Vast improvements have been made to the capabilities of advanced manufacturing (AM), yet there are still limitations on which materials can effectively be used in the technology. To this end, parts created using AM would benefit from the ability to be developed from feedstock materials incorporating additional functionality. A common three-dimensional (3D) printing polymer, acrylonitrile butadiene styrene, was combined with bismuth and polyvinylidene fluoride via a solvent treatment to fabricate multifunctional composite materials for AM. Composites of varying weight percent loadings were extruded into filaments, which were subsequently 3D printed into blocks via fused filament fabrication. Investigating the material properties demonstrated that in addition to the printed blocks successfully performing as radiation shields, the chemical, thermal, and mechanical properties are suitable for AM. Thus, this work demonstrates that it is possible to enhance AM components with augmented capabilities while not significantly altering the material properties which make AM possible.

Bismuth telluride have regained significant attention as a prototype of topological insulator. Thin films of high quality have been investigated as a basic platform for novel spintronic devices. Low mobility of bismuth and high desorption coefficient of telluride compose a scenario where growth parameters have drastic effects on structural and electronic properties of the films. Recently [J. Phys. Chem. C 2019, 123, 24818−24825], a detailed investigation has been performed on the dynamics of defects in epitaxial films of this material, revealing the impact of film/substrate lattice misfit on the films’ lateral coherence. Very small lattice misfit (<0.05%) are expected to have no influence on quality of epitaxial system with atomic layers weakly bonded to each other by van der Waals forces, contrarily to what was observed. In this work, we investigate the correlation between lattice misfit and size and morphology of the film crystalline domains. Three-dimensional reciprocal-space maps of film Bragg reflections obtained with synchrotron X-rays are used to visualize the spatial conformation of the crystallographic domains through film thickness, while atomic force microscopy images provide direct information of the domains morphology at the film surface.

As a pure element, bismuth is a semimetal which possesses several interesting physical properties, not all of them well understood. The recent discovery of superconductivity, as predicted by our group, and the increasing superconducting transition temperature as the pressure applied increases, are some examples of its particularities. Also, the fact that the amorphous phase is superconductive with a transition temperature several orders of magnitude larger than the crystalline at ambient pressure is unusual. These phenomena have also motivated our predictions for the transition temperatures of Bi-bilayers and the Bi-IV phase. When mixed with other elements, bismuth seems to contribute to the superconducting character of the resulting material. Here we study the binary copper-bismuth amorphous system which is known to superconduct in diverse compositions. Using ab initio molecular dynamics and the undermelt-quench method, we generate an amorphous structure for a 144-atom supercell corresponding to the Cu61Bi39 system. We calculate the electronic and vibrational densities of states for the amorphous system and estimate a superconducting critical temperature of 4.2 K for the amorphous state.

The microstructure of In(As,Bi)/GaAs heterostructures grown by low-temperature molecular beam epitaxy with special attention to the interfaces was studied by scanning/transmission electron microscopy, energy dispersive X-ray microanalysis, and X-ray diffraction and reflectivity. Two samples grown at similar conditions with and without the presence of the Bi-contained layer, formed at 350 °C, are considered. These samples were jointly analyzed to clarify Bi influence on the crystal structure. Two types of QD-like clusters at the GaAs/In(As,Bi) interface were found. The first type exhibited a zinc blend crystal structure, which is typical for A3B5 semiconductors. The second type adopted a tetragonal PbO crystal structure and was found in different orientations. The joint analysis by electron microscopy and X-ray methods demonstrated that the incorporation of Bi atoms into the InAs layer leads to the strain relaxation at the interface in the growth direction. According to electron microscopy data, this strain release is more pronounced around the clusters of the second type.

An experimental study of cadmium substitution into AgXS2 phases (X = As, Bi, Sb) indicates significant amounts of cadmium can be incorporated in the structure by the mechanism 2Cd ⇌ Ag + X. The limit of substitution of Cd in the high-temperature polymorph of miargyrite, β-AgSbS2 is 6.2 at.%, whereas the low-temperature polymorph, α-AgSbS2, can accommodate at least 12 at.% cadmium. Substitution of Cd into the cubic β-AgSbS2 induces a small monoclinic distortion and the unit cell becomes pseudo-cubic. The α ⇌ β transition in Cd-substituted miargyrites is modified by the solute ions, with both a reduction of Tc and transition smearing evident. Similar effects are also recorded in Cd-substituted AgAsS2 and AgBiS2.

