO and ASTM charge referencing guides need to be rewritten.

Ti n+1C n MXenes with fully saturated and thermally stable Cl terminations.

MXenes are a rapidly growing family of 2D materials that exhibit a highly versatile structure and composition, allowing for significant tuning of the materials properties. These properties are, however, ultimately limited by the surface terminations, which are typically a mixture of species, including F and O that are inherent to the MXene processing. Other and robust terminations are lacking. Here, we apply high-resolution scanning transmission electron microscopy (STEM), corresponding image simulations and first-principles calculations to investigate the surface terminations on MXenes synthesized from MAX phases through Lewis acidic melts. The results show that atomic Cl terminates the synthesized MXenes, with mere residual presence of other termination species. Furthermore, in situ STEM-electron energy loss spectroscopy (EELS) heating experiments show that the Cl terminations are stable up to 750 °C. Thus, we present an attractive new termination that widely expands the MXenes' functionalization space and enables new applications.

Self-structuring in Zr1-xAlxN films as a function of composition and growth temperature.

Nanostructure formation via surface-diffusion-mediated segregation of ZrN and AlN in Zr1-xAlxN films during high mobility growth conditions is investigated for 0 ≤ × ≤ 1. The large immiscibility combined with interfacial surface and strain energy balance resulted in a hard nanolabyrinthine lamellar structure with well-defined (semi) coherent c-ZrN and w-AlN domains of sub-nm to ~4 nm in 0.2 ≤ × ≤ 0.4 films, as controlled by atom mobility. For high AlN contents (x > 0.49) Al-rich ZrN domains attain wurtzite structure within fine equiaxed nanocomposite wurtzite lattice. Slow diffusion in wurtzite films points towards crystal structure dependent driving force for decomposition. The findings of unlikelihood of iso-structural decomposition in c-Zr1-xAlxN, and stability of w-Zr1-xAlxN (in large × films) is complemented with first principles calculations.

Selectable phase formation in VAlN thin films by controlling Al+ subplantation depth.

We report on a thin film synthesis technique which allows for unprecedented control over the crystalline phase formation in metastable transition metal nitride based layers. For the model material system of V0.26Al0.74N, a complete transition from hexagonal to supersaturated cubic structure is achieved by tuning the incident energy, hence subplantation depth, of Al+ metal ions during reactive hybrid high power impulse magnetron sputtering of Al target and direct current magnetron sputtering of V target in Ar/N2 gas mixture. These findings enable the phase selective synthesis of novel metastable materials that combine excellent mechanical properties, thermal stability, and oxidation resistance.

Ti2Au2C and Ti3Au2C2 formed by solid state reaction of gold with Ti2AlC and Ti3AlC2.

Incorporation of layers of noble metals in non-van der Waals layered materials may be used to form novel layered compounds. Recently, we demonstrated a high-temperature-induced exchange process of Au with Si in the layered phase Ti3SiC2, resulting in the formation of Ti3AuC2 and Ti3Au2C2. Here, we generalize this technique showing that Au/Ti2AlC and Au/Ti3AlC2 undergo an exchange reaction at 650 °C to form Ti2Au2C and Ti3Au2C2 and determine their structures by electron microscopy, X-ray diffraction, and ab initio calculations. These results imply that noble-metal-containing layered phases should be possible to synthesize in many systems. The metal to be introduced should be inert to the transition-metal carbide layers, and exhibit negative heat of mixing with the initial A element in a liquid phase or two-phase liquid/solid region at the annealing temperature.

Direct observation of spinodal decomposition phenomena in InAlN alloys during in-situ STEM heating.

The spinodal decomposition and thermal stability of thin In0.72Al0.28N layers and In0.72Al0.28N/AlN superlattices with AlN(0001) templates on Al2O3(0001) substrates was investigated by in-situ heating up to 900 °C. The thermally activated structural and chemical evolution was investigated in both plan-view and cross-sectional geometries by scanning transmission electron microscopy in combination with valence electron energy loss spectroscopy. The plan-view observations demonstrate evidence for spinodal decomposition of metastable In0.72Al0.28N after heating at 600 °C for 1 h. During heating compositional modulations in the range of 2-3 nm-size domains are formed, which coarsen with applied thermal budgets. Cross-sectional observations reveal that spinodal decomposition begin at interfaces and column boundaries, indicating that the spinodal decomposition has a surface-directed component.

