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Syntheses and characterization of one-dimensional alkali metal antimony(III) thiostannates(IV), A{sub 2}Sb{sub 2}Sn{sub 3}S{sub 10} (A=K, Rb, Cs)

Three new isostructural quaternary antimony(III) thiostannates(IV), A{sub 2}Sb{sub 2}Sn{sub 3}S{sub 10} (A=K, Rb, Cs) have been synthesized by using alkali metal thiosulfate flux and structurally characterized by X-ray diffraction. Their structures contain A{sup +} ions around the [Sb{sub 2}Sn{sub 3}S{sub 10}]{sup 2−} chains, which are built from SbS{sub 3} pyramids, SnS{sub 6} octahedra and SnS{sub 4} tetrahedra. Raman and Mössbauer spectroscopic measurements corroborate the oxidation states and coordination environments of Sb(III) and Sn(IV). All three compounds are wide band gap semiconductors. Potassium compound undergoes partial exchange with strontium, cadmium and lead ions. - Graphical abstract: Syntheses, crystal structure, spectroscopic and partial ion-exchange studies of new one-dimensional alkali metal antimony(III) thiostannates(IV), A{sub 2}Sb{sub 2}Sn{sub 3}S{sub 10} (A=K, Rb, Cs) are described. - Highlights: • Syntheses of new alkali metal antimony(III) thiostannates(IV), A{sub 2}Sb{sub 2}Sn{sub 3}S{sub 10} (A=K, Rb, Cs). • Wide band gap semiconductors with one-dimensional structure. • Topotactic partial exchange of K{sup +} ions of K{sub 2}Sb{sub 2}Sn{sub 3}S{sub 10} with Sr{sup 2+}, Cd{sup 2+} and Pb{sup 2+} ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Specific features of doping with antimony during the ion-beam crystallization of silicon

A method of doping during the growth of thin films by ion-beam crystallization is proposed. By the example of Si and Sb, the possibility of controllably doping semiconductors during the ion-beam crystallization process is shown. A calibrated temperature dependence of the antimony vapor flow rate in the range from 150 to 400°C is obtained. It is established that, an increase in the evaporator temperature above 200°C brings about the accumulation of impurities in the layer growth direction. Silicon layers doped with antimony to a concentration of 10{sup 18} cm{sup –3} are grown. It is shown that, as the evaporator temperature is increased, the efficiency of the activation of antimony in silicon nonlinearly decreases from ~10{sup 0} to ~10{sup –3}.

36 MATERIALS SCIENCE↗

Interaction between antimony atoms and micropores in silicon

The interaction between Sb atoms and micropores of a getter layer in silicon is studied. The getter layer was obtained via implantation of Sb{sup +} ions into silicon and subsequent heat treatment processes. The antimony atoms located in the vicinity of micropores are captured by micropores during gettering annealing and lose its electrical activity. The activation energy of capture process to the pores for antimony is lower than that of antimony diffusion in silicon deformation fields around microvoids on the diffusion process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Realization of unpinned two-dimensional dirac states in antimony atomic layers

Two-dimensional (2D) Dirac states with linear dispersion have been observed in graphene and on the surface of topological insulators. 2D Dirac states discovered so far are exclusively pinned at high-symmetry points of the Brillouin zone, for example, surface Dirac states at $\overline{Γ}$ in topological insulators Bi 2 Se(Te) 3 and Dirac cones at Κ and K' points in graphene. The low-energy dispersion of those Dirac states are isotropic due to the constraints of crystal symmetries. In this work, we report the observation of novel 2D Dirac states in antimony atomic layers with phosphorene structure. The Dirac states in the antimony films are located at generic momentum points. This unpinned nature enables versatile ways such as lattice strains to control the locations of the Dirac points in momentum space. In addition, dispersions around the unpinned Dirac points are highly anisotropic due to the reduced symmetry of generic momentum points. The exotic properties of unpinned Dirac states make antimony atomic layers a new type of 2D Dirac semimetals that are distinct from graphene.

