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At least 667 records · Page 37

Semiconductor-Based, Solar-Driven Photochemical Cells for Fuel Generation from Carbon Dioxide in Aqueous Solutions

There has been active interest to identify new methods to reduce CO 2 into usable fuel sources. In this work, we demonstrate two types of photo-electrochemical cells (PECs) that photoreduce CO 2 directly to formate in aqueous solutions both in the presence and absence of external bias or additional electron sources. The photocathodes were either a CuFeO 2 /CuO electrode or a bilayer of CdTe on NiO, whereas the photoanode was a bilayer of NiO x on CdS. The PECs were characterized by using both electrochemistry and spectroscopy, and the products formed from CO 2 reduction were characterized and quantified by using 1 H NMR spectroscopy and ESI-MS. In addition, an organohydride catalyst was tested in conjunction with the PECs, which not only showed a significant gain of 85 times in CO 2 reduction (27 μm formate without the catalyst, 2.3 mm formate with it) compared to the NiO/CdTe photocathode system but could also generate methanol under an external bias (10 μm).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Application of copper thiocyanate for high open‐circuit voltages of CdTe solar cells

Abstract Copper thiocyanate (CuSCN) has proven to be a low‐cost, efficient hole‐transporting material for the emerging organic–inorganic perovskite solar cells. Herein, we report that CuSCN can also be applied to CdTe thin‐film solar cells to achieve high open‐circuit voltages ( V OC s). By optimizing the thickness of the thermally evaporated CuSCN films, CdTe cells fabricated by close space sublimation in the superstrate configuration have achieved V OC s as high as 872 mV, which is about 20–25 mV higher than the highest V OC for the reference cells using the standard Cu/Au back contacts. CuSCN is a wide bandgap p ‐type conductor with a conduction band higher than that of CdTe, leading to a conduction band offset that reflects electrons in CdTe, partially explaining the improved V OC s. However, due to the low conductivity of CuSCN, CdTe cells using CuSCN/Au back contacts exhibited slightly lower fill factors than the cells using Cu/Au back contacts. With optimized CdS:O window layers, the power conversion efficiency of the best CdTe cell, using CuSCN/Au back contact, is 14.7%: slightly lower than that of the best cell (15.2%) using Cu/Au back contact. Copyright © 2015 John Wiley & Sons, Ltd.

Paudel, Naba R.↗

Accelerated development of CuSbS 2 thin film photovoltaic device prototypes

Development of alternative thin film photovoltaic technologies is an important research topic because of the potential of low-cost, high-efficiency solar cells to produce terawatt levels of clean power. However, this development of unexplored yet promising absorbers can be hindered by complications that arise during solar cell fabrication. Here, a high-throughput combinatorial method is applied to accelerate development of photovoltaic devices, in this case, using the novel CuSbS2 absorber via a newly developed three-stage self-regulated growth process to control absorber purity and orientation. Photovoltaic performance of the absorber, using the typical substrate CuInxGa1 - xSe2 (CIGS) device architecture, is explored as a function of absorber quality and thickness using a variety of back contacts. This study yields CuSbS2 device prototypes with ~1% conversion efficiency, suggesting that the optimal CuSbS2 device fabrication parameters and contact selection criteria are quite different than for CIGS, despite the similarity of these two absorbers. The CuSbS2 device efficiency is at present limited by low short-circuit current because of bulk recombination related to defects, and a small open-circuit voltage because of a theoretically predicted cliff-type conduction band offset between CuSbS2 and CdS. Overall, these results illustrate both the potential and limits of combinatorial methods to accelerate the development of thin film photovoltaic devices using novel absorbers.

