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 investigate the electronic structures and chemical bonding correlated to the thermoelectric properties of epitaxially grown chromium-based multicomponent nitride Cr(Mo,V)Nx thin films. The small amount of N vacancies causes Cr 3d and N 2p states to appear at the Fermi level and reduces the band gap in Cr0.51N0.49. Incorporating holes by alloying of V in N-deficient CrN results in an enhanced thermoelectric power factor with marginal change in the charge transfer of Cr to N compared with Cr0.51N0.49. Further alloying of Mo, isoelectronic to Cr, increases the density of states at the Fermi level due to hybridization of the (Cr, V) 3d and Mo 4d-N 2p states in Cr(Mo,V)Nx. This hybridization and N off-stoichiometry result in more metal-like electrical resistivity and reduction in Seebeck coefficient. The N deficiency in Cr(Mo,V)Nx also depicts a critical role in reduction of the charge transfer from metal to N site compared with Cr0.51N0.49 and Cr0.50V0.03N0.47. In this paper, we envisage ways for enhancing thermoelectric properties through electronic band engineering by alloying and competing effects of N vacancies.

Growth temperature (Ts) and ion irradiation energy (Ei) are important factors that influence film growth as well as their properties. In this study, we investigate the evolution of crystal structure and residual stress of TiNb-CrAlHfN films under various Ts and Ei conditions, where the latter is mainly controlled by tuning the flux of sputtered Hf ions using bipolar high-power impulse magnetron (BP-HiPIMS). The results show that TiNbCrAlHfN films exhibit the typical FCC NaCl-type structure. By increasing Ts from room temperature to 600 degrees C, the film texture changes from high-surface-energy (111) to low-surface-energy (100) accompanied by a higher crystal-linity in the out-of-plane direction and a more disordered growth tilt angle to the surface plane. In addition, compressive stress decreases with increasing Ts, which is ascribed to changes in the film growth both in the early and post-coalescence stages and more tensile thermal stress at elevated Ts. In contrast, a clear texture transition window is seen under various Ei of Hf+ ions, i.e., high-surface-energy planes change to low-surface-energy planes as Ei exceeds-110 eV, while low-surface-energy planes gradually transform back to high-surface-energy planes when Ei increases from 210 to 260 eV, indicating renucleation events for Ei > 210 eV. Compressive stress in-creases with increasing Ei but is still lower than that of a reference series with DC substrate bias UDC =-100 V. The study shows that it is possible to tailor properties of FCC-structured high-entropy nitrides by varying Ts and Ei in a similar fashion to conventional transition metal nitrides using the approach of unipolar and bipolar HiPIMS co-sputtering.

Multicomponent or high-entropy oxide films are of interest due to their remarkable structure and properties. Here, energetic ion irradiation is utilized for controlling the phase formation and structure of AlCrNbTi oxide at growth temperature of 500 degrees C. The ion acceleration is achieved by using a high-power impulse magnetron sputtering (HiPIMS) discharge, accompanied by a 10 & mu;s-long synchronized substrate bias (Usync), to minimize the surface charging effect and accelerate early-arriving ions, mainly Al+, O+, Ar2+, and Al2+. By increasing the magnitude of Usync from-100 V to-500 V, the film structure changes from amorphous to single-phase corundum, followed by the formation of high-number-density stacking faults (or nanotwins) at Usync =-500 V. This approach paves the way to tailor the high-temperature-phase and defect formation of oxide films at low growth temperature, with prospects for use in protective-coating and dielectric applications.

As a single-phase alloy, CrFeCoNi is a face centered cubic (fcc) material related to the archetypical highentropy Cantor alloy CrFeCoNiMn. For thin films, CrFeCoNi of approximately equimolar composition tends to assume an fcc structure when grown at room temperature by magnetron sputtering. However, the single-phase solid solution state is typically not achieved for thin films grown at higher temperatures. The same holds true for Cantor alloy-based ceramics (nitrides and oxides), where phase formation is extremely sensitive to process parameters such as the amount of reactive gas. This study combines theoretical and experimental methods to understand the phase formation in nitrogen-containing CrFeCoNi thin films. Density functional theory calculations considering three competing phases (CrN, Fe-Ni and Co) show that the free energy of mixing, Delta G of (CrFeCoNi)(1-x)N-x solid solutions has a maximum at x = 0.20-0.25, and AG becomes lower when x < 0.20 and x > 0.25. Thin films of (CrFeCoNi)1-xNx (0.14 >= x <= 0.41) grown by magnetron sputtering show stabilization of the metallic fcc when x <= 0.22 and the stabilization of the NaCl B1 structure when x > 0.33, consistent with the theoretical prediction. In contrast, films with intermediate amounts of nitrogen (x = 0.22) grown at higher temperatures show segregation into multiple phases of CrN, Fe-Ni-rich and Co. These results offer an explanation for the requirement of kinetically limited growth conditions at low temperature for obtaining single-phase CrFeCoNi Cantor-like nitrogen-containing thin films and are of importance for understanding the phase-formation mechanisms in multicomponent ceramics. The results from the study further aid in making correlations between the observed mechanical properties and the crystal structure of the films.

