David Mandrus

Filled Skutterudite Antimonides: A New Class of Thermoelectric Materials

A class of thermoelectric materials has been synthesized with a thermoelectric figure of merit ZT (where T is temperature and Z is a function of thermopower, electrical resistivity, and thermal conductivity) near 1 at 800 kelvin. Although these materials have not been optimized, this value is comparable to the best ZT values obtained for any previously studied thermoelectric material. Calculations indicate that the optimized material should have ZT values of 1.4. These ternary semiconductors have the general formula RM4X12 (where R is lanthanum, cerium, praseodymium, neodymium, or europium; M is iron, ruthenium, or osmium; and X is phosphorus, arsenic, or antimony) and represent a new approach to creating improved thermoelectric materials. Several alloys in the composition range CeFe4−xCoxSb12 or LaFe4−xCoxSb12 (0 < x < 4) have large values of ZT.

Electrical control of neutral and charged excitons in a monolayer semiconductor

Monolayer group-VI transition metal dichalcogenides have recently emerged as semiconducting alternatives to graphene in which the true two-dimensionality is expected to illuminate new semiconducting physics. Here we investigate excitons and trions (their singly charged counterparts), which have thus far been challenging to generate and control in the ultimate two-dimensional limit. Utilizing high-quality monolayer molybdenum diselenide, we report the unambiguous observation and electrostatic tunability of charging effects in positively charged (X(+)), neutral (X(o)) and negatively charged (X(-)) excitons in field-effect transistors via photoluminescence. The trion charging energy is large (30 meV), enhanced by strong confinement and heavy effective masses, whereas the linewidth is narrow (5 meV) at temperatures <55 K. This is greater spectral contrast than in any known quasi-two-dimensional system. We also find the charging energies for X(+) and X(-) to be nearly identical implying the same effective mass for electrons and holes.

Superconductivity at 22 K in Co-Doped BaFe2As2 Crystals

Here we report bulk superconductivity in BaFe1.8Co0.2As2 single crystals below Tc=22 K, as demonstrated by resistivity, magnetic susceptibility, and specific heat data. Hall data indicate that the dominant carriers are electrons, as expected from simple chemical reasoning. This is the first example of superconductivity induced by electron doping in this family of materials. In contrast with cuprates, the BaFe2As2 system appears to tolerate considerable disorder in the FeAs planes. First principles calculations for BaFe1.8Co0.2As2 indicate the interband scattering due to Co is weak.

Localized vibrational modes in metallic solids

Filled skutterudite antimonides, are cubic compounds with the formula RM4Sb12, where R is a rare-earth element (such as La or Ce), and M is a transition metal (for example, Fe or Co). The rare-earth ion is weakly bound in an oversized atomic cage formed by the other atoms. Its presence has been shown to cause a dramatic reduction in the lattice component of the thermal conductivity, while having little effect on the electronic properties of the compound. This combination of properties makes filled skutterudites of interest as thermoelectric materials. It has been suggested that localized, incoherent vibrations of the rare-earth ion are responsible for the reduction in thermal conductivity, but no direct evidence for these local vibrational modes exists. Here we report the observation of local modes in La-filled skutterudites, using heat capacity, elastic constant and inelastic neutron scattering measurements. The La atoms show unusual thermodynamic behaviour, characterized by the presence of two low-energy localized modes. Our results suggest that consideration of local modes will play an important role in the design of the next generation of thermoelectric materials.

Bulk Superconductivity at 14 K in Single Crystals of Fe1+yTexSe1-x

Resistivity, magnetic susceptibility, and heat-capacity measurements are reported for single crystals of Fe{sub 1+y}Te{sub x}Se{sub 1-x} grown via a modified Bridgeman method with 0 < y < 0.15 and x = 1, 0.9, 0.75, 0. 67, 0.55, and 0.5. Although resistivity measurements show traces of superconductivity near 14 K for all x except x = 1, only crystals grown with compositions near x = 0.5 exhibit bulk superconductivity. The appearance of bulk superconductivity correlates with a reduction in the magnitude of the magnetic susceptibility at room temperature and smaller values of y, the concentration of Fe in the Fe(2) site.