Canonite from Alfenza grows as crowded, radiating, acicular aggregates covering bismuthinite crystals. Individual crystals have a lozenge-shaped habit on {010}, the presumed cleavage plane of cannonite. Crystal structure refinements in the P21/c space group of two single crystals led to the following cell parameters: a = 7.7196(5) Å, b = 13.8856(9), c = 5.6980(4), b = 109.174(1)º (R1 = 0.0424); and a = 7.7100(8), b = 13.8717(14), c = 5.6939(6), b = 109.155(2)º (R1 = 0.0438). Hydrogen atoms were also localized in the density-difference Fourier map and refined with soft restraints on the bond distances. Raman and IR spectroscopy confirm the presence of OH groups and the absence of molecular water, and deliver OH···O geometry wholly comparable with the structure refinement. Electron microprobe analyses revealed no significant levels of elements other than those expected in the ideal formula except fluorine which was present up to 0.14 a.p.f.u. The crystal structure can be described in terms of anion-centred OBi4 edge-sharing tetrahedra forming chains running parallel to z and strongly cemented along x by isolated SO4 tetrahedra. Each OBi4 tetrahedron is further connected along y by OH groups, making walls of composition Bi4O2(SO4)2(OH)4 parallel to (010). These walls are tied to each other along y by fewer Bi–O–S bridges and weaker OH···O bonds.

Coupling oxidation type semiconductors is a feasible strategy to improve the photocatalytic activity of reduction type g-C3N4 photocatalysts. In this work, Bi2O3 was used as an oxidation type semiconductor to construct direct Z-scheme Bi2O3/g-C3N4 photocatalysts by a one-step calcination method. The obtained Bi2O3/g-C3N4 composites exhibited excellent photocatalytic activity and stability toward methylene blue degradation under visible light irradiation. The composite with 1% weight content of Bi2O3 to g-C3N4 exhibited the highest photocatalytic activity with an apparent rate constant of 0.063 min−1, which was 3.0 and 3.7 times higher than that of pure Bi2O3 and g-C3N4, respectively. The enhanced photocatalytic activity of the Bi2O3/g-C3N4 composite was mainly attributed to the improved charge separation efficiency and stronger redox ability. This work gave a new insight in developing g-C3N4-based Z-scheme heterojunction photocatalysts with enhanced photocatalytic activity.

Pb-based organometal halide perovskite solar cells have passed the threshold of 20 % power conversion efficiency (PCE). However, the main issues hampering commercialization are toxic Pb contained in these cells and their instability in ambient air. Therefore, great attention is devoted to replace Pb by Sn or Bi, which are less harmful and - in the case of Bi - also expected to yield enhanced stability. In literature, the most efficient hybrid organic-inorganic methylammonium bismuth iodide (MBI) perovskite solar cells reach PCE up to 0.2 %. In this work, we present spin-coated MBI perovskite solar cells and highlight the impact of the concentration of the perovskite solution on the layer morphology and photovoltaic (PV) characteristics. The solar cells exhibit open-circuit voltages of 0.73 V, which is the highest value published for this type of solar cell. The PCE increases from 0.004 % directly after processing to 0.17 % after 48 h of storage in air. 300 h after exposure to air, the cells still yield 56 % of their peak PCE and 84 % of their maximum open-circuit voltage.

Polymer-non-leaded metal (tin, bismuth-tin (BiSn) alloy, and tungsten) composites were prepared to investigate the effectiveness of their X-ray shielding. Films of the composites were found to exhibit excellent X-ray shielding due to the uniform dispersion of metal particles in the polymer matrix, as were fabrics impregnated with the BiSn alloy. The fabricated composites effectively absorb penetrating photons. The preparation of composites with a uniform dispersion and a multilayered structure can limit the formation of pin holes. Multilayered BiSn composites exhibit significantly enhanced shielding. The lamination of a tungsten composite film or a BiSn composite film onto a BiSn-coated layered sheet results in better and more uniform shielding. Thus non-leaded BiSn metal-polymer composites can be used in X-ray shielding applications instead of the lead. One advantage that metal BiSn has over tungsten is its low melting temperature, which means that it can be processed in a normal extruder or in internal mixers such as those used in polymer processing.

Using a 72-atom supercell we report ab initio calculations of the electronic and vibrational densities of states for the bismuth (111) bilayers (bismuthene) with periodic boundary conditions and a vacuum of 5 Å, 10 Å and 20 Å. We find that the electronic density of states shows a metallic character at the Fermi level and that the vibrational density of states manifests the expected gap due to the layers. Our results indicate that a vacuum down to 5 Å does not affect the electronic and vibrational structures noticeably. A comparison of present results with those obtained for the Wyckoff structure is displayed. Assuming that the Cooper pairing potential is similar for all phases and structures of bismuth, an estimate of the superconducting transition temperature gives 2.61 K for the bismuth bilayers.

