Alloy Thin Films Research Articles

High-throughput aqueous passivation behavior of thin-film vs. bulk multi-principal element alloys in sulfuric acid

Multi-principal element alloys have the potential to show excellent passivation behavior. However, the detailed compositional and crystal structure design of these alloys requires a high-throughput strategy. We used combinatorial thin-film libraries of single-phase (FeCoNi)1-x-yCrxAly alloys and compared their passivation behaviors to corresponding bulk alloys. Our results demonstrate that the detailed passivation behaviors of thin-films and bulk alloys are different which is related to both nanoscale porosity within the thin-films and grain boundary dissolution. Nevertheless, we found that comparisons made among suitably designed sets of thin-film alloys can be used to determine the best corrosion performing bulk alloy composition.

The growth evolution of SnSe-doped SnTe alloy by in-situ selenization substitution method

In the era of increasing environmental pollution and energy crisis, the development of thermoelectric materials to achieve the reuse of waste heat energy is of great significance. SnTe, as an environmentally friendly thermoelectric material, its high electronic-thermal conductivity and coupled high electrical conductivity originated from intrinsic high carrier hole concentration leads to the unsatisfactory thermoelectric properties. With a lot of research going on to optimize thermoelectric performance by decoupling the thermo-electrical contradiction, the entropy engineering strategy, which can independently modulate lattice thermal conductivity is proved to be feasible by increasing the internal configurational entropy through doping. However, due to the uncontrollable growth microscopic process and the perturbation of film quality, the desired precise phase doping remains a challenge. In this work, we report an instantiation of the entropy increase of SnSe-doped SnTe alloy thin films prepared by two-step magnetron sputtering and selenization method. The microstructure and physical properties of thin films were investigated for replaying and controlling the growth evolution of in-situ selenization substitution. When the reaction temperature and duration were adjusted to 300℃ and 30 mins respectively, the desired pure phase doping was obtained. This work provides a new method of doping modification of SnTe materials, and the product as a new functional material expands the thermoelectric material library. In particular, it has positive reference significance for the development of synthesis controllability and structure establishment of complex polycrystalline materials.

Porous-anodic-alumina-templated Ta-Nb-alloy/oxide coatings via the magnetron-sputtering/anodizing as novel 3D nanostructured electrodes for energy-storage applications

The Ta-52 at.%Nb thin alloy films were magnetron sputter-deposited over a low-aspect-ratio nanoporous anodic-alumina template formed in 0.05 M tartaric acid solution at 250 V and modified by the pore-widening technique to enlarge the pores up to ∼500 nm. The alloy coated the pores evenly, thus forming a 3D continuous conducting nanofilm on the template. Partially anodizing the templated alloy in a borate buffer solution of pH 7.5 generated a compact amorphous mixed-oxide anodic film thickening proportionally to the applied voltage. It was revealed that the oxide on the Ta-52 at.%Nb alloy grows with a slower migration of Ta5+ ions relative to Nb5+ ions, resulting in mixing Ta2O5 and Nb2O5 in the film depth and forming a few-nm-thick Nb2O5 outmost layer. The unique migration of Ta4+, Ta3+, Nb4+, and Nb3+ ions is assumed accountable for forming corresponding suboxides in the 3D anodic film in contrast to a flat Ta-52 at.%Nb alloy film used as a reference. The 3D anodic films behave as an n-type semiconductor with a low donor density Nd = ∼2 × 1018 cm−3, appropriate for dielectric applications. An unusual two-layered structure with a sharp electrical interface revealed in the 3D oxide films anodized to 30–130 V, comprising a low-resistivity layer superimposed on the high-resistivity layer, is explained by an immobile negative space charge in the outer film part. The air-annealing at moderate temperatures releases the space charge and transforms the two layers into a high-resistivity single layer having substantially improved dielectric properties and thermostable (up to 250 °C) capacitance of 1.2 μF cm−2 achieved for the film anodized to practical 50 V. The 3D films having up to 4.5 times enlarged effective surface area can be utilized as novel metal/oxide nanostructured electrodes for electrolytic microcapacitors suitable for classical electronic circuits and energy-storage applications.

