No Arabic abstract
Here we investigate the thermodynamic and electronic properties of Eu$_{11}$InSb$_9$ single crystals. Electrical transport data show that Eu$_{11}$InSb$_9$ has a semiconducting ground state with a relatively narrow band gap of $320$~meV. Magnetic susceptibility data reveal antiferromagnetic order at low temperatures, whereas ferromagnetic interactions dominate at high temperature. Specific heat, magnetic susceptibility, and electrical resistivity measurements reveal three phase transitions at $T_{N1}=9.3$~K, $T_{N2} =8.3$~K, and $T_{N3} =4.3$~K. Unlike Eu$_{5}$In$_{2}$Sb$_6$, a related europium-containing Zintl compound, no colossal magnetoresistance (CMR) is observed in Eu$_{11}$InSb$_9$. We attribute the absence of CMR to the smaller carrier density and the larger distance between Eu ions and In-Sb polyhedra in Eu$_{11}$InSb$_9$. Our results indicate that Eu$_{11}$InSb$_9$ has potential applications as a thermoelectric material through doping or as a long-wavelength detector due to its narrow gap.
ABSTRACT: Narrow-gap semiconductors are sought-after materials due to their potential for long-wavelength detectors, thermoelectrics, and more recently non-trivial topology. Here we report the synthesis and characterization of a new family of narrow-gap semiconductors, $R$$_{3}$Cd$_{2}$As$_{6}$ ($R=$ La, Ce). Single crystal x-ray diffraction at room temperature reveals that the As square nets distort and Cd vacancies order in a monoclinic superstructure. A putative charge-density ordered state sets in at 279~K in La$_{3}$Cd$_{2}$As$_{6}$ and at 136~K in Ce$_{3}$Cd$_{2}$As$_{6}$ and is accompanied by a substantial increase in the electrical resistivity in both compounds. The resistivity of the La member increases by thirteen orders of magnitude on cooling, which points to a remarkably clean semiconducting ground state. Our results suggest that light square net materials within a $I4/mmm$ parent structure are promising clean narrow-gap semiconductors.
We present an extension and revision of the spectroscopic and structural data of the mixed stack charge transfer (CT) crystal 3,3$^prime$,5,5$^prime$-tetramethylbenzidine--tetrafluoro-tetracyanoquinodimethane (TMB-TCNQF$_4$), associated with new electric and dielectric measurements. Refinement of syncrotron structural data at low temperature have led to revise the previously reported [Phys. Rev. Mat. textbf{2}, 024602 (2018)] $C2/m$ structure. The revised structure is $P2_1/m$, with two dimerized stacks per unit cell, and is consistent with the vibrational data. However, polarized Raman data in the low-frequency region also indicate that by increasing temperature above 200 K the structure presents an increasing degree of disorder mainly along the stack axis. This finds confirmation in the analysis of the anisotropic displacement parameters of the structure. TMB-TCNQF$_4$ is confirmed to be a narrow gap semiconductor ($E_a sim 0.3$ eV) with room $T$ conductivity of $sim 10^{-4}~ Omega^{-1}$ cm$^{-1}$, while dielectric measurement have evidenced a typical relaxor ferroelectric behavior already at room $T$, with a peak in real part of dielectric constant $epsilon(T, u)$ around 200 K and 0.1 Hz. The relaxor behavior is explained in terms of the presence of spin solitons separating domains of opposite polarity that yield to ferrolectric nanodomains.
The solid solution Eu(Ga_1-xAl_x)_4 was grown in single crystal form to reveal a rich variety of crystallographic, magnetic, and electronic properties that differ from the isostructural end compounds EuGa_4 and EuAl_4, despite the similar covalent radii and electronic configurations of Ga and Al. Here we report the onset of magnetic spin reorientation and metamagnetic transitions for x = 0 - 1 evidenced by magnetization and temperature-dependent specific heat measurements. T_N changes non-monotonously with x, and it reaches a maximum around 20 K for x = 0.50, where the a lattice parameter also shows an extreme (minimum) value. Anomalies in the temperature-dependent resistivity consistent with charge density wave behavior exist for x = 0.50 and 1 only. Density functional theory calculations show increased polarization between the Ga-Al covalent bonds in the x = 0.50 structure compared to the end compounds, such that crystallographic order and chemical pressure are proposed as the causes of the charge density wave behavior.
New carbon forms exhibiting extraordinary physico-chemical properties can be generated from nanostructured precursors under extreme pressure. Nevertheless, synthesis of such fascinating materials is often not well understood that results, as is the case of C60 precursor, in irreproducibility of the results and impeding further progress in the materials design. Here the semiconducting amorphous carbon having bandgaps of 0.1-0.3 eV and the advantages of isotropic superhardness and superior toughness over single-crystal diamond and inorganic glasses are produced from transformation of fullerene at high pressure and moderate temperatures. A systematic investigation of the structure and bonding evolution was carried out by using rich arsenal of complimentary characterization methods, which helps to build a model of the transformation that can be used in further high p,T synthesis of novel nanocarbon systems for advanced applications. The produced amorphous carbon materials have the potential of demanding optoelectronic applications that diamond and graphene cannot achieve
We review many-body effects, their microscopic origin, as well as their impact onto thermoelectricity in correlated narrow-gap semiconductors. Members of this class---such as FeSi and FeSb$_2$---display an unusual temperature dependence in various observables: insulating with large thermopowers at low temperatures, they turn bad metals at temperatures much smaller than the size of their gaps. This insulator-to-metal crossover is accompanied by spectral weight-transfers over large energies in the optical conductivity and by a gradual transition from activated to Curie-Weiss-like behaviour in the magnetic susceptibility. We show a retrospective of the understanding of these phenomena, discuss the relation to heavy-fermion Kondo insulators---such as Ce$_3$Bi$_4$Pt$_3$ for which we present new results---and propose a general classification of paramagnetic insulators. From the latter FeSi emerges as an orbital-selective Kondo insulator. Focussing on intermetallics such as silicides, antimonides, skutterudites, and Heusler compounds we showcase successes and challenges for the realistic simulation of transport properties in the presence of electronic correlations. Further, we advert to new avenues in which electronic correlations may contribute to the improvement of thermoelectric performance.