Rhombohedral Boron Monosulfide as a p-Type Semiconductor.

Two-dimensional materials have wide ranging applications in electronic devices and catalysts owing to their unique properties. Boron-based compounds, which exhibit a polymorphic nature, are an attractive choice for developing boron-based two-dimensional materials. Among them, rhombohedral boron monosulfide (r-BS) has recently attracted considerable attention owing to its unique layered structure similar to that of transition metal dichalcogenides and a layer-dependent bandgap. However, experimental evidence that clarifies the charge carrier type in the r-BS semiconductor is lacking. In this study, we synthesized r-BS and evaluated its performance as a semiconductor by measuring the Seebeck coefficient and photo-electrochemical responses. The properties unique to p-type semiconductors were observed in both measurements, indicating that the synthesized r-BS is a p-type semiconductor. Moreover, a distinct Fano resonance was observed in Fourier transform infrared absorption spectroscopy, which was ascribed to the Fano resonance between the E(2) (TO) phonon mode and electrons in the band structures of r-BS, indicating that the p-type carrier was intrinsically doped in the synthesized r-BS. These results demonstrate the potential future application prospects of r-BS.

Thermoelectric materials taking advantage of spin entropy: lessons from chalcogenides and oxides.

The interplay between charges and spins may influence the dynamics of the carriers and determine their thermoelectric properties. In that respect, magneto-thermoelectric power MTEP, i.e. the measurements of the Seebeck coefficient S under the application of an external magnetic field, is a powerful technique to reveal the role of magnetic moments on S. This is illustrated by different transition metal chalcogenides: CuCrTiS4 and CuMnTiS4 magnetic thiospinels, which are compared with magnetic oxides, Curie-Weiss (CW) paramagnetic misfit cobaltites, ruthenates, either ferromagnetic perovskite or Pauli paramagnet quadruple perovskites, and CuGa1-x Mn x Te2 chalcopyrite telluride and Bi1.99Cr0.01Te3 in which diluted magnetism is induced by 3%-Mn and 1%-Cr substitution, respectively. In the case of a ferromagnet (below TC) and CW paramagnetic materials, the increase of magnetization at low T when a magnetic field is applied is accompanied by a decrease of the entropy of the carriers and hence S decreases. This is consistent with the lack of MTEP in the Pauli paramagnetic quadruple perovskites. Also, no significant MTEP is observed in CuGa1-x Mn x Te2 and Bi1.99Cr0.01Te3, for which Kondo-type interaction between magnetic moments and carriers prevails. In contrast, spin glass CuCrTiS4 exhibits negative MTEP like in ferromagnetic ruthenates and paramagnetic misfit cobaltites. This investigation of some chalcogenides and oxides provides key ingredients to select magnetic materials for which S benefits from spin entropy.

Spin-Driven Multiferroic Properties of PbMn7O12 Perovskite.

We synthesize PbMn7O12 perovskite under high-pressure (6 GPa) and high-temperature (1373 K) conditions and investigate its structural, magnetic, dielectric, and ferroelectric properties. We find that PbMn7O12 exhibits rich physical properties from interplay among charge, orbital, and spin degrees of freedom and rich structural properties. PbMn7O12 crystallizes in space group R3̅ near room temperature and shows a structural phase transition at TCO = 397 K to a cubic structure in space group Im3̅; the Im3̅-to-R3̅ transition is associated with charge ordering. Below TOO = 294 K, a structural modulation transition associated with orbital ordering takes place. There are two magnetic transitions with Néel temperatures of TN1 = 83 K and TN2 = 77 K and probably a lock-in transition at TN3 = 43 K (on cooling). There is huge hysteresis on specific heat (between ∼37 and 65 K at 0 Oe), dielectric constant (between ∼20 and 70 K at 0 Oe), and dc and ac magnetic susceptibilities around the lock-in transition. Sharp dielectric constant, dielectric loss, and pyroelectric current anomalies are observed at TN2, indicating that electric polarization is developed at this magnetic transition, and PbMn7O12 perovskite is a spin-driven multiferroic. Polarization of PbMn7O12 is measured to be ∼4 µC/m(2). Field-induced transitions are detected at ∼63 and ∼170 kOe at 1.6-2 K; similar high-magnetic field properties are also found for CdMn7O12, CaMn7O12, and SrMn7O12. PbMn7O12 exhibits a quite small magnetodielectric effect, reaching approximately -1.3 to -1.7% at 10 K and 90 kOe.