The Cantor alloy (CoCrFeMnNi) and its variants, in bulk as well as thin films, have been extensively studied. They are known to exhibit cubic crystal structures and thermodynamic stability regardless of their complex chemical composition. Therefore, they may find use as hard, wear-resistant, corrosion and oxidation-resistant coatings. The addition of light elements, such as nitrogen, is known to help improve these properties further through processes such as amorphization and nitride compound formation. Here, we investigate the ternary CrFeCo system to study the effects of nitrogen addition. (CrFeCo)N_y multicomponent thin films are grown on silicon substrates by DC magnetron sputtering. Changes in crystal structure, morphology, mechanical and electrical properties with gradual increases of nitrogen in the film are described and discussed. Increased addition of nitrogen from 14 at.% to 28 at.% in the film leads to a transformation from an fcc to a bcc crystal structure, affects both the mechanical and electrical properties. XPS analysis shows the tendency of nitrogen to bond with Cr over other metals. The films display hardness values between 7 and 11 GPa with resistivities values ranging between 28 and 165 μΩ cm.

During direct current magnetron sputtering (dcMS) of thin films, the ion energy and flux are complex parameters that influence thin film growth and can be exploited to tailor their properties. The ion energy is generally controlled by the bias voltage applied at the substrate. The ion flux density however is controlled by more complex mechanisms. In this study, we look into magnetic-field-assisted dcMs, where a magnetic field applied in the deposition chamber by use of a solenoid coil at the substrate position, influences the energetic bombardment by Ar ions during deposition. Using this technique, CrFeCoNi multicomponent nitride thin films were grown on Si(100) substrates by varying the bias voltage and magnetic field systematically. Plasma diagnostics were performed by a Langmuir wire probe and a flat probe. On interpreting the data from the current-voltage curves it was confirmed that the ion flux at the substrate increased with increasing coil magnetic field with ion energies corresponding to the applied bias. The increased ion flux assisted by the magnetic field produced by the solenoid coil aids in the stabilization of NaCl B1 crystal structure without introducing Ar ion implantation.

The Cantor alloy CrFeCoMnNi is generally fcc structured, but moderate changes in the composition can have a large influence on the phase formation. The aim of this study was to understand the changes brought on in lownitrogen-containing (CrFeCo)1-yNy thin films with y = 0.19 on the addition of copper, an interesting metal in terms of atomic size and nitride formation enthalpy. (CrFeCoCux)1-yNy films were grown by reactive magnetron sputtering. The amount of copper in the films was increased from x = 0 to x = 0.15 to study competitive phase formation. Without Cu, two-phase fcc + bcc films were obtained. The addition of Cu was found to stabilize the bcc structure despite the fact that Cu as a pure metal is fcc. Nanoindentation tests showed slight increase in hardness with initial Cu addition from 11 GPa to 13.7 +/- 0.2 GPa. The occurrence of pile up as opposed to cracking is an indication of the films ductility.

In this Letter, we investigate the mechanical stability of HEA-based multilayers after Xe-ion irradiation. CrFeCoNi/TiNbZrTa metallic and nitride thin films with a bilayer thickness of 30 nm were grown by reactive dc-magnetron sputtering on Al2O3(0001) substrates for irradiation studies and on Si(100) substrates for other characterizations. The films were subjected to 3-MeV Xe-ion irradiation at room temperature (RT) and at 500 degrees C. The crystal structure and mechanical properties of the films before and after irradiation were studied by x-ray diffraction and nanoindentation. Before irradiation, both the metallic and nitride multilayers displayed a lower hardness (7 and 20 GPa, respectively). Annealing at 500 degrees C for 150 min increased the hardness of the multilayer samples, but it also induced intermixing of elements between the sublayers of the metallic multilayer. Irradiation hardening was observed only in the metallic multilayer at room temperature. When comparing the effects of irradiation damage vs the effects of annealing on the mechanical properties, it was observed that annealing the multilayers had a more pronounced effect.

