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At least 19 records

Upcycling Metal(loid) Contaminants to Produce Critical Raw Materials: The Nexus of Water Treatment and Material Criticality

The Critical Raw Materials Act adopted by the European Commission in 2024 signals a growing shift in the societal value of many elements, which has important implications for the water treatment sector. This legislation partly aims to increase production of Critical Raw Materials (CRMs) from waste streams, with many CRMs being elements with which the water sector has decades of experience, such as the notorious contaminant and newly classified CRM, arsenic. In this Perspective, we use arsenic as a case study to explore how water treatment waste can be repurposed to contribute to CRM supply chain requirements. Combining arsenic mass balances for indicative groundwater treatment plants and EU statistics of water use and arsenic compound consumption, we propose that arsenic upcycling integrated with water treatment can help offset imports of arsenic compounds. However, research is now needed to develop more holistic treatment systems that integrate CRM upcycling with contaminant removal and to better understand the political, institutional, and social drivers that can accelerate adoption of such systems at water utilities. With this work, we intend to stimulate a discussion of water treatment as a discipline that can both improve water quality by removing metal(loid) contaminants and generate local sources of CRMs.

Arsenic↗

First-principles study of tantalum-arsenic binary compounds

The electronic properties and phase stability of binary tantalum arsenides are investigated using first-principles calculations. We have found strong covalent bonding between Ta and As in TaAs 2 . In the lower As content compounds, the Ta is less covalent and donates charge to the As backbone. The covalency of other compounds becomes smaller with the increase of Ta composition. Compounds on the convex hull are TaAs 2 , TaAs, Ta 5 As 4 , and Ta 3 As, while Ta 2 As is slightly above the hull. Trends in the electronic and other properties are discussed. We identify the space group of TaAs 2 to be centrosymmetric C2/m and find semimetallic behavior in TaAs and TaAs 2 . The other binary compounds are metallic systems with finite density of states at the Fermi level. The plasma energies show moderate conductivity anisotropy in Ta 5 As 4 and Ta 2 As, which are also the most conductive compounds among the binary phases.

36 MATERIALS SCIENCE↗

Sodium meta-arsenite prevents the development of autoimmune diabetes in NOD mice

Sodium meta-arsenite (SA) is an orally available arsenic compound. We investigated the effects of SA on the development of autoimmune type 1 diabetes. Female non-obese diabetic (NOD) mice were orally intubated with SA (5 mg/kg/day) from 8 weeks of age for 8 weeks. The cumulative incidence of diabetes was monitored until 30 weeks of age, islet histology was examined, and lymphocytes including T cells, B cells, CD4+ IFN-γ+ cells, CD8+ IFN-γ+ cells, CD4+ IL-4+ cells, and regulatory T cells were analyzed. We also investigated the diabetogenic ability of splenocytes using an adoptive transfer model and the effect of SA on the proliferation, activation, and expression of glucose transporter 1 (Glut1) in splenocytes treated with SA in vitro and splenocytes isolated from SA-treated mice. SA treatment decreased the incidence of diabetes and delayed disease onset. SA treatment reduced the infiltration of immunocytes in islets, and splenocytes from SA-treated mice showed a reduced ability to transfer diabetes. The number of total splenocytes and T cells and both the number and the proportion of CD4+ IFN-γ+ and CD8+ IFN-γ+ T cells in the spleen were significantly reduced in SA-treated NOD mice compared with controls. The number, but not the proportion, of regulatory T cells was decreased in SA-treated NOD mice. Treatment with SA either in vitro or in vivo inhibited proliferation of splenocytes. In addition, the expression of Glut1 and phosphorylated ERK1/2 was decreased by SA treatment. These results suggest that SA reduces proliferation and activation of T cells, thus preventing autoimmune diabetes in NOD mice. - Highlights: • SA prevents the development of diabetes and delays the age of onset in NOD mice. • SA decreases the number but not the proportion of T lymphocytes in NOD mice. • SA reduces IFN-γ-producing T lymphocytes in NOD mice. • SA reduces proliferation and activation of T lymphocytes in vitro and in vivo. • SA reduces the expression of glucose transporter 1 (Glut1) in splenocytes.

