Substitution of Re7+ into CaMnO3: an efficient free electron generation dopant for tuning of thermoelectric properties.

Highly dense CaMn1-xRexO3 (0 ≤ x ≤ 0.04) samples were prepared by solid-state synthesis. The effect of Re doping was assessed by the characterisation of crystal structure, oxygen content, and electrical and thermal transport properties. The oxidation state of the substituted Re was determined by X-ray absorption near edge spectra to be Re7+, and led to expansion of the lattice and an increase in electron carrier concentration due to the formation of Mn3+. The thermal behaviour of the electrical conductivity and the thermopower over a wide temperature range allowed identification of different conduction mechanisms: (1) below 110 K, 3D variable range hopping, (2) between 110 and 650 K, small polaron transport, and (3) above 650 K, activation of carriers over a mobility edge. Evaluation of the power factor expected for different dopant oxidation states as a function of dopant concentration shows that the doping strategy using a heavy heptavalent ion allows accessibility of the peak power factor at lower dopant concentrations, lowering the amount of non-ionised impurities, and therefore improves the electronic substitution efficiency, the ratio of activated carriers over the nominal doping concentration, compared to previously studied dopants. An increased power factor and a reduced lattice thermal conductivity are obtained with a peak figure of merit ZT = 0.16(3) at 947 K for CaMn0.98Re0.02O3. This is an approximately two-fold increase compared to undoped CaMnO3, and is comparable to the highest values reported for highly dense B-site doped CaMnO3

ZnO:Co Diluted Magnetic Semiconductor or Hybrid Nanostructure for Spintronics?

We have studied the influence of intrinsic and extrinsic defects in the magnetic and electrical transport properties of Co-doped ZnO thin films. X ray absorption measurements show that Co substitute Zn in the ZnO structure and it is in the 2+ oxidation state. Magnetization (M) measurements show that doped samples are mainly paramagnetic. From M vs. H loops measured at 5 K we found that the values of the orbital L and spin S numbers are between 1 and 1.3 for L and S = 3/2, in agreement with the representative values for isolated Co 2+. The obtained negative values of the Curie-Weiss temperatures indicate the existence of antiferromagnetic interactions between transition metal atoms.Comment: To be published in Journal of Materials Scienc

Growth and characterization of heteroepitaxial La-substituted BaSnO3_3 films on SrTiO3_3 (001) and SmScO3_3 (110) substrates

Heteroepitaxial growth of BaSnO$_3$ (BSO) and Ba$_{1-x}$La$_x$SnO$_3$ (x = 7 %) (LBSO) thin films on different perovskite single crystal (SrTiO$_3$ (001) and SmScO$_3$ (110)) substrates has been achieved by Pulsed Laser Deposition (PLD) under optimized deposition conditions. X-ray diffraction measurements indicate that the films on either of these substrates are relaxed due to the large mismatch and present a high degree of crystallinity with narrow rocking curves and smooth surface morphology while analytical quantification by proton induced x-ray emission (PIXE) confirms the stoichiometric La transfer from a polyphasic target, producing films with La contents above the bulk solubility limit. The films show degenerate semiconducting behavior on both substrates, with the observed room temperature resistivities, Hall mobilities and carrier concentrations of 4.4 $m \Omega cm$, 10.11 $cm^2 V^{-1} s^{-1}$, and 1.38 $\cdot 10^{20} cm^{-3}$ on SmScO$_3$ and 7.8 $m \Omega cm$, 5.8 $cm^2 V^{-1} s^{-1}$, and 1.36 $\cdot 10^{20} cm^{-3}$ on SrTiO$_3$ ruling out any extrinsic contribution from the substrate. The superior electrical properties observed on the SmScO3 substrate are attributed to reduction in dislocation density from the lower lattice mismatch.Comment: 11 pages, 3 figures, supplementary informations 2 figure

Bi-induced band gap reduction in epitaxial InSbBi alloys

The properties of molecular beam epitaxy-grown InSb1−xBix alloys are investigated. Rutherford backscattering spectrometry shows that the Bi content increases from 0.6% for growth at 350 °C to 2.4% at 200 °C. X-ray diffraction indicates Bi-induced lattice dilation and suggests a zinc-blende InBi lattice parameter of 6.626 Å. Scanning electron microscopy reveals surface InSbBi nanostructures on the InSbBi films for the lowest growth temperatures, Bi droplets at intermediate temperatures, and smooth surfaces for the highest temperature. The room temperature optical absorption edge was found to change from 172 meV (7.2 μm) for InSb to ∼88 meV (14.1 μm) for InSb0.976Bi0.024, a reduction of ∼35 meV/%Bi. The work at Liverpool and Warwick was supported by the University of Liverpool and the Engineering and Physical Sciences Research Council (EPSRC) under Grant Nos. EP/G004447/2 and EP/H021388/1. RBS measurements performed at Lawrence Berkeley National Lab were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. Barry Karlin and Joe Woicik are thanked for use of the X24a HAXPES end station at the National Institute of Standards and Technology bending magnet beamline X24 at the National Synchrotron Light Source at Brookhaven National Laboratory. The National Synchrotron Light Source is supported by the U.S. Department of Energy, Contract No. DE-AC02-98CH10886. The work at Binghamton was supported by a Grant from State University of New York Research Foundation Collaboration Fund