Rare Earth Material for Hydrogen Gas Sensing: PtGd Alloy Thin Films as a Promising Frontier.

At the focus of our investigation lies the precision fabrication of ultrathin platinum-gadolinium (PtGd) alloy films, with the aim to use these films for resistive hydrogen gas sensing. The imperative for sensitive and selective sensors to harness hydrogen's potential as an alternative energy source drives our work. Applying rare earth materials, we enhance the capabilities of hydrogen gas sensing applications. Our study pioneers PtGd alloy thin films for hydrogen gas sensing, addressing a gap in existing literature. Here, we demonstrate the functional characteristics of 2 nm thick PtxGd100'x (x = 25, 50 and 75) alloy films, analyzing their hydrogen gas sensing properties, comprehensively examining the interplay between alloy composition, temperature fluctuation and hydrogen concentration. The effect of composition and structural properties on the sensing response were assessed using EDX and XPS. The films are tested at a temperature range between 25 °C and 150 °C with hydrogen gas concentrations ranging from 10 ppm to 5%. Hydrogen gas sensing mechanisms in PtGd alloy ultrathin films are explained by surface scattering. The unique combination of Pt and Gd offers promising characteristics for gas sensing applications, including high reactivity with hydrogen gas and tunable sensitivity based on the alloy composition.

High thermoelectric power factor of SbPbTe thin alloy film grown by thermal evaporation and post-annealing treatment

Simple chemical compositions are frequently preferred in practical thermoelectric material applications due to their high growth success rates and increased stability. In this study, an n-type SbPbTe thin alloys film with equal amounts of all elements was grown, and the effect of equal contributions on thermoelectric properties and post-annealing treatment for 1–4 h was investigated. The as-grown SbPbTe thin alloys film and post annealed sample exhibited uniform composition distributions, single-phase microstructures, and non-uniform grain sizes at both micro- and nanoscales. The 4-h post annealed SbPbTe thin alloys film demonstrated maximum thermoelectric power factor of 21.2 μWcm−1K−2 at 500 K. This improvement was attributed to a decrease in electrical conductivity and the maintenance of a relatively maximum Seebeck coefficient achieved through the adjustment of carrier concentrations. The small grain size distribution over the surface contributed to strengthened grain boundary scattering, enhanced the charge carrier density and energy filtering effect. The thermoelectric power factor for the 4-h annealed sample peaks at 500 K, indicating optimal thermoelectric performance, as calculated from the Seebeck coefficient and electrical conductivity values. These findings provide insights into the structural and thermoelectric properties of SbPbTe thin alloy films, pointing to potential ways to improve their thermoelectric efficiency.

Effect of sputtering power and substrate bias on microstructure, mechanical properties and corrosion behavior of CoCrFeMnNi high entropy alloy thin films deposited by magnetron sputtering method

The CoCrFeMnNi high entropy alloy thin films with crystalline (solid solution) structure or amorphous state were fabricated by magnetron sputtering process at different target powers and different substrate bias. Effects of the target power and substrate bias on the characteristics of the CoCrFeMnNi thin films such as microstructures, morphology and surface topography, as well as mechanical properties and corrosion behavior were studied. Phase prediction was calculated by using thermodynamic and kinetic criteria under various deposition conditions. The enthalpy, entropy, δ and Ω parameters, and electronegativity differences influenced the solid solution stability of thin films. These parameters led to the formation of solid solutions with crystalline or amorphous structures under specific limits, which corresponded to the practical XRD and TEM analysis results. Using a substrate bias in the deposition of CoCrFeMnNi thin film changed the amorphous structure to a crystalline (solid solution (BCC + FCC)) at higher target powers (200 and 300 W). On the other hand, the film structure was entirely amorphous at all sputtering target powers without the substrate bias. The mechanical properties, such as hardness, Young's modulus, film strength, and fracture toughness of CoCrFeMnNi thin film, can be enhanced by using the substrate bias and increasing the sputtering power. The potentiodynamic polarization test in 3.5 wt% NaCl aqueous solution indicated that the deposition of CoCrFeMnNi thin films at different sputtering powers and without substrate bias could increase the corrosion resistance of 304 stainless steel substrate. Using the substrate bias of −100 V in the fabrication of CoCrFeMnNi thin film decreased the corrosion current density and increased its polarization resistance.