Multilayers of high entropy alloys (HEA) are picking up interest due to the possibility of altering material properties by tuning crystallinity, thickness, and interfaces of the layers. This study investigates the growth mechanism and mechanical properties of CrFeCoNi/TiNbZrTa multilayers grown by magnetron sputtering. Multilayers of bilayer thickness (A) from 5 nm to 50 nm were grown on Si(1 0 0) substrates. Images taken by transmission electron microscopy and energy-dispersive X-ray spectroscopy mapping revealed that the layers were well defined with no occurrence of elemental mixing. Multilayers with A < 20 nm exhibited an amorphous structure. As A increased, the CrFeCoNi layer displayed a higher crystallinity in comparison to the amorphous TiNbZrTa layer. The mechanical properties were influenced by the crystallinity of the layers and stresses in the film. The film with A = 20 nm had the highest hardness of approximately 12.5 GPa owing grain refinement of the CrFeCoNi layer. An increase of A >= 30 nm resulted in a drop in the hardness due to the increase in crystal domains of the CrFeCoNi layer. Micropillar compression induced shear in the material rather than fracture, along with elemental intermixing in the core of the deformed region of the compressed micropillar.

Thin films of CrMoVN are deposited on c-plane sapphire (Al2O3 (0001)) by direct current reactive magnetron sputtering, to investigate the effects of Mo and V addition to CrN-based films. All films grow epitaxially, but Mo incorporation affects the crystal structure and nitrogen content. All films in the CrMoVN series are understoichiometric in nitrogen, but largely retain the NaCl B1 structure of stoichiometric CrN films. Addition of vanadium increases the phase-stability range of the cubic phase, allowing for higher solubility of Mo than what has previously been reported for cubic CrN. The Seebeck coefficient and electrical resistivity are greatly affected by the alloying, showing a decrease of the Seebeck coefficient along with a decrease in resistivity. Cr0.83Mo0.11V0.06Nz shows a 70% increase in power factor (S2 sigma = 0.22 mW m-1 K-2) compared to the reference CrNz (S2 sigma = 0.13 mW m-1 K-2). Thermoelectric (TE) materials are in use in several applications, but often have too low efficiency. For more widespread use of these materials, fundamental research on TE material system is necessary. In this work, alloying in CrN, with the hope of pushing a material with great promise closer to applications, is investigated.image (c) 2023 WILEY-VCH GmbH

Zinc metal batteries (ZnBs) are poised as the next-generation energy storage solution, complementing lithium-ion batteries, thanks to their cost-effectiveness and safety advantages. These benefits originate from the abundance of zinc and its compatibility with non-flammable aqueous electrolytes. However, the inherent instability of zinc in aqueous environments, manifested through hydrogen evolution reactions (HER) and dendritic growth, has hindered commercialization due to poor cycling stability. Enter potassium polyacrylate (PAAK)-based water-in-polymer salt electrolyte (WiPSE), a novel variant of water-in-salt electrolytes (WiSE), designed to mitigate side reactions associated with water redox processes, thereby enhancing the cyclic stability of ZnBs. In this study, WiPSE was employed in ZnBs featuring lignin and carbon composites as cathode materials. Our research highlights the crucial function of acrylate groups from WiPSE in stabilizing the ionic flux on the surface of the Zn electrode. This stabilization promotes the parallel deposition of Zn along the (002) plane, resulting in a significant reduction in dendritic growth. Notably, our sustainable Zn-lignin battery showcases remarkable cyclic stability, retaining 80% of its initial capacity after 8000 cycles at a high current rate (1 A g-1) and maintaining over 75% capacity retention up to 2000 cycles at a low current rate (0.2 A g-1). This study showcases the practical application of WiPSE for the development of low-cost, dendrite-free, and scalable ZnBs. A dendrite-free and long-life cycle Zn-lignin battery was demonstrated using water-in-polymer salt electrolyte. image

We experimentally investigated the detection performance of highly disordered NbxTi1-xN based superconducting nanowire single photon detectors (SNSPDs). The dependence on the composition of the transition temperature T-c for NbxTi1-xN films show a dome-like behavior on the Nb content, with a maximal T-c at x(Nb) similar to 0.65, and the Nb0.65Ti0.35N films also combine relatively large sheet resistance and intermediate residual resistivity ratio. Moreover, 60-nm-wide and 7-nm-thick Nb0.65Ti0.35N nanowires show a switching current as high as 14.5 mu A, and saturated intrinsic detection efficiency with a plateau of more than 2 mu A at 2.4 K. Finally, the corresponding SNSPDs on an alternative SiO2/Ta2O5 dielectric mirror showed a system detection efficiency of approximately 92% for 1550 nm photons, and the timing jitter is around 26 ps. Our results demonstrate that the highly disordered NbxTi1-xN films are promising for fabricating SNSPDs for near-and middle-infrared single photons with high detection efficiency and low timing jitter.

