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Grzegorz Greczynski

Publications and source records attributed to Grzegorz Greczynski.

13 recordsLinked to original sources

Robust Superconductivity and High Upper Critical Fields in Epitaxial cubic W2N Thin Films

Transition Metal Nitrides are a versatile class of materials, combining chemical robustness, high hardness, and superconducting behaviour with critical temperatures between 2 to 10 K. While several binary TMNs have been explored, superconductivity in stoichiometric W2N has remained largely unexplored. Here, we report on superconducting thin films of stoichiometric W2N, demonstrating a distinctly high upper critical field of 8.5 T, uncommon among binary TMNs. This robust superconducting response under high magnetic fields highlights the technological relevance of W2N for integrated quantum and cryogenic electronic platforms. Overall, these results position stoichiometric W2N as a promising addition to the TMN superconducting landscape, opening new avenues for functional materials design based on chemically stable and mechanically resilient nitrides.

cond-mat.supr-con

Phase selection and texturing in molybdenum oxide films grown by reactive magnetron sputtering

Molybdenum oxide films offer a rich variety of properties for diverse applications, but exclusive synthesis of desired phases is a major challenge. Here, we demonstrate that oxygen flow ratio fO2 = [O2]/[Ar+O2] is crucial not only for phase selection of non-layered monoclinic MoO2 and layered orthorhombic alpha-MoO3 but also for controlling grain size and preferred orientation. Both mica and sapphire support exclusive MoO2 formation in the 0.15 < fO2 < 0.25 window at deposition temperatures Tdep = 400 and 500 degree C and alpha-MoO3 formation in the 0.35 < fO2 < 0.5 window at 400 degree C. Within fO2 windows favoring exclusive phase formation, high fO2 fosters large grains with out-of-plane 0k0 texture, except for MoO2 films on c-sapphire that show no systematic trends. These findings provide a framework for rational synthesis of phase-pure monoclinic MoO2 and orthorhombic MoO3 with control over texture and microstructure to access desired properties.

cond-mat.mtrl-sci

Binding energy referencing in X-ray photoelectron spectroscopy: expanded data set confirms that adventitious carbon aligns to the vacuum level

The correct referencing of the binding energy (BE) scale is essential for the accuracy of chemical analysis by x-ray photoelectron spectroscopy. The C 1s C C/C-H peak from adventitious carbon (AdC), most commonly used for that purpose, was previously shown to shift by several eVs following changes in the sample work function, thus indicating that AdC aligns to the sample vacuum level (VL). Here, results from a much larger sample set are presented including 360 specimens of thin-film samples comprising metals, nitrides, carbides, borides, oxides, carbonitrides, and oxynitrides. Irrespective of the material system the C 1s peak of AdC is found to follow changes in the sample work function fully confirming previous results. Several observations exclude differential charging as plausible explanation. All experimental evidence points instead to the VL alignment at the AdC/sample interface as the source of shifts. Should the C 1s peak of AdC be used for spectra referencing the measurement of sample work function is necessary, irrespective of whether samples are measured grounded or insulated from the spectrometer.

cond-mat.mtrl-sci

Electronic structure and thermoelectric properties of epitaxial Sc1-xVxNy thin films grown on MgO(001)

The electronic structure of Sc1-xVxNy epitaxial films with different alloying concentrations of V are investigated with respect to effects on thermoelectric properties. Band structure calculations on Sc0.75V0.25N indicate that V 3d states lie in the band gap of the parent ScN compound in the vicinity of the Fermi level. Thus, theoretically the presence of light (dispersive) bands at the Γ-point with band multiplicity is expected to lead to lower electrical resistivity while flat (heavy) bands at X-W-K symmetry points are associated with higher Seebeck coefficient than that of ScN. With this aim, epitaxial Sc1-xVxNy thin film samples were deposited on MgO(001) substrates. All the samples showed N substoichiometry and pseudocubic crystal structure. The N-vacancy-induced states were visible in the Sc 2p XAS spectra. The reference ScN and Sc1-xVxNy samples up to x = 0.12 were n type, exhibiting carrier concentration of 1021 cm-3, typical for degenerate semiconductors. For the highest V alloying of x = 0.15, holes became the majority charge carrier as indicated by the positive Seebeck coefficient. The underlying electronic structure and bonding mechanism in Sc1-xVxNy influence the electrical resistivity, Seebeck coefficient, and Hall effect. Thus, the work contributes to the fundamental understanding of the correlated defects and thermoelectric properties to the electronic structure in Sc-N system with V alloying.