Core-shell formation in self-induced InAlN nanorods.

We have examined the early stages of self-induced InAlN core-shell nanorod (NR) formation processes on amorphous carbon substrates in plan-view geometry by means of transmission electron microscopy methods. The results show that the grown structure phase separates during the initial moments of deposition into a majority of Al-rich InAlN and a minority of In-enriched InAlN islands. The islands possess polygonal shapes and are mainly oriented along a crystallographic c-axis. The growth proceeds with densification and coalescence of the In-enriched islands, resulting in a base for the In-enriched NR cores with shape transformation to hexagonal. The Al-rich shell formation around such early cores is observed at this stage. The matured core-shell structure grows axially and radially, eventually reaching a steady growth state which is dominated by the axial NR growth. We discuss the NR formation mechanism by considering the adatom surface kinetics, island surface energy, phase separation of InAlN alloys, and incoming flux directions during dual magnetron sputter epitaxy.

Effects of configurational disorder on the elastic properties of icosahedral boron-rich alloys based on B6O, B13C2, and B4C, and their mixing thermodynamics.

The elastic properties of alloys between boron suboxide (B6O) and boron carbide (B13C2), denoted by (B6O)(1-x)(B13C2)(x), as well as boron carbide with variable carbon content, ranging from B13C2 to B4C are calculated from first-principles. Furthermore, the mixing thermodynamics of (B6O)(1-x)(B13C2)(x) is studied. A superatom-special quasirandom structure approach is used for modeling different atomic configurations, in which effects of configurational disorder between the carbide and suboxide structural units, as well as between boron and carbon atoms within the units, are taken into account. Elastic properties calculations demonstrate that configurational disorder in B13C2, where a part of the C atoms in the CBC chains substitute for B atoms in the B12 icosahedra, drastically increase the Young's and shear modulus, as compared to an atomically ordered state, B12(CBC). These calculated elastic moduli of the disordered state are in excellent agreement with experiments. Configurational disorder between boron and carbon can also explain the experimentally observed almost constant elastic moduli of boron carbide as the carbon content is changed from B4C to B13C2. The elastic moduli of the (B6O)(1-x)(B13C2)(x) system are also practically unchanged with composition if boron-carbon disorder is taken into account. By investigating the mixing thermodynamics of the alloys, in which the Gibbs free energy is determined within the mean-field approximation for the configurational entropy, we outline the pseudo-binary phase diagram of (B6O)(1-x)(B13C2)(x). The phase diagram reveals the existence of a miscibility gap at all temperatures up to the melting point. Also, the coexistence of B6O-rich as well as ordered or disordered B13C2-rich domains in the material prepared through equilibrium routes is predicted.

A theoretical investigation of mixing thermodynamics, age-hardening potential, and electronic structure of ternary M(1)1-x M(2)xB2 alloys with AlB2 type structure.

Transition metal diborides are ceramic materials with potential applications as hard protective thin films and electrical contact materials. We investigate the possibility to obtain age hardening through isostructural clustering, including spinodal decomposition, or ordering-induced precipitation in ternary diboride alloys. By means of first-principles mixing thermodynamics calculations, 45 ternary M(1)1-x M(2)xB2 alloys comprising M(i)B2 (M(i) = Mg, Al, Sc, Y, Ti, Zr, Hf, V, Nb, Ta) with AlB2 type structure are studied. In particular Al1-xTixB2 is found to be of interest for coherent isostructural decomposition with a strong driving force for phase separation, while having almost concentration independent a and c lattice parameters. The results are explained by revealing the nature of the electronic structure in these alloys, and in particular, the origin of the pseudogap at EF in TiB2, ZrB2, and HfB2.

Mo2Ga2C: a new ternary nanolaminated carbide.

We report the discovery of a new hexagonal Mo2Ga2C phase, wherein two Ga layers ­ instead of one ­ are stacked in a simple hexagonal arrangement in between Mo2C layers. It is reasonable to assume this compound is the first of a larger family.

Atom probe tomography study of Mg-doped GaN layers.

Atom probe tomography studies on highly Mg-doped homoepitaxial GaN (0001) layers with concentrations of 5 × 10(19) cm(-3) and 1 × 10(20) cm(-3) were performed. Mg cluster formation was observed only in the higher doped sample whereas in the lower doped sample the Mg distribution was homogeneous. CL measurements have shown that the emission normally attributed to stacking faults was only present in the lower doped layers (with Mg concentration of ∼5 × 10(19) cm(-3) or less), but absent in the higher doped layer, where Mg clusters were detected. Mg clusters are proposed to produce a screening effect, thereby destroying the exciton binding on the SFs and thus rendering them optically inactive.