Thermoelectricity Generation and Electron-Magnon Scattering in a Natural Chalcopyrite Mineral from a Deep-Sea Hydrothermal Vent.

Current high-performance thermoelectric materials require elaborate doping and synthesis procedures, particularly in regard to the artificial structure, and the underlying thermoelectric mechanisms are still poorly understood. Here, we report that a natural chalcopyrite mineral, Cu1+x Fe1-x S2 , obtained from a deep-sea hydrothermal vent can directly generate thermoelectricity. The resistivity displayed an excellent semiconducting character, and a large thermoelectric power and high power factor were found in the low x region. Notably, electron-magnon scattering and a large effective mass was detected in this region, thus suggesting that the strong coupling of doped carriers and antiferromagnetic spins resulted in the natural enhancement of thermoelectric properties during mineralization reactions. The present findings demonstrate the feasibility of thermoelectric energy generation and electron/hole carrier modulation with natural materials that are abundant in the Earth's crust.

Phase characterization, thermal stability, high-temperature transport properties, and electronic structure of rare-earth Zintl phosphides Eu3M2P4 (M = Ga, In).

Two rare-earth-containing ternary phosphides, Eu3Ga2P4 and Eu3In2P4, were synthesized by a two-step solid-state method with stoichiometric amounts of the constitutional elements. Refinements of the powder X-ray diffraction are consistent with the reported single-crystal structure with space group C2/c for Eu3Ga2P4 and Pnnm for Eu3In2P4. Thermal gravimetry and differential scanning calorimetry (TG-DSC) measurements reveal high thermal stability up to 1273 K. Thermal diffusivity measurements from room temperature to 800 K demonstrate thermal conductivity as low as 0.6 W/m·K for both compounds. Seebeck coefficient measurements from room temperature to 800 K indicate that both compounds are small band gap semiconductors. Eu3Ga2P4 shows p-type conductivity and Eu3In2P4 p-type conductivity in the temperature range 300-700 K and n-type conductivity above 700 K. Electronic structure calculations result in band gaps of 0.60 and 0.29 eV for Eu3Ga2P4 and Eu3In2P4, respectively. As expected for a valence precise Zintl phase, electrical resistivity is large, approximately 2600 and 560 mΩ·cm for Eu3Ga2P4 and Eu3In2P4 at room temperature, respectively. Measurements of transport properties suggest that these Zintl phosphides have potential for being good high-temperature thermoelectric materials with optimization of the charge carrier concentration by appropriate extrinsic dopants.

Phase range of the type-I clathrate Sr8Al(x)Si(46-x) and crystal structure of Sr8Al10Si36.

Samples of the type-I clathrate Sr(8)Al(x)Si(46-x) have been prepared by direct reaction of the elements. The type-I clathrate structure (cubic space group Pm3n) which has an Al-Si framework with Sr(2+) guest atoms forms with a narrow composition range of 9.54(6) ≤ x ≤ 10.30(8). Single crystals with composition A(8)Al(10)Si(36) (A = Sr, Ba) have been synthesized. Differential scanning calorimetry (DSC) measurements provide evidence for a peritectic reaction and melting point at ∼1268 and ∼1421 K for Sr(8)Al(10)Si(36) and Ba(8)Al(10)Si(36), respectively. Comparison of the structures reveals a strong correlation between the 24k-24k framework sites distances and the size of the guest cation. Electronic structure calculation and bonding analysis were carried out for the ordered models with the compositions A(8)Al(6)Si(40) (6c site occupied completely by Al) and A(8)Al(16)Si(30) (16i site occupied completely with Al). Analysis of the distribution of the electron localizability indicator (ELI) confirms that the Si-Si bonds are covalent, the Al-Si bonds are polar covalent, and the guest and the framework bonds are ionic in nature. The Sr(8)Al(6)Si(40) phase has a very small band gap that is closed upon additional Al, as observed in Sr(8)Al(16)Si(30). An explanation for the absence of a semiconducting "Sr(8)Al(16)Si(30)" phase is suggested in light of these findings.