cond-mat.mtrl-sci

Thermoelectric properties and electronic structure of Cr(Mo,V)Nx thin films studied by synchrotron and lab-based X-ray spectroscopy

Chromium-based nitrides are used in hard, resilient coatings, and show promise for thermoelectric applications due to their combination of structural, thermal, and electronic properties. Here, we investigated the electronic structures and chemical bonding correlated to the thermoelectric properties of epitaxially grown chromium-based multicomponent nitride Cr(Mo,V)Nx thin films. Due to minuscule N vacancies, finite population of Cr 3d and N 2p states appear at the Fermi level and diminishes the band opening for Cr0.51N0.49. Incorporating holes by alloying V in N deficient CrN matrix results in enhanced thermoelectric power factor with marginal change in the charge transfer of Cr to N compared to Cr0.51N0.49. Further alloying Mo isoelectronic to Cr increases the density of states across the Fermi level due to hybridization of the (Cr, V) 3d and Mo 4d-N 2p states in Cr(Mo,V)Nx. The hybridization effect with reduced N 2p states off from stoichiometry drives the system towards metal like electrical resistivity and reduction in Seebeck coefficient compensating the overall power factor still comparable to Cr0.51N0.49. The N deficiency also depicts a critical role in reduction of the charge transfer from metal to N site. The present work envisages ways for enhancing thermoelectric properties through electronic band engineering by alloying and competing effects of N vacancies.

cond-mat.mtrl-sci

Electronic excitation of transition metal nitrides by light ions with keV energies

We investigated the specific electronic energy deposition by protons and He ions with keV energies in different transition metal nitrides of technological interest. Data were obtained from two different time-of-flight ion scattering setups and show excellent agreement. For protons interacting with light nitrides, i.e. TiN, VN and CrN, very similar stopping cross sections per atom were found, which coincide with literature data of N2 gas for primary energies <= 25 keV. In case of the chemically rather similar nitrides with metal constituents from the 5th and 6th period, i.e. ZrN and HfN, the electronic stopping cross sections were measured to exceed what has been observed for molecular N2 gas. For He ions, electronic energy loss in all nitrides was found to be significantly higher compared to the equivalent data of N2 gas. Additionally, deviations from velocity proportionality of the observed specific electronic energy loss are observed. A comparison with predictions from density functional theory for protons and He ions yields a high apparent efficiency of electronic excitations of the target for the latter projectile. These findings are considered to indicate the contributions of additional mechanisms besides electron hole pair excitations, such as electron capture and loss processes of the projectile or promotion of target electrons in atomic collisions.

cond-mat.mtrl-sci

Influence of Si doping and O2-flow on arc deposited (Al,Cr)2O3 coatings

(Al,Cr)2O3 coatings with Al/(Al+Cr) = 0.5 or Al = 70 at.%, doped with 0, 5 or 10 at.% Si, were deposited on hard metal and Si(100) substrates to elucidate the influence of Si on the resulting coatings. The chemical analysis of the coatings showed between 3.3 and 7.4 at.% metal fraction Si incorporated into all studied coatings depending on cathode Si-composition. The incorporated Si content does not change significantly with different oxygen flow covering a wide range of deposition conditions from low to high O2 flow during growth. The addition of Si promotes the metastable B1-like cubic structure over the thermodynamically stable corundum structure. The hardness determined by nanoindentation of the as-deposited coatings is slightly reduced upon Si-incorporation as well as upon increased Al-content. Si is found enriched in droplets but can also be found at a lower content, evenly spread, without visible segregation on the ~5 nm scale, in the actual oxide coating. The positive effect of improved cathode erosion upon Si-incorporation has to be balanced against the promotion of the metastable B1-like structure, having lower room temperature hardness and inferior thermal stability compared to the corundum structure.

cond-mat.mtrl-sci

Reactive magnetron sputtering of tungsten target in krypton/trimethylboron atmosphere