36 MATERIALS SCIENCE↗

Mineralogical controls on antimony and arsenic mobility during tetrahedrite-tennantite weathering at historic mine sites Špania Dolina-Piesky and Lubietová-Svätodušná, Slovakia

The legacy of copper (Cu) mining at Špania Dolina-Piesky and Lubietová-Svätodušná (central Slovakia) is waste rock and soil, surface waters, and groundwaters contaminated with antimony (Sb), arsenic (As), Cu, and other metals. Copper ore is hosted in chalcopyrite (CuFeS2) and sulfosalt solid-solution tetrahedrite-tennantite {Cu6[Cu4(Fe,Zn)2]Sb4S13–Cu6[Cu4(Fe,Zn)2]As4S13} that show wide-spread oxidation characteristic by olive-green color secondary minerals. Tetrahedrite-tennantite can be a significant source of As and Sb contamination. Synchrotron-based μ-XRD, μ-XRF, and μ-XANES combined with electron microprobe analyses have been used to determine the mineralogy, chemical composition, element distribution, and Sb speciation in tetrahedrite-tennantite oxidation products in waste rock. Our results show that the mobility of Sb is limited by the formation of oxidation products such as tripuhyite and roméite group mineral containing 36.54 wt% Sb for samples where the primary mineral chemical composition is close to tetrahedrite end-member. Antimony K-edge μ-XANES spectra of these oxidation products indicate that the predominant Sb oxidation state is 5+. Arsenic and Cu are also hosted by amorphous phases containing 6.23 wt% Sb on average and these are intergrown with tripuhyite and roméite. Antimony in this environment is not very mobile, meaning it is not easily released from solid phases to water, especially compared to As, Cu, and S. For samples where the primary sulfosalt is close to tennantite composition, the oxidation products associated with tennantite relicts contain 2.43 wt% Sb and are amorphous. The variable solubility of the secondary minerals that have been identified is expected to influence mobility of Sb and As in near-surface environment.

58 GEOSCIENCES↗

Concentration transient analysis of antimony surface segregation during Si(100) molecular beam epitaxy

Antimony surface segregation during Si(100) molecular beam epitaxy (MBE) was investigated at temperatures T(sub s) = 515 - 800 C using concentration transient analysis (CTA). The dopant surface coverage Theta, bulk fraction gamma, and incorporation probability sigma during MBE were determined from secondary-ion mass spectrometry depth profiles of modulation-doped films. Programmed T(sub s) changes during growth were used to trap the surface-segregated dopant overlayer, producing concentration spikes whose integrated area corresponds to Theta. Thermal antimony doping by coevaporation was found to result in segregation strongly dependent on T(sub s) with Theta(sub Sb) values up to 0.9 monolayers (ML): in films doped with Sb(+) ions accelerated by 100 V, Theta(sub Sb) was less than or equal to 4 x 10(exp -3) ML. Surface segregation of coevaporated antimony was kinematically limited for the film growth conditions in these experiments.

Markert, L. C.↗

Epitaxial Silicon Doped With Antimony

High-purity epitaxial silicon doped with antimony made by chemical vapor deposition, using antimony pentachloride (SbCI5) as source of dopant and SiH4, SiCI2H2, or another conventional source of silicon. High purity achieved in layers of arbitrary thickness. Epitaxial silicon doped with antimony needed to fabricate impurity-band-conduction photodetectors operating at wavelengths from 2.5 to 40 micrometers.

Huffman, James E.↗

Laser Ablation Generation of Antimony Selenide Clusters: Laser Desorption Ionization (LDI) Quadrupole Ion Trap Time of Flight Mass Spectrometry

