High-entropy alloys (HEAs) are at the focus of current research for their diverse properties, including superconductivity and structural polymorphism. However, the polymorphic transition has been observed only in nonsuperconducting HEAs and mostly under high pressure. Here we report the discovery of superconductivity and temperature-driven polymorphism in the (V$_{0.5}$Nb$_{0.5}$)$_{3-x}$Mo$_{x}$Al$_{0.5}$Ga$_{0.5}$ (0.2 $\leq$ $x$ $\leq$ 1.4) HEAs. It is found that the as-cast HEA is of a single body-centered cubic (bcc) structure for $x$ = 0.2 and a mixture of the bcc and A15 structures for higher $x$ values. Upon annealing, the bcc structure undergoes a polymorphic transformation to the A15 one and all HEAs exhibits bulk superconductivity. For $x$ = 0.2, whereas the bcc polymorph is not superconducting down to 1.8 K, the A15 polymorph has a superconducting transition temperature $T_{\rm c}$ of 10.2 K and an estimated zero-temperature upper critical field $B_{\rm c2}$(0) of 20.1 T, both of which are the highest among HEA superconductors. With increasing Mo content $x$, both $T_{\rm c}$ and $B_{\rm c2}$(0) of the A15-type HEAs decrease, yet the large ratio of $B_{\rm c2}$(0)/$T_{\rm c}$ signifies a disorder-induced enhancement of the upper critical field over a wide $x$ range. The decrease in $T_{\rm c}$ is attributed to the decrease in both the electronic specific-heat coefficient and electron-phonon coupling strength. Furthermore, the valence electron count dependence of $T_{\rm c}$, which is different from both the binary A15 and other structurally different HEA superconductors, suggests that $T_{\rm c}$ may be increased further by reducing the number of valence electrons. Our results not only uncover HEA superconductors of a new structural type, but also provide the first example of polymorphism dependent superconductivity in HEAs.
We consider a system where structural polymorphism suggests the possible existence of superconductivity through the implied structural instability. SrPd2Bi2 has two poly-morphs which can be controlled by the synthesis temperature: a tetragonal form (CaBe2Ge2-type) and a monoclinic form (BaAu2Sb2-type). Though the crystallographic difference between the two forms may at first seem trivial, we show that tetragonal SrPd2Bi2 is superconducting at 2.0 K whereas monoclinic SrPd2Bi2 is not. We rationalize this finding and place it in context with other 1-2-2 phases
Polymorphism in materials often leads to significantly different physical properties - the rutile and anatase polymorphs of TiO2 are a prime example. Polytypism is a special type of polymorphism, occurring in layered materials when the geometry of a repeating structural layer is maintained but the layer stacking sequence of the overall crystal structure can be varied; SiC is an example of a material with many polytypes. Although polymorphs can have radically different physical properties, it is much rarer for polytypism to impact physical properties in a dramatic fashion. Here we study the eff…
We report neutron scattering measurements, which reveal spin-liquid polymorphism in a '11' iron chalcogenide superconductor, a poorly-metallic magnetic FeTe tuned towards superconductivity by substitution of a small amount of Tellurium with iso-electronic Sulphur. We observe liquid-like magnetic dynamics, which is described by a competition of two phases with different local structure, whose relative abundance depends on temperature. One is the ferromagnetic (FM) plaquette phase observed in the non-superconducting FeTe, which preserves the C$_4$ symmetry of the underlying square lattice and is…
We report here the structural, electrical and magnetic properties of as-cast V$_{1-x}$Zr$_x$ alloys ($x$ =0 - 0.4) at low temperatures. We observe that all the alloys undergo successive peritectic and eutectic reactions during cooling from the melt which leads to the formation of five phases, namely, a body centred cubic $β$-V phase, two phases with slightly different compositions having face centred cubic ZrV$_2$ structure, a hexagonal closed packed $α$-Zr phase, and the $β$-Zr precipitates. The amount of each phase is found to be dependent on the concentration of zirconium in vanadium. The $…