14 SOLAR ENERGY↗

Locating the electrical junctions in Cu(In,Ga)Se 2 and Cu 2 ZnSnSe 4 solar cells by scanning capacitance spectroscopy

Here, we determined the electrical junction (EJ) locations in Cu(In,Ga)Se 2 (CIGS) and Cu 2 ZnSnSe 4 (CZTS) solar cells with ~20-nm accuracy by developing scanning capacitance spectroscopy (SCS) applicable to the thin-film devices. Cross-sectional sample preparation for the SCS measurement was developed by high-energy ion milling at room temperature for polishing the cross section to make it flat, followed by low-energy ion milling at liquid nitrogen temperature for removing the damaged layer and subsequent annealing for growing a native oxide layer. The SCS shows distinct p-type, transitional, and n-type spectra across the devices, and the spectral features change rapidly with location in the depletion region, which results in determining the EJ with ~20-nm resolution. We found an n-type CIGS in the region next to the CIGS/CdS interface; thus, the cell is a homojunction. The EJ is ~40 nm from the interface on the CIGS side. In contrast, such an n-type CZTS was not found in the CZTS/CdS cells. The EJ is ~20 nm from the CZTS/CdS interface, which is consistent with asymmetrical carrier concentrations of the p-CZTS and n-CdS in a heterojunction cell. Our results of unambiguously determination of the junction locations contribute significantly to understanding the large open-circuit voltage difference between CIGS and CZTS.

14 SOLAR ENERGY↗

Revealing the beneficial role of K in grain interiors, grain boundaries, and at the buffer interface for highly efficient CuInSe 2 solar cells

K incorporation within grain boundaries, grain interiors, and interfaces has been studied within CuInSe 2 solar cells to better understand the beneficial or detrimental role of K distribution among these regions in chalcopyrite–based solar cells. Solar cells have been fabricated with intentional K introduction into specific regions of the device including the CuInSe 2 /CdS interface (CuInSe 2 /KInSe 2 /CdS) and the grain interiors (Cu 0.93 K 0.07 InSe 2 /CdS). A control CuInSe 2 /CdS device was also studied to separate effects of K originating from the soda–lime glass substrate from those of intentionally introduced K. The experiment was designed to understand K effects in Cu(In,Ga)Se 2 solar cells while mitigating complications from multiple elements in the 3 + site. The distribution of all elements within these samples has been directly observed with sub–nm resolution via atom probe tomography. In addition, electron beam–induced current measurements have been performed to correlate the atom probe tomography compositional profiles to the nanoscale carrier collection properties. The experiments show that a large decrease in the Cu/In ratio at the CdS interface can be achieved by forming KInSe 2 at the absorber surface, which drastically improves the device efficiency. The results presented here show a direct link between K concentration, Cu depletion, and In accumulation, such that the Cu/In ratio significantly reduces with K incorporation. In conclusion, the findings help clarify the mechanism behind K–induced efficiency enhancement.

14 SOLAR ENERGY↗

Behavior of Na and RbF-Treated CdS/Cu(In,Ga)Se 2 Solar Cells with Stress Testing under Heat, Light, and Junction Bias

In this work, the effects of Na and RbF alkali treatment on the metastability behavior of CdS/Cu(In,Ga)Se 2 solar cells are investigated with stress factors of heat, junction bias, and illumination. Four device types with and without Na or RbF treatments are subjected to heat- and light-soaking under open- and short-circuit (OC, SC) junction bias. Low-Na devices show a higher bandgap due to increased minimum Ga content, higher recombination current, and lower open-circuit voltage (V OC ). Devices with RbF post-deposition treatment (PDT) show an improvement in net doping density ≈10 16 cm –3 , V OC , and efficiency. Heat- and light-soaking under OC junction bias provokes an increase in net carrier concentration and V OC irrespective of the alkali treatments. After SC stress, a decrease in V OC and net carrier concentration is observed, which can be stabilized by RbF-PDT. An increase in Na and oxygen concentration in CIGS is observed for baseline and low-Na devices, respectively, after OC stress. The oxygen concentration in CdS decreases after heat- and light-soaking for devices without RbF-PDT, whereas it remains unchanged for devices with RbF-PDT. The atomic concentration profiles in CIGS significantly stabilize as a function of stress with the addition of RbF-PDT.