Small anisotropy, weak thermal fluctuations, and high field superconductivity in Co-doped iron pnictide Ba(Fe1−xCox)2As2

We performed high-field magnetotransport and magnetization measurements on a single crystal of the 122-phase iron pnictide Ba(Fe1−xCox)2As2. Unlike the high-temperature superconductor cuprates and 1111-phase oxypnictides, Ba(Fe1−xCox)2As2 showed practically no broadening of the resistive transitions under magnetic fields up to 45 T. We report the temperature dependencies of the upper critical field Hc2 both parallel and perpendicular to the c-axis, the irreversibility field Hirrc(T), and a rather unusual symmetric volume pinning force curve Fp(H) suggestive of a strong pinning nanostructure. The anisotropy parameter γ=Hc2ab/Hc2c deduced from the slopes of dHc2ab/dT=4.9 T/K and dHc2c/dT=2.5 T/K decreases from ∼2 near Tc, to ∼1.5 at lower temperatures, much smaller than γ for 1111pnictides and high-Tc cuprates.

New Fe-based superconductors: properties relevant for applications

Less than two years after the discovery of high temperature superconductivity in oxypnictide LaFeAs(O, F) several families of superconductors based on Fe layers (1111, 122, 11, 111) are available. They share several characteristics with cuprate superconductors that compromise easy applications, such as the layered structure, the small coherence length and unconventional pairing. On the other hand, the Fe-based superconductors have metallic parent compounds and their electronic anisotropy is generally smaller and does not strongly depend on the level of doping, and the supposed order parameter symmetry is s-wave, thus in principle not so detrimental to current transmission across grain boundaries. From the application point of view, the main efforts are still devoted to investigate the superconducting properties, to distinguish intrinsic from extrinsic behaviors and to compare the different families in order to identify which one is the fittest for the quest for better and more practical superconductors. The 1111 family shows the highest Tc, huge but also the most anisotropic upper critical field and in-field, fan-shaped resistive transitions reminiscent of those of cuprates. On the other hand, the 122 family is much less anisotropic with sharper resistive transitions as in low temperature superconductors, but with about half the Tc of the 1111 compounds. An overview of the main superconducting properties relevant to applications will be presented. Upper critical field, electronic anisotropy parameter, and intragranular and intergranular critical current density will be discussed and compared, where possible, across the Fe-based superconductor families.

Probing excitonic states in suspended two-dimensional semiconductors by photocurrent spectroscopy

The optical response of semiconducting monolayer transition-metal dichalcogenides (TMDCs) is dominated by strongly bound excitons that are stable even at room temperature. However, substrate-related effects such as screening and disorder in currently available specimens mask many anticipated physical phenomena and limit device applications of TMDCs. Here, we demonstrate that that these undesirable effects are strongly suppressed in suspended devices. Extremely robust (photogain > 1,000) and fast (response time < 1 ms) photoresponse allow us to study, for the first time, the formation, binding energies, and dissociation mechanisms of excitons in TMDCs through photocurrent spectroscopy. By analyzing the spectral positions of peaks in the photocurrent and by comparing them with first-principles calculations, we obtain binding energies, band gaps and spin-orbit splitting in monolayer TMDCs. For monolayer MoS2, in particular, we obtain an extremely large binding energy for band-edge excitons, Ebind ≥ 570 meV. Along with band-edge excitons, we observe excitons associated with a van Hove singularity of rather unique nature. The analysis of the source-drain voltage dependence of photocurrent spectra reveals exciton dissociation and photoconversion mechanisms in TMDCs.

Structural disorder and thermal conductivity of the semiconducting clathrate Sr8Ga16Ge30

Abstract The temperature dependence of the atomic displacement parameters for Sr8Ga16Ge30 determined from refinements of neutron powder and single-crystal diffraction data shows that the anomalously large values for one of the two unique Sr atoms persist from 295 to 11 K. Its position is better described by a fractionally occupied four-fold split site, but the rms displacement remains the largest of all of the atoms in the structure. Difference Fourier maps of this Sr site show a residual nuclear density with lobes in the directions of the split-atom positions. The Ga and Ge atoms appear to be fully disordered on the three distinct framework sites. The measured atomic displacement parameters are used to derive estimates of the following thermodynamic related quantities: Debye temperature, 271 K; mean velocity of sound, 2600 m/s; temperature of the Einstein “rattler”, 85 K; mean free path of heat-carrying phonons, 5.36 A; and lattice thermal conductivity, 0.008 W/cm-K.

Spin-layer locking effects in optical orientation of exciton spin in bilayer WSe2

Monolayer and few-layer materials present interesting spin and pseudospin states. A study of the coupling between spin, valley and layer degrees of freedom in bilayer WSe2 reveals coherent superpositions of distinct valley configurations and suggests the possibility of electrical control of the spin states.