60 APPLIED LIFE SCIENCES↗

Venus: Halide cloud condensation and volatile element inventories

Several Venus cloud condensates, including A12C16 as well as halides, oxides and sulfides of arsenic and antimony, are assessed for their thermodynamic and geochemical plausibility. Aluminum chloride can confidently be ruled out, and condensation of arsenic sulfides on the surface will cause arsenic compounds to be too rare to produce the observed clouds. Antimony may conceivably be sufficiently volatile, but the expected molecular form is gaseous SbS, not the chloride. Arsenic and antimony compounds in the atmosphere will be regulated at very low levels by sulfide precipitation, irrespective of the planetary inventory of As and Sb. Thus the arguments for a volatile-deficient origin for Venus based on the depletion of water and mercury (relative to Earth) cannot be tested by a search for atmospheric arsenic or antimony.

Lewis, J. S.↗

Structural and thermoelectric properties of zintl-phase CaLiPn (Pn=As, Sb, Bi)

First-principles calculations were carried out to study the structural, mechanical, dynamical and transport properties of zintl phase materials CaLiPn (Pn=As, Sb and Bi). We have used two different approaches to solve the system based on density functional theory. The plane wave pseudopotential approach has been used to study the structural and dynamical properties whereas, full potential linear augment plane wave method is used to examine the electronic structure, mechanical and thermoelectric properties. The calculated ground-state properties agree quite well with experimental values. The computed electronic structure shows the investigated compounds to be direct band gap semiconductors. Further, we have calculated the thermoelectric properties of all the investigated compounds for both the carriers at various temperatures. We found a high thermopower for both the carriers, especially n-type doping to be more favourable, which enabled us to predict that CaLiPn might have promising applications as a good thermoelectric material. Further, the phonon dispersion curves of the investigated compounds showed flat phonon modes and we also find lower optical and acoustic modes to cut each other at the lower frequency range, which further indicate the investigated compounds to possess reasonably low thermal conductivity. We have also analysed the low value of the thermal conductivity through the empirical relations and discussions are presented here. - Highlights: • Electronic band structure and chemical bonding. • Single crystalline elastic constants and poly crystalline elastic moduli. • Thermoelectric properties of zintl phase. • Lattice dynamics and phonon density of states.

36 MATERIALS SCIENCE↗

Synthesis and structural characterization of the Zintl phases Na{sub 3}Ca{sub 3}TrPn{sub 4}, Na{sub 3}Sr{sub 3}TrPn{sub 4}, and Na{sub 3}Eu{sub 3}TrPn{sub 4} (Tr=Al, Ga, In; Pn=P, As, Sb)

15 new quaternary Zintl phases have been synthesized by solid-state reactions from the respective elements, and their structures have been determined by single-crystal X-ray diffraction. Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) crystallize in the hexagonal crystal system with the non-centrosymmetric space group P6{sub 3}mc (No. 186). The structure represents a variant of the K{sub 6}HgS{sub 4} structure type (Pearson index hP22) and features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. The nominal formula rationalization [Na{sup +}]{sub 3}[E{sup 2+}]{sub 3}[TrPn{sub 4}]{sup 9–} follows the octet rule, suggesting closed-shell configurations for all atoms and intrinsic semiconducting behavior. However, structure refinements for several members hint at disorder and mixing of cations that potentially counteract the optimal valence electron count. - Graphical abstract: The hexagonal, non-centrosymmetric structure of Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. - Highlights: • 15 quaternary phosphides, arsenides, and antimonides are synthesized and structurally characterized. • The structure is a variant of the hexagonal K{sub 6}HgS{sub 4}-type, with distinctive pattern for the cations. • Occupational and/or positional disorder of yet unknown origin exists for some members of the series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic and optical properties of the LiCdX (X = N, P, As and Sb) filled-tetrahedral compounds with the Tran–Blaha modified Becke–Johnson density functional

Highlights: • Electronic and optical properties of the LiCdX compounds have been predicted. • Tran–Blaha-modified Becke–Johnson functional significantly improves the band gap. • We predict a direct band gap in all of the considered LiCdX compounds. • Origin of the peaks in the optical spectra is determined. - Abstract: The structural, electronic and optical properties of the LiCdN, LiCdP, LiCdAs and LiCdSb filled-tetrahedral compounds have been explored from first-principles. The calculated structural parameters are consistent with the available experimental results. Since DFT with the common LDA and GGA underestimates the band gap, we use a new developed functional able to accurately describe the electronic structure of semiconductors, namely the Tran–Blaha-modified Becke–Johnson potential. The four investigated compounds demonstrate semiconducting behavior with direct band gap ranging from about 0.32 to 1.65 eV. The charge-carrier effective masses are evaluated at the topmost valence band and at the bottommost conduction band. The evolution of the value and nature of the energy band gap under pressure effect is also investigated. The frequency-dependent complex dielectric function and some macroscopic optical constants are estimated. The microscopic origins of the structures in the optical spectra are determined in terms of the calculated energy band structures.

