Terahertz HgTe Nanocrystals: Beyond Confinement.

We report the synthesis of nanocrystals with an optical feature in the THz range. To do so, we develop a new synthetic procedure for the growth of HgTe, HgSe, and HgS nanocrystals, with strong size tunability from 5 to 200 nm. This is used to tune the absorption of the nanocrystals all over the infrared range up to terahertz (from 2 to 65 µm for absorption peak and even 200 µm for cutoff wavelength). The interest for this procedure is not limited to large sizes since for small objects we demonstrate low aggregation and good shape control (i.e., spherical object) while using nonexpansive and simple mercury halogenide precursors. By integrating these nanocrystals into an electrolyte-gated transistor, we evidence a change of carrier density from p-doped to n-doped as the confinement is vanishing.

Optical spectroscopy shows that the normal state of URu2Si2 is an anomalous Fermi liquid.

Fermi showed that, as a result of their quantum nature, electrons form a gas of particles whose temperature and density follow the so-called Fermi distribution. As shown by Landau, in a metal the electrons continue to act like free quantum mechanical particles with enhanced masses, despite their strong Coulomb interaction with each other and the positive background ions. This state of matter, the Landau-Fermi liquid, is recognized experimentally by an electrical resistivity that is proportional to the square of the absolute temperature plus a term proportional to the square of the frequency of the applied field. Calculations show that, if electron-electron scattering dominates the resistivity in a Landau-Fermi liquid, the ratio of the two terms, b, has the universal value of b = 4. We find that in the normal state of the heavy Fermion metal URu(2)Si(2), instead of the Fermi liquid value of 4, the coefficient b = 1 ± 0.1. This unexpected result implies that the electrons in this material are experiencing a unique scattering process. This scattering is intrinsic and we suggest that the uranium f electrons do not hybridize to form a coherent Fermi liquid but instead act like a dense array of elastic impurities, interacting incoherently with the charge carriers. This behavior is not restricted to URu(2)Si(2). Fermi liquid-like states with b ≠ 4 have been observed in a number of disparate systems, but the significance of this result has not been recognized.

Metavalent Bonding in Crystalline Solids: How Does It Collapse?

The chemical bond is one of the most powerful, yet much debated concepts in chemistry, explaining property trends in solids. Recently, a novel type of chemical bonding was identified in several higher chalcogenides, characterized by a unique property portfolio, unconventional bond breaking, and sharing of about one electron between adjacent atoms. This metavalent bond is a fundamental type of bonding in solids, besides covalent, ionic, and metallic bonding, raising the pertinent question as to whether there is a well-defined transition between metavalent and covalent bonds. Here, three different pseudo-binary lines, namely, GeTe1- x Sex , Sb2 Te3(1- x ) Se3 x , and Bi2-2 x Sb2 x Se3 , are studied, and a sudden change in several properties, including optical absorption ε2 (ω), optical dielectric constant ε∞ , Born effective charge Z*, electrical conductivity, as well as bond breaking behavior for a critical Se or Sb concentration, is evidenced. These findings provide a blueprint to experimentally explore the influence of metavalent bonding on attractive properties of phase-change materials and thermoelectrics. Particularly important is its impact on optical properties, which can be tailored by the amount of electrons shared between adjacent atoms. This correlation can be used to design optoelectronic materials and to explore systematic changes in chemical bonding with stoichiometry and atomic arrangement.

Synthesis and characterisation of the vibrational and electrical properties of antiferromagnetic 6L-Ba2CoTeO6 ceramics.

Optimal processing conditions for fabrication of dense single-phase 6L-Ba2CoTeO6 ceramics via the solid-state reaction method were determined. These ceramics possess a room-temperature crystal structure described by the centrosymmetric P3[combining macron]m1 space group. Polarized Raman spectroscopy enabled the observation of all the 25 predicted Raman modes and assignment of their symmetries. On cooling, BCTO ceramics exhibit two antiferromagnetic transitions at 3 K and 12.5 K, in broad agreement with a recent single-crystal study [P. Chanlert, N. Kurita, H. Tanaka, D. Goto, A. Matsuo and K. Kindo, Phys. Rev. B: Condens. Matter Mater. Phys., 2016, 93, 094420]. Low temperature Fourier-transform infrared reflectivity analyses suggest the antiferromagnetic phase transitions to be driven by small distortions of the CoO6 octahedra, lowering locally their C3v symmetry. This causes splitting of the associated vibrational modes, but without a long-range structural change. AC impedance spectroscopy revealed BCTO ceramics to be leaky insulators with an activation energy for conduction of ∼0.15-0.25 eV, which suggests electron hopping between mixed oxidation states of Co.