Enhancing atomic ordering, magnetic and transport properties of Mn2VGa Heusler alloy thin films toward negatively spin-polarized charge injection

Magnetic materials with negative spin polarization have attracted attention for their potential to increase the design freedom of spintronic devices. This study investigated the effects of off-stoichiometry on the atomic ordering, microstructure, and magneto-transport properties in Mn2+xV1−xGa (x = −0.2, 0, +0.2, +0.4) Heusler alloy films, which are predicted to have large negative spin polarization derived from a pseudo band gap in the majority spin channel. The Mn2+xV1−xGa films epitaxially grown on MgO(001) substrates exhibits variations of B2 and L21 order with the Mn concentration. A high-quality L21 ordered film was achieved in the Mn-rich composition (x = +0.2) with B2 and L21 order parameters of 0.97 and 0.86, respectively, and a saturation magnetization of 1.4 μB/f.u., which agrees with the Slater-Pauling rule. Scanning transmission electron microscopy observations showed that B2 and L21 phases coexist in Mn-poor and stoichiometric films, while the L21 phase is dominant in the Mn-rich film with small amounts of Mn–V and Mn–Ga disorders, as revealed by laboratory and anomalous X-ray diffraction. Combined first-principles calculations and anisotropic magnetoresistance analysis confirms that the addition of excess Mn preserves the high spin polarization by suppressing the formation of detrimental antisites of V atoms occupying Mn sites. Therefore, the Mn-rich composition is promising for negatively spin-polarized charge injection in Mn2VGa-based spintronic applications.

Self-organized composite morphologies and interface instability of immiscible alloy thin films during physical vapor deposition: Insights from phase-field simulations

In this paper, we carried out phase-field simulations for investigating self-organized composite morphologies formation and interface instability of two phase immiscible binary alloy thin-film growth during physical vapor deposition. Predicted results show that for lower the deposition rate the solid-gas interface keeps planar and the lateral composition modulation (LCM) configuration occurs. As the deposition rate increases, the self-organized composite morphology gradually transfers to vertical composition modulations (VCM) configuration and the random composition modulations (RCM) configuration with the decrease of the boundary layer of the incident vapor and the unsteady solid-gas interface. Results show that the nanoprecipitate concentration modulation (NCPM) depends strongly on the nominally phase fraction. Moreover, we found that the historical dependence of self-organized composite morphologies and solid-gas interface stability, i.e., the initial condition can strongly influence the microstructure of the thin film during physical vapor deposition. Finally, we provide an analysis method for interface instability based on fast Fourier transform (FFT), and the frequency characteristics of cellular and bump structures are identified.

Mapping the microstructure and the mechanical performance of a combinatorial Co–Cr–Cu–Fe–Ni–Zn high-entropy alloy thin film processed by magnetron sputtering technique

The Co–Cr–Cu–Fe–Ni–Zn compositional library was studied on a combinatorial high-entropy alloy thin film processed on a silicon substrate by magnetron sputtering technique. The thickness of the coating was between 2 and 3 μm while the lateral dimension was 10 cm. The chemical composition in the layer depended on the location and for each constituent element the concentration varied between 5 and 42 at.%. The phase composition and the microstructure were mapped using synchrotron X-ray diffraction, and the crystallite size as well as the density of lattice defects (dislocations and twin faults) were determined by diffraction line profile profile analysis. In addition, selected locations were studied by transmission electron microscopy. The influence of the chemical composition on the microstructure and the mechanical behavior was revealed. The mechanical performance was characterized by nanoindentation mapping which determined the hardness and the elastic modulus versus the element concentrations. It was found that the coating contains single phase face-centered cubic (FCC) and body-centered cubic (BCC) regions as well as an intermediate two-phase area. In the whole combinatorial sample, the microstructure consisted of nanocrystalline columns growing perpendicular to the coating surface and having pores between them. Due to the porosity, the hardness and the elastic modulus were relatively low despite the nanostructure and the very high defect density. The highest hardness (3.4 GPa) and elastic modulus (119 GPa) were measured in the BCC region with the chemical composition of 10%Co–38%Cr–13%Cu–27%Fe–5%Ni–7%Zn (at.%).