We give a brief review of superconductivity at ambient pressure in elements, alloys, and simple three-dimensional compounds. Historically these were the first superconducting materials studied, and based on the experimental knowledge gained from them the BCS theory of superconductivity was developed in 1957. Extended to include the effect of phonon retardation, the theory is believed to describe the subset of superconducting materials known as `conventional superconductors', where superconductivity is caused by the electron-phonon interaction. These include the elements, alloys and simple comp…
Here we report the observation of extraordinary superconductivity in a pressurized commercial niobium-titanium alloy. We find that its zero-resistance superconductivity persists from ambient pressure to the pressure as high as 261.7 GPa, a record high pressure up to which a known superconducting state can continuously survives. Remarkably, at such an ultra-high pressure, although the ambient pressure volume is shrunk by 45% without structural phase transition, the superconducting transition temperature (TC) increases to ~19.1 K from ~9.6 K, and the critical magnetic field (HC2) at 1.8 K has be…
We present a detailed study of the superconducting properties in the beta-phase Mo$_{1-x}$Re$_x$ (x = 0.25 and 0.4) solid solution alloys pursued through magnetization and heat capacity measurements. The temperature dependence of the upper critical field H$_{C2}$(T) in these binary alloys shows a deviation from the prediction of the Werthamer-Helfand-Hohenberg (WHH) theory. The temperature dependence of superfluid density estimated from the variation of lower critical field H$_{C1}$ with temperature, cannot be explained within the framework of a single superconducting energy gap. The heat capa…
In a short review-article we first discuss the results, which are mainly devoted to the generalizations of the famous Kohn-Luttinger mechanism of superconductivity in purely repulsive fermion systems at low electron densities. In the context of repulsive-U Hubbard model and Shubin-Vonsovsky model we consider briefly the superconducting phase diagrams and the symmetries of the order parameter in novel strongly correlated electron systems including idealized monolayer and bilayer graphene. We stress that purely repulsive fermion systems are mainly the subject of unconventional low-temperature su…
We investigated the effect of alloying on the upper critical field $H_{c2}$ in 12 $MgB_2$ films, in which disorder was introduced by growth, carbon doping or He-ion irradiation, finding a significant $H_{c2}$ enhancement in C-alloyed films, and an anomalous upward curvature of $H_{c2}(T)$. Record high values of $H_{c2}^{\perp}(4.2) \simeq 35T$ and $H_{c2}\|(4.2) \simeq 51T$ were observed perpendicular and parallel to the ab plane, respectively. The temperature dependence of $H_{c2}(T)$ is described well by a theory of dirty two-gap superconductivity. Extrapolation of the experimental data to T…
We report the superconducting properties of new hexagonal Nb$_{10+2x}$Mo$_{35-x}$Ru$_{35-x}$Rh$_{10}$Pd$_{10}$ high-entropy alloys (HEAs) (0 $\leq$ $x$ $\leq$ 5). With increasing $x$, the superconducting transition temperature $T_{\rm c}$ shows a maximum of 6.19 K at $x$ = 2.5, while the zero-temperature upper critical field $B_{\rm c2}$(0) increases monotonically, reaching 8.3 T at $x$ = 5. For all $x$ values, the specific heat jump deviates from the Bardeen-Cooper-Schreiffer behavior. In addition, we show that $T_{\rm c}$ of these HEAs is not determined mainly by the density of states at the…
Magnesium diboride crystals were grown with low melting alloy flux. The sample with superconductivity at 38.3 K was prepared in the zinc-magnesium flux and another sample with superconductivity at 34.11 K was prepared in the cadmium-magnesium flux. MgB4 was found in both samples, and MgB4's magnetization curve being above zero line had not superconductivity. Magnesium diboride prepared by these two methods is all flaky and irregular shape and low quality of single crystal. However, these two metals should be the optional flux for magnesium diboride crystal growth. The study of single crystal g…