Multicomponent as well as high-entropy-based nitrides have received increasing interest in the field of materials science and engineering. The structural characteristics of these compounds result in a mix of covalent, metallic, and ionic bonds that give rise to a number of attractive properties including high hardness, electrical and thermal conductivities as well as chemical stability. These properties render these materials promising candidates for various industrial applications involving harsh operating conditions. Herein, the corrosion resistances of dc magnetron sputtered nitrogen-containing TiZrTaNby thin films with Nb content ranging from 8.0 to 24.5 at% have been investigated to provide insights regarding the corrosion resistances of multicomponent systems containing more than one passive element. The corrosion resistances and anodic behavior of the films were examined by electrochemical means in 0.1 M H2SO4 and 0.1 M HCl solutions. The results demonstrate that despite the significant differences in the concentration of one of the two main passive elements in the films i.e., Nb, the corrosion resistance did not differ significantly between the films. To provide insights into this phenomenon, the surface chemical state and composition of the prepared films were probed using X-ray photoelectron spectroscopy. It was shown that all samples exhibited Ta-rich surfaces after positive polarization up to 3.0 V vs. Ag/AgCl (3 M NaCl) as a result of the anodic dissolution of Zr and Ti. The thickness of the oxide layer formed upon different anodic polarization was studied using transmission electron microscopy, while complementary electrochemical impedance studies were performed. The extent of Nb dissolution from the surface of the films was, on the other hand, found to be small. These findings highlight the dominant role of Ta in the passivation of the films and demonstrate the minor effect of Nb concentration on the corrosion resistances of the films. However, it was demonstrated that the presence of Nb was still important for the corrosion resistance of the films above 1.4 V vs. Ag/AgCl (3 M NaCl), when replacing Nb with Cr, due to transpassive dissolution of Cr. These results facilitate the design of highly corrosion resistant multicomponent nitrides containing more than one passive element.(c) 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Mg3Bi2-based compounds are of great interest for thermoelectric applications near room temperature. Here, undoped p-type Mg3SbxBi2-x thin films were synthesized using magnetron sputtering (three elemental targets in Ar atmosphere) with a growth temperature of 200 ? on three different substrates, namely, Si as well as c- and r-sapphire. The elemental composition was measured with energy-dispersive x-ray spectroscopy and the structure by x-ray diffraction. The electrical resistivity and the Seebeck coefficient were determined under He atmosphere from room temperature to the growth temperature. All samples are crystalline exhibiting the La2O3-type crystal structure (space group P-3m1). The observed thermoelectric response is consistent with a semiconductive behavior. With increasing x, the samples become more electrically resistive due to the increasing bandgap. High Bi content (x < 1) is thus beneficial due to lower resistivity and a higher power factor near room temperature. Thermoelectric thin films synthesized at low temperatures may provide novel pathways to enable flexible devices on polymeric and other heat-sensitive substrates.

Mg3Sb2-based thermoelectric materials attract attention for applications near room temperature. Here, Mg-Bi films were synthesized using magnetron sputtering at deposition temperatures from room temperature to 400 & DEG;C. Single-phase Mg3Bi2 thin films were grown on c-plane-oriented sapphire and Si(100) substrates at a low deposition temperature of 200 & DEG;C. The Mg3Bi2 films grew epitaxially on c-sapphire and fiber-textured on Si(100). The orientation relationships for the Mg3Bi2 film with respect to the c-sapphire substrate are (0001) Mg3Bi2||(0001) Al2O3 and [11 2 over bar 0] Mg3Bi2||[11 2 over bar 0] Al2O3. The observed epitaxy is consistent with the relatively high work of separation, calculated by the density functional theory, of 6.92 J m(-2) for the Mg3Bi2 (0001)/Al2O3 (0001) interface. Mg3Bi2 films exhibited an in-plane electrical resistivity of 34 mu omega m and a Seebeck coefficient of +82.5 mu V K-1, yielding a thermoelectric power factor of 200 mu W m(-1) K-2 near room temperature.

High entropy ceramics have rapidly developed as a class of materials based on high entropy alloys; the latter being materials that contain five or more elements in near-equal proportions. Their unconventional compositions and chemical structures hold promise for achieving unprecedented combinations of mechanical, electrical and chemical properties. In this thesis, high entropy ceramic films, (TiNbZrTa)N_x were deposited using reactive magnetron sputtering with segmented targets. The stoichiometry x was tuned with two deposition parameters, i.e., substrate temperature and nitrogen flow ratio f_N, their effect on microstructure and mechanical, electric, and electrochemical properties were investigated.

Understoichiometric MeN_x (Me = TiNbZrTa, 0.25 ≤ x ≤ 0.59) films were synthesized at a constant f_N when substrate temperature was varied from room temperature (RT) to 700 °C. For low-temperature deposition, the coatings exhibited fcc solid-solution polycrystalline structures. A NaCl-type structure with (001) preferred orientation was observed in MeN_0.46 coating deposited at 400 ºC, while an hcp structure was found for the coatings deposited above 500 ºC. The maximum hardness value of 26 GPa as well as the highest   and   values (0.12 and 0.34 GPa) were obtained for the MeN_0.46 coating. These films exhibited low RT electrical resistivities. In 0.1 M H₂SO₄ aqueous solution, the most corrosion resistant film was MeN_0.46 featured dense structure and low roughness.