The binary system Sb-Se was studied via laser ablation using antimony-selenium mixtures made from powdered elements in various ratios generating new Sb{sub m}Se{sub n} clusters. The results show that in addition to Sb{sub m}{sup +} (m = 1–8) and Se{sub n}{sup +} (n = 2–9) clusters, a series of Sb{sub m}Se{sub n}{sup +} clusters such as SbSe{sub 1–8}{sup +}, Sb{sub 2}Se{sub 1–6}{sup +}, Sb{sub 3}Se{sub 1–5}{sup +}, Sb{sub 4}Se{sub 1–3}{sup +}, and Sb{sub 5}Se{sub 1,2}{sup +} is generated. In addition, some low intensity oxidized clusters like Se{sub 6}O{sub 2}{sup +}, Se{sub 7}O{sub 2}{sup +}, and SbSe{sub 2-6}O{sub 5}{sup +} and partially hydroxylated clusters (SbSeO{sub 2}H{sub 7}{sup +}, SbSe{sub 5}O{sub 4}H{sup +}) are also formed. In total, 24 new antimony selenide clusters were generated. The knowledge gained can contribute to the elucidation of the structure of Sb{sub m}Se{sub n} glasses. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A heat flux sensor leveraging the transverse Seebeck effect in elemental antimony

Certain configurations of anisotropic single crystal materials can generate a thermoelectric voltage orthogonal to an induced temperature gradient. This phenomenon is known as the Transverse Seebeck Effect (TSE) and can be leveraged to fabricate simple and robust heat flux sensors. Only a small number of materials have been considered as TSE-based transducers and, among these, few have been developed into sensors with ruggedization against chemical and mechanical degradation. Here, we report on the fabrication and characterization of a rugged TSE-based heat flux sensor using prismatic antimony single crystals. The heat flux sensor was tested under static and dynamic heating scenarios. The sensor has a linear responsivity of 16.8 µV/(W/cm2) to heat fluxes spanning more than two orders of magnitude and a time constant of 4.4 s. The sensor’s response to localized heating, probed with a laser scanning technique, validated that the transduction mechanism is primarily the TSE by ruling out a sizable contribution from the conventional Seebeck effect. Finite element analysis corroborated that components used in the sensor package are the primary determinants of the time constant and the decrement of the responsivity from its theoretical maximum. Design principles that may be applied to elicit a faster transient response or higher responsivity are proposed. Furthermore, the results establish single crystal antimony as a promising transducer material for heat flux measurement systems and demonstrate potential effects of ruggedization on sensor performance.

36 MATERIALS SCIENCE↗

The h –Sb x WO 3+2 x Oxygen Excess Antimony Tungsten Bronze

Here, we describe the previously unreported oxygen excess hexagonal antimony tungsten bronze with composition Sb 0.5 W 3 O 10 , in the following denoted as h –Sb x WO 3+2 x with x = 0.167, to demonstrate its analogy to classical A x WO 3 tungsten bronzes. This compound forms in a relatively narrow temperature range between 580 °C < T < 620 °C. It was obtained as a dark–blue polycrystalline powder, and as thin, needle–shaped, blue single crystals. h –Sb x WO 3+2 x crystallizes in the hexagonal space group P 6/ mmm with the cell parameters a=7.4369(4) Å and c=3.7800(2) Å. The antimony and excess oxygen occupy the hexagonal channels within the network of corner–sharing WO 6 octahedra. h –Sb x WO 3+2 x has a resistivity of ρ 300 K ≈1.28 mΩ cm at room temperature, with little if any temperature–dependence on cooling. DFT calculations on a simplified model for this compound find a metallic–like electronic structure with the Fermi level falling within rather flat bands, especially around the Γ point.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of indium and antimony doping in SnS single crystals

Highlights: • Single crystals growth of pure SnS, indium doped SnS and antimony doped SnS by direct vapour transport (DVT) technique. • Doping of In and Sb occurred in SnS single crystals by cation replacement. • The replacement mechanism ascertained by EDAX, XRD and substantiated by Raman spectra analysis. • Dopants concentration affects the optical energy bandgap. • Doping influences electrical transport properties. - Abstract: Single crystals of pure SnS, indium (In) doped SnS and antimony (Sb) doped SnS were grown by direct vapour transport (DVT) technique. Two doping concentrations of 5% and 15% each were employed for both In and Sb dopants. Thus in total five samples were studied viz., pure SnS (S1), 5% In doped SnS (S2), 15% In doped SnS (S3), 5% Sb doped SnS (S4) and 15% Sb doped SnS (S5). The grown single crystal samples were characterized by evaluating their surface microstructure, stoichiometric composition, crystal structure, Raman spectroscopy, optical and electrical transport properties using appropriate techniques. The d.c. electrical resistivity and thermoelectric power variations with temperature showed semiconducting and p-type nature of the as-grown single crystal samples. The room temperature Hall Effect measurements further substantiated the semiconducting and p-type nature of the as-grown single crystal samples. The obtained results are deliberated in detail.

