Semiconductors with chiral geometries at the nanoscale and mesoscale provide a rich materials platform for polarization optics, photocatalysis, and biomimetics. Unlike metallic and organic optical materials, the relationship between the geometry of chiral semiconductors and their chiroptical properties remains, however, vague. Homochiral ensembles of semiconductor helices with defined geometries open the road to understanding complex relationships between geometrical parameters and chiroptical properties of semiconductor materials. We show that semiconductor helices can be prepared with an absolute yield of ca 0.1% and an enantiomeric excess (e.e.) of 98% or above from cysteine-stabilized cadmium telluride nanoparticles (CdTe NPs) dispersed in methanol. This high e.e. for a spontaneously occurring chemical process is attributed to chiral self-sorting based on the thermodynamic preference of NPs to assemble with those of the same handedness. The dispersions of homochiral self-assembled helices display broadband visible and near-infrared (Vis-NIR) polarization rotation with anisotropy (g) factors approaching 0.01. Calculated circular dichroism (CD) spectra accurately reproduced experimental CD spectra and gave experimentally validated spectral predictions for different geometrical parameters enabling de novo design of chiroptical semiconductor materials. Unlike metallic, ceramic, and polymeric helices that serve predominantly as scatterers, chiroptical properties of semiconductor helices have nearly equal contribution of light absorption and scattering, which is essential for device-oriented, field-driven light modulation. Deconstruction of a helix into a series of nanorods provides a simple model for the light-matter interaction and chiroptical activity of helices. This study creates a framework for further development of polarization-based optics toward biomedical applications, telecommunications, and hyperspectral imaging.
We are developing room temperature compound semiconductor detectors for applications in energy-resolved high-flux single x-ray photon-counting spectral computed tomography (CT), including functional imaging with nanoparticle contrast agents for medical applications and non destructive testing (NDT) for security applications. Energy-resolved photon-counting can provide reduced patient dose through optimal energy weighting for a particular imaging task in CT, functional contrast enhancement through spectroscopic imaging of metal nanoparticles in CT, and compositional analysis through multiple basis function material decomposition in CT and NDT. These applications produce high input count rates from an x-ray generator delivered to the detector. Therefore, in order to achieve energy-resolved single photon counting in these applications, a high output count rate (OCR) for an energy-dispersive detector must be achieved at the required spatial resolution and across the required dynamic range for the application. The required performance in terms of the OCR, spatial resolution, and dynamic range must be obtained with sufficient field of view (FOV) for the application thus requiring the tiling of pixel arrays and scanning techniques. Room temperature cadmium telluride (CdTe) and cadmium zinc telluride (CdZnTe) compound semiconductors, operating as direct conversion x-ray sensors, can provide the required speed when connected to application specific integrated circuits (ASICs) operating at fast peaking times with multiple fixed thresholds per pixel provided the sensors are designed for rapid signal formation across the x-ray energy ranges of the application at the required energy and spatial resolutions, and at a sufficiently high detective quantum efficiency (DQE). We have developed high-flux energy-resolved photon-counting x-ray imaging array sensors using pixellated CdTe and CdZnTe semiconductors optimized for clinical CT and security NDT. We have also fabricated high-flux ASICs with a two dimensional (2D) array of inputs for readout from the sensors. The sensors are guard ring free and have a 2D array of pixels and can be tiled in 2D while preserving pixel pitch. The 2D ASICs have four energy bins with a linear energy response across sufficient dynamic range for clinical CT and some NDT applications. The ASICs can also be tiled in 2D and are designed to fit within the active area of the sensors. We have measured several important performance parameters including; the output count rate (OCR) in excess of 20 million counts per second per square mm with a minimum loss of counts due to pulse pile-up, an energy resolution of 7 keV full width at half maximum (FWHM) across the entire dynamic range, and a noise floor about 20keV. This is achieved by directly interconnecting the ASIC inputs to the pixels of the CdZnTe sensors incurring very little input capacitance to the ASICs. We present measurements of the performance of the CdTe and CdZnTe sensors including the OCR, FWHM energy resolution, noise floor, as well as the temporal stability and uniformity under the rapidly varying high flux expected in CT and NDT applications.