Although Pb-based perovskite solar cells already achieve power conversion efficiencies (PCE) beyond 20 %, the use of toxic Pb is causing considerable environmental concern. As a consequence, a variety of alternative cations have been investigated to replace Pb2+ in the perovskite structure. Methylammonium bismuth iodide (MA3Bi2I9, MBI) has shown promising results for environmentally benign and chemically stable devices. While the PCE of MBI-based solar cells are still comparably low, structural improvements have been made by using chemical vapor deposition (CVD). CVD allows for the well-controlled formation of coherent and dense MBI layers in contrast to solution-processing. In this work, CVD as a possible MBI fabrication method for efficient and size-scalable solar cells is discussed. The precursors MA iodide (MAI) and Bi iodide (BiI3) are deposited in an alternating deposition process forming the desired MBI perovskite on the heated substrate. Substrate temperatures as well as deposition times of each precursor are varied with the aim of forming coherent and dense MBI layers. Optimized films are further processed to solar cell prototypes and compared with solution-processed reference devices. The results reveal that CVD possesses great potential to enable the manufacture of MBI photovoltaic (PV) devices processed in a solvent-free environment.

Bismuth displays puzzling superconducting properties. In its crystalline equilibrium phase, it does not seem to superconduct at accessible low temperatures. However, in the amorphous phase it displays superconductivity at ∼ 6 K. Under pressure bismuth has been found to superconduct at Tcs that go from 3.9 K to 8.5 K depending on the phase obtained. So the question is: what electronic or vibrational changes occur that explains this radical transformation in the conducting behavior of this material? In a recent publication we argue that changes in the density of electronic and vibrational states may account for the behavior observed in the amorphous phase with respect to the crystal. We have now undertaken an ab initio computational study of the effects of pressure alone maintaining the original crystalline structure and compressing our supercell computationally. From the results obtained we infer that if the crystal structure remains the same (except for the contraction), no superconductivity will appear.

The TiO2 hollow spheres (TiO2HS) were successfully prepared by a hydrothermal method and added to Vulcan XC-72 carbon black as the support materials for Pd nanoparticles. A facile approach to promote ethylene glycol (EG) electrooxidation in alkaline medium was carried out by the PdBi/TiO2HS-C catalyst. The results show that Pd and Bi nanoparticles are uniformly dispersed on the surface of carbon-doped TiO2 hollow spheres, the appropriate amount of Bi modification into Pd/TiO2HS-C catalyst can enhance remarkably the electrocatalytic activity for EG oxidation, in which the PdBi/TiO2HS-C (Pd:Bi = 1:0.1) catalyst exhibits excellent stability. The high electrochemical performance is attributed to the unique structure and high surface area of the TiO2HS, metal nanoparticles uniform distribution, the electronic effect between Pd and Bi as well as the bifunctional effect between metal nanoparticles and the support TiO2HS-C. The results obtained are significant for the development of new Pd-based TiO2HS-C electrocatalysts for alcohol fuel cells.

In this paper, the effect of shock compression on the synthesis of a Bi-based oxide superconductor was investigated. Bi1.85-Pb0.35-Sr1.90-Ca2.05-Cu3.05-Ox calcined powder was shock-compacted around 20 GPa and 30 GPa, and divided specimens were annealed at 845 °C for 1, 6 and 48 hours. The specimens were evaluated by x-ray diffraction and scanning electron microscope.

Bismuth vanadate (BiVO4) is a photoelectrode for the oxidation of water. It is of fundamental importance to understand the electrical and photoelectrochemical properties of this material. In metal oxides, the electronic transport is described by the small polaron model, first described by Mott. In this model, the resistivity varies with temperature as $\rho \,\left( T \right)\, \propto \,Te^{({{E_a } \mathord{\left/ {\vphantom {{E_a } {(k_B T))}}} \right. \kern-\nulldelimiterspace} {(k_B T))}}} $, where Ea is the hopping activation energy, kB is the Boltzmann constant and T is the absolute temperature. Resistivity measurements confirm that small polaron hopping dominates in temperature ranges from 250 K to 300 K. In addition measurements from 175K to 250K show the variable range hopping dominates the transport. To this end, the electronic transport properties of BiVO4 single crystal were characterized using resistivity measurements and Hall effect measurements over temperatures ranging from 175 K to 300 K.

