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At least 127 records · Page 7

High-Temperature Air Stability of Electrodeposited Copper Cobalt Oxide and Copper Manganese Oxide Absorber Coatings for Concentrating Solar Power

The solar absorptance of a thermal receiver surface significantly affects the photothermal conversion efficiency of concentrating solar power (CSP) plants. The stability of solar receivers and coatings applied to improve solar absorptance at high temperatures is critical for efficient and long-term operation. This study analyzes the high-temperature air stability of multiscale fractal textured electrodeposited copper manganese oxide and copper cobalt oxide solar receiver coatings over a range of temperatures. The study also investigates the effect of high temperature on phase stability, chemical and morphological evolution, and the optical properties of the two solar absorber materials. A computational model is developed to determine the absorptance of the textured absorbers and is shown to match the experimental measurements closely over a range of heat treatment temperatures from 450 °C to 850 °C and durations up to 100 h. Degradation curves and coating stability maps are developed from the study. Copper manganese oxide and copper cobalt oxide coatings exhibit good thermal stability up to ~815 °C and 630 °C, respectively, with minimal changes in their optical and structural properties with thermal efficiency greater than 90%. Furthermore, the study offers valuable insights into the high-temperature annealing effects on the optical and structural properties of multiscale copper alloyed coatings fabricated by electrodeposition and presents a means of designing the optimal temperature range for maximizing absorber efficiency in practical applications.

14 SOLAR ENERGY↗

Mechanistic Study of Controlled Zinc Electrodeposition Behaviors Facilitated by Nanoscale Electrolyte Additives at the Electrode Interface

Nanoparticle organic hybrid materials (NOHMs) are liquid-like materials composed of an inorganic core to which a polymeric canopy is ionically tethered. NOHMs have unique properties including negligible vapor pressure, high oxidative thermal stability, and the ability to bind to reactive species of interest due to the tunability of their polymeric canopy. This makes them promising multifunctional materials for a wide range of energy and environmental technologies, including electrolyte additives for electrochemical energy storage (e.g., flow batteries) and the electrochemical conversion of CO 2 to chemicals and fuels. Due to their unique transport behaviors in fluid systems, an understanding of the near-electrode surface behavior of NOHMs in electrolyte solutions and their effect on electrochemical reactions is still lacking. In this work, the complexation of zinc (Zn) by NOHMs with an ionically tethered polyetheramine canopy (HPE) (NOHM-I-HPE) was studied using attenuated total reflectance Fourier transform infrared and Carbon-13 nuclear magnetic resonance spectroscopy. Additionally, various electrochemical techniques were employed to discern the role of NOHM-I-HPE during zinc electrodeposition, and the results were compared to those of the electrochemical system containing untethered HPE polymers. Our findings confirmed that NOHM-I-HPE and HPE reversibly complex zinc in the aqueous electrolyte. NOHM-I-HPE and HPE were found to block some of the electrode active sites, reducing the overall current density during electrodeposition, while facilitating the formation of smooth zinc deposits, as revealed by surface imaging and diffraction techniques. Observed variations in the current density responses and the degree of passivation created by the NOHM-I-HPE and HPE adsorbed on the electrode surface revealed that their different packing behaviors at the electrode–electrolyte interface influence the zinc deposition mechanism. The presence of the nanoparticle and ordering offered by the NOHMs as well as the structured conformation of the polymeric canopy allowed the formation of void spaces and free volumes for enhanced transport behaviors. Furthermore, these findings provided insights into how structured electrolyte additives such as NOHMs can allow for advancements in electrolyte design for controlled deposition of metal species from energy-dense electrolytes or for other electrochemical reactions.

25 ENERGY STORAGE↗

Understanding the Polymorphism of Cobalt Nanoparticles Formed in Electrodeposition–An In Situ XRD Study

An advanced synchrotron-based in situ X-ray diffraction (XRD) technique is successfully developed and employed to track and monitor the formation and phase selection of cobalt (Co) in electrodeposition in real time and verify DFT computational results. The impacts of a number of controlling factors including the pH of the electrolyte and deposition overpotential are systematically studied. The results show that the yielded phase of the electrodeposited Co is controlled by both thermodynamics and kinetics. The low pH low overpotential condition favors the formation of the thermodynamically stable fcc phase. While the high pH high overpotential condition promotes the formation of the metastable hcp phase. The experimental results agree well with the nanometric phase diagram computed with DFT. Layer-by-layer alternative stacking of fcc-hcp polymorphic phases can be facilely fabricated by just varying the overpotential. This work not only offers an effective means to control the phase of electroplating of Co but also presents a new approach to reveal the fundamental insights of the formation of metals under electrochemical reduction driving force.