36 MATERIALS SCIENCE↗

Low-temperature heat capacity and localized vibrational modes in natural and synthetic tetrahedrites

The heat capacity of natural (Cu{sub 12−x} (Fe, Zn, Ag){sub x}(Sb, As){sub 4}S{sub 13}) and synthetic (Cu{sub 12−x}Zn{sub x}Sb{sub 4}S{sub 13} with x = 0, 1, 2) tetrahedrite compounds was measured between 2 K and 380 K. It was found that the temperature dependence of the heat capacity can be described using a Debye term and three Einstein oscillators with characteristic temperatures that correspond to energies of ∼1.0 meV, ∼2.8 meV, and ∼8.4 meV. The existence of localized vibrational modes, which are assigned to the displacements of the trigonally coordinated Cu atoms in the structure, is discussed in the context of anharmonicity and its effect on the low lattice thermal conductivity exhibited by these compounds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ultrahigh sensitive sub-terahertz detection by InP-based asymmetric dual-grating-gate high-electron-mobility transistors and their broadband characteristics

We report on room-temperature plasmonic detection of sub-terahertz radiation by InAlAs/InGaAs/InP high electron mobility transistors with an asymmetric dual-grating-gate structure. Maximum responsivities of 22.7 kV/W at 200 GHz and 21.5 kV/W at 292 GHz were achieved under unbiased drain-to-source condition. The minimum noise equivalent power was estimated to be 0.48 pW/Hz{sup 0.5} at 200 GHz at room temperature, which is the record-breaking value ever reported for plasmonic THz detectors. Frequency dependence of the responsivity in the frequency range of 0.2–2 THz is in good agreement with the theory.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Single photon emission at 1.55 μm from charged and neutral exciton confined in a single quantum dash

We investigate charged and neutral exciton complexes confined in a single self-assembled InAs/InGaAlAs/InP quantum dash emitting at 1.55 μm. The emission characteristics have been probed by measuring high-spatial-resolution polarization-resolved photoluminescence and cross-correlations of photon emission statistics at T = 5 K. The photon auto-correlation histogram of the emission from both the neutral and charged exciton indicates a clear antibunching dip with as-measured g{sup (2)}(0) values of 0.18 and 0.31, respectively. It proves that these exciton complexes confined in single quantum dashes of InP-based material system can act as true single photon emitters being compatible with standard long-distance fiber communication technology.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Temperature dependence of ballistic mobility in a metamorphic InGaAs/InAlAs high electron mobility transistor

We have investigated the temperature dependence of ballistic mobility in a 100 nm-long InGaAs/InAlAs metamorphic high-electron-mobility transistor designed for millimeter-wavelength RF applications. To extract the temperature dependence of quasi-ballistic mobility, our experiment involves measurements of the effective mobility in the low-bias linear region of the transistor and of the collision-dominated Hall mobility using a gated Hall bar of the same epitaxial structure. The data measured from the experiment are consistent with that of modeled ballistic mobility based on ballistic transport theory. These results advance the understanding of ballistic transport in various transistors with a nano-scale channel length that is comparable to the carrier's mean free path in the channel.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermal conduction in lattice–matched superlattices of InGaAs/InAlAs

