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1.
Nanoscale Adv ; 3(16): 4756-4766, 2021 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-36134325

RESUMEN

Two-dimensional (2D) magnets such as chromium trihalides CrX3 (X = I, Br, Cl) represent a frontier for spintronics applications and, in particular, CrCl3 has attracted research interest due its relative stability under ambient conditions without rapid degradation, as opposed to CrI3. Herein, mechanically exfoliated CrCl3 flakes are characterized at the atomic scale and the electronic structures of pristine, oxidized, and defective monolayer CrCl3 phases are investigated employing density functional theory (DFT) calculations, scanning tunneling spectroscopy (STS), core level X-ray photoemission spectroscopy (XPS), and valence band XPS and ultraviolet photoemission spectroscopy (UPS). As revealed by atomically resolved transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis, the CrCl3 flakes show spontaneous surface oxidation upon air exposure with an extrinsic long-range ordered oxidized O-CrCl3 structure and amorphous chromium oxide formation on the edges of the flakes. XPS proves that CrCl3 is thermally stable up to 200 °C having intrinsically Cl vacancy-defects whose concentration is tunable via thermal annealing up to 400 °C. DFT calculations, supported by experimental valence band analysis, indicate that pure monolayer (ML) CrCl3 is an insulator with a band gap of 2.6 eV, while the electronic structures of oxidized and Cl defective phases of ML CrCl3, extrinsically emerging in exfoliated CrCl3 flakes, show in-gap spin-polarized states and relevant modifications of the electronic band structures.

2.
Adv Mater ; 31(11): e1807240, 2019 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-30614584

RESUMEN

The extraordinary superconductivity has been observed in a pressurized commercial niobium-titanium alloy. 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 survive. 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 been enhanced to 19 T from 15.4 T. These results set new records for both the TC and the HC2 among all the known alloy superconductors composed of only transition metal elements. The remarkable high-pressure superconducting properties observed in the niobium-titanium alloy not only expand the knowledge on this important commercial superconductor but also are helpful for a better understanding on the superconducting mechanism.

3.
Proc Natl Acad Sci U S A ; 114(37): 9832-9837, 2017 09 12.
Artículo en Inglés | MEDLINE | ID: mdl-28855335

RESUMEN

The optimal functionalities of materials often appear at phase transitions involving simultaneous changes in the electronic structure and the symmetry of the underlying lattice. It is experimentally challenging to disentangle which of the two effects--electronic or structural--is the driving force for the phase transition and to use the mechanism to control material properties. Here we report the concurrent pumping and probing of Cu2S nanoplates using an electron beam to directly manipulate the transition between two phases with distinctly different crystal symmetries and charge-carrier concentrations, and show that the transition is the result of charge generation for one phase and charge depletion for the other. We demonstrate that this manipulation is fully reversible and nonthermal in nature. Our observations reveal a phase-transition pathway in materials, where electron-induced changes in the electronic structure can lead to a macroscopic reconstruction of the crystal structure.

4.
Proc Natl Acad Sci U S A ; 113(46): E7144-E7150, 2016 11 15.
Artículo en Inglés | MEDLINE | ID: mdl-27803330

RESUMEN

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.

5.
Proc Natl Acad Sci U S A ; 113(25): E3475-81, 2016 06 21.
Artículo en Inglés | MEDLINE | ID: mdl-27274081

RESUMEN

The recent discovery of extreme magnetoresistance (XMR) in LaSb introduced lanthanum monopnictides as a new platform to study this effect in the absence of broken inversion symmetry or protected linear band crossing. In this work, we report XMR in LaBi. Through a comparative study of magnetotransport effects in LaBi and LaSb, we construct a temperature-field phase diagram with triangular shape that illustrates how a magnetic field tunes the electronic behavior in these materials. We show that the triangular phase diagram can be generalized to other topological semimetals with different crystal structures and different chemical compositions. By comparing our experimental results to band structure calculations, we suggest that XMR in LaBi and LaSb originates from a combination of compensated electron-hole pockets and a particular orbital texture on the electron pocket. Such orbital texture is likely to be a generic feature of various topological semimetals, giving rise to their small residual resistivity at zero field and subject to strong scattering induced by a magnetic field.