14 SOLAR ENERGY↗

Emission from Crystals Irradiated with a Beam of Runaway Electrons

An investigation of the spectral and amplitude-temporal characteristics of emission from different crystals, promising in terms of their application as detectors of runaway electrons, is performed. This emission is excited by subnanosecond electron beams generated in a gas diode. It is found out that at the electron energies of tens–hundreds of kiloelectronvolts, the main contribution into the emission from CsI, ZnS, type IIa artificial and natural diamonds, sapphire, CaF{sub 2}, ZrO{sub 2}, Ga{sub 2}O{sub 3}, CaCO{sub 3}, CdS, and ZnSe crystals comes from the cathodoluminescence; the radiation pulse duration depends on the crystal used and sufficiently exceeds the Cherenkov radiation pulse duration. It is demonstrated that the latter radiation exhibits low intensity and can be detected in the short-wave region of the spectrum in the cases where a monochromator and a high-sensitivity photomultiplier tube (PMT) are used.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High-Resolution Electron Microscopy and Kinetic Studies of Precipitation Hardening Reactions in Cast Al-5.8Zn-2.2Mg-2.5Cu

Precipitation age hardening (T6) response of Al-5.8Zn-2.2Mg-2.5Cu alloy in near-net-shaped cast condition was investigated. Cast samples were manufactured using the controlled diffusion solidification (CDS) technology combined with a metallic mold tilt pour gravity casting process. This study was conducted using (1) non-isothermal aging during differential scanning calorimetry (DSC) experiments and (2) isothermal aging during which transient bulk and micro-hardness measurements taken at four aging temperatures of 343, 393, 433 and 473 K. A detailed microstructural investigation combined with a quantitative image analysis was carried out on both DSC and hardness specimens using high-resolution electron microscopy (HREM) and energy-dispersive spectroscopy (EDS) elemental mappings. Hardness measurements were analyzed using a kinetic modeling approach (single state variable combined with a kinetic equation that is valid for the Al-Zn-Mg-Cu alloys). The results confirm the formation of hardening phases of GP zone, intermediate hardening metastable phase η′ and equilibrium phase η. The results of calorimetric measurements, electron microscopy and selected area diffraction patterns are in good agreement and confirm transient precipitation/dissolution sequences. A mean value of activation energy Q{sub A} of 75 kJ/mol was evaluated for combined bulk diffusion rate of alloying elements during precipitation of strengthening phases within Al matrix.

36 MATERIALS SCIENCE↗

Adenosine stress myocardial perfusion imaging in octogenarians: Safety, tolerability, and long-term prognostic implications of hemodynamic response and SPECT-related variables

Background: Evaluation of tolerability, safety, and prognostic implications of adenosine stress myocardial perfusion imaging (MPI) in octogenarians. Methods: 370 octogenarians (49% known coronary artery disease) were studied. Hemodynamic response, MPI-related data, and rest-left ventricular ejection fraction (LVEF) based on echocardiography were registered per patient, and prospective follow-up was performed to document all-cause death (ACD), cardiac death (CD), myocardial infarction (MI), and late revascularization. Results: No deaths or MIs were observed during adenosine infusion or the short-term post-infusion period. 86% of patients were able to tolerate a 6-minute infusion. All side effects terminated spontaneously after infusion cessation, except for one case of pulmonary oedema. After 9.3 years, there were 124 ACDs, 62 CDs, 16 MIs, and 35 revascularizations. Differences between survival curves of summed stress score (SSS)-based risk groups were significant for all end points (P < .001). SSS and LVEF were independent predictors of all end points (P ≤ .01) and lung uptake of cardiac end points. ΔHR <10 bpm (OR = 1.78, P = .004) and inability to increase HR by >10 bpm and decrease systolic blood pressure by >10 mmHg (OR = 2, P = .02) during adenosine infusion were independent predictors of ACD and CD, respectively. Hemodynamic response variables, SSS, and lung uptake provided incremental prognostic value over pre-test data for ACD and CD. Conclusions: In octogenarians, adenosine stress MPI is well tolerated and provides effective long-term risk stratification.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Bis–Calix[4]pyrroles: Preparation, structure, complexation properties and beyond