Infrared dispersion analysis and Raman scattering spectra of taurine single crystals.

A comprehensive set of optical vibrational modes of monoclinic taurine crystals was determined by Raman scattering, and infrared reflectivity and transmission spectroscopies. By using appropriate scattering/reflection geometries, the vibrational modes were resolved by polarization and the most relevant modes of the crystal could be assigned. In particular, we were able to review the symmetry of the gerade modes and to resolve ambiguities in the literature. Owing to the non-orthogonal character of Bu modes in monoclinic crystals (lying on the optic axial plane), we carried out a generalized Lorentz dispersion analysis consisting of simultaneous adjust of infrared-reflectivity spectra at various light polarization angles. The Au modes (parallel to the C2-axis) were treated within the classical Lorentz model. The behavior of off-diagonal and diagonal terms of the complex dielectric tensors and the presence of anomalous dispersion were discussed as consequences of the low symmetry of the crystal.

HgSe Self-Doped Nanocrystals as a Platform to Investigate the Effects of Vanishing Confinement.

Self-doped colloidal quantum dots (CQDs) attract a strong interest for the design of a new generation of low-cost infrared (IR) optoelectronic devices because of their tunable intraband absorption feature in the mid-IR region. However, very little remains known about their electronic structure which combines confinement and an inverted band structure, complicating the design of optimized devices. We use a combination of IR spectroscopy and photoemission to determine the absolute energy levels of HgSe CQDs with various sizes and surface chemistries. We demonstrate that the filling of the CQD states ranges from 2 electrons per CQD at small sizes (<5 nm) to more than 18 electrons per CQD at large sizes (≈20 nm). HgSe CQDs are also an interesting platform to observe vanishing confinement in colloidal nanoparticles. We present lines of evidence for a semiconductor-to-metal transition at the CQD level, through temperature-dependent absorption and transport measurements. In contrast with bulk systems, the transition is the result of the vanishing confinement rather than the increase of the doping level.

Silicon beam splitter for far-infrared and terahertz spectroscopy.

Silicon beam splitters several millimeters thick offer numerous advantages over thin freestanding dielectric beam splitters. For routine spectroscopy for which resolutions of better than 1 cm(-1) are not required, a silicon beam splitter can replace several Mylar beam splitters to span the entire far-infrared region. In addition to superior long-wavelength performance that extends well into the terahertz region, the silicon beam splitter has the additional advantage that its efficiency displays little polarization dependence.

Transparent conducting oxides: texture and microstructure effects on charge carrier mobility in MOCVD-derived CdO thin films grown with a thermally stable, low-melting precursor.

A series of low-melting, thermally stable cadmium metal-organic chemical vapor deposition (MOCVD) precursors have been synthesized, structurally and spectroscopically characterized, and implemented in growth of highly conductive and transparent CdO thin films. One member of the series, bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(N,N-diethyl-N',N'-dimethyl-ethylenediamine)cadmium(II), Cd(hfa)(2)()(N,N-DE-N',N'-DMEDA), represents a particularly significant improvement over previously available Cd precursors, owing to the low melting point and robust thermal stability. High-quality CdO films were grown by MOCVD on glass and single-crystal MgO(100) between 300 and 412 degrees C. Film growth parameters and substrate surface have large effects on microstructure and electron carrier transport properties. Enhanced mobilities observed for highly biaxially textured films grown on MgO(100) vs glass are attributed, on the basis of DC charge transport and microstructure analysis, to a reduction in neutral impurity scattering and/or to a more densely packed grain microstructure. Although single-grained films grown on MgO(100) exhibit greater mobilities than analogues with discrete approximately 100 nm grains and similar texture, this effect is attributed, on the basis of charge transport and Hall effect measurements as well as optical reflectivity analysis, to differences in carrier concentration rather than to reduced grain boundary scattering. Unprecedented conductivities and mobilities as high as 11,000 S/cm and 307 cm(2)/V.s, respectively, are obtained for epitaxial single-grained films (X-ray diffraction parameters: fwhm(omega) = 0.30 degrees, fwhm(phi) = 0.27 degrees ) grown in situ on MgO(100) at a relatively low temperature (400 degrees C).