Kejun Bu

Ammonia and iron cointercalated iron sulfide (NH3)Fe0.25Fe2S2: hydrothermal synthesis, crystal structure, weak ferromagnetism and crossover from a negative to positive magnetoresistance

The discovery of superconductivity in anti-PbO-type FeS has aroused a renewed interest in the intercalation compounds of FeS. Here we report a novel intercalation compound of FeS with the chemical composition of (NH3)Fe0.25Fe2S2, which is synthesized via a new hydrothermal reaction. This material crystallizes in the tetragonal space group I4/mmm, preserving the FeS tetrahedral layers with ammonia and excess iron forming planes in between. The microstructure and thermal stability of the sample were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermogravimetric analyses (TGA). These results suggest that (NH3)Fe0.25Fe2S2 is not sensitive to electron beam irradiation and is more thermally stable than the other ammonia intercalated iron selenide superconductors. Physical property measurements show that it is a ferromagnetic semiconductor. By using first-principles calculations we assess that the low-temperature ferromagnetism originates from the interlayer rather than the intralayer iron. The transport properties at low temperatures are dominated by electron-like carriers and the sign reversal and strong temperature dependence of the Hall coefficient may be caused by a multi-band effect. Most importantly, an unusual crossover from negative to positive magnetoresistance with increasing temperature was identified, which reveals relatively strong coupling between carriers and magnetic moments as well as disorder.

Suppression of superconductivity and structural phase transitions under pressure in tetragonal FeS

Pressure is a powerful tool to study iron-based superconductors. Here, we report systematic high-pressure transport and structural characterizations of the newly discovered superconductor FeS. It is found that superconductor FeS (tetragonal) partly transforms to a hexagonal structure at 0.4 GPa, and then completely transforms to an orthorhombic phase at 7.4 GPa and finally to a monoclinic phase above 9.0 GPa. The superconducting transition temperature of tetragonal FeS was gradually depressed by pressure, different from the case in tetragonal FeSe. With pressure increasing, the S-Fe-S angles only slightly change but the anion height deviates farther from 1.38 Å. This change of anion height, together with the structural instability under pressure, should be closely related to the suppression of superconductivity. We also observed an anomalous metal-semiconductor transition at 6.0 GPa and an unusual increased resistance with further compression above 9.6 GPa. The former can be ascribed to the tetragonal-orthorhombic structural phase transition, and the latter to the electronic structure changes of the high-pressure monoclinic phase. Finally, a phase diagram of tetragonal FeS as functions of pressure and temperature was mapped out for the first time, which will shed new light on understanding of the structure and physics of the superconducting FeS.

Intermediate Band Material of Titanium-Doped Tin Disulfide for Wide Spectrum Solar Absorption

Intermediate band (IB) materials are of great significance due to their superior solar absorption properties. Here, two IBs peaking at 0.88 and 1.33 eV are reported to be present in the forbidden gap of semiconducting SnS2 ( Eg = 2.21 eV) by doping titanium up to 6 atom % into the Sn site via a solid-state reaction at 923 K. The solid solution of Sn1- xTi xS2 is able to be formed, which is attributed to the isostructural structure of SnS2 and TiS2. These two IBs were detected in the UV-vis-NIR absorption spectra with the appearance of two additional absorption responses at the respective regions, which in good agreement with the conclusion of first-principles calculations. The valence band maximum (VBM) consists mostly of the S 3p state, and the conduction band minimum (CBM) is the hybrid state composing of Ti 3d (eg), S 3p, and Sn 5s, and the IBs are mainly the nondegenerate t2g states of Ti 3d orbitals. The electronic states of Ti 3d reveal a good ability to transfer electrons between metal and S atoms. These wide-spectrum absorption IBs bring about more solar energy utilization to enhance solar thermal collection and photocatalytic degradation of methyl orange.

Nano Titanium Monoxide Crystals and Unusual Superconductivity at 11 K

Nano TiO2 is investigated intensely due to extraordinary photoelectric performances in photocatalysis, new-type solar cells, etc., but only very few synthesis and physical properties have been reported on nanostructured TiO or other low valent titanium-containing oxides. Here, a core-shell nanoparticle made of TiO core covered with a ≈5 nm shell of amorphous TiO1+x is newly constructed via a controllable reduction method to synthesize nano TiO core and subsequent soft oxidation to form the shell (TiO1+x ). The physical properties measurements of electrical transport and magnetism indicate these TiO@TiO1+x nanocrystals are a type-ІІ superconductor of a recorded Tconset = 11 K in the binary Ti-O system. This unusual superconductivity could be attributed to the interfacial effect due to the nearly linear gradient of O/Ti ratio across the outer amorphous layer. This novel synthetic method and enhanced superconductivity could open up possibilities in interface superconductivity of nanostructured composites with well-controlled interfaces.