Crystal structure and a giant magnetoresistance effect in the new Zintl compound Eu3Ga2P4.

Single-crystalline samples of a new Zintl compound, Eu(3)Ga(2)P(4), have been synthesized by a Ga-flux method. Eu(3)Ga(2)P(4) is found to crystallize in a monoclinic unit cell, space group C2/c, isostructural to Ca(3)Al(2)As(4). The structure is composed of a pair of edge-shared GaP(4) tetrahedra, which link by corner-sharing to form Ga(2)P(4) two-dimensional layers, separated by Eu(2+) ions. Magnetic susceptibility showed a Curie-Weiss behavior with an effective magnetic moment consistent with the value for Eu(2+) magnetic ions. Below 15 K, ferromagnetic ordering was observed and the saturation magnetic moment was 6.6 µ(B). Electrical resistivity measurements on a single crystal showed semiconducting behavior. Resistivity in the temperature range between 280 and 300 K was fit by an activation model with an energy gap of 0.552(2) eV. The temperature dependence of the resistivity is better described by the variable-range-hopping model for a three-dimensional conductivity, suggesting that Eu-P bonds are involved in the conductivity. A large magnetoresistance, up to -30%, is observed with a magnetic field H = 2 T at T = 100 K, suggesting strong coupling of carriers with the Eu(2+) magnetic moment.

Pressure-induced transitions inRCo5(R=Y, La) studied by x-ray emission spectroscopy, x-ray diffraction and density functional theory.

The hydrostatic pressure dependent evolution of the electronic and magnetic structure of LaCo5and YCo5was investigated by means of x-ray emission spectroscopy, x-ray diffraction, and spin-polarized density functional theory (DFT) calculations. Using experimental lattice parameters the DFT correctly predicts the pressure of the magnetic transition in both compounds to be 26 GPa (La) and 22-23 GPa (Y). The transition was experimentally resolved in the changes of the electronic structure via the integrated absolute difference of the CoKßemission spectra. Comparison of theory and experiment confirm for the first time a common feature in both LaCo5and YCo5to be the source of the transition; the Fermi-level crossing of an up-spin polarized flat band driving the systems into a low spin configuration via a Lifshitz type transition of the Fermi surface. Another phase transition observed around 12 GPa in LaCo5was clarified to be caused by the change in the down-spin density of states at the Fermi level.

High-endurance micro-engineered LaB6 nanowire electron source for high-resolution electron microscopy.

The size tunability and chemical versatility of nanostructures enable electron sources of high brightness and temporal coherence, both of which are important characteristics for high-resolution electron microscopy1-3. Despite intensive research efforts in the field, so far, only conventional field emitters based on a bulk tungsten (W) needle have been able to yield atomic-resolution images. The absence of viable alternatives is in part caused by insufficient fabrication precision for nanostructured sources, which require an alignment precision of subdegree angular deviation of a nanometre-sized emission area with the macroscopic emitter axis4. To overcome this challenge, in this work we micro-engineered a LaB6 nanowire-based electron source that emitted a highly collimated electron beam with good lateral and angular alignment. We integrated a passive collimator structure into the support needle tip for the LaB6 nanowire emitter. The collimator formed an axially symmetric electric field around the emission tip of the nanowire. Furthermore, by means of micromanipulation, the support needle tip was bent to align the emitted electron beam with the emitter axis. After installation in an aberration-corrected transmission electron microscope, we characterized the performance of the electron source in a vacuum of 10-8 Pa and achieved atomic resolution in both broad-beam and probe-forming modes at 60 kV beam energy. The natural, unmonochromated 0.20 eV electron energy loss spectroscopy resolution, 20% probe-forming efficiency and 0.4% probe current peak-to-peak noise ratio paired with modest vacuum requirements make the LaB6 nanowire-based electron source an attractive alternative to the standard W-based sources for low-cost electron beam instruments.