36 MATERIALS SCIENCE↗

Rh → Sb Interactions Supported by Tris(8-quinolyl)antimony Ligands

The study of ambiphilic systems combining L-type and Z-type ligands within the same construct has emerged as a field of active investigation, especially in the cases of ligands containing a group 13 element as a σ-acceptor for transition metals. (1) Parallel to these developments, several groups have investigated more atypical systems in which the Z-type ligand is a group 15 element. (2) Our contributions to this area have focused on the use of phosphinostibine ligands for the generation of transition metal complexes in which the antimony moiety acts as a Z-type ligand. (1d,3) We have shown that the magnitude of the resulting M → Sb interaction can be readily modulated by the oxidation state of the antimony atom (4) as well as its charge which can be manipulated by abstraction of anionic ligands. (5) Our work has also shown that these effects can be leveraged to enhance the catalytic properties of the transition metal center. (4,5) Some of the simplest systems that we have investigated are those resulting from the reaction of platinum dichloride with the bis- or tris-phosphinostibines ClSb(o-dppp) 2 and Sb(o-dppp) 3 , respectively (o-dppp = o-(Ph 2 P)C 6 H 4 ). These reactions proceed by oxidative insertion of the stibine into a Pt- Cl bond to produce complexes A and B, (6) respectively (Chart 1). Reasoning that the properties of these complexes may also be influenced by the nature of the L-type buttresses, we have now questioned whether stibines featuring nitrogen donor ligands could also display the redox noninnocence of their phosphine counterparts and support the formation of such complexes. Following up on some of our work with ambiphilic tellurium-quinoline ligands, (7) we now report on the reaction of tris-(8-quinolyl)stibines (8) toward (MeCN) 3 RhCl 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Annealing effects on structural, electrical and optical properties of antimony-tinoxide thin films deposited by sol gel dip coating technique

Antimony-doped tin dioxide possess interesting physical and chemical properties. These properties have a wide range of applications such as catalysis and optoelectronic devices. In the present study, antimony-doped tin oxide (SnO2:Sb) thin films were deposited on the quartz substrates by sol-gel dip coating technique. The films were annealed at temperatures 350°C, 550°C and 850°C in air for 2 hours. The structure and surface morphologies were observed by X-ray diffraction (XRD) and Scanning electron microscopy (SEM). XRD patterns shows tetragonal structure for the SnO2:Sb films annealed at different temperatures. Crystallite size increased from 6 to 14 nm as annealing temperature increased from 350°C to 850°C. SEM studies reveals crack free and smooth surface for all the films. The grains are found to be homogenously distributed for films annealed at higher temperature. The electrical conductivity of the films annealed at 350°C and 550°C decreased and increased for the films annealed at 850°C. The optical properties of the films were investigated in the UV-visible-NIR region (200-900 nm) using UV spectra. The transmittance of the films decreased for films annealed at higher temperature. The optical energy band gap values (4.13 eV-4.83 eV) increased with the increase in annealing temperature.

36 MATERIALS SCIENCE↗

Thermoelectric properties of antimony selenide hexagonal nanotubes

Antimony selenide (Sb 2 Se 3 ) is a material widely used in photodetectors and relatively new as a possible material for thermoelectric applications. Taking advantage of the new properties after nanoscale fabrication, this material shows great potential for the development of efficient low temperature thermoelectric devices. Here, for this paper, we study the synthesis, the crystal properties and the thermal and thermoelectric transport response of Sb 2 Se 3 hexagonal nanotubes (HNT) in the temperature range between 120 and 370 K. HNT have a moderate electrical conductivity ~10 2 S m -1 while maintaining a reasonable Seebeck coefficient ~430 μV K -1 at 370 K. The electrical conductivity in Sb 2 Se 3 HNT is about 5 orders of magnitude larger and its thermal conductivity one half of what is found in bulk. Moreover, the calculated figure of merit (ZT) at room temperature is the largest value reported in antimony selenide 1D structures.