The MeN_x films (x=0, 0.57 < x ≤ 0.83) were deposited with different f_N. The maximum hardness was achieved at 22.1 GPa for MeN_0.83 film. Their resistivities increased from 95 to 424 μΩcm with increasing nitrogen content. The corrosion resistance is related to the amount of nitrogen in the films. The corrosion current density was around 10^-8 A/cm², while the films with lower nitrogen contents (x < 0.60) exhibited a nearly stable current plateau up to 4.0 V, similar to the metallic films, while the films with a higher nitrogen content only featured a plateau up to 2.0 V, above which a higher nitrogen content resulted in higher currents. The reason was that the oxidation of these films at potentials above about 2.0 V vs. Ag/AgCl resulted in the formation of porous oxide layers as significant fraction of the generated N₂ was lost to the electrolyte.

Hence, these observed effects of deposition temperature and nitrogen content on the overall properties of nonstoichiometric MeN_x films provide insights regarding protective multicomponent nitride films, e.g. as corrosion resistant coatings on metallic bipolar plates in fuel cells or batteries.

This thesis focuses on understanding the process-structure-property relation-ships for several refractory-metal-based high-entropy alloys and nitrides synthesized by magnetron sputtering.  

The thesis begins with the growth of TiZrNbTaN_x understoichiometric nitrides by controlling substrate temperature and nitrogen flow ratio fN. Their effects on microstructure and mechanical, electric, and electrochemical properties were investigated. TiZrNbTaN_0.46 deposited at 400 ºC shows a NaCl-type structure with (001) preferred orientation and exhibits the highest corrosion resistance in 0.1 M H₂SO₄ aqueous solution. A stable passive region up to 3.0 V vs. Ag/AgCl could be achieved when x< 0.64. The densification effects were explored by ion energy for (TiZrTaMe)N_1–x (Me = Hf, Nb, Mo, or Cr) films and by high-power impulse magnetron sputtering technique for TiNbCrAl films.

The local chemical distortions in the TiZrTaNb-based system with different nitrogen content were investigated by X-ray absorption fine structure spectros-copy. The influence of crystallinity on superconducting transition behavior was studied in (TiZrHf)_x(TaNb)_1-x, (TiZrNbTa)_1-xW_x, and (TiZrNbTa)_1-xV_x systems. The highest superconducting transition temperature (T_c) reaches 8.05 K for the TiZrNbTa film (x=0). The superconducting transition temperature T_c of these films deposited at the fixed temperature decreases monotonically as a function of x, and T_c can be increased by elevating the deposition temperature. 

Furthermore, the structural stability and elemental segregation under Xe-ion irradiation of TiZrNbTaV-based HEA and HEN films, and high-entropy TiZrN-bTa/CrFeCoNi metallic and nitride multilayer coatings were investigated. The microstructure of TiZrNbTaVN film remain stable after irradiation at room temperature and 500 °C. The as-deposited TiZrNbTaV film exhibited an amorphous structure and became a bcc phase structure after irradiation at 500 °C. Thermal-induced and irradiation-induced grain growth resulted in a grain-size distribution. For the multilayer coatings, the microstructure of metallic multilayers was not stable and the interdiffusion or mixing of the constituent elements is prominent under ion irradiation and/or heat treatment. no diffusion and phase trans-formation were observed for the nitride multilayers after irradiation at 500 °C.

Multicomponent TixNbCrAl nitride films were deposited on Si(100) substrates by reactive direct current magnetron sputtering (dcMS) and high power impulse magnetron sputtering (HiPIMS) in the absence of substrate heating and bias. Three single Ti, Nb, and Cr50Al50 targets were either driven by three de or three HiPIMS power supplies. The Ti content in the films was varied by tuning the power applied to the Ti target. The composition was determined by ion beam analysis. The nitrogen content is nearly stoichiometric (48-50 at.%) in the HiPIMS series, while the dcMS are understoichiometric (39-45 at.%). The crystal structure, stress and density of the studied film were investigated by X-ray techniques and the microstructure was examined by scanning electron microscopy. All the Ti-containing films for both series exhibit an fcc NaCl-type phase structure. In particular, the dcMS series shows a (111) preferred orientation, resulting in a faceted surface morphology compared to a dense and smooth microstructure of the HiPIMS films. The compressive stress of the HiPIMS series (&gt; 2.0 GPa) is significantly larger than the values of the dcMS series (&lt;0.5 GPa). Nanoindentation measurements show a maximum hardness of 29.9 GPa and Youngs modulus of 304 GPa were obtained in the HiPIMS series. The results may promote HiPIMS techniques for the synthesis of complex multicomponent films for the application aspect to protective and hard coatings.

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.