Herein, we report the synthesis and detailed superconducting properties of a new high entropy alloy superconductor with nominal composition Nb$_{20}$Re$_{20}$Zr$_{20}$Hf$_{20}$Ti$_{20}$ using powder X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), magnetization, transport, and thermodynamic measurements. The room temperature powder XRD confirms that the alloy is arranged on a simple body centered cubic crystal lattice with lattice parameter a = 3.38 (1) $\textÅ$. EDX measurement yields an average composition of Nb$_{21}$Re$_{16}$Zr$_{20}$Hf$_{23}$Ti$_{20}$ (in atomic $\%$).…
A model of alloy is considered which includes both quenched disorder in the electron subsystem (``alloy'' subsystem) and electron-phonon interaction. For given approximate solution for the alloy part of the problem, which is assumed to be conserving in Baym's sense, we construct the generating functional and derive the Eliashberg-type equations which are valid to the lowest order in the adiabatic parameter.The renormalization of bare electron-phonon interaction vertices by disorder is taken into account consistently with the approximation for the alloy self-energy. For the case of exact config…
We studied the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) like state establishing due to the proximity effect in superconducting Nb/Cu41Ni59 bilayers. Using a special wedge-type deposition technique, series of 20-35 samples could be fabricated by magnetron sputtering during one run. The layer thickness of only a few nanometers, the composition of the alloy, and the quality of interfaces were controlled by Rutherford backscattering spectrometry, high resolution transmission electron microscopy, and Auger spectroscopy. The magnetic properties of the ferromagnetic alloy layer were characterized with…
A polycrystalline sample of the high-entropy-alloy-type telluride AgInSnPbBiTe5 was synthesized using high-pressure synthesis. Superconductivity with a transition temperature (Tc) of 2.6 K was observed in AgInSnPbBiTe5. Elemental and structural analyses revealed that five metals are mixed in a metal site of an NaCl-type structure. Since AgInSnPbBiTe5 has a cation site (Ag, In, Sn, Pb, and Bi) and an anion site (Te), this is the first example of a high-entropy-alloy (HEA) pseudo-binary superconductor.
Niobium-zirconium (Nb-Zr) alloy is an old superconductor that is a promising new candidate for superconducting radio-frequency (SRF) cavity applications. Using density-functional and Eliashberg theories, we show that addition of Zr to a Nb surface in small concentrations increases the critical temperature $T_c$ and improves other superconducting properties. Furthermore, we calculate $T_c$ for Nb-Zr alloys across a broad range of Zr concentrations, showing good agreement with the literature for disordered alloys as well as the potential for significantly higher $T_c$ in ordered alloys near 75%N…
High Critical Temperature and Field Superconductivity in Nb$_{0.85}$X$_{0.15}$, (X = Ti, Zr, Hf) Alloys: Promising Candidates for Superconducting Devices
High-entropy alloys (HEA) form through the random arrangement of five or more chemical elements on a crystalline lattice. Despite the significant amount of resulting compositional disorder, a subset of HEAs enters a superconducting state below critical temperatures $T_c<10$ K. The superconducting properties of the known HEAs seem to suffice a Bardeen-Cooper-Schrieffer (BCS) description, but little is known about their superconducting order parameter and the microscopic role of disorder. We report on magnetic susceptibility measurements on films of the superconducting HEA (TaNb)$_{1-x}$(ZrHfTi)…
The superconducting high-entropy alloys (HEAs) recently attract considerable attention due to their exciting properties, such as the robustness of superconductivity against atomic disorder and extremely high-pressure. The well-studied crystal structure of superconducting HEAs is body-centered-cubic (bcc) containing Nb, Ti, and Zr atoms. The same elements are contained in Al5Nb24Ti40V5Zr26, which is a recently discovered bcc HEA and shows a gum-metal-like behavior after cold rolling. The gum metal is also an interesting system, exhibiting superelasticity and low Young's modulus. If gum metals s…