36 MATERIALS SCIENCE↗

Facile Room-Temperature Electrodeposition of Rare Earth Metals in a Fluorine-Free Task-Specific Electrolyte

Electrochemical deposition of rare earth metals at room temperature has attracted increasing interest due to its advantage in energy efficiency over traditional hydrometallurgical and pyrometallurgical processes. Recent progress has been made with fluorinated electrolyte systems; however, the formation of an electrode-passivating fluoride layer by electrolyte decomposition is often overlooked. Such a passivation layer causes significant and rapid decay of the deposition current and significantly hinders practical application. To address this issue, we demonstrate a fluorine (F)-free task-specific electrolyte utilizing the borohydride anion for the efficient electrodeposition of rare earth metals. By eliminating the passivation effect, the deposition process exhibits a stable current and accumulates a thick neodymium deposit on the electrode. Raman spectroscopy of the electrolyte reveals a synergetic effect between rare earth borohydride and lithium borohydride which promotes the dissociation of both borohydride salts, resulting in significantly increased ionic conductivity and electrochemical performance. Cyclic voltammetry and in-depth X-ray photoelectron spectroscopy of the deposits suggest that the electrodeposition of rare earth metals could undergo a Li-mediated reduction process. Finally, quantitative analysis of the deposits reveals that the overall concentration of the rare earth elements reaches 75% which contains 40–48% metallic phase.

36 MATERIALS SCIENCE↗

Electrodeposition and analysis of thick bismuth films

Due to its unique physical and chemical properties, bismuth is an attractive candidate for a wide range of applications such as battery anodes, radiation shielding, and semiconductors, to name a few. This work presents the electrodeposition of mechanically stable and homogenous bismuth films at micron-scale thicknesses. A simple one-step electrodeposition process using either a pulse/reverse or direct current source yielded thick, homogenous, and mechanically stable bismuth films. Morphology, electrochemical behavior, adhesion, and mechanical stability of bismuth coatings plated with varying parameters were characterized via optical profilometry, cyclic voltammetry, electron microscopy, and tribology. Scratch testing on thick electroplated coatings (> 100 µm) revealed similar wear resistance properties between the pulse/reverse plated and direct current electroplated films. This study presents a versatile bismuth electroplating process with the possibility to replace lead in radiation shields with an inexpensive, non-toxic metal, or to make industrially relevant electrocatalytic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Research on pulse electrodeposition of Fe-Ni alloy

Fe-Ni alloys were fabricated on steel substrates by means of pulse electrodeposition in sulfate solutions. The layers were electrodeposited using different peak current densities, duty cycles and frequencies. Fe contents, microhardnesses and crystalline phases were examined systematically. The Fe content in the deposit decreased and the microhardness increased with increasing duty cycle and peak current density. The pulse frequency had little effect on Fe content but led to a slight decrease in microhardness. X-ray diffraction patterns show that the crystalline phases vary with changes in peak current density and duty cycle but are barely influenced by frequency. When the peak current density or duty cycle is relatively low, crystalline Fe-Ni alloy and pure Fe phases coexist; the pure Fe phases disappear as the peak current density or duty cycle increases. At still larger peak current densities or duty cycles, crystalline Fe-Ni alloy and pure Ni phases coexist.

36 MATERIALS SCIENCE↗

Hanle measurements of electrodeposited Fe/GaAs spin tunnel contacts

We report spin transport in electrodeposited Fe/n-GaAs tunnel diodes via three-terminal Hanle measurements. For temperatures between 20 K and 150 K, the spin resistance was up to 20 times higher than expected from theoretical calculations and 1000 times larger compared to a vacuum-deposited counterpart. This higher spin resistance was correlated with a higher contact resistance, and a higher concentration of oxygen impurities in the electrodeposited Fe film and interface, as detected via x-ray photoelectron and Auger spectroscopies, and inferred from Fe film nucleation rates. These results can be explained via a small effective tunnel-contact area of 5%, but extra spin filtering via interfacial states or magnetic oxide layers cannot be ruled out. The spin diffusion times (8.5 ± 0.4 ns to 1.8 ± 0.4 ns, for 20 K to 150 K) extracted from Lorentzian fits were in good agreement with values obtained from earlier 4-terminal Hanle measurements (7.8 ± 0.4 ns to 3.2 ± 0.4 ns, for 25 K to 77 K), both 10 times slower than reported vacuum-deposited contacts.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