Synthesis, Structure, and Optical Properties of Antiperovskite-Derived Ba2MQ3X (M = As, Sb; Q = S, Se; X = Cl, Br, I) Chalcohalides

Six isostructural antiperovskite-derived chalcohalides, Ba2MQ3X (M = As, Sb; Q = S, Se; X = Cl, Br, I), crystallizing in the space group Pnma, have been synthesized by solid-state reactions. The crystal structure features a 3D framework with the [XBa5]9+ disordered square pyramids as building blocks and [MQ3]3- units filling the interspace. [XBa5]9+ disordered square pyramids are edge-sharing along [010], derived from the fusing of the two pyramids in octahedral [XBa6]11+. Surprisingly, Ba2AsS3X (X = Cl, Br, I) show almost the same optical band gap of 2.80 eV, and Ba2AsSe3X (X = Br, I) also have a similar band gap of 2.28 eV. The optical band gap of Ba2SbS3I is 2.64 eV. First-principles calculations reveal that the optical absorption is attributed to the transitions between Q np at the valence band maximum (VBM) and M np-Q np at the conduction band minimum (CBM). These compounds also possess interesting photoluminescence properties with splitting emission peaks on excitation at 200 nm.

2H-NbS 2 film as a novel counter electrode for meso-structured perovskite solar cells

We report the use of 2H-NbS2 film as a novel counter electrode in perovskite solar cells fabricated with a cold isostatic pressing method. The 2H-NbS2 film, which was prepared through an exfoliation method followed by restacking from LixNbS2 powder, shows high electrical conductivity of 8.7 × 103 S cm−1 and work function of 5.20 eV. The two-dimensional transition metal dichalcogenide was used for the first time as a counter electrode in meso-structured perovskite solar cells. Through this process, we demonstrated a new alternative to noble metals. The perovskite solar cell base on the 2H-NbS2 counter electrode showed an open-circuit voltage of 1.046 V, comparable to that of gold, and a power conversion efficiency of 8.3%.

Boron Embedded in Metal Iron Matrix as a Novel Anode Material of Excellent Performance

Boron, the most ideal lithium-ion battery anode material, demonstrates highest theoretical capacity up to 12 395 mA h g-1 when forming Li5 B. Furthermore, it also exhibits promising features such as light weight, considerable reserves, low cost, and nontoxicity. However, boron-based materials are not in the hotspot list because Li5 B may only exist when B is in atomically isolated/dispersed form, while the aggregate material can barely be activated to store/release Li. At this time, an ingenious design is demonstrated to activate the inert B to a high specific capacity anode material by dispersing it in a Fe matrix. The above material can be obtained after an electrochemical activation of the precursors Fe2 B/Fe and B2 O3 /Fe. The latter harvests the admirable capacity, ultrahigh tap density of 2.12 g cm-3 , excellent cycling stability of 3180 mA h cm-3 at 0.1 A g-1 (1500 mA h g-1 ) after 250 cycles, and superlative rate capability of 2650 mA h cm-3 at 0.5 A g-1 , 2544 mA h cm-3 at 1.0 A g-1 , and 1696 mA h cm-3 at 2.0 A g-1 . Highly conductive matrix promoted reversible Li storage of boron-based materials might open a new gate for advanced anode materials.

Effects of Iron Doping on the Physical Properties of Quaternary Ferromagnetic Sulfide: Ba2Fe0.6V1.4S6

The mixed-metal sulfide compound with the formula Ba2Fe0.6V1.4S6 was successfully synthesized via solid-state reaction. Ba2Fe0.6V1.4S6 has a quasi-one-dimensional structure and crystallizes in the hexagonal space group P63/mmc. The structure is composed of face-sharing anion octahedron [MS6]8- (M = V or Fe) units to construct infinite chains along the c axis, in which the Fe atoms randomly occupy the V sites. The Ba2+ ions reside between adjacent chains. Magnetic susceptibility measurements reveal a transition between paramagnetism and ferromagnetism around 25 K. The small polaron hopping (SPH) conduction behavior has been observed in the higher temperature region (75-300 K), while in the lower temperature region (25-74 K), the resistivity features a variable range hopping mechanism (VRH). The analysis of density of states indicates that Fe-3dz2 and S-3p states mainly dominate the valence band maximum, while Fe-3dz2 states contribute significantly to the magnetic susceptibility.

Crystal structure of the mixed-metal tris­ulfide BaCu1/3Ta2/3S3

In the structure of BaCu1/3Ta2/3S3, the Cu and Ta atoms are occupationally disordered on the same site in a ratio of 1/3:2/3.