Calix[4]pyrrole and its derivatives are key members of the supramolecular Parthenon along with other well-recognized receptor systems, such as crown ethers, cyclodextrins (CDs), cucurbiturils, calixarenes and pillararenes. Calix[4]pyrroles are relatively easy–to–make and widely recognized for their ability to bind anions and ion pairs. Many review papers relating to aspects of calix[4]pyrrole chemistry have been published within the past decades. These reviews have focused primarily on monomeric calix[4]pyrroles. The emergent area of Bis–calix[4]pyrroles, species wherein two calix[4]pyrrole subunits are linked by one or more “walls”, has not benefited from such treatment, even though the species in question often exhibit enhanced binding affinities and selectivities relative to their single calix[4[pyrrole congeners. This review is designed to summarize recent progress involving bis–calix[4]pyrroles. Advances in the design, synthesis, and coordination chemistry of bis–calix[4]pyrroles containing “one wall”, “two walls”, “three walls”, and “four walls”, as well as their possible application in ion recognition, sensing and logic gate construction, will be detailed. Lastly, the hope is that this review will provide a guide for the design and preparation of new multi-component calix[4]pyrrole receptors possessing improved recognition properties, thereby advancing host–guest chemistry in new and useful directions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Submicron-scale mineralogy of lithotypes and the implications for trace element associations: Blue Gem coal, Knox County, Kentucky

Transmission electron microscopy accompanied by energy-dispersive spectroscopy and selected area electron diffraction of density-gradient separates from two lithotypes of the low-ash, low-sulfur Blue Gem coal, eastern Kentucky, revealed an array of previously unrecognized (in this coal, and arguable in most others) sub-micron minerals, some <10 nm in size. The first sample representing the 1.22–1.24 specific gravity fraction of the middle bench contains a mineral identified as a La-, Ce-, Nd-bearing monazite; other minerals with CrFe, CuFeS, FeZn-S, and Pb; and areas, probably comprising agglomerates of several grains, if not several minerals, with concentrations of Mg, Ca, Ti, Fe, Zn, Zr, and Mo. The second sample representing the 1.30–1.31 specific gravity fraction of the basal lithotype has aggregates of particles enriched in Mg, Ca, Ti, and Fe. Individual grains not specifically quantified include CrNiMnCuFeS, AgS, and CuS. Detailed investigation of one area (most of the variation within a <4 μm 2 region) demonstrates the presence of greenockite (CdS); minute phases containing NiCoGe and AgCdBi, the latter with a more evident S association than the former; metallic Bi; nisnite (Ni 3 Sn); silver cadmium; manganosite (MnO); and siderite. Some minerals, such as the monazite, are most likely of detrital or tuffaceous origin. Many of the other assemblages could be of hydrothermal origin, a hypothesis supported by known regional geochemical and coal rank trends, but not previously demonstrated in mineral assemblages at the 10's of nm scale in this region.

01 COAL, LIGNITE, AND PEAT↗

Advances in multi-dimensional cellulose-based fluorescent carbon dot composites

Recently, fluorescent materials composed of carbon dots (CDs) have attracted increasing attention in diverse fields, including the environment, food, biology, and medicine. Cellulose has emerged as a promising class of materials for carriers due to its low cost, fascinating biodegradability, and various morphologies, especially in available different dimensions. By taking advantage of the respective superiority of fluorescent materials and cellulose carriers, the performance of fluorescence composite materials can be optimized and their application may be extended. Here, in this review, the study emphasizes the synthesis and applications of cellulose-based fluorescent materials with different dimensions. Moreover, some effective strategies and potential challenges for further development of cellulose-based fluorescent materials are discussed. A deeper understanding will provide a guide for the materials with ideal fluorescent performances.

42 ENGINEERING↗

Behaviour of cadmium isotopes in sulfidic waters and sediments of the Black Sea: Implications for global cadmium cycling and the application of cadmium isotopes as a paleo-oceanographic proxy

