Interface electronic structures of reversible double-docking self-assembled monolayers on an Au(111) surface

PubMed Central

Zhang, Tian; Ma, Zhongyun; Wang, Linjun; Xi, Jinyang; Shuai, Zhigang

2014-01-01

Double-docking self-assembled monolayers (DDSAMs), namely self-assembled monolayers (SAMs) formed by molecules possessing two docking groups, provide great flexibility to tune the work function of metal electrodes and the tunnelling barrier between metal electrodes and the SAMs, and thus offer promising applications in both organic and molecular electronics. Based on the dispersion-corrected density functional theory (DFT) in comparison with conventional DFT, we carry out a systematic investigation on the dual configurations of a series of DDSAMs on an Au(111) surface. Through analysing the interface electronic structures, we obtain the relationship between single molecular properties and the SAM-induced work-function modification as well as the level alignment between the metal Fermi level and molecular frontier states. The two possible conformations of one type of DDSAM on a metal surface reveal a strong difference in the work-function modification and the electron/hole tunnelling barriers. Fermi-level pinning is found to be a key factor to understand the interface electronic properties. PMID:24615153

Effective work function engineering for a TiN/XO(X = La, Zr, Al)/SiO{sub 2} stack structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Dongjin, E-mail: dongjin0710.lee@samsung.com; Lee, Jieun; Jung, Kyoungho

In this study, we demonstrated that work function engineering is possible over a wide range (+200 mV to −430 mV) in a TiN/XO (X = La, Zr, or Al)/SiO{sub 2} stack structures. From ab initio simulations, we selected the optimal material for the work function engineering. The work function engineering mechanism was described by metal diffusion into the TiN film and silicate formation in the TiN/SiO{sub 2} interface. The metal doping and the silicate formation were confirmed by transmission electron microscopy and energy dispersive spectroscopy line profiling, respectively. In addition, the amount of doped metal in the TiN film depended on the thickness ofmore » the insertion layer XO. From the work function engineering technique, which can control a variety of threshold voltages (Vth), an improvement in transistors with different V{sub th} values in the TiN/XO/SiO{sub 2} stack structures is expected.« less

Low work function, stable thin films

DOEpatents

Dinh, Long N.; McLean, II, William; Balooch, Mehdi; Fehring, Jr., Edward J.; Schildbach, Marcus A.

2000-01-01

Generation of low work function, stable compound thin films by laser ablation. Compound thin films with low work function can be synthesized by simultaneously laser ablating silicon, for example, and thermal evaporating an alkali metal into an oxygen environment. For example, the compound thin film may be composed of Si/Cs/O. The work functions of the thin films can be varied by changing the silicon/alkali metal/oxygen ratio. Low work functions of the compound thin films deposited on silicon substrates were confirmed by ultraviolet photoelectron spectroscopy (UPS). The compound thin films are stable up to 500.degree. C. as measured by x-ray photoelectron spectroscopy (XPS). Tests have established that for certain chemical compositions and annealing temperatures of the compound thin films, negative electron affinity (NEA) was detected. The low work function, stable compound thin films can be utilized in solar cells, field emission flat panel displays, electron guns, and cold cathode electron guns.

Work-function calculations for a symmetrical total-charge-density profile at the metallic surface

NASA Astrophysics Data System (ADS)

Wojciechowski, K. F.; Sobańska-Nowotnik, M.

1983-07-01

It is shown that, if the total-charge-density profile nT(x) at the surface of jellium satisfies the Budd-Vannimenus constraint and also is a symmetrical function of x, relative to the ordinate axis, then the work-function variation versus the Wigner-Seitz radius rs does not depend on the form of nT(x). Also the simple linear-density profile is used to calculate the work function by application of the variational principle for the energy, including the first and second density-gradient corrections to the kinetic energy and the first gradient correction to the exchange and correlation energy. The results for the work function are in good agreement with the polycrystalline values for low-density metals.

Functional Metal Matrix Composites: Self-lubricating, Self-healing, and Nanocomposites-An Outlook

NASA Astrophysics Data System (ADS)

Dorri Moghadam, Afsaneh; Schultz, Benjamin F.; Ferguson, J. B.; Omrani, Emad; Rohatgi, Pradeep K.; Gupta, Nikhil

2014-06-01

Many different types of advanced metal matrix composites are now available, some of which possess functional properties. Recent work on particle-reinforced, self-lubricating and self-healing metals and metal matrix nanocomposites (MMNCs) synthesized by solidification synthesis is reviewed. Particle-based MMNCs have been developed by several modern processing tools based on either solid- or liquid-phase synthesis techniques that are claimed to exhibit exciting mechanical properties including improvements of modulus, yield strength, and ultimate tensile strength. This article presents a brief and objective review of the work done over the last decade to identify the challenges and future opportunities in the area of functional nanocomposites. Increasing interest in lightweight materials has resulted in studies on hollow particle-filled metal matrix syntactic foams. Syntactic foams seem especially suitable for development with functional properties such as self-healing and self-lubrication. The metal matrix micro and nanocomposites, and syntactic foams having combinations of ultrahigh strength and wear resistance, self-lubricating, and/or self-healing properties can lead to increased energy efficiency, reliability, comfort of operation, reparability, and safety of vehicles. The focus of the present review is aluminum and magnesium matrix functional materials.

Silver Makes Better Electrical Contacts to Thiol-Terminated Silanes than Gold.