Multicomponent or high-entropy ceramics show unique combinations of mechanical, electrical, and chemical properties of importance in coating applications. However, generalizing controllable thin-film processes for these complex materials remains a challenge. Here, understoichiometric (TiZrTaMe)N1–x (Me = Hf, Nb, Mo, or Cr, 0.12 ≤ x ≤ 0.30) films were deposited on Si(100) substrates at 400 °C by reactive magnetron sputtering using single elemental targets. The influence of ion energy during film growth was investigated by varying the negative substrate bias voltage from ∼10 V (floating potential) to 130 V. The nitrogen content for the samples determined by elastic recoil detection analysis varied from 34.9 to 43.8 at. % (0.12 ≤ x ≤ 0.30), and the metal components were near-equimolar and not affected by the bias voltage. On increasing the substrate bias, the phase structures of (TiZrTaMe)N1–x (Me = Hf, Nb, or Mo) films evolved from a polycrystalline fcc phase to a (002) preferred orientation along with a change in surface morphology from faceted triangular features to a dense and smooth structure with nodular mounds. All the four series of (TiZrTaMe)N1–x (Me = Hf, Nb, Mo, or Cr) films exhibited increasing intrinsic stress with increasing negative bias. The maximum compressive stress reached ∼3.1 GPa in Hf- and Cr-containing films deposited at −130 V. The hardness reached a maximum value of 28.0 ± 1.0 GPa at a negative bias ≥100 V for all the four series of films. The effect of bias on the mechanical properties of (TiNbZrMe)N1–x films can thus guide the design of protective high-entropy nitride films.

Multicomponent (TiNbZrTa)N_x films were deposited on Si(100) substrates at room temperature using magnetron sputtering with a nitrogen flow ratio f_N [f_N = N₂/(Ar + N₂)], which was varied from 0 to 30.8%. The nitrogen content in the films varied between 0 and 45.2 at.%, i.e., x = 0 to 0.83. The microstructure was characterized by X-ray diffraction and electron microscopy. The metallic TiNbZrTa film comprised a dominant bcc solid-solution phase, whereas a single NaCl-type face-centred cubic structure was observed in all nitrogen-containing films (TiNbZrTa)N_x. The mechanical, electrical, and electrochemical properties of these films varied with nitrogen content. The maximum hardness was achieved at 22.1 ± 0.3 GPa when N = 43.0 at.%. The resistivities increased from 95 to 424 μΩcm with increasing nitrogen content. A detailed study of the variation of morphology and chemical bonding with nitrogen content was performed and the corrosion resistance of the TiNbZrTa nitride films was explored in 0.1 M H₂SO₄. While all the films had excellent corrosion resistances at potentials up to 2.0 V vs. Ag/AgCl, the metallic film and the films with low nitrogen contents (x < 0.60) exhibited an almost stable current plateau up to 4.0 V vs. Ag/AgCl. For the films with higher nitrogen contents (x ≥ 0.68), the current plateau was retained up to 2.0 V vs. Ag/AgCl, above which a higher nitrogen content resulted in a higher current. The decrease in the corrosion resistance at these high potentials indicate the presence of a potential-dependent activation effect resulting in an increased oxidation rate of the nitrides (present under the passive oxide film) yielding a release of nitrogen from the films. TEM results indicate that the oxide layer formed after this corrosion measurement was thick and porous for the film with x = 0.76, in very good agreement with the increased corrosion rate for this film. The results demonstrate that an increased nitrogen content in (TiNbZrTa)N_x system improves their mechanical properties with retained high corrosion resistance at potentials up to 2.0 V vs. Ag/AgCl in 0.1 M H₂SO₄. At even higher potentials, however, the corrosion resistance decreases with increasing nitrogen concentration for films with sufficiently high nitrogen contents (i.e. x ≥ 0.68).

A series of (TiNbZrTa)Nx coatings with a thickness of similar to 1.1 mu m were deposited using reactive magnetron sputtering with segmented targets. The deposition temperature was varied from room temperature to 700 degrees C resulting in coatings with different microstructures. The coatings were characterized by electron microscopy, atomic force microscopy, compositional analysis, and X-ray diffraction. Effects of the deposition temperature on the electrical, mechanical and corrosion properties were studied with four-point probe, nanoindentation and potentiodynamic polarization measurements, respectively. X-ray photoelectron spectroscopy (XPS) analyses reveal a gradual change in the chemical state of all elements with increasing growth temperature from nitridic at room temperature to metallic at 700 degrees C. A NaCl-type structure with (001) preferred orientation was observed in the coating deposited at 400 degrees C, while an hcp structure was found for the coatings deposited above 400 degrees C. The resistivities of the TiNbZrTa nitride coatings were found to be around 200 mu Ocm. In 0.1 M H2SO4 aqueous solution, a corrosion current density of 2.8 x 10(-8) A/cm(2) and a passive behaviour up to 1.5 V vs. Ag/AgCl were found for the most corrosion resistant coating. The latter corrosion current is about two orders of magnitude lower than that found for a reference hyper-duplex stainless steel.