6.
Proc Natl Acad Sci U S A ; 112(51): E7048-54, 2015 Dec 22.
Artículo en Inglés | MEDLINE | ID: mdl-26644566

RESUMEN

We present transition metal-embedded (T@Gan) endohedral Ga-clusters as a favorable structural motif for superconductivity and develop empirical, molecule-based, electron counting rules that govern the hierarchical architectures that the clusters assume in binary phases. Among the binary T@Gan endohedral cluster systems, Mo8Ga41, Mo6Ga31, Rh2Ga9, and Ir2Ga9 are all previously known superconductors. The well-known exotic superconductor PuCoGa5 and related phases are also members of this endohedral gallide cluster family. We show that electron-deficient compounds like Mo8Ga41 prefer architectures with vertex-sharing gallium clusters, whereas electron-rich compounds, like PdGa5, prefer edge-sharing cluster architectures. The superconducting transition temperatures are highest for the electron-poor, corner-sharing architectures. Based on this analysis, the previously unknown endohedral cluster compound ReGa5 is postulated to exist at an intermediate electron count and a mix of corner sharing and edge sharing cluster architectures. The empirical prediction is shown to be correct and leads to the discovery of superconductivity in ReGa5. The Fermi levels for endohedral gallide cluster compounds are located in deep pseudogaps in the electronic densities of states, an important factor in determining their chemical stability, while at the same time limiting their superconducting transition temperatures.

7.
Proc Natl Acad Sci U S A ; 112(11): E1174-80, 2015 Mar 17.
Artículo en Inglés | MEDLINE | ID: mdl-25737540

RESUMEN

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 effects of polytypism and polymorphism on the superconductivity of TaSe2, one of the archetypal members of the large family of layered dichalcogenides. We show that it is possible to access two stable polytypes and two stable polymorphs in the TaSe(2-x)Te(x) solid solution and find that the 3R polytype shows a superconducting transition temperature that is between 6 and 17 times higher than that of the much more commonly found 2H polytype. The reason for this dramatic change is not apparent, but we propose that it arises either from a remarkable dependence of Tc on subtle differences in the characteristics of the single layers present or from a surprising effect of the layer-stacking sequence on electronic properties that are typically expected to be dominated by the properties of a single layer in materials of this kind.

8.
Adv Mater ; 26(15): 2346-51, 2014 Apr 16.
Artículo en Inglés | MEDLINE | ID: mdl-24847529

RESUMEN

Pressure-induced superconductivity is oberserved in Ca10(Pt3As8)(Fe2As2)5 by in situ high-pressure resistance and magnetic susceptibility measurements. Scaling of the pressure-induced and doping-induced superconductivity shows that the electronic phase diagrams of the pressurized and chemically doped 10­3­8 compound are similar in the moderate pressure and doping range but are disparate at higher pressure and heavy doping.

9.
Adv Mater ; 26(15): 2346-51, 2014 Apr 16.
Artículo en Inglés | MEDLINE | ID: mdl-24469882

RESUMEN

Pressure-induced superconductivity is oberserved in Ca10 (Pt3 As8 )(Fe2 As2 )5 by in situ high-pressure resistance and magnetic susceptibility measurements. Scaling of the pressure-induced and doping-induced superconductivity shows that the electronic phase diagrams of the pressurized and chemically doped 10-3-8 compound are similar in the moderate pressure and doping range but are disparate at higher pressure and heavy doping.

10.
Proc Natl Acad Sci U S A ; 108(45): E1019-26, 2011 Nov 08.
Artículo en Inglés | MEDLINE | ID: mdl-22042837

RESUMEN

It has been argued that the very high transition temperatures of the highest T(c) cuprate superconductors are facilitated by enhanced CuO(2) plane coupling through heavy metal oxide intermediary layers. Whether enhanced coupling through intermediary layers can also influence T(c) in the new high T(c) iron arsenide superconductors has never been tested due the lack of appropriate systems for study. Here we report the crystal structures and properties of two iron arsenide superconductors, Ca(10)(Pt(3)As(8))(Fe(2)As(2))(5) (the "10-3-8 phase") and Ca(10)(Pt(4)As(8))(Fe(2)As(2))(5) (the "10-4-8 phase"). Based on -Ca-(Pt(n)As(8))-Ca-Fe(2)As(2)- layer stacking, these are very similar compounds for which the most important differences lie in the structural and electronic characteristics of the intermediary platinum arsenide layers. Electron doping through partial substitution of Pt for Fe in the FeAs layers leads to T(c) of 11 K in the 10-3-8 phase and 26 K in the 10-4-8 phase. The often-cited empirical rule in the arsenide superconductor literature relating T(c) to As-Fe-As bond angles does not explain the observed differences in T(c) of the two phases; rather, comparison suggests the presence of stronger FeAs interlayer coupling in the 10-4-8 phase arising from the two-channel interlayer interactions and the metallic nature of its intermediary Pt(4)As(8) layer. The interlayer coupling is thus revealed as important in enhancing T(c) in the iron pnictide superconductors.

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