W-B-C films were deposited on Si(100) substrates held at elevated temperature by reactive sputtering from a W target in Kr/trimethylboron (TMB) plasmas. Quantitative analysis by X-ray photoelectron spectroscopy (XPS) shows that the films are W-rich between ~ 73 and ~ 93 at.% W. The highest metal content is detected in the film deposited with 1 sccm TMB. The C and B concentrations increase with increasing TMB flow to a maximum of ~18 and ~7 at.%, respectively, while the O content remains nearly constant at 2-3 at.%. Chemical bonding structure analysis performed after samples sputter-cleaning reveals C-W and B-W bonding and no detectable W-O bonds. During film growth with 5 sccm TMB and 500 oC or with 10 sccm TMB and 300-600 oC thin film X-ray diffraction shows the formation of cubic 100-oriented WC1-x with a possible solid solution of B. Lower flows and lower growth temperatures favor growth of W and W2C, respectively. Depositions at 700 and 800 oC result in the formation of WSi2 due to a reaction with the substrate. At 900 oC, XPS analysis shows ~96 at.% Si in the film due to Si interdiffusion. Scanning electron microscopy images reveal a fine-grained microstructure for the deposited WC1-x films. Nanoindentation gives hardness values in the range from ~23 to ~31 GPa and reduced elastic moduli between ~220 and 280 GPa in the films deposited at temperatures lower than 600 oC. At higher growth temperatures the hardness decreases by a factor of 3 to 4 following the formation of WSi2 at 700-800 oC and Si-rich surface at 900 oC.

cond-mat.mtrl-sci

Compositional dependence of epitaxial Tin+1SiCn MAX-phase thin films grown from a Ti3SiC2 compound target

We investigate sputtering of a Ti3SiC2 compound target at temperatures ranging from RT (no applied external heating) to 970 oC as well as the influence of the sputtering power at 850 oC for the deposition of Ti3SiC2 films on Al2O3(0001) substrates. Elemental composition obtained from time-of-flight energy elastic recoil detection analysis shows an excess of carbon in all films, which is explained by differences in angular distribution between C, Si and Ti, where C scatters the least during sputtering. The oxygen content is 2.6 at.% in the film deposited at RT and decreases with increasing deposition temperature, showing that higher temperatures favor high purity films. Chemical bonding analysis by X-ray photoelectron spectroscopy shows C-Ti and Si-C bonding in the Ti3SiC2 films and Si-Si bonding in the Ti3SiC2 compound target. X-ray diffraction reveals that the phases Ti3SiC2, Ti4SiC3, and Ti7Si2C5 can be deposited from a Ti3SiC2 compound target at substrate temperatures above 850 oC and with growth of TiC and the Nowotny phase Ti5Si3Cx at lower temperatures. High-resolution scanning transmission electron microscopy shows epitaxial growth of Ti3SiC2, Ti4SiC3, and Ti7Si2C5 on TiC at 970 oC. Four-point probe resistivity measurements give values in the range 120 to 450 micro-Ohm-cm and with the lowest values obtained for films containing Ti3SiC2, Ti4SiC3, and Ti7Si2C5.

cond-mat.mtrl-sci

Effect of impurities on morphology and growth mode of (111) and (001) epitaxial-like ScN films

ScN material is an emerging semiconductor with an indirect bandgap. It has attracted attention for its thermoelectric properties, use as seed layers, and for alloys for piezoelectric application. ScN or other transition metal nitride semiconductors used for their interesting electrical properties are sensitive to contaminants, such as oxygen or fluorine. In this present article, the influence of depositions conditions on the amount of oxygen contaminants incorporated in ScN films were investigated and their effects on the electrical properties (electrical resistivity and Seebeck coefficient) were studied. The epitaxial-like films of thickness 125 +-5 nm to 155 +-5 nm were deposited by D.C.-magnetron sputtering on c-plane Al2O3, MgO(111) and r-plane Al2O3 at a substrate temperature ranging from 700 to 950 degree C. The amount of oxygen contaminants presents in the film, dissolved into ScN or as an oxide, was related to the adatom mobility during growth, which is affected by the deposition temperature and the presence of twin domain growth. The lowest values of electrical resistivity of 50 micro-ohm cm were obtained on ScN(111)/MgO(111) and on ScN(001)/r-plane Al2O3 grown at 950 degree C with no twin domains and the lowest amount of oxygen contaminant. At the best, the films exhibited an electrical resistivity of 50 micro-ohm cm with Seebeck coefficient values maintained at -40 microV K-1, thus a power factor estimated at 3.2 10-3 W m-1 K-2 (at room temperature).