Microstructural stability and mechanical property of AlCrFeMoTi high-entropy amorphous alloy thin films under He+ ions irradiation

High-entropy amorphous materials have recently proved exceptional radiation resistance, showing potential as a candidate materials for nuclear industry applications. This study synthesized nearly equi-atomic AlCrFeMoTi high-entropy amorphous thin films with a thickness of about 499 nm using magnetron sputtering. The prepared films were subjected to low dose, 0.5 MeV He+ ion irradiation, with varying irradiation damage ranging from 0.01 to 0.1 displacement per atom (dpa). Increasing the irradiation dose led to a decrease in the radius of the inner diffraction halo (r) and an increase in the crystal-like order, indicating an irradiation-induced structural relaxation process within the amorphous matrix. This relaxation results in more efficient atomic packing, yielding a denser amorphous structure and enhanced hardness of AlCrFeMoTi high-entropy amorphous thin films. This study demonstrates that AlCrFeMoTi high-entropy amorphous thin films exhibit remarkable radiation resistance, with stable microstructure and mechanical properties under He+ irradiation, making them promising candidates for applications in the nuclear industry.

Negative spin polarization of Mn2VGa Heusler alloy thin films studied in current-perpendicular-to-plane giant magnetoresistance devices

Negative spin polarization of Mn2VGa Heusler alloy thin films studied in current-perpendicular-to-plane giant magnetoresistance devices

Synergistic engineering of palladium-cobalt nanoalloys on graphite sheet for efficient and sustainable hydrogen evolution reaction

The electrochemical hydrogen evolution reaction (HER)—a carbon-free route for hydrogen (H2) production—is of the utmost importance for H2-economy. Currently, HER performance is mainly restricted by the lack of promising alternatives to Pt-based electrocatalysts. In this study, we developed bimetallic PdCo alloy thin films with outstanding catalytic properties for the HER under acidic conditions. A simple aerosol-assisted chemical vapor deposition technique designed in-house was used to produce bimetallic alloy thin films on graphite sheets. The thin-film morphological patterns were significantly changed by varying the deposition time from 30 to 90 min. The optimized PdCo catalyst deposited for 30 min had a unique nanostructure with numerous active sites and exhibited faster HER kinetics than its analogs and pure Pd. As-prepared PdCo-30 electrode produced current densities of 10 and 1000 mA cm−2 at overpotentials of 41 and 161 mV, respectively, along with a Tafel slope of 42 mV/dec, high conductivity (0.28 Ω), and catalytic stability of ∼24 h in 0.5 M H2SO4. The excellent HER activity of the PdCo alloy was attributed to the synergy between the noble transition metal and the thin nanostructured layer of the bimetallic catalyst, which promoted formation of extensive electroactive sites on the conductive graphite surface. Density functional theory calculations confirmed the experimental findings. The Gibbs free energy (ΔGH*) of the PdCo alloy (−0.43 eV) was significantly lower than that of pure Pd (−0.57 eV), confirming the enhancement in HER activity due to the introduction of Co into the Pd lattice.

Investigation of isothermal entropy change, relative cooling power, and refrigerant capacity of GdCoAl nanocomposite thin film by changing the Al ratio at low magnetic fields of 100 Oe and 1000 Oe

There are two challenges with magnetocaloric materials (MCMs): the production of low-cost materials and the applicability of MCMs at low magnetic fields. Due to the abundance of Al, the effects of Al composition in GdCoAl nanocomposite thin film alloys were investigated by fabricating Gd19.60Co20.00Al60.40 and Gd38.62Co28.43Al32.95 alloys. Nanometric grains were seen in the surface images with different grain dimensions by changing the Al ratio. With an increase in the Al ratio, the Z-height dimension decreased. The grains were homogeneous and small for the ternary thin film with a high Al ratio. It was established that the alloy with a higher amount of Al had a higher Curie temperature at a lower (100 Oe) magnetic field; it performed worse when compared to the low Al ratio sample regarding RCP and RC due to the small full width at half maxima. However, Gd19.60Co20.00Al60.40 at a higher magnetic field intensity of 1000 Oe, performed better.