Understanding the relative importance of interface scattering and phonon-phonon interactions on thermal transport in superlattices (SLs) is essential for the simulation of practical devices, such as quantum cascade lasers (QCLs). While several studies have looked at the dependence of the thermal conductivity of SLs on period thickness, few have systematically examined the effect of varying material thickness ratio. Here, we study through-plane thermal conduction in lattice-matched In{sub 0.53}Ga{sub 0.47}As/In{sub 0.52}Al{sub 0.48}As SLs grown by metalorganic chemical vapor deposition as a function of SL period thickness (4.2 to 8.4 nm) and layer thickness ratio (1:3 to 3:1). Conductivities are measured using time-domain thermoreflectance and vary between 1.21 and 2.31 W m{sup −1} K{sup −1}. By studying the trends of the thermal conductivities for large SL periods, we estimate the bulk conductivities of In{sub 0.53}Ga{sub 0.47}As and In{sub 0.52}Al{sub 0.48}As to be approximately 5 W m{sup −1} K{sup −1} and 1 W m{sup −1} K{sup −1}, respectively, the latter being an order of magnitude lower than theoretical estimates. Furthermore, we find that the Kapitza resistance between alloy layers has an upper bound of ≈0.1 m{sup 2} K GW{sup −1}, and is negligible compared to the intrinsic alloy resistances, even for 2 nm thick layers. A phonon Boltzmann transport model yields good agreement with the data when the alloy interfaces are modeled using a specular boundary condition, pointing towards the high-quality of interfaces. We discuss the potential impact of these results on the design and operation of high-power QCLs comprised of In{sub 1−x}Ga{sub x}As/In{sub 1−y}Al{sub y}As SL cores.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Anomalous lasing of high-speed 850 nm InGaAlAs oxide-confined vertical-cavity surface-emitting lasers with a large negative gain-to-cavity wavelength detuning

The impact of a large negative quantum well gain-to-cavity etalon wavelength detuning on the static and dynamic characteristics of 850 nm InGaAlAs high-speed oxide-confined vertical-cavity surface-emitting lasers (VCSELs) was investigated. Three distinct lasing regimes were revealed in large square aperture (≥7 μm per side) devices with large detuning including: (1) an anomalous lasing via higher order Hermite–Gaussian modes at low forward bias current; (2) lasing via the lowest order Hermite–Gaussian modes at high bias current; and (3) simultaneous lasing via both types of transverse modes at intermediate bias currents. In contrast to conventional multimode VCSELs a two-resonance modulation response was observed for the case of co-lasing via multiple transverse modes with high spectral separation. The reduction in the oxide aperture area resulted in classical lasing via the lowest order modes with a conventional single-resonance frequency response.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

High power operation of λ ∼ 5.2–11 μm strain balanced quantum cascade lasers based on the same material composition

A technique based on composite quantum wells for design and growth of strain balanced Al{sub 0.63}In{sub 0.37}As/Ga{sub 0.35}In{sub 0.65}As/Ga{sub 0.47}In{sub 0.53}As quantum cascade lasers (QCLs) by molecular beam epitaxy (MBE), emitting in 5.2–11 μm wavelength range, is reported. The strained Al{sub 0.63}In{sub 0.37}As provides good electron confinement at all wavelengths, and strain balancing can be achieved through composite wells of Ga{sub 0.35}In{sub 0.65}As/Ga{sub 0.47}In{sub 0.53}As for different wavelength. The use of these fixed composition materials can avoid the need for frequent calibration of a MBE reactor to grow active regions with different strain levels for different wavelengths. Experimental results for QCLs emitting at 5.2, 6.7, 8.2, 9.1, and 11 μm exhibit good wall plug efficiencies and power across the whole wavelength range. It is shown that the emission wavelength can be predictably changed using the same design template. These lasers are also compatible with a heterogeneous broadband active region, consisting of multiple QCL cores, which can be produced in a single growth run.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Optical spin polarization and Hanle effect in GaAsSb: Temperature dependence

Continuous-wave optical orientation spectroscopy and the Hanle effect are used to investigate the optical spin polarization and spin dephasing time (gT{sub s}) in GaAsSb with a Sb concentration of ∼6% as a function of temperature. Optical and spin polarizations up to ∼21% were achieved at ∼120 K, and the scaled spin lifetime gT{sub s} decreased monotonously from ∼1.5 ns at 5 K to ∼20 ps at 200 K. We demonstrate that the spin properties of GaAs could be modified by incorporating a small percentage of Sb into it, as a result of an increase in the spin–orbit interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Comparative analysis of quantum cascade laser modeling based on density matrices and non-equilibrium Green's functions

We study the operation of an 8.5 μm quantum cascade laser based on GaInAs/AlInAs lattice matched to InP using three different simulation models based on density matrix (DM) and non-equilibrium Green's function (NEGF) formulations. The latter advanced scheme serves as a validation for the simpler DM schemes and, at the same time, provides additional insight, such as the temperatures of the sub-band carrier distributions. We find that for the particular quantum cascade laser studied here, the behavior is well described by simple quantum mechanical estimates based on Fermi's golden rule. As a consequence, the DM model, which includes second order currents, agrees well with the NEGF results. Both these simulations are in accordance with previously reported data and a second regrown device.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