The increasing industrial utilization of tellurium has resulted in an important environmental pollution with the soluble, extremely toxic oxyanion tellurite. In this context, the use of microorganisms for detoxifying tellurite or tellurium biorecovery has gained great interest. The ability of different Shewanella strains to reduce tellurite to elemental tellurium was assessed; the results showed that the reduction process is dependent on electron transport and the ∆pH gradient. While S. baltica OS155 showed the highest tellurite resistance, S. putrefaciens was the most efficient in reducing tellurite. Moreover, pH-dependent tellurite transformation was associated with tellurium precipitation as tellurium dioxide. In summary, this work highlights the high tellurite reduction/detoxification ability exhibited by a number of Shewanella species, which could represent the starting point to develop friendly methods for the recovery of elemental tellurium (or tellurium dioxide).
A sampling trip to Central Gold Mine, Nopiming Provincial Park, Canada, was taken in September 2011. Abundance, distribution, and physiology of aerobic anoxygenic phototrophs (AAP) from 4 locations were studied. Enumeration revealed 14.6% of culturable microbes were AAP. Five strains (NM4.16, NM4.18, C4, C9, C11) were chosen for analysis. All grow best on complex media without vitamin requirements and with an optimal pH 7.0-8.0, with strain C4 preferring pH 6.0. Strain NM4.18 tolerates the highest pH 11.0. Optimal temperature for all is 28 °C (range of 2-37 °C except NM4.16, which survives 45 °C). Strains C9, C11, and NM4.18 grew in 1.0%, 2.0%, and 5.0% NaCl, respectively, while NM4.16 and C4 grew only without NaCl. Isolates were all highly resistant to toxic metal(oid) oxides: tellurite (1500 μg/mL, all), tellurate (1500 μg/mL, C11), selenite (5000 μg/mL, C9, C11, and NM4.18), selenate (1000 μg/mL, C9 and C11), and orthometavanadate and metavanadate (5000 μg/mL, C11 and NM4.18). They could reduce tellurite to the less toxic elemental tellurium. Full 16S rRNA gene sequencing revealed all strains are Alphaproteobacteria, with C4 and NM4.16 closely related to Porphyrobacter colymbi (99.4% and 99.7% sequence similarity, respectively), C9 to Brevundimonas variabilis (99.1%), C11 to Brevundimonas bacteroides (98.6%), and NM4.18 to Erythromonas ursincola (98.5%).
The conversion of chalcogen atoms to other types in transition metal dichalcogenides has significant advantages for tuning bandgaps and constructing in-plane heterojunctions; however, difficulty arises from the conversion of sulfur or selenium to tellurium atoms owing to the low decomposition temperature of tellurides. Here, we propose the use of sodium for converting monolayer molybdenum disulfide (MoS2) to molybdenum ditelluride (MoTe2) under Te-rich vapors. Sodium easily anchors tellurium and reduces the exchange barrier energy by scooting the tellurium to replace sulfur. The conversion was initiated at the edges and grain boundaries of MoS2, followed by complete conversion in the entire region. By controlling sodium concentration and reaction temperature of monolayer MoS2, we tailored various phases such as semiconducting 2H-MoTe2, metallic 1T'-MoTe2, and 2H-MoS2-x Te x alloys. This concept was further extended to WS2. A high valley polarization of ~37% in circularly polarized photoluminescence was obtained in the monolayer WS2-x Te x alloy at room temperature.
The ability to solution deposit semiconductor films has received a great deal of recent attention as a way to potentially lower costs for many optoelectronic applications; however, most bulk semiconductors are insoluble in common solvents. Here we describe a novel and relatively nonhazardous binary solvent mixture comprised of 1,2-ethanedithiol and 1,2-ethylenediamine that possesses the remarkable ability to rapidly dissolve a series of nine bulk V2VI3 chalcogenides (V = As, Sb, Bi; VI = S, Se, Te) at room temperature and atmospheric pressure. After solution deposition and low-temperature annealing, the chalcogenides can be fully recovered as good quality, highly crystalline thin films with negligible organic content, as demonstrated for Sb2Se3 and Bi2S3.