The cadmium isotope system has found use as a tracer for biological productivity, redox and organic carbon burial in the oceans. There are, however, very few observational constraints on Cd isotopic behaviour in modern sulfidic marine conditions, limiting our understanding of the modern Cd cycle, and our ability to use Cd isotope measurements of ancient sedimentary deposits as a paleoceanographic proxy. Here we study the behaviour of dissolved Cd in the water column of the Black Sea and its incorporation into sediments on the basin floor. The isotopic composition of dissolved Cd in the upper ∼50 m of the Black Sea water column is controlled by a combination of biological uptake and regeneration along with mixing of river water and Mediterranean seawater. Cadmium declines to <2 % of its peak subsurface concentration within the zone of nitrate-reduction but above the sulfide chemocline. The isotopic composition of dissolved Cd below the sulfide chemocline evolves in a manner that is consistent with experimental Cd sulfide fractionation factors, providing field-based support for these earlier studies. In contrast, the stability of the dissolved Cd isotopic signature above the chemocline, despite a large reduction in dissolved Cd concentrations, is explained by diffusion towards the Cd-sulfide sink below the chemocline. Sediments accumulating in the deep Black Sea below the sulfide chemocline have isotopic compositions that are similar to dissolved Cd in its near-surface aqueous concentration maximum. Sediments accumulating at shallower depths have lighter isotopic compositions that are likely affected by non-sulfidic burial pathways mediated by macrofaunal mixing and diagenesis of shallow burial phases. Our study shows that the isotopic composition of bulk sediments accumulating under sulfidic conditions is similar to dissolved Cd in the upper water column, supporting its use as a paleo-chemical proxy for ancient seawater as long as basin-scale controls on open ocean seawater sources are considered. We show that Cd burial in the deep Black Sea, predominantly as CdS, accounts for ∼0.5–15 % of total annual Cd burial in the global ocean.

Biogeochemical cycles↗

Model predictive current profile control in tokamaks by exploiting spatially moving electron cyclotron current drives

The plasma control systems in next-generation tokamaks like ITER will balance competing control objectives to achieve the desired level of performance in advanced scenarios while preventing magnetohydrodynamic instabilities and disruptions. During normal tokamak operation, the points of incidence of the electromagnetic waves generated by the electron cyclotron heating and current drives (EC H&CDs) are usually fixed in space. However, the points of incidence can be modified in real-time by changing the angles of the mirrors that reflect the EC H&CD waves. Altering the points of incidence, in turn, varies the ability of the plasma control system to regulate a plasma property. For instance, changing the EC H&CD wave incidence location may place the power demands necessary to achieve a particular plasma target within saturation limits. Therefore, using the EC H&CD deposition location, which is related to the EC H&CD mirror angle, as a supplementary controllable variable may facilitate access to a given target scenario. However, active scenario-control algorithms have not been designed so far to fully exploit this capability in real time. In this work, a model predictive controller that can handle actuation locations as control inputs is developed. In particular, the controller is designed to regulate both the auxiliary powers and the EC H&CD deposition locations in a pre-defined optimal sense to achieve the control objective of attaining and sustaining a target current profile. Further, the proposed controller is tested for a DIII-D tokamak scenario in nonlinear simulations using the Control Oriented Transport SIMulator (COTSIM).

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Investigation of nanocrystalline CdS/Si diode using complex impedance spectroscopy

Highlights: ► CdS/n-Si device was fabricated as a heterostructure. ► AFM was used to examine the structure of CdS/n-Si. ► Complex impedance Z′and Z″were calculated. ► AC conductivity was explained by the power law relation. ► CBH model was used to describe the AC conduction mechanism. -- Abstract: CdS/n-Si device was fabricated via depositing CdS thin film onto pre-cleaned n-silicon substrates. The atomic force microscope was used to examine the crystal size of the deposited films and its roughness. The AC conductivity and the real part of complex impedance Z′as a function of frequency at different temperatures were studied. The AC conductivity dependence of the applied frequency was explained on the basis of the power law relation. The bulk resistance has been calculated at different temperatures from the complex impedance Z″. The temperature dependence of capacitance for CdS/n-Si device at different frequencies was also investigated.