Strong coupling between 4f valence instability and 3d ferromagnetism in Yb(x)Fe4Sb12 studied by resonant x-ray emission spectroscopy.

We have investigated the temperature and pressure dependency of the electronic structure of Yb-filled skutterudites, YbFe(4)Sb(12) and Yb(0.88)Fe(4)Sb(12), using x-ray absorption and emission spectroscopies. An anomalous increase of the Yb valence, which is beyond the conventional Anderson model picture, is found to coincide with the onset of the ferromagnetic order in the x=0.88 sample below 20 K. In contrast, the nearly stoichiometric YbFe(4)Sb(12) is paramagnetic down to 2 K and the Yb valence is independent of temperature. This evidences a close interplay between the magnetic instability of the Fe 3d electrons and valence instability of the Yb 4f electrons. Under pressure, a sudden increase in the valence is found to occur around 13 GPa for YbFe(4)Sb(12) and 17 GPa for Yb(0.88)YbFe(4)Sb(12).

Flexible n-Type Abundant Chalcopyrite/PEDOT:PSS/Graphene Hybrid Film for Thermoelectric Device Utilizing Low-Grade Heat.

Combining inorganic thermoelectric (TE) materials with conductive polymers is one promising strategy to develop flexible thermoelectric (FTE) films and devices. As most inorganic materials tried up until now in FTE composites are composed of scarce or toxic elements, and n-type FTE materials are particularly desired, we combined the abundant, inexpensive, nontoxic Zn-doped chalcopyrite (Cu1-xZnxFeS2, x = 0.01, 0.02, 0.03) with a flexible electrical network constituted by poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) and graphene for n-type FTE films. Hybrid films from the custom design of binary Cu1-xZnxFeS2/PEDOT:PSS to the optimum design of ternary Cu0.98Zn0.02FeS2/PEDOT:PSS/graphene are characterized. Compared with the binary film, a 4-fold enhancement in electrical conductivity was observed in the ternary film, leading to a maximum power factor of ∼ 23.7 µW m-1 K-2. The optimum ternary film could preserve >80% of the electrical conductivity after 2000 bending cycles, exhibiting an exceptional flexibility due to the network constructed by PEDOT:PSS and graphene. A five-leg thermoelectric prototype made of optimum films generated a voltage of 4.8 mV with a ΔT of 13 °C. Such an evolution of an inexpensive chalcopyrite-based hybrid film with outstanding flexibility exhibits the potential for cost-sensitive FTE applications.

Drastic power factor improvement by Te doping of rare earth-free CoSb3-skutterudite thin films.

In the present study, we have focused on the elaboration of control of Te-doped CoSb3 thin films by RF magnetron sputtering which is an attractive technique for industrial development of thermoelectric (TE) thin films. We have successfully synthesized sputtering targets with a reliable approach in order to obtain high-quality films with controlled stoichiometry. TE properties were then probed and revealed a reliable n-type behavior characterized by poor electrical transport properties. Tellurium substitution was realized by co-sputtering deposition and allowed obtaining a significant enhancement of the power factor with promising values of PF ≈ 0.21 mW m-1 K-2 near room temperature. It is related to the Te doping effect which leads to an increase of the Seebeck coefficient and the electrical conductivity simultaneously. However, despite this large improvement, the properties remained far from the bulk material and further developments are necessary to improve the carrier mobility reduced by the thin film formatting.

Observation of enhanced thermopower due to spin fluctuation in weak itinerant ferromagnet.

