Superconductivity (and Magnetism) in the Nickel Borocarbides

An overview of superconductivity in the rare-earth nickel borocarbides (RNi₂B₂C, where R represents a rare earth element or Y) is presented, with an emphasis on the interplay between magnetism and superconductivity in general and the behavior of the nonmagnetic superconductors YNi₂B₂C and LuNi₂B₂C, in particular. Some open questions are identified.     

Alpha Lead Oxide (α‐PbO): A New 2D Material with Visible Light Sensitivity

Even though transition metal dichalcogenides (TMDCs) are deemed to be novel photonic and optoelectronic 2D materials, the visible band gap being often limited to monolayer, hampers their potential in niche applications due to fabrication challenges. Uncontrollable defects and degraded functionalities at elevated temperature and under extreme environments further restrict their prospects. To address such limitations, the discovery of a new 2D material, α‐PbO is reported. Micromechanical as well as sonochemical exfoliation of 2D atomic sheets of α‐PbO are demonstrated and its optical behavior is investigated. Spectroscopic investigations indicate layer dependent band gaps. In particular, even multilayered PbO sheets exhibit visible band gap > 2 eV (direct) which is rare among semiconducting 2D materials. The emission lifetime of multilayer PbO atomic sheets is 7 ns (dim light) as compared to the monolayer which gives 2.5 ns lifetime and an intense light. Density functional theory calculations of layer dependent band structure of α‐PbO matches well with experimental results. Experimental findings suggest that PbO atomic sheets exhibit hydrophobic nature, thermal robustness, microwave stability, anti‐corrosive behaviour and acid resistance. This new low‐cost, abundant and robust 2D material is expected to find many applications in the fields of electronics, optoelectronics, sensors, photocatalysis and energy storage.     

Bandgap properties of the indium sulfide thin-films grown by co-evaporation

In the present study the optical properties of co-evaporated indium sulfide thin films are investigated. Before being optically characterized, the composition as well as the crystalline properties of the film have been checked with the help of energy dispersive spectroscopy (EDX) and X-Ray diffraction (XRD) analyses. The optical absorption coefficient α of this indium sulfide film has been deduced from reflectivity R(λ) and transmission T(λ) measurements. The fit of the curve representing α(hν) suggests that the β-In₂S₃ has an indirect bandgap of 2.01 eV. Density functional theory (DFT) calculations are performed on this indium sulfide compound, using TB-LMTO code. Through these band structure investigations, an indirect bandgap is predicted as observed experimentally. The top of the valence band is mainly formed by the orbitals of the sulfur atoms. This observation suggests that an over or under stoichiometry in sulfur may affect both the nature and the width of the indium sulfide bandgap.     

Electronic structure of YBa2Cu3O7 and YBa2Cu3O6—charge-self-consistent band structure calculations

Charge self-consistent LCAO band structure (CSCBS) calculations are reported for orthorhombic YBa₂Cu₃O₇ and tetragonal YBa₂Cu₃O₆ assuming ordered vacancy models. The effective atomic charges are used to study the charge transfer. In YBa₂Cu(1)₁Cu(2)₂O₇, the two types of copper atoms have their energy bands almost overlapping with effective valency of each copper as 7/3 (or effective valency of each oxygen as approximately — 13/7), so that electron hopping can take place without any loss or gain of energy while in YBa₂Cu(1)₁Cu(2)₂O₆, Cu(1)₁ is monovalent and Cu(2)₂ are divalent with significant difference in their bands. Therefore, YBa₂Cu₃O₇ should conduct much better compared to YBa₂Cu₃O₆. This corroborates the experimental observations that YBa₂Cu₃O₇ is a (super)conductor while YBa₂Cu₃O₆ is not. The calculated effective charges and DOS support the above view.     

Tetrathiapentalene-based organic conductors

The synthesis, structure and properties of tetrathiapentalene-based (TTP) organic conductors are reviewed. Among various TTP-type donors, bis-fused tetrathiafulvalene, 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (BDT-TTP) and its derivatives afford many metallic radical cation salts stable down to low temperatures, regardless of the size and shape of the counter anions. Most BDT-TTP conductors have a β-type donor arrangement with almost uniform stacks. Introduction of appropriate substituents results in molecular packing that differs from the β-type. A vinylogous TTP, 2-(1,3-dithiol-2-ylidene)-5-(2-ethanediylidene-1,3-dithiole)-1,3,4,6-tetrathiapentalene (DTEDT) has yielded an organic superconductor (DTEDT)₃Au(CN)₂ as well as metallic radical cation salts, regardless of the counter anions. (Thio)pyran analogs of TTP, namely (T)PDT-TTP and its derivatives produce molecular conductors with novel molecular arrangements. A TTP analog with reduced π-electron system 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) has afforded several organic superconductors. Highly conducting molecular metals with unusual oxidation states (+1, +5/3 and neutral) have been developed on the basis of 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (BDT-TTP) derivatives and analogous metal derivatives M(dt)₂ (M = Ni, Au).     