BaFe2Se3 is a potential superconductor material exhibiting transition at 11 K and ambient pressure. Here we extended the structural and performed electrical resistivity measurements on this compound up to 51 GPa and 20 GPa, respectively, in order to distinguish if the superconductivity in this sample is intrinsic to the BaFe2Se3 phase or if it is originating from minor FeSe impurities that show a similar superconductive transition temperature. The electrical resistance measurements as a function of pressure show that at 5 GPa the superconducting transition is observed at around 10 K, similar t…
We report experimental studies of the temperature and magnetic field dependence of resistivity and dc magnetic susceptibility and the temperature dependence of zero field heat capacity in a Ti$_{0.6}$V$_{0.4}$ alloy. The temperature dependence of the normal state dc magnetic susceptibility in this Ti$_{0.6}$V$_{0.4}$ alloy shows T$^2$lnT behavior. The temperature dependence of resistivity follows a T$^2$ behaviour in the range 20-50 K. On the other hand, a term $T^3$ lnT is needed in the expression containing the electronic and lattice heat capacities to explain the temperature dependence of h…
Research on high-entropy-alloy (HEA) superconductors is a growing field in material science. In this study, we explored new HEA-type superconductors and discovered a CuAl2-type superconductor Co0.2Ni0.1Cu0.1Rh0.3Ir0.3Zr2 with a HEA-type transition metal site. A superconducting transition was observed at 8.0 K after electrical resistivity, magnetization, and specific heat measurements. The bulk characteristics of the superconductivity were confirmed through the specific heat measurements. The discovery of superconductivity in HEA-type Co0.2Ni0.1Cu0.1Rh0.3Ir0.3Zr2 will provide a novel pathway to…
We report the observation of extraordinarily robust zero-resistance superconductivity in the pressurized (TaNb)0.67(HfZrTi)0.33 high entropy alloy - a new kind of material with a body-centered cubic crystal structure made from five randomly distributed transition metal elements. The transition to superconductivity (TC) increases from an initial temperature of 7.7 K at ambient pressure to 10 K at ~ 60 GPa, and then slowly decreases to 9 K by 190.6 GPa, a pressure that falls within that of the outer core of the earth. We infer that the continuous existence of the zero-resistance superconductivit…
Using density-functional-based method, we study the k-resolved sigma- and pi-band holes in Mg_{1-x}Al_{x}B_{2} and Mg(B_{1-y}C_{y})_{2} alloys. We find that the calculated profiles of the loss of sigma- and pi-band holes in these two systems as a function of impurity concentration are in qualitative agreement with experiments, as expected. We also describe its implications vis-a-vis superconductivity in Mg_{1-x}Al_{x}B_{2} and Mg(B_{1-y}C_{y})_{2}.
We have found that body-centered cubic (bcc) HfMoNbTiZr is a type-II BCS high-entropy alloy (HEA) superconductor with a superconducting critical temperature of $T_\mathrm{c}$=4.1 K. By employing a Debye temperature $θ_\mathrm{D}$ of 263 K and $T_\mathrm{c}$, the electron-phonon coupling constant $λ_\mathrm{e-p}$ is calculated to be 0.63. The electronic structure calculation revealed band broadening with energy uncertainties due to atomic disorders. The superconducting properties are compared among equiatomic quinary bcc HEA superconductors. $T_\mathrm{c}$ decreases with decreasing $λ_\mathrm{e…
Hydrogen-based superconductors provide a route to the long-sought goal of room-temperature superconductivity, but the high pressures required to metallize these materials limit their immediate application. For example, carbonaceous sulfur hydride, the first room-temperature superconductor, can reach a critical temperature (Tc) of 288 K only at the extreme pressure of 267 GPa. The next recognized challenge is the realization of room-temperature superconductivity at significantly lower pressures. Here, we propose a strategy for the rational design of high-temperature superconductors at low press…