36 MATERIALS SCIENCE↗

Dielectric Losses and Charge Transfer in Antimony-Doped TlGaS{sub 2} Single Crystal

Effect of semimetallic antimony (0.5 mol % Sb) on the dielectric properties and ac-conductivity of TlGaS{sub 2}-based single crystals grown by the Bridgman–Stockbarger method has been studied. The experimental results on the frequency dispersion of dielectric coefficients and the conductivity of TlGa{sub 0.995}Sb{sub 0.005}S{sub 2} single crystals allowed the revealing of the dielectric loss nature, the charge transfer mechanism, and the estimation of the parameters of the states localized in the energy gap. The antimony-doping of the TlGaS{sub 2} single crystal leads to an increase in the density of states near the Fermi level and a decrease in the average time and average distance of hopes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High Angle Remediation Antimony, Mercury, and Pu-239/240 Contaminated Soil at LANL near Los Alamos Town Site - 18579

The Manhattan Project and early Cold War era operations at Los Alamos National Laboratory (LANL) left behind soil contaminated with antimony, mercury, and Pu-239/240. TerranearPMC (TPMC) successfully completed a phased three-year high-angle legacy cleanup project to excavate contaminated soil from a steep, difficult-to-access canyon wall in the Upper Los Alamos Canyon Aggregate Area bordering Los Alamos town site. The first and third phases of the project (years 2015 and 2017) utilized a Menzi Muck (spider excavator) in concert with a 275 US ton telescoping crane to remove ∼158 cubic yards (cy) of mercury-contaminated rock and soil (i.e. media) from one solid waste management unit (SWMU) in 2015; and ∼70 cy of antimony contaminated media, and ∼65 cy of collocated mercury and Pu-239/240 contaminated media from two SWMUs in 2017. All soil excavated from the site was containerized in soft-sided 1.0 cy, 1.77 cy, and 3.5 cy IP-1 containers and shipped to an approved, licensed, off-site disposal facility. The crane was also used to move the spider excavator, field personnel, tools, the packaged waste, and restoration materials into and out of the canyon. In 2016, conventional but miniaturized excavation equipment was used to remove about 133 cy of Pu-239/240 contaminated media from four SWMUs west of both the 2015 and 2017 excavations. A total of 398 soil screening, waste composite, characterization/bounding, and confirmation samples were collected during the project. Media that was left in place after the excavation was sampled to confirm that human health concerns and environmental risk issues had been mitigated. This proven technical approach was the preferred method for cleaning up ∼426 cy of contaminated media from steep, difficult-to-access legacy waste sites within the Upper Los Alamos Canyon Aggregate Area between 2015 and 2017. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Preparation and Characterization of Antimony and Arsenic Tricyanide and Their 2,2′‐Bipyridine Adducts

Abstract The arsenic(III) and antimony(III) cyanides M(CN) 3 (M=As, Sb) have been prepared in quantitative yields from the corresponding trifluorides through fluoride–cyanide exchange with Me 3 SiCN in acetonitrile. When the reaction was carried out in the presence of one equivalent of 2,2′‐bipyridine, the adducts [M(CN) 3 ⋅ (2,2′‐bipy)] were obtained. The crystal structures of As(CN) 3 , [As(CN) 3 ⋅ (2,2′‐bipy)] and [Sb(CN) 3 ⋅ (2,2′‐bipy)] were determined and are surprisingly different. As(CN) 3 possesses a polymeric three‐dimensional structure, [As(CN) 3 ⋅ (2,2′‐bipy)] exhibits a two‐dimensional sheet structure, and [Sb(CN) 3 ⋅ (2,2′‐bipy)] has a chain structure, and none of the structures resembles those found for the corresponding arsenic and antimony triazides.

Deokar, Piyush↗