Multiferroic BFO/SRO/Si trilayers have been prepared by pulsed laser deposition in the form of thin films. As a function of the BFO layer thickness, magnetic and magneto-transport properties have been investigated at room temperature and down to 5 K. At low BFO layer thickness, a residual γ-Fe2O3 phase, which interacts interfacially with the SRO and BFO layers, is responsible for moderately hard magnetic properties of the film. On increasing BFO layer thickness, more homogeneous deposits are obtained with uniform magnetic and magneto-resistive properties.

Recently there have been reports of hot carrier thermoelectric response in nanostructured materials like graphene and MoS. We report observing that thermoelectric nanowire junctions detect light. In these experiments we employed devices composed of bismuth nanowire arrays which are capped with a transparent indium tin oxide electrode. The incident surface features very low optical reflectivity and enhanced light trapping. The unique attributes of the thermoelectric arrays are the combination of strong temporal and optical wavelength dependences of the photocurrent. Under infrared illumination, the signal can be completely described by “quasi-equilibrium” thermoelectric effects considering cooling rates given by heat diffusion through the array. The thermal diffusivity is found to be less (by a factor of 3.5) than in the bulk, a result that we discuss in terms of phonon confinement effects. In addition to a thermoelectric response, under visible illumination, we observe a photovoltaic response.

It has been argued that for the simulation of amorphous materials, the larger the periodic supercell the better the representation. We contend that for certain properties there is a minimum supercell size above which one obtains a good representation of the topological and electronic collective properties of the material independent of the size. To show this contention we have chosen two periodic supercells of bismuth, one with 64 atoms and another with 216 atoms, which were amorphized using our undermelt-quench approach [1]. The originally crystalline structures were subjected to a heating-and-cooling process starting at an initial temperature of 300 K and linearly going up to 540 K, in 100 simulational steps, 4.5 K just below the melting temperature of bismuth (the undermelt section of the process) under normal conditions of pressure. Next, the sample was cooled down to 0K (the quench section of the process), in 225 simulational steps with the same absolute cooling rate as the heating process. Then the samples obtained were geometry-optimized to find the final metastable amorphous structures. These structures were analyzed by calculating their radial (pair) distribution functions, the plane angle distributions and the electron densities of states. Results will be presented that manifest that after proper normalization due to the difference in the number of atoms and the number of electron energy levels, the two structures are, for all practical purpose, the same, indicating that in this case, the size of the cell does not seem to play a major role in the properties determined.

We present theoretical calculations of the phonon-drag contribution to the Nernst thermoelectric power Syx in Bismuth nanowires. We investigate the thermopower Syx with diameters L ranging from 22 to 900 nm at low temperatures (0.1 - 4.0 K) and high magnetic fields (up to 16 T). We find that the peak of thermopower Syx around 14.75 T exhibits the size effect in two different ways: for wires with L≥200 nm, the peak height increases with decreasing L; for wires with L<200 nm, on the other hand, the peak height rapidly decreases with decreasing L. The dependence is accounted for by considering the contributions of discrete quantized phonon modes. We also discuss the temperature dependence of Syx.

As thermoelectric (TE) element length decreases, the impact of contact resistance on TE device performance grows more significant. In fact, for a TE device containing 100-μm tall Bi2Te3TE elements, the figure of merit ratio (ZTDevice/ZTMaterial) drops from 0.9 to 0.5 as the contact resistivity increases from 5 x 10-07 to 5 x 10-06 Ω-cm2. To understand the effects of contact resistance on bulk TE device performance, a reliable experimental measurement method is needed. There are many popular methods to extract contact resistance such as Transmission Line Measurements (TLM) and Kelvin Cross Bridge Resistor method (KCBR), but they are only well-suited for measuring metal contacts on thin films and do not necessarily translate to measuring contact resistance on bulk thermoelectric materials. The authors present a new measurement technique that precisely measures contact resistance (on the order of 5 x 10-07 Ω-cm2) on bulk thermoelectric materials by processing stacks of bulk, metal-coated TE wafers using TE industry standard processes. One advantage of this technique is that it exploits realistic TE device manufacturing techniques and results in an almost device-like structure, therefore representing a realistic value for electrical contact resistance in a bulk TE device. Contact resistance measurements for metal contacts to n- and p-type Bi2Te3 alloys are presented and an estimate of the accuracy of the measurements is discussed.