High tech applications, primarily photovoltaics, have greatly increased demand for the rare and versatile but toxic element tellurium (Te). Here we examine dated lake sediment Te concentration profiles collected near potential point sources (metal smelters, coal mining/combustion facilities, oil sands operations) and from rural regions and remote natural areas of Canada. Te contamination was most prevalent near a Cu/Zn smelter where observed deposition infers 21 g Te released per metric ton (t) of Cu processed. Globally, 9,500 t is predicted to have been atmospherically deposited near Cu smelters post-1900. In a remote area of central Canada (Experimental Lakes Area; ELA), preindustrial Te deposition rates were equivalent to the estimated average global mass flux supplied from natural sources; however more surprisingly, modern Te deposition rates were 6-fold higher and comparable with Te measurements in precipitation. We therefore suggest that sediment cores reliably record atmospheric Te deposition and that anthropogenic activities have significantly augmented atmospheric Te levels, making it an emerging contaminant of potential concern. Lake water residence time was found to influence lake sediment Te inventories among lakes within a region. The apparent settling rate for Te was comparable to macronutrients (C, N, P), likely indicative of significant biological processing of Te.
We propose a general strategy to synthesize largely unexplored soluble chalcogenidometallates of cadmium, lead and bismuth. These compounds can be used as “solders” for semiconductors widely used in photovoltaics and thermoelectrics. The addition of solder helped to bond crystal surfaces and link nano- or mesoscale particles together. For example, CdSe nanocrystals with Na2Cd2Se3 solder was used as a soluble precursor for CdSe films with electron mobilities exceeding 300 centimeters squared per volt-second. CdTe, PbTe and Bi2Te3 powders were molded into various shapes in the presence of a small additive of composition-matched chalcogenidometallate or chalcogel, thus opening new design spaces for semiconductor technologies.
Bulk tellurium (Te) is composed of one-dimensional (1D) helical chains which have been considered to be coupled by van der Waals (vdW) interactions. However, on the basis of first-principles density functional theory calculations, we here propose a different bonding nature between neighboring chains: i.e., helical chains made of normal covalent bonds are connected together by coordinate covalent bonds. It is revealed that the lone pairs of electrons of Te atoms participate in forming coordinate covalent bonds between neighboring chains, where each Te atom behaves as both an electron donor to neighboring chains and an electron acceptor from neighboring chains. This ligand-metal-like bonding nature in bulk Te results in the same order of bulk moduli along the directions parallel and perpendicular to the chains, contrasting with the large anisotropy of bulk moduli in vdW crystals. We further find that the electron effective masses parallel and perpendicular to the chains are almost the same as each other, consistent with the observed nearly isotropic electrical resistivity. It is thus demonstrated that the normal/coordinate covalent bonds parallel/perpendicular to the chains in bulk Te lead to a minor anisotropy in structural and transport properties.
In this paper, we report on the use of CuInX2 (X = Te, Se, S) as a cation supply layer in filamentary switching applications. Being used as absorber layers in solar cells, we take advantage of the reported Cu ionic conductivity of these materials to investigate the effect of the chalcogen element on filament stability. In-situ XRD showed material stability attractive for Back-End-Of-Line in semiconductor industry. When integrated in 580 μm diameter memory cells, more volatile switching was found at low compliance current using CuInS2 and CuInSe2 compared to CuInTe2, which is ascribed to the natural tendency for Cu to diffuse back from the switching layer to the cation supply layer, to form energetically more preferred Cu-S and Cu-Se bonds. Low-current and scaled behavior was also confirmed using C-AFM. Hence, by varying the chalcogen element, a method is presented to modulate the filament stability.