physics.app-ph

Effect of ion-implantation-induced defects and Mg dopants on thermoelectric properties of ScN

For applications in energy harvesting, environmentally friendly cooling, and as power sources in remote or portable applications, it is desired to enhance the efficiency of thermoelectric materials. One strategy consists of reducing the thermal conductivity while increasing or retaining the thermoelectric power factor. An approach to achieve this is doping to enhance the Seebeck coefficient and electrical conductivity, while simultaneously introducing defects in the materials to increase phonon scattering. Here, we use Mg ion implantation to induce defects in epitaxial ScN (111) films. The films were implanted with Mg+ ions with different concentration profiles along the thickness of the film, incorporating 0.35 to 2.2 at.% of Mg in ScN. Implantation at high temperature (600 C), with few defects due to the temperature, does not substantially affect the thermal conductivity compared to a reference ScN. Samples implanted at room temperature, in contrast, exhibited a reduction of the thermal conductivity by a factor of three. The sample doped with 2.2 at.% Mg also showed an increased power factor after implantation. This study thus shows the effect of ion-induced defects on thermal conductivity of ScN films. High-temperature implantation allows the defects to be annealed out during implantation, while the defects are retained for room-temperature implanted samples, allowing for a drastic reduction in thermal conductivity.

physics.app-ph

Chemical bonding in carbide MXene nanosheets

The chemical bonding in the carbide core and the surface chemistry in a new group of transition-metal carbides Tin+1Cn-Tx (n=1,2) called MXenes have been investigated by surface-sensitive valence band X-ray photoelectron spectroscopy. Changes in band structures of stacked nano sheets of different thicknesses are analyzed in connection to known hybridization regions of TiC and TiO2 that affect elastic and transport properties. By employing high excitation energy, the photoelectron cross-section for the C 2s - Ti 3d hybridization region at the bottom of the valence band is enhanced. As shown in this work, the O 2p and F 2p bands are shown to strongly depend both on the bond lengths to the surface groups and the adsorption sites. The effect of surface oxidation and Ar+ sputtering on the electronic structure is also discussed.

cond-mat.mtrl-sci

Chemical Bonding in Epitaxial ZrB2 Studied by X-ray Spectroscopy

The chemical bonding in an epitaxial ZrB2 film is investigated by Zr K-edge (1s) X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies and compared to the ZrB2 compound target from which the film was synthesized as well as a bulk α-Zr reference. Quantitative analysis of X-ray Photoelectron Spectroscopy spectra reveals at the surface: ~5% O in the epitaxial ZrB2 film, ~19% O in the ZrB2 compound target and ~22% O in the bulk α-Zr reference after completed sputter cleaning. For the ZrB2 compound target, X-ray diffraction (XRD) shows weak but visible -111, 111, and 220 peaks from monoclinic ZrO2 together with peaks from ZrB2 and where the intensity distribution for the ZrB2 peaks show a randomly oriented target material. For the bulk α-Zr reference no peaks from any crystalline oxide were visible in the diffractogram recorded from the 0001-oriented metal. The Zr K-edge absorption from the two ZrB2 samples demonstrate more pronounced oscillations for the epitaxial ZrB2 film than in the bulk ZrB2 attributed to the high atomic ordering within the columns of the film. The XANES exhibits no pre-peak due to lack of p-d hybridization in ZrB2, but with a chemical shift towards higher energy of 4 eV in the film and 6 eV for the bulk compared to α-Zr (17.993 keV) from the charge-transfer from Zr to B. The 2 eV larger shift in bulk ZrB2 material suggests higher oxygen content than in the epitaxial film, which is supported by XPS. In EXAFS, the modelled cell-edge in ZrB2 is slightly smaller in the thin film (a=3.165 Å, c=3.520 Å) in comparison to the bulk target material (a=3.175 Å, c=3.540 Å) while in hexagonal closest-packed metal (α-phase, a=3.254 Å, c=5.147 Å).

cond-mat.mtrl-sci