InSb thin films grown by electrodeposition

We have grown InSb thin films on Cu substrates using the electrodeposition technique. The electrochemical bath from which the InSb thin films were grown was made up of a mixture of aqueous solutions of 0.05 M InCl{sub 3} and 0.03M SbCl{sub 3}, 0 .20M citric acid and 0.30M sodium citrate. Citric acid and sodium citrate were used as complexing agents to bring the reduction potential of In and Sb closer to maintain binary growth. The electrodeposited films were characterized by structural, morphological and optical studies. X-ray diffraction studies show that the films are polycrystalline InSb having the zinc blende structure. Scanning electron microscopy (SEM) studies reveal that the surface of the films is uniformly covered with submicron sized spherical particles. FTIR spectra of InSb thin films show a sharp absorption peak at wave number 1022 cm{sup −1} corresponding to the band gap. Hot probe analysis shows that the InSb thin films have p type conductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electrodeposited cobalt sulfide hole collecting layer for polymer solar cells

In polymer solar cells based on the blend of regioregular poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester, the hole collecting layer has to be endowed with its ionization potential close to or greater than that of P3HT (∼5 eV). Conductive polymer blends such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and metal oxides such as vanadium pentoxide (V{sub 2}O{sub 5}) and molybdenum trioxide (MoO{sub 3}) satisfy this requirement and have been the most common materials used so far in bulk heterojunction structures. We report here cobalt sulfide (CoS) to be a promising hole collecting material deposited by convenient and room temperature electrodeposition. By simply tuning the CoS electrodeposition parameters, power conversion efficiencies similar (within 15%) to a reference structure with PEDOT:PSS were obtained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning of deep level emission in highly oriented electrodeposited ZnO nanorods by post growth annealing treatments

Highly dense and c-axis oriented zinc oxide (ZnO) nanorods with hexagonal wurtzite facets were deposited on fluorine doped tin oxide coated glass substrates by a simple and cost-effective electrodeposition method at low bath temperature (80 °C). The as-grown samples were then annealed at various temperatures (T{sub A} = 100–500 °C) in different environments (e.g., zinc, oxygen, air, and vacuum) to understand their photoluminescence (PL) behavior in the ultra-violet (UV) and the visible regions. The PL results revealed that the as-deposited ZnO nanorods consisted of oxygen vacancy (V{sub O}), zinc interstitial (Zn{sub i}), and oxygen interstitial (O{sub i}) defects and these can be reduced significantly by annealing in different environments at optimal annealing temperatures. However, the intensity of deep level emission increased for T{sub A} greater than the optimized values for the respective environments due to the introduction of various defect centers. For example, for T{sub A} ≥ 450 °C in the oxygen and air environments, the density of O{sub i} defects increased, whereas, the green emission associated with V{sub O} is dominant in the vacuum annealed (T{sub A} = 500 °C) ZnO nanorods. The UV peak red shifted after the post-growth annealing treatments in all the environments and the vacuum annealed sample exhibited highest UV peak intensity. The observations from the PL data are supported by the micro-Raman spectroscopy. The present study gives new insight into the origin of different defects that exist in the electrodeposited ZnO nanorods and how these defects can be precisely controlled in order to get the desired emissions for the opto-electronic applications.

36 MATERIALS SCIENCE↗

Microscopic and magnetic properties of template assisted electrodeposited iron nanowires

Nanowires of magnetic materials such as Iron, nickel, cobalt, and alloys of them are one of the most widely investigated structures because of their possible applications in high density magnetic recording media, sensor elements, and building blocks in biological transport systems. In this work, Iron nanowires have been prepared by electrodeposition technique using Anodized Aluminium Oxide (AAO) templates. The electrolyte used consisted of FeSO{sub 4.}6H{sub 2}O buffered with H{sub 3}BO{sub 3} and acidized by dilute H{sub 2}SO{sub 4}. FESEM analysis shows that the asdeposited nanowires are parallel to one another and have high aspect ratio with a reasonably high pore-filing factor. To fabricate the working electrode, a thin film of copper (∼ 220 nm thick) was coated on back side of AAO template by e-beam evaporation system to create electrical contact with the external circuit. The TEM results show that electrodeposited nanowires have diameter around 100 nm and are polycrystalline in structure. Magnetic properties show the existence of anisotropy for in and out of plane configuration. These nanowires have potential applications in magnetic data storage, catalysis and magnetic sensor applications.