Effect of growth conditions on magnetization reversal and magnetic anisotropy in Co2Fe0.5Ti0.5Si quaternary Heusler alloy thin films

Ferromagnetic resonance and magneto-optic Kerr effect (MOKE) techniques are employed to unravel the nature of ‘in-plane’ (IP) magnetic anisotropy and magnetization reversal (MR) processes in magnetron-sputtered 100 nm Co2Fe0.5Ti0.5Si (CFTS) thin films, deposited (and subsequently annealed) at different substrate temperatures (Ts) ranging from 200 °C to 550 °C. By varying TS, the CFTS films are produced with different amounts of anti-site (AS) atomic disorder. Irrespective of the degree of AS disorder, the IP uniaxial magnetic anisotropy (UMA) is prevalent in all the CFTS films. The TS450 and TS500 films, deposited at T S = 450 °C and 500 °C, stand out as they have (i) the least AS disorder, (ii) lowest value (α = 0.0055) of the Gilbert damping constant, (iii) high saturation magnetization ( ≅770 G ) at 300 K, (iv) UMA energy density as high as ≅1.6×104erg/cc at 120 K dropping to ≅1.0×104erg/cc at 300 K, (v) spin-wave stiffness ( D ) at T = 0 K, D0≅175 meVÅ2 and, as in other CFTS films, the electron–magnon interaction is primarily responsible for the thermal renormalization of D . Furthermore, in the TS450 and TS500 films, MOKE hysteresis loops at various angles ( ψH ) that the field makes with the easy axis in the film plane, reveals two mutually exclusive UMAs, UMA1≫UMA2 , with easy axes perpendicular to each other. By contrast, only a single UMA is observed in all the remaining films. When ψH=0∘ , MOKE domain images reveal that, consistent with the uniaxial nature of magnetic anisotropy, an abrupt reversal of magnetization is accompanied by the formation of 180° domains. When ψH = 90°, due to the presence of two UMAs in TS450 and TS500 films, following the field reversal, first the reverse domains nucleate and then grow at the expense of the fundamental domains through field-induced domain wall motion.

Increased thermal conductivity and decreased electron–phonon coupling factor of the aluminum scandium intermetallic phase (Al3Sc) compared to solid solutions

Aluminum scandium alloys and their intermetallic phases have arisen as potential candidates for the next generation of electrical interconnects. In this work, we measure the in-plane thermal conductivity and electron–phonon coupling factor of aluminum scandium alloy thin films deposited at different temperatures, where the temperature is used to control the grain size and volume fraction of the Al3Sc intermetallic phase. As the Al3Sc intermetallic formation increases with higher deposition temperature, we measure increasing in-plane thermal conductivity and a decrease in the electron–phonon coupling factor, which corresponds to an increase in grain size. Our findings demonstrate the role that chemical ordering from the formation of the intermetallic phase has on thermal transport.

Influence of the Pd Oxidation State in PdNi Thin Films on Surface Acoustic Wave Hydrogen Sensing Performance.

PdNi alloy thin films demonstrate exceptional hydrogen sensing performance and exhibit significant potential for application in surface acoustic wave (SAW) hydrogen sensors. However, the long-term stability of SAW H2 sensors utilizing PdNi films as catalysts experiences a substantial decrease during operation. In this paper, X-ray photoelectron spectroscopy (XPS) is employed to investigate the failure mechanisms of PdNi thin films under operational conditions. The XPS analysis reveals that the formation of PdO species on PdNi thin films plays a crucial role in the failure of hydrogen sensing. Additionally, density functional theory (DFT) calculations indicate that hydrogen atoms encounter a diffusion energy barrier during the penetration process from the PdNiOx surface to the subsurface region. The identification of PdNi film failure mechanisms through XPS and DFT offers valuable insights into the development of gas sensors with enhanced long-term stability. Guided by these mechanisms, we propose a method to restore the hydrogen sensing response time and magnitude to a certain extent by reducing the partially oxidized surface of the PdNi alloy under a hydrogen atmosphere at 70 °C, thereby restoring Pd to its metallic state with zero valence.