A variety of bulk high-entropy alloy superconductors have been recently discovered; however, for thin films, only the TaNbHfZrTi highentropy alloy system has been investigated for its superconducting properties. Here, (TiZrNbTa)_1-xW_x and (TiZrNbTa)_1-xV_x superconducting films have been produced by DC magnetron sputtering at different growth temperatures. The phase formation and superconducting behavior of these films depend on the content of alloying x and deposition temperature. A single body-centered cubic (bcc) phase can be formed in the low x range with enough driving energy for crystallinity, but phase transition between amorphous or two bcc structures is observed when increasing x. The highest superconducting transition temperature T_c reaches 8.0 K for the TiZrNbTa film. The superconducting transition temperature T_c of these films deposited at the same temperature decreases monotonically as a function of x. Increasing deposition temperature to 400 °C can enhance T_c for these films while retaining nearly equivalent compositions. Our experimental observations suggest that T_c of superconducting high entropy alloys relate to the atomic radii difference and electronegativity difference of involved elements beyond the valence electron number.

High-entropy materials, an exciting new class of structural materials involvingfive or more elements, are emerging as unexplored ground forsuperconductors. Here, the effects of nitrogen stoichiometry are investigatedon local chemical structure of TiZrNbTa-based thin films by variousX-ray-based techniques. Lattice distortion and short-range order of a set ofTiZrNbTaNxsamples, including bond lengths of different atomic pairs andcoordination numbers of substituting atoms are quantitatively studied. Themaximum superconducting transition temperature Tcis found at 10 K for anear-stoichiometric (TiZrNbTa)N1.08film, which is>8 K measured for ametallic TiZrNbTa film. The underlying electronic structure and chemicalbonding in these high entropy nitrides thus influence the superconductingmacroscopic properties.

An Fe50Mn30Co10Cr10 dual-phase high-entropy alloy (DP-HEA) was irradiated at room temperature with 3 MeV Fe ions to a dose of 50 displacement per atom (dpa). Potentials of special elemental designed DP-HEAs with low stacking fault energy (SFE) as promising candidate materials for future nuclear energy systems are evaluated. Transmission electron microscopy (TEM) analysis finds that FCC gamma-gamma, HCP epsilon-epsilon twinning structures and FCC gamma-HCP epsilon co-existed structures of the DP-HEA, which correlate with the combined high strength and high ductility featured by this alloy, remain stable under a displacement damage of 50 dpa. No elemental segregation after irradiation was detected by energy dispersive spectroscopy. The results indicate that TWIP and TRIP mechanisms, owned by many other DP-HEAs, may still work effectively, and the materials still possess the merits of combined high strength and ductility brought by TWIP and TRIP mechanisms under irradiation conditions. Defects free channels (DFCs) and abundant Lomer-Cottrell (L-C) locks are observed in the irradiated samples after tensile deformation. The immobile L-C locks restrict DFCs growth, prevent the pile-up of dislocation along grain boundaries, thus sustaining dislocations in the grain interior. This study provides a new strategy to improve simultaneously the irradiation resistance and mechanical properties of structural materials by introducing the TWIP and TRIP mechanisms. (C) 2021 Elsevier B.V. All rights reserved.

The study aims to understand the irradiation behavior of multilayer coatings composed of high-entropy materials. Here, we report the structural stability and elemental segregation of high-entropy TiNbZrTa/CrFeCoNi metallic and nitride multilayer coatings under 3-MeV Xe20+ ion-irradiation at room temperature and 500 degrees C, respectively. Transmission electron microscopy analysis shows that the microstructure of nanocrystalline CrFeCoNi high-entropy-alloy sublayers are not stable and readily transforms into amorphous state at 500 degrees C and/or under irradiation conditions. The elemental distribution, acquired by energy-dispersive X-ray spectroscopy under scanning transmission electron microscopy mode, shows preferential diffusion of Co and Ni into TiNbZrTa sublayers, while Fe and Cr preferentially remain within the previous CrFeCoNi sublayers. TiNbZrTaN/CrFeCoNiNx nitride multilayers exhibit a higher crystallinity and structural stability as well as resistance to diffusion at high-temperature and/or irradiation conditions than their TiNbZrTa/CrFeCoNi metallic multilayer counterparts. These findings are explained by atomic size differences, the difference in Gibbs free energy of the mixing system, and interstitial-solute-induced chemical heterogeneity. Our findings thus provide a design strategy of high entropy nitride for nuclear fuel cladding. (C) 2022 The Author(s). Published by Elsevier Ltd.