36 MATERIALS SCIENCE↗

Electrodeposition of gold nanoparticles on mesoporous TiO{sub 2} photoelectrode to enhance visible region photocurrent

Electrodeposition of gold nanoparticles (Au NPs) on the mesoporous TiO{sub 2} photoelectrode to enchance visible region photocurrent have been investigated. Mesoporous TiO{sub 2} was prepared by a sol gel method and immobilized to the fluorine doped tin oxide (FTO) substrate by dip coating technique. Gold nanoparticles were electrodeposited on the TiO{sub 2} surface and the result FTO/TiO{sub 2}/Au was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), UV-Vis diffuse reflectance spectroscopy (DRS), and X-ray diffraction (XRD). The generated photocurrent was evaluated with an electrochemical workstation (e-DAQ/e-recorder 401) using 60 W wolfram lamp as visible light source. The photoelectrochemical evaluation indicated that the presence of gold nanoparticles on TiO{sub 2} photoelectrode shall enhance the photocurrent up to 50%.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High current density electron emission from an electrodeposited metal nanowire array

High-current electron field emitters are of interest for many applications, but state-of-the-art devices suffer from limitations such as high turn-on macroscopic field, low macroscopic current density, poor emission stability, and short lifetime. Field emitter arrays with a high spatial density of uniform emitters have the potential to address these problems. This work presents the process development, fabrication, and testing of a novel field emitter array. The authors employed electron beam lithography and templated electrodeposition to fabricate a high spatial density array of metallic nanowires, resulting in electron emission with high macroscopic current density (2 A/cm 2 ) and low turn-on macroscopic field (4.35 V/ μ m). Templated electrodeposition of metallic nanowire arrays is a promising method for producing high performance field emitters.

42 ENGINEERING↗

Backward-Diode Heterostructure Based on a Zinc-Oxide Nanoarray Formed by Pulsed Electrodeposition and a Cooper-Iodide Film Grown by the SILAR Method

A heterostructure promising for designing a backward diode is formed from a zinc-oxide nanorod array and a nanostructured copper-iodide film. The effect of modes of successive ionic layer adsorption and reaction (SILAR) deposition and the subsequent iodization of CuI films on smooth glass, mica, and fluorine-doped tin oxide (FTO) substrates and on the surface of electrodeposited nanostructured zinc-oxide arrays on the film structure and electrical and optical properties is investigated. A connection between the observed variations in the structure and properties of this material and intrinsic and iodination-induced point defects is established. It is found that the cause and condition for creating a backward-diode heterostructure based on a zinc-oxide nanoarray formed by pulsed electrodeposition and a copper-iodide film grown by the SILAR method is the formation of a p{sup +}-CuI degenerate semiconductor by the excessive iodination of layers of this nanostructured material through its developed surface. The n-ZnO/p{sup +}-CuI barrier heterostructure, which is fabricated for the first time, has the I–V characteristic of a backward diode, the curvature factor of which (γ = 12 V{sup –1}) confirms its high Q factor.

36 MATERIALS SCIENCE↗

Mechanisms of Current Transfer in Electrodeposited Layers of Submicron Semiconductor Particles

Current–voltage (I–V) characteristics of conductance in multigrain layers of submicron particles of silicon, gallium arsenide, indium arsenide, and indium antimonide have been studied. Nanoparticles of all semiconductors were obtained by processing initial single crystals in a ball mill and applied after sedimentation onto substrates by means of electrodeposition. Detailed analysis of the I–V curves of electrodeposited layers shows that their behavior is determined by the mechanism of intergranular tunneling emission from near-surface electron states of submicron particles. Parameters of this emission process have been determined. The proposed multigrain semiconductor structures can be used in gas sensors, optical detectors, IR imagers, etc.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Progress and Perspectives: Zirconium Electrodeposition from Different Electrolytes