Increasing demand for higher energy efficiency calls for waste heat recovery technology. Thus, facilitating practical thermoelectric generation systems is strongly desired. One option is enhancing the thermoelectric power factor, S 2/r, where S is the Seebeck coefficient and r is the electrical resistivity, although it is still challenging because of the trade-off between S and r. We demonstrate that enhanced S 2/r can be achieved by incorporating magnetic interaction in ferromagnetic metals via the spin fluctuation arising from itinerant electrons. We show that electron-doped Heusler alloys exhibit weak ferromagnetism at T C near room temperature with a small magnetic moment. A pronounced enhancement around T C was observed, with a 20% improvement in the power factor from the case where spin fluctuation is suppressed by applying magnetic field. This result supports the merit of using spin fluctuation to further enhance thermoelectric properties and the potential to further probe correlations and synergy between magnetic and thermoelectric fields.

Thermoelectric Enhancement of Silicon Membranes by Ultrathin Amorphous Films.

We propose a simple, low-cost, and large-area method to increase the thermoelectric figure of merit (ZT) in silicon membranes by the deposition of an ultrathin aluminum layer. Transmission electron microscopy showed that short deposition of aluminum on a silicon substrate covers the surface with an ultrathin amorphous film, which, according to recent theoretical works, efficiently destroys phonon wave packets. As a result, we measured 30-40% lower thermal conductivity in silicon membranes covered with aluminum films while the electrical conductivity was not affected. Thus, we have achieved 40-45% higher ZT values in membranes covered with aluminum films. To demonstrate a practical application, we applied this method to enhance the performance of a silicon membrane-based thermoelectric device and measured 42% higher power generation.

Electronic structure of ferromagnetic heavy fermion, YbPdSi, YbPdGe, and YbPtGe studied by photoelectron spectroscopy, x-ray emission spectroscopy, and DFT + DMFT calculations.

Electronic structures of ferromagnetic heavy fermion Yb compounds of YbPdSi, YbPdGe, and YbPtGe are studied by photoelectron spectroscopy around the Yb 4d-4f resonance, resonant x-ray emission spectroscopy at the Yb L 3 absorption edge, and density functional theory combined with dynamical mean field theory calculations. These compounds all have a temperature-independent intermediate Yb valence with large [Formula: see text] and small [Formula: see text] components. The magnitude of the Yb valence is evaluated to be YbPtGe [Formula: see text] YbPdGe [Formula: see text] YbPdSi, suggesting that YbPtGe is the closest to the quantum critical point among the three Yb compounds. Our results support the scenario of the coexistence of heavy fermion behavior and ferromagnetic ordering which is described by a magnetically-ordered Kondo lattice where the magnitude of the Kondo effect and the RKKY interaction are comparable.

Pressure-induced anomalous valence crossover in cubic YbCu5-based compounds.

A pressure-induced anomalous valence crossover without structural phase transition is observed in archetypal cubic YbCu5 based heavy Fermion systems. The Yb valence is found to decrease with increasing pressure, indicating a pressure-induced crossover from a localized 4f 13 state to the valence fluctuation regime, which is not expected for Yb systems with conventional c-f hybridization. This result further highlights the remarkable singularity of the valence behavior in compressed YbCu5-based compounds. The intermetallics Yb2Pd2Sn, which shows two quantum critical points (QCP) under pressure and has been proposed as a potential candidate for a reentrant Yb2+ state at high pressure, was also studied for comparison. In this compound, the Yb valence monotonically increases with pressure, disproving a scenario of a reentrant non-magnetic Yb2+ state at the second QCP.

Anisotropic magnetic properties and magnetic structure of YbPdSi.