Chiral Nanoporous Structures Fabricated via Plasmon-Induced Dealloying of Au-Ag Alloy Thin Films

Chiral Nanoporous Structures Fabricated via Plasmon-Induced Dealloying of Au-Ag Alloy Thin Films

Graphite sheet-supported bimetallic RhNi thin film alloys for enhanced and durable hydrogen evolution in acidic environments

Noble metal-based materials are excellent catalysts for hydrogen production from water electrolysis, but their high cost and limited availability hinder widespread use. However, precious metals can be effectively utilized in catalysts by forming alloys with low-cost 3d transition metals, thereby reducing the need for precious metals, while enhancing the performance. In this study, aerosol-assisted chemical vapor deposition was employed to deposit bimetallic rhodium-nickel (RhNi) alloy thin films on a graphite sheet for hydrogen evolution reaction (HER) catalysis in a 0.5 M H2SO4 solution. Thin-film morphological patterns were significantly changed as the deposition time varied from 45 to 135 min. The RhNi alloy fabricated for 90 min outperformed its counterparts, displaying lower overpotential of 40 and 197 mV at 10 and 1000 mA cm−2, small Tafel kinetics (54 mV dec−1), high conductivity (0.57 Ω) and large electrochemical surface area (3312 cm2), and extended stability (48 h) compared to pure Rh metal and other reported catalysts. The superior HER performance arises from the synergistic effects between Rh and Ni metals, coupled with a uniform layer of spherical particles that enhance conductive properties and reaction rates by providing maximized active sites on graphite surface. This work provides valuable guidelines for efficiently preparing highly active and durable thin-film electrocatalyst within short time span and applying directly in fuel cell for hydrogen production.

Exploring the structural mechanics of titanium nickel solid alloy using COMSOL Multiphysics: A Poisson equation and continuity equation perspective

This study investigates the structural mechanics of titanium-nickel (Ti-Ni) alloy thin film using computational modelling through COMSOL Multiphysics based on Poisson’s equation and continuity equation for stress check by considering its linear elastic, conservation of charge and providing insight into nanomaterial deformation. In the COMSOL environment the parameters for titanium nickel (Ti-Ni) are embedded in the COMSOL Simulink interface. The Thin film layer was designed by defining the layer geometry of the size and shape of the layer with a width of 500 μm, depth of 200 μm and height of 3 μm subjected to boundary conditions such as von – mises stress, surface temperature, iso-surface temperature, multi-slice electric potential, displacement component, surface elastic strain energy density and total enthalpy. The results displayed a trend that is, as the surface temperature increases there will be an increase in the current densities associated with high electrical conduction. On the same note, the designed thin film layer will pass the percolation threshold. The results of surface elastic strain energy density and total enthalpy imply that the designed thin film layer is effective and efficient as a structural pseudopotential device (photodiode).

Molecular beam epitaxy growth and characterization of GePb alloys

Pb based group-IV alloys such as GePb have been gaining interest as a potential alternative for infrared detectors, quantum materials, and high-speed electronic devices. Challenges remain in their growth due to the extremely low solid solubility of Pb in the Ge–Pb system. This paper reports molecular beam epitaxy growth of GePb alloy thin films on Ge(100) substrates. Effusion cells of Ge and Pb are used to control the flux ratio independently. The optimal substrate temperature is found to be near the thermocouple temperature of 300 °C based on the characterization of the grown films using high-resolution x-ray diffraction. A large change in the Ge:Pb beam equivalent pressure ratio from 10:1 to 1:1 results in only a minimal increase of the Pb composition from 0.74% to 2.84% as estimated from Raman spectroscopy and Rutherford backscattering spectrometry. Scanning electron microscopy images show a large volume of Pb islands on the surface that form into either long trapezoidal rods or uniform droplets, with increasing Pb flux and growth time the density of Pb islands increased.