Zirconium (Zr) possesses outstanding properties, including exceptional chemical resistance and a high melting point, and is therefore desirable for use in a wide variety of challenging environments, such as in nuclear reactors and the chemical processing industry. To minimize the amount of Zr required for any given application, developing methods for generating metallic Zr coatings is highly advantageous. Owing to Zr’s highly negative reduction potential, electrodeposition in traditional solvents at near ambient temperatures remains challenging and thus not well understood. Due to the extreme conditions required to deposit this metal, extensive work has been conducted in molten salt electrolytes, however the broad applicability of this methodology is limited due to its corrosivity. The primary focus of this article is to present an overview of Zr’s electrochemical behavior and to consolidate the efforts of researchers in exploring electrodeposition techniques for Zr involving aqueous, organic, ionic liquid, deep eutectic, and molten salt solvents. With this information, we highlight trends across solvent systems and opportunities for future research.

42 ENGINEERING↗

Establishing Pb-203 production from electrodeposited Tl targets at Brookhaven National Laboratory

Background: Promising developments in Pb-212 radiopharmaceutical therapies have increased demand for Pb-203 diagnostic agents. Building on previous work from various isotope production facilities, this study optimized Pb-203 production from electrodeposited Tl targets at Brookhaven National Laboratory (BNL). The additional supply of Pb-203 may help meet growing preclinical and clinical demands. Results: Two Tl targets were irradiated at the Brookhaven Linac Isotope Producer facility with 30 ± 1 MeV protons, measured using previously published cross section data. Distribution coefficients for Pb Resin in acetate media were investigated for both Na + and K + cations, where potassium acetate was ~ 4 times more effective at stripping Pb from the Pb Resin. The Tl electrodeposition was optimized to deposit 350 mg of Tl (~ 60 mg/cm 2 ) on Au backing in under 6 h. The proposed separation process was completed in < 1.5 h and achieved > 98% and 92 ± 3% recovery of Tl and Pb, respectively, with an overall Tl-Pb separation factor of 6 × 10 5 . The experimentally measured half-life of Pb-203 was 52.4 ± 0.7 h, agreeing with 51.93 ± 0.02 h reported by the National Nuclear Data Center. The radioisotopic purity of the Pb fraction at 24 h post end of bombardment (EOB) from a 24 h irradiation was 66% Pb-203, 28% Pb-201, and 6% Pb-200. Following chemical separation, the Pb-203 produced in this work (21 MBq Pb-203 EOB) achieved apparent molar activities of 10 ± 5 and 0.9 ± 0.5 GBq/µmol for [ 203 Pb]Pb-DOTAM and [ 203 Pb]Pb-DO3A, respectively, decay corrected to EOB. Data derived from this work suggests BNL can produce > 10’s GBq Pb-203 with > 99% radiochemical and radioisotopic purity from Tl-205 for worldwide distribution. Conclusions: The production and separation of Pb-203 from natural Tl target material was successfully demonstrated at BNL. Existing methods were adapted and optimized for the facilities at BNL. Results from this work will guide future large-scale Pb-203 production opportunities at BNL for clinical applications.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Development of Electrodeposited CIGS Solar Cells: Cooperative Research and Development Final Report, CRADA Number CRD-09-357

At present, most PV materials are fabricated by vacuum technologies. Some of the many disadvantages of vacuum technology are complicated instrumentation, material waste, high cost of deposition per surface area, and instability of some compounds at the deposition temperature. Solution-based approaches for thin-film deposition on large areas are particularly desirable because of the low capital cost of the deposition equipment, relative simplicity of the processes, ease of doping, uniform deposition on a variety of substrates (including interior and exterior of tubes and various nonplanar devices), and potential compatibility with high-throughput (e.g., roll-to-roll) processing. Of the nonsilicon solar photovoltaic device modules that have been deployed to date, those based on the n-CdS/p-CdTe is a leading candidate. Two features in the optical characteristics of CdTe absorber are particularly attractive for photovoltaic conversion of sunlight; (a) its energy bandgap of 1.5 eV, which provides an optimal match with the solar spectrum and thus facilitates its efficient utilization and (b) the direct mode of the main optical transition which results in a large absorption coefficient and turn permits the use of thin layer (1-2 um) of active material. Thin films of CdTe required for these devices have been fabricated by a variety of methods (e.g., vapor transport deposition, vacuum deposition, screen printing and close-spaced sublimation). Electrodeposition is another candidate deserves more attention. This project will focus on delivering low-cost, high efficiency electrodeposited CdTe-based device.

14 SOLAR ENERGY↗