Superconducting high entropy alloy (HEA) are emerging as a new class of superconducting materials. It provides a unique opportunity to understand the complex interplay of disorder and superconductivity. We report the synthesis and detail bulk and microscopic characterization of Nb$_{60}$Re$_{10}$Zr$_{10}$Hf$_{10}$Ti$_{10}$ HEA alloy using transport, magnetization, specific heat, and muon spin rotation/relaxation ($μ$SR) measurements. Bulk superconductivity with transition temperature $T_{C}$ = 5.7 K confirmed by magnetization, resistivity, and heat capacity measurements. Zero-field $μ$SR measu…
Based on the first-principles electronic structure calculations and the symmetry analysis, we predict that the topological superconductivity may occur on the surface of the LnPd$_{2}$Sn (Ln=Sc, Y, Lu) class of Heusler alloys. The calculated electronic band structure and topological invariant demonstrate that the LnPd$_{2}$Sn family is topologically nontrivial. The further slab calculations show that the nontrivial topological surface states of LnPd$_{2}$Sn exist within the bulk band gap and meanwhile they cross the Fermi level. Considering that the LnPd$_{2}$Sn class of compounds were all foun…
NbSe$_{2}$ and NbS$_{2}$ are isostructural two-dimensional materials that exhibit contrasting superconducting properties when reduced to the single monolayer limit. Monolayer NbSe$_{2}$ is an Ising superconductor, while there have been no reports of superconductivity in monolayer NbS$_{2}$. NbS$_{x}$Se$_{2-x}$ alloys exhibit an intriguing non-monotonic dependence of the superconducting transition temperature with sulfur content, which has been interpreted as a manifestation of fractal superconductivity. However, several key questions about this result are not known: (1) Does the electronic str…
High entropy alloys (HEAs) are the new class of materials with an attractive combination of tunable mechanical and physicochemical properties. They crystallize mainly in cubic structures, however, for practical applications, HEAs with hexagonal close-packed (hcp) structure are highly desirable in connection to their in general high hardness. Herein, we report the synthesis, structure and detailed superconducting properties of Re$_{0.56}$Nb$_{0.11}$Ti$_{0.11}$Zr$_{0.11}$Hf$_{0.11}$-the first hexagonal superconducting high entropy alloy (HEA) composed of five randomly distributed transition-meta…
We synthesized new REO0.5F0.5BiS2 (RE: rare earth) superconductors with the high-entropy-alloy-type (HEA-type) REO blocking layers. According to the RE concentration and the RE ionic radius, the lattice constant of a systematically changed in the HEA-type samples. A sharp superconducting transition was observed in the resistivity measurements for all the HEA-type samples, and the transition temperature of the HEA-type samples was higher than that of typical REO0.5F0.5BiS2. The sharp superconducting transition and the enhanced superconducting properties of the HEA-type samples may indicate the …
Effect of Deposition Pressure on the Superconductivity of Ti40V60 Alloy Thin Films
Free Electron Laser Utilization Laboratory, Raja Ramanna Center for Advanced Technology（自由电子激光利用实验室，拉贾·拉曼纳先进技术中心）；Homi Bhabha National Institute（霍米·巴巴国立研究所）；UGC-DAE Consortium for Scientific Research（UGC-DAE科学研究联盟）
The Korringa-Kohn-Rostoker method with the coherent potental approximation (KKR-CPA) is applied to study the first superconducting high entropy alloy (HEA) Ta34Nb33Hf8Zr14Ti11 (discovered in 2014 with Tc = 7.3 K), focusing on estimations of the electron-phonon coupling constant λ. Electronic part of λhas been calculated using the rigid muffin-tin approximation (RMTA), while the phonon part has been approximated using average atomic mass and experimental Debye temperature. The estimated λ= 1.16 is close to the value determined from specific heat measurements, λ= 0.98, and suggests rather strong…
Using the Korringa-Kohn-Rostoker coherent-potential approximation in the atomic-sphere approximation (KKR-ASA CPA) we have studied the changes in the electronic structure and the superconducting transition temperature T_{c} in Nb_{1-x}B_{2} alloys as a function of x. We find that the variation in the electronic structure of Nb_{1-x}B_{2} alloys as a function of x is consistent with the rigid-band model. However, the variation of T_{c}, obtained using the Allen-Dynes equation within the Gaspari-Gyorffy formalism to estimate the electron-phonon matrix elements, does not follow the expected trend…