YbPdSi with orthorhombic crystal structure (space group Pmmn) exhibits a magnetic transition at [Formula: see text] K, below which a ferromagnetic moment develops with an enhanced electronic specific-heat coefficient [Formula: see text] mJ K(-2) mol(-1). We have investigated the magnetization, electrical resistivity, and specific heat of YbPdSi using single crystalline samples as functions of temperature and magnetic field. It has been found that the ferromagnetic moment points to the c-direction, although the magnetic moments have an Ising-like anisotropy along the b-direction above the magnetic-transition temperature. Field dependence of the magnetization and electrical resistivity shows a metamagnetic-like transition at [Formula: see text] T when field is applied along the b-axis below T = 3 K, suggesting the existence of an antiferromagnetic component along this direction. The magnetic structure has been investigated by neutron diffraction using powder samples. The magnetic unit cell is identical to the crystal unit cell. The Rietveld fitting has revealed that Yb at the 2a and 2b positions exhibit a collinear ferromagnetic order along the c-axis, whereas Yb at the 4e position undergoes a non-collinear order, involving the ferromagnetic moment along the c-axis and an antiferromagnetic component along the b-axis. The ferromagnetic moments determined by the neutron diffraction are 0.26, 1.3, and 0.15 [Formula: see text] for Yb at the 4e, 2b, and 2a sites, respectively. The reduced moments for the 4e and the 2a sites suggest that the Kondo screening effect is important in YbPdSi.

Magnetic structure of the ferromagnetic Kondo-lattice compounds YbPtGe and YbPdGe.

YbPtGe and YbPdGe exhibit ferromagnetic ordering below Tc = 5.4 and 11.4 K with enhanced electronic specific heat coefficients of γ = 209 and 150 mJ K(-2) mol, respectively. In order to shed light on the origin of the coexistence of a ferromagnetic state and heavy-fermion behavior, we studied the powder neutron diffraction of YbPtGe and YbPdGe at low temperatures. Weak reflections due to magnetic ordering have been resolved. The data were analyzed using the Rietveld method together with group theory analysis. It has been found that YbPtGe exhibits a non-collinear ferromagnetic structure, with a spontaneous moment along the c-axis and a weak antiferromagnetic component along the a-axis. The presence of this antiferromagnetic component explains the origin of the observed metamagnetic-like behavior. In the case of YbPdGe, magnetization measurements confirmed the ferromagnetic moment along the b-axis and revealed a metamagnetic transition at 0.2 T for a field parallel to the c-axis. The neutron diffraction results indicate that the magnetic structure of YbPdGe is also of a non-collinear type, with ferromagnetic moments parallel to the b-axis and weak antiferromagnetic components along the c-axis, which is consistent with the magnetization data. A comparison of the results for YbPtGe and YbPdGe has been made. It is suggested that both the Kondo screening effect of ferromagnetic moments and the fluctuation of antiferromagnetic components can contribute to the enhanced mass in the ferromagnetic state.

High-pressure synthesis, crystal structure and magnetic properties of TlCrO3 perovskite.

TlMO(3) perovskites (M(3+) = transition metals) are exceptional members of trivalent perovskite families because of the strong covalency of Tl(3+)-O bonds. Here we report on the synthesis, crystal structure and properties of TlCrO(3) investigated by Mössbauer spectroscopy, specific heat, dc/ac magnetization and dielectric measurements. TlCrO(3) perovskite is prepared under high pressure (6 GPa) and high temperature (1500 K) conditions. The crystal structure of TlCrO(3) is refined using synchrotron X-ray powder diffraction data: space group Pnma (no. 62), Z = 4 and lattice parameters a = 5.40318(1) Å, b = 7.64699(1) Å and c = 5.30196(1) Å at 293 K. No structural phase transitions are found between 5 and 300 K. TlCrO(3) crystallizes in the GdFeO(3)-type structure similar to other members of the perovskite chromite family, ACrO(3) (A(3+) = Sc, In, Y and La-Lu). The unit cell volume and Cr-O-Cr bond angles of TlCrO(3) are close to those of DyCrO(3); however, the Néel temperature of TlCrO(3) (TN≈ 89 K) is much smaller than that of DyCrO(3) and close to that of InCrO(3). Isothermal magnetization studies show that TlCrO(3) is a fully compensated antiferromagnet similar to ScCrO(3) and InCrO(3), but different from RCrO(3) (R(3+) = Y and La-Lu). Ac and dc magnetization measurements with a fine step of 0.2 K reveal the existence of two Néel temperatures with very close values at T(N2) = 87.0 K and T(N1) = 89.3 K. Magnetic anomalies near T(N2 )are suppressed by static magnetic fields and by 5% iron doping.