Mechanical and tribological behavior of silicon nitride and silicon carbon nitride coatings for total joint replacements.

Total joint replacements currently have relatively high success rates at 10-15 years; however, increasing ageing and an active population places higher demands on the longevity of the implants. A wear resistant configuration with wear particles that resorb in vivo can potentially increase the lifetime of an implant. In this study, silicon nitride (SixNy) and silicon carbon nitride (SixCyNz) coatings were produced for this purpose using reactive high power impulse magnetron sputtering (HiPIMS). The coatings are intended for hard bearing surfaces on implants. Hardness and elastic modulus of the coatings were evaluated by nanoindentation, cohesive, and adhesive properties were assessed by micro-scratching and the tribological performance was investigated in a ball-on-disc setup run in a serum solution. The majority of the SixNy coatings showed a hardness close to that of sintered silicon nitride (~18 GPa), and an elastic modulus close to that of cobalt chromium (~200 GPa). Furthermore, all except one of the SixNy coatings offered a wear resistance similar to that of bulk silicon nitride and significantly higher than that of cobalt chromium. In contrast, the SixCyNz coatings did not show as high level of wear resistance.

Crystal phase engineered quantum wells in ZnO nanowires.

We report the fabrication of quantum wells in ZnO nanowires (NWs) by a crystal phase engineering approach. Basal plane stacking faults (BSFs) in the wurtzite structure can be considered as a minimal segment of zinc blende. Due to the existing band offsets at the wurtzite (WZ)/zinc blende (ZB) material interface, incorporation of a high density of BSFs into ZnO NWs results in type II band alignment. Thus, the BSF structure acts as a quantum well for electrons and a potential barrier for holes in the valence band. We have studied the photoluminescence properties of ZnO NWs containing high concentrations of BSFs in comparison to high-quality ZnO NWs of pure wurtzite structure. It is revealed that BSFs form quantum wells in WZ ZnO nanowires, providing an additional luminescence peak at 3.329 eV at 4 K. The luminescence mechanism is explained as an indirect exciton transition due to the recombination of electrons in the QW conduction band with holes localized near the BSF. The binding energy of electrons is found to be around 100 meV, while the excitons are localized with the binding energy of holes of ∼5 meV, due to the coupling of BSFs, which form QW-like structures.

Blind deconvolution of time-of-flight mass spectra from atom probe tomography.

A major source of uncertainty in compositional measurements in atom probe tomography stems from the uncertainties of assigning peaks or parts of peaks in the mass spectrum to their correct identities. In particular, peak overlap is a limiting factor, whereas an ideal mass spectrum would have peaks at their correct positions with zero broadening. Here, we report a method to deconvolute the experimental mass spectrum into such an ideal spectrum and a system function describing the peak broadening introduced by the field evaporation and detection of each ion. By making the assumption of a linear and time-invariant behavior, a system of equations is derived that describes the peak shape and peak intensities. The model is fitted to the observed spectrum by minimizing the squared residuals, regularized by the maximum entropy method. For synthetic data perfectly obeying the assumptions, the method recovered peak intensities to within ±0.33 at%. The application of this model to experimental APT data is exemplified with Fe-Cr data. Knowledge of the peak shape opens up several new possibilities, not just for better overall compositional determination, but, e.g., for the estimation of errors of ranging due to peak overlap or peak separation constrained by isotope abundances.

InGaN quantum dot formation mechanism on hexagonal GaN/InGaN/GaN pyramids.

Growing InGaN quantum dots (QDs) at the apex of hexagonal GaN pyramids is an elegant approach to achieve a deterministic positioning of QDs. Despite similar synthesis procedures by metal organic chemical vapor deposition, the optical properties of the QDs reported in the literature vary drastically. The QDs tend to exhibit either narrow or broad emission lines in the micro-photoluminescence spectra. By coupled microstructural and optical investigations, the QDs giving rise to narrow emission lines were concluded to nucleate in association with a (0001) facet at the apex of the GaN pyramid.

Selective homoepitaxial growth and luminescent properties of ZnO nanopillars.