Band gap reduction in InNxSb1-x alloys: Optical absorption, k . P modeling, and density functional theory

Using infrared absorption, the room temperature band gap of InSb is found to reduce from 174 (7.1 μm) to 85 meV (14.6 μm) upon incorporation of up to 1.13% N, a reduction of ∼79 meV/%N. The experimentally observed band gap reduction in molecular-beam epitaxial InNSb thin films is reproduced by a five band k ⋅· P band anticrossing model incorporating a nitrogen level, EN, 0.75 eV above the valence band maximum of the host InSb and an interaction coupling matrix element between the host conduction band and the N level of β = 1.80 eV. This observation is consistent with the presented results from hybrid density functional theory

Band gap reduction in InNxSb1-x alloys: Optical absorption, k · P modeling, and density functional theory

Using infrared absorption, the room temperature band gap of InSb is found to reduce from 174 (7.1 μm) to 85 meV (14.6 μm) upon incorporation of up to 1.13% N, a reduction of ∼79 meV/%N. The experimentally observed band gap reduction in molecular-beam epitaxial InNSb thin films is reproduced by a five band k · P band anticrossing model incorporating a nitrogen level, EN, 0.75 eV above the valence band maximum of the host InSb and an interaction coupling matrix element between the host conduction band and the N level of β = 1.80 eV. This observation is consistent with the presented results from hybrid density functional theory

High Bi content GaSbBi alloys

The epitaxial growth, structural, and optical properties of GaSb 1– x Bi x alloys have been investigated. The Bi incorporation into GaSb is varied in the range 0 < x ≤ 9.6% by varying the growth rate (0.31–1.33 μm h−1) at two growth temperatures (250 and 275 °C). The Bi content is inversely proportional to the growth rate, but with higher Bi contents achieved at 250 than at 275 °C. A maximum Bi content of x = 9.6% is achieved with the Bi greater than 99% substitutional. Extrapolating the linear variation of lattice parameter with Bi content in the GaSbBi films enabled a zinc blende GaBi lattice parameter to be estimated of 6.272 Å. The band gap at 300 K of the GaSbBi epitaxial layers decreases linearly with increasing Bi content down to 410 ± 40 meV (3 μm) for x = 9.6%, corresponding to a reduction of ∼35 meV/%Bi. Photoluminescence indicates a band gap of 490 ± 5 meV at 15 K for x = 9.6%

Band gap temperature-dependence of close-space sublimation grown Sb2Se3 by photo-reflectance

The candidate photovoltaic absorber antimony selenide Sb2Se3 has been prepared by the commercially attractive close-space sublimation method. Structure, composition, and morphology are studied by x-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. Large rhubarb-like grains favorable for photovoltaics naturally develop. The temperature-dependence of the direct band gap is determined by photoreflectance between 20 and 320 K and is well described by the Varshni and Bose–Einstein relations, blue-shifting with decreasing temperature from 1.18 to 1.32 eV. The 300 K band gap matches that seen in high quality single-crystal material, while the 0 K gap is consistent with that found in first-principles calculations, further supporting the array of beneficial photovoltaic properties indicated for this material

Modular Design via Multiple Anion Chemistry of the High Mobility van der Waals Semiconductor Bi₄O₄SeCl₂

Making new van der Waals materials with electronic or magnetic functionality is a chemical design challenge for the development of two-dimensional nanoelectronic and energy conversion devices. We present the synthesis and properties of the van der Waals material Bi4O4SeCl2, which is a 1:1 superlattice of the structural units present in the van der Waals insulator BiOCl and the three-dimensionally connected semiconductor Bi2O2Se. The presence of three anions gives the new structure both the bridging selenide anion sites that connect pairs of Bi2O2 layers in Bi2O2Se and the terminal chloride sites that produce the van der Waals gap in BiOCl. This retains the electronic properties of Bi2O2Se while reducing the dimensionality of the bonding network connecting the Bi2O2Se units to allow exfoliation of Bi4O4SeCl2 to 1.4 nm height. The superlattice structure is stabilized by the configurational entropy of anion disorder across the terminal and bridging sites. The reduction in connective dimensionality with retention of electronic functionality stems from the expanded anion compositional diversity