36 MATERIALS SCIENCE↗

Microwave-assisted synthesis and photovoltaic measurements of CuInS{sub 2} nanoparticles prepared by using metal–organic precursors

Highlights: ► CuInS{sub 2} nanoparticles were prepared using complexes via a microwave-assisted method. ► The effect of preparation parameters on the morphology of CuInS{sub 2} was investigated. ► The as-deposited CdS/CuInS{sub 2} films were used for the photovoltaic measurements. -- Abstract: In this work, CuInS{sub 2} (CIS) nanoparticles have been synthesized with the aid of (1,8-diamino-3,6-dioxaoctan)copper(II) sulfate ([Cu(DADO)]SO{sub 4}) and bis(propylenediamine)copper(II) sulfate ([Cu(pn){sub 2}]SO{sub 4}) complexes as copper precursor in the presence of microwave irradiation. Besides, L-cystine, InCl{sub 3}, and sodium dodecyl sulfate (SDS) were applied as sulfur source, indium precursor, and capping agent, respectively. To investigate the effect of preparation parameters like microwave power and irradiation time on the morphology and particle size of CuInS{sub 2}, the experiment was carried out at different conditions. The as-synthesized CuInS{sub 2} nanoparticles were characterized by XRD, FT-IR, PL, SEM, TEM, and EDS. The XRD results showed that pure tetragonal CuInS{sub 2} could be only obtained after annealing at 400 °C for 2 h. The SEM images indicated that with decreasing the microwave power and irradiation time, particle size of CuInS{sub 2} nanoparticles decreased. To fabricate a solar cell, CdS film was directly deposited on top of the CIS film prepared by Doctor's blade method through chemical bath deposition. The as-deposited CdS/CuInS{sub 2} films were used for the photovoltaic measurements.

36 MATERIALS SCIENCE↗

AgSb(S{sub x}Se{sub 1−x}){sub 2} thin films for solar cell applications

Highlights: ► AgSb(S{sub x}Se{sub 1−x}){sub 2} thin films were formed by heating Na{sub 2}SeSO{sub 3} dipped Sb{sub 2}S{sub 3}/Ag layers. ► S/Se ratio was varied by changing the dipping time in Na{sub 2}SeSO{sub 3} solution. ► Characterized the films using XRD, XPS, SEM, Optical and electrical measurements. ► Band gap engineering of 1−1.1 eV for x = 0.51 and 0.52 respectively. ► PV Glass/FTO/CdS/AgSb(S{sub x}Se{sub 1−x}){sub 2}/C were prepared showing V{sub oc} = 410 mV, J{sub sc} = 5.7 mA/cm{sup 2}. - Abstract: Silver antimony sulfoselenide (AgSb(S{sub x}Se{sub 1−x}){sub 2}) thin films were prepared by heating glass/Sb{sub 2}S{sub 3}/Ag layers after selenization using sodium selenosulphate solution. First, Sb{sub 2}S{sub 3} thin films were deposited on glass substrates from a chemical bath containing SbCl{sub 3} and Na{sub 2}S{sub 2}O{sub 3}. Then Ag thin films were thermally evaporated onto glass/Sb{sub 2}S{sub 3}, followed by selenization by dipping in an acidic solution of Na{sub 2}SeSO{sub 3}. The duration of selenium dipping was varied as 30 min and 2 h. The heating condition was at 350 °C for 1 h in vacuum. Analysis of X-ray diffraction pattern of the thin films formed after heating showed the formation of AgSb(S{sub x}Se{sub 1−x}){sub 2}. Morphology and elemental analysis were done by scanning electron microscopy and energy dispersive X-ray detection. Depth profile of composition of the thin films was performed by X-ray Photoelectron Spectroscopy. The spectral study showed the presence of Ag, Sb, S, and Se, and the corresponding binding energy analysis confirmed the formation of AgSb(S{sub x}Se{sub 1−x}){sub 2}. Photovoltaic structures (PV) were prepared using AgSb(S{sub x}Se{sub 1−x}){sub 2} thin films as absorber and CdS thin films as window layers on FTO coated glass substrates. The PV structures were heated at 60–80 °C in air for 1 h to improve ohmic contact. Analysis of J–V characteristics of the PV structures showed V{sub oc} from 230 to 490 mV and J{sub sc} 0.28 to 5.70 mA/cm{sup 2}, under illumination of AM1.5 radiation using a solar simulator.

36 MATERIALS SCIENCE↗