High spatial density ZnO nanopillars (NPs) have been fabricated on catalyst- and pattern-free Si wafers using atmospheric pressure metal organic chemical vapor deposition (APMOCVD) at a moderate temperature (500 °C). The nanopillar diameter is ∼ 35 nm and the length is ∼ 150 nm, with a density of ∼ 2 × 10(9) cm( - 2). The growth evolution of the nanopillars, providing the (0001)(NP) ∐ (0001)(ZNO grain) ∐ (100)(Si surface) epitaxial relationship, is extensively studied by scanning and high resolution transmission microscopy. The approach to obtaining the ZnO 1D structures is explained in terms of selective homoepitaxial growth via the crystallographic anisotropy of the seeding layer. The advanced PL properties of ZnO NPs, e.g. indications of free excitonic and absence of defect emission, are related to their single crystalline nature within one pillar and most probably better stoichiometry and less contamination. The observed efficient monochromatic UV emission from the ZnO NPs at room temperature points toward their potential application as building blocks for nanoscale optoelectronic devices.

Protein adsorption on thin films of carbon and carbon nitride monitored with in situ ellipsometry.

Thin films of amorphous carbon and amorphous, graphitic and fullerene-like carbon nitride were deposited by reactive magnetron sputtering and optically characterized with spectroscopic ellipsometry. Complementary studies using scanning electron microscopy and atomic force microscopy were performed. The films were exposed to human serum albumin (HSA) and the adsorption was monitored in situ using dynamic ellipsometry. From the ellipsometric data the adsorbed amount of proteins was quantified in terms of surface mass density using de Feijter's model. The results indicate larger adsorption of proteins onto the amorphous films compared to the films with a more textured structure. Complementary studies with 125I-labeled HSA showed an apparent protein adsorption up to six times larger compared to the ellipsometry measurement. In addition, the four types of films were incubated in blood plasma followed by exposure to anti-fibrinogen, anti-HMWK or anti-C3c, revealing the materials' response to complement and contact activation. The amorphous and graphitic carbon nitride exhibit rather high immune activity compared to a titanium reference, whereas the amorphous carbon and the fullerene-like CNx show less immune complement deposition. Compared to the reference, all films exhibit indications of a stronger ability to initiate the intrinsic pathway of coagulation. Finally, the surfaces' bone-bonding ability was investigated by examination of their ability to form calcium phosphate crystals in a simulated body fluid, with a-CNx depositing most calcium phosphate after 21 days of incubation.

Aligned AlN nanowires by self-organized vapor-solid growth.

Highly oriented AlN single crystal nanowires with aspect ratio up to 600, diameter in the range of 40-500 nm, and 100 microm lengths, have been synthesized via a vapor-solid growth mechanism. The results were obtained at 1750 degrees C and 850 mbar nitrogen pressure on vicinal SiC substrates pretreated by SiC sublimation epitaxy in order to attain distinguishable terraces. It was found that the nanowires change in thickness after they have reached a critical length, and this fact contributes to an understanding of the growth mechanism of AlN nanowires. The nanowires are hexagonally shaped and perfectly aligned along the [0001] direction with a small tilt given by the substrate vicinality. Under nitrogen excess a preferential growth along the c-axis of the wurtzite structure takes place while below some critical value of nitrogen pressure the growth mode switches to lateral. The AlN nanowires are shown to have a dislocation free wurtzite crystal structure. Some possible applications are discussed.

P2Y2- and P2Y4 purinergic receptors are over-expressed in human colon cancer.

1. A characteristic of cancer is altered signal transduction leading to uninhibited growth. Adenosine-5'-triphosphate (ATP), a natural ligand at P2X- and P2Y purinergic receptors may regulate cell growth in non-neoplastic, as well as neoplastic tissues. In the human colon cancer cell line, HT-29, we previously demonstrated the expression of purinergic receptors of the P2Y(2)- and P2Y(4) subclasses. 2. The aim of the current study was to investigate whether these two purinergic receptors are expressed also in human colon cancer, and, if so, how such expression is related to that in tumour-free colonic tissue. 3. The immunohistochemical findings of both P2Y(2)- and P2Y(4) receptors in the tumours from three patients, prompted us to conduct an investigation of a consecutive series of patients utilizing Western blotting for protein detection and densitometry for quantitation. 4. Both P2Y(2)- and P2Y(4) purinergic receptors could be identified in tumour-free tissue, and both were significantly over-expressed in each of the 10 colon cancers.