PubMed

Li, Haixing; Su, Timothy A; Camarasa-Gómez, María; Hernangómez-Pérez, Daniel; Henn, Simon E; Pokorný, Vladislav; Caniglia, Caravaggio D; Inkpen, Michael S; Korytár, Richard; Steigerwald, Michael L; Nuckolls, Colin; Evers, Ferdinand; Venkataraman, Latha

2017-11-06

We report that the single-molecule junction conductance of thiol-terminated silanes with Ag electrodes are higher than the conductance of those formed with Au electrodes. These results are in contrast to the trends in the metal work function Φ(Ag)<Φ(Au). As such, a better alignment of the Au Fermi level to the molecular orbital of silane that mediates charge transport would be expected. This conductance trend is reversed when we replace the thiols with amines, highlighting the impact of metal-S covalent and metal-NH 2 dative bonds in controlling the molecular conductance. Density functional theory calculations elucidate the crucial role of the chemical linkers in determining the level alignment when molecules are attached to different metal contacts. We also demonstrate that conductance of thiol-terminated silanes with Pt electrodes is lower than the ones formed with Au and Ag electrodes, again in contrast to the trends in the metal work-functions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Generation of low work function, stable compound thin films by laser ablation

DOEpatents

Dinh, Long N.; McLean, II, William; Balooch, Mehdi; Fehring, Jr., Edward J.; Schildbach, Marcus A.

2001-01-01

Generation of low work function, stable compound thin films by laser ablation. Compound thin films with low work function can be synthesized by simultaneously laser ablating silicon, for example, and thermal evaporating an alkali metal into an oxygen environment. For example, the compound thin film may be composed of Si/Cs/O. The work functions of the thin films can be varied by changing the silicon/alkali metal/oxygen ratio. Low work functions of the compound thin films deposited on silicon substrates were confirmed by ultraviolet photoelectron spectroscopy (UPS). The compound thin films are stable up to 500.degree. C. as measured by x-ray photoelectron spectroscopy (XPS). Tests have established that for certain chemical compositions and annealing temperatures of the compound thin films, negative electron affinity (NEA) was detected. The low work function, stable compound thin films can be utilized in solar cells, field emission flat panel displays, electron guns, and cold cathode electron guns.

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

NASA Astrophysics Data System (ADS)

Liu, Zhen-Fei; Egger, David A.; Refaely-Abramson, Sivan; Kronik, Leeor; Neaton, Jeffrey B.

2017-03-01

The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density functional theory calculations, especially those using local and semi-local functionals, often underestimate level alignment leading to inaccurate electronic structure and charge transport properties. In this work, we develop a new fully self-consistent predictive scheme to accurately compute level alignment at certain classes of complex heterogeneous molecule-metal interfaces based on optimally tuned range-separated hybrid functionals. Starting from a highly accurate description of the gas-phase electronic structure, our method by construction captures important nonlocal surface polarization effects via tuning of the long-range screened exchange in a range-separated hybrid in a non-empirical and system-specific manner. We implement this functional in a plane-wave code and apply it to several physisorbed and chemisorbed molecule-metal interface systems. Our results are in quantitative agreement with experiments, the both the level alignment and work function changes. Our approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.

Metal-phthalocyanine functionalized carbon nanotubes as catalyst for the oxygen reduction reaction: A theoretical study

NASA Astrophysics Data System (ADS)

Orellana, Walter

2012-07-01

The covalent functionalization of metallic single-walled carbon nanotubes (CNTs) with transition metal phthalocyanines (MPc, with M = Mn, Fe and Co) are addressed by density functional calculations. The CNT-MPc catalytic activity toward the oxygen reduction reaction (ORR) is investigated through the O2 stretching frequency adsorbed on the phthalocyanine metal center. We find better reduction abilities when the CNT functionalization occurs through sp2-like bonds. Multiple stable-spin states for the M-O2 adduct are also found for M = Mn and Fe, suggesting higher ORR rates. The CNT-MPc complexes show metallic characteristics, suggesting favorable conditions to work as ORR cathode catalysts in fuel cells.

Electronic structures of 1-ML C84/Ag(111): Energy level alignment and work function variation

NASA Astrophysics Data System (ADS)

Wang, Peng; Zhao, Li-Li; Zhang, Jin-Juan; Li, Wen-Jie; Liu, Wei-Hui; Chen, Da; Sheng, Chun-Qi; Wang, Jia-Ou; Qian, Hai-Jie; Ibrahim, Kurash; Li, Hong-Nian

2017-12-01

The electronic structures of fullerene/metal interface are critical to the performance of devices based on fullerene in molecular electronics and organic electronics. Herein, we investigate the electronic structures at the interface between C84 and Ag(111) by photoelectron spectroscopy and soft X-ray absorption spectroscopy techniques. It is observed that C84 monolayer on Ag(111) surface (1-ML C84/Ag(111)) has metallic nature. A charge transfer from substrate to the unoccupied states of C84 is determined to be 1.3 electrons per molecule. However, the work function of 1-ML C84 (4.72 eV) is observed slightly larger than that of the clean Ag(111) substrate (4.50 eV). A bidirectional charge transfer model is introduced to understand the work function variation of the fullerene/metal system. In addition to the charge transfer from substrate to the adsorbate's unoccupied states, there exists non-negligible back charge transfer from fullerene occupied molecular orbital to the metal substrate through interfacial hybridization. The Fermi level will be pinned at ∼4.72 eV for C84 monolayer on coinage metal substrate.

Atomic layer deposited TaCy metal gates: Impact on microstructure, electrical properties, and work function on HfO2 high-k dielectrics

NASA Astrophysics Data System (ADS)

Triyoso, D. H.; Gregory, R.; Schaeffer, J. K.; Werho, D.; Li, D.; Marcus, S.; Wilk, G. D.

2007-11-01

TaCy has been reported to have the appropriate work function for negative metal-oxide semiconductor metal in high-k metal-oxide field-effect transistors. As device size continues to shrink, a conformal deposition for metal gate electrodes is