Tetrathiapentalene-based organic conductors

Abstract

The synthesis, structure and properties of tetrathiapentalene-based (TTP) organic conductors are reviewed. Among various TTP-type donors, bis-fused tetrathiafulvalene, 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (BDT-TTP) and its derivatives afford many metallic radical cation salts stable down to low temperatures, regardless of the size and shape of the counter anions. Most BDT-TTP conductors have a β-type donor arrangement with almost uniform stacks. Introduction of appropriate substituents results in molecular packing that differs from the β-type. A vinylogous TTP, 2-(1,3-dithiol-2-ylidene)-5-(2-ethanediylidene-1,3-dithiole)-1,3,4,6-tetrathiapentalene (DTEDT) has yielded an organic superconductor (DTEDT)₃Au(CN)₂ as well as metallic radical cation salts, regardless of the counter anions. (Thio)pyran analogs of TTP, namely (T)PDT-TTP and its derivatives produce molecular conductors with novel molecular arrangements. A TTP analog with reduced π-electron system 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) has afforded several organic superconductors. Highly conducting molecular metals with unusual oxidation states (+1, +5/3 and neutral) have been developed on the basis of 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (BDT-TTP) derivatives and analogous metal derivatives M(dt)₂ (M = Ni, Au).     

Enhanced Thermoelectric Performance in Black Phosphorus Nanotubes by Band Modulation through Tailoring Nanotube Chirality

Black phosphorus (BP) has attracted great attention for applications in thermoelectric devices, owing to its unique in‐plane anisotropic electrical and thermal properties. However, its limited conversion efficiency hinders practical application. Here, the thermoelectric properties of 1D BP nanotubes (BPNTs) with different tube chirality are investigated using first‐principles calculations and Boltzmann transport theory. The results reveal that variation of crystallographic orientation has a distinct impact on band dispersions, which provides a wide tunability of electronic transport. It is shown that (1,1)‐oriented BPNT structure can yield an order‐of‐magnitude enhanced thermoelectric figure of merit ZT at room temperature (as high as 1.0), compared with the bulk counterpart. The distinct enhancement is attributed to the favorable multiple band structures that lead to high carrier mobility of 2430 cm² V^?1 s^?1. Further performance improvement can be realized by suitable doping, such as N‐alloying, reaching an increase of room‐temperature ZT by a factor of 3 over that of pristine BPNT. The work provides an applicable method to achieve band engineering design, and presents a new strategy of designing 1D BPNT that are promising candidates for flexible, eco‐friendly, and high‐performance thermoelectrics.     

Wide-gap layered oxychalcogenide semiconductors: Materials, electronic structures and optoelectronic properties

Applying the concept of materials design for transparent conductive oxides to layered oxychalcogenides, several p-type and n-type layered oxychalcogenides were proposed as wide-gap semiconductors and their basic optical and electrical properties were examined. The layered oxychalcogenides are composed of ionic oxide layers and covalent chalcogenide layers, which bring wide-gap and conductive properties to these materials, respectively. The electronic structures of the materials were examined by normal/inverse photoemission spectroscopy and energy band calculations. The results of the examinations suggested that these materials possess unique features more than simple wide-gap semiconductors. Namely, the layered oxychalcogenides are considered to be extremely thin quantum wells composed of the oxide and chalcogenide layers or 2D chalcogenide crystals/molecules embedded in an oxide matrix. Observation of step-like absorption edges, large band gap energy and large exciton binding energy demonstrated these features originating from 2D density of states and quantum size effects in these layered materials.     

Crystal Chemical Concept of Arrangement and Function of Layered Superconducting Materials

The crystal chemical concept of arrangement and function of layered superconducting materials is supposed. The concept is based on the results of our investigation of crystal chemistry of high-temperature superconductors (HTSC) cuprates, diborides AB₂, and borocarbides of nickel RNi₂B₂C. According to these results (1) the main role in appearance of superconductivity played by the structural fragments—sandwiches A₂(CuO₂) in HTSC cuprates, A₂(B₂) in diborides, and RB(Ni) in nickel borocarbides but not the separate planes of CuO₂, B₂, or Ni; (2) correlations between T _c and crystal chemical parameters of these sandwiches have similar character in all three classes of compounds, despite distinction of a nature of their superconductivity. The central idea of the concept consists of following: in contrast to metallic conduction, for which it is enough to provide only concentration and mobility of charge carriers, for occurrence of a superconductivity it is necessary to create in addition a space (channels) for stream of charge carriers, compression of stream of carriers, and focusing to direction on path of motion.     

新型Ni基高温合金中析出相的热力学模拟计算

利用Thermo-Calc热力学计算软件与相应的Ni基高温合金数据库,计算了一种新型镍基高温合金中可能析出的平衡相,并研究了化学成分的变化对主要析出相的影响,分析了各相的析出规律,为进一步挖掘合金组织潜力和改善合金使用性能提供了理论依据.