Refractory high-entropy protective coatings are of interest for nuclear fuel cladding applications due to their corrosion resistant properties and irradiation resistance at elevated temperature. Here, TiZrNbTaV metallic and (TiZrNbTaV)N films were deposited by magnetron co-sputtering. The metal elemental contents of both films were nearly equiatomic. These films were irradiated by Xe ions at room temperature and 500 degrees C, and examined by X-ray diffraction and transmission electron microscopy. The as-deposited (TiZrNbTaV)N film showed a single NaCl-type fcc phase and a pronounced columnar growth structure, which could remain intact after irradiation treatments. In contrast, the as-deposited TiZrNbTaV film exhibited an amorphous structure and formed a bcc phase structure after irradiation at 500 degrees C. The TiZrNbTaV film after irradiation at 500 degrees C composed of depth -dependent size of grains. This distribution of grain size is consistent with simulated displacement damage. The stable structure of (TiZrNbTaV)N film under high temperature irradiation indicates that these materials have potential for use as protective coatings for nuclear fuel claddings.

Introducing porosity is attractive for tailoring electronic, thermal, and mechanical properties of inorganic materials. Nanoporosity is typically either inherent in crystallographic channels in the structure or obtained by external templating during synthesis and sintering. However, controllably engineering porosity in materials with laminated crystal structures without channels remains a challenge. Here, we demonstrate the realization of faceted and oriented nanopores in textured Ca3Co4O9-a laminated ceramic with a misfit-layered structure of importance for thermoelectric applications-from chemical reactions in CaO/Co3O4 multilayers. We show that CaO conversion to Ca(OH)(2) and the cobalt oxide stoichiometry are key determinants of nanoporosity. Adjusting the unreacted CaO fraction alters the nanopore size and fraction and the thermoelectric properties of Ca3Co4O9. The preferred orientation of Ca3Co4O9 is underpinned by the texture of the reactant multilayers and reactant-product crystallographic relationships and density difference. Oriented pore formation is attributed to basal plane removal driven by local densification of textured Ca3Co4O9 nuclei through growth and impingement. These findings point to possibilities for controllably engineering nanoporosity and properties in a variety of inorganic materials with laminated crystal structures.

Superconducting high entropy alloys (HEAs) are a novel class of superconductors, with applications for electronic devices. Here, we investigated the effect of Mo alloying on superconducting properties of high entropy films with the composition (TaNb)(1-)(x)(ZrHfTi)(x)Mo-y. For near-equimolar composition, the crystalline HEAs grains are transformed into amorphous aggregations with a size in a few nanometer scale, forming a crystal/glass nanocomposite. In both crystalline and amorphous HEAs, the constituent atoms exhibit a homogeneous random distribution. The entropy-affected phase formations suppress the superconducting transitions in HEAs, which broadens the normal-to-superconducting transition regime and suppresses the zero-resistivity critical temperature to a lower constant value of approximately 2.9 K.

High entropy alloys are multielement materials exhibiting enhanced properties compared to their binary or ternary equivalents. Here, the authors investigate the influence of microstructure and elemental distribution on the transport and superconducting properties of (TaNb)(1-x)(ZrHfTi)(x) thin films. Superconducting high entropy alloys (HEAs) may combine extraordinary mechanical properties with robust superconductivity. They are suitable model systems for the investigation of the interplay of disorder and superconductivity. Here, we report on the superconductivity in (TaNb)(1-x)(ZrHfTi)(x) thin films. Beyond the near-equimolar region, the films comprise hundreds-of-nanometer-sized crystalline grains and show robust bulk superconductivity. However, the superconducting transitions in these nanocomposites are dramatically suppressed in the near-equimolar configurations, i.e., 0.45 &lt; x &lt; 0.64, where elemental distributions are equivalently homogeneous. Crystal/glass high entropy alloy nanocomposite phase separation was observed for the films in the near-equimolar region, which yields a broadened two-step normal to superconducting transition. Furthermore, the diamagnetic shielding in these films is only observed far below the onset temperature of superconductivity. As these unusual superconducting transitions are observed only in the samples with the high mixing entropy, this compositional range influences the collective electronic properties in these materials.

Nanocomposites have been long exploited for achieving balanced material properties. Here, we synthesized nominal (Mg2Sn0.85Sb0.15)1-x-(Mg3Sb2)x (x = 0-0.15) nano-composites, achieving a significant reduction of the lattice thermal conductivity of Mg2Sn0.85Sb0.15 from 2.03 Wm-1K-1 to 1.38 Wm-1K-1 due to phonon scattering by VMg point defects, Mg3Sb2 nanoparticles, and heterogeneous interfaces. Hence, a significantly enhanced thermoelectric figure of merit, ZT, is achieved. At 773 K, the sample of x = 0.075 reaches a ZT of 1.4, corresponding to a 14% enhancement compared to the Mg2Sn0.85Sb0.15 (x = 0) sample. The strategy of introducing heterogeneous structures has important implications for reducing thermal conductivity for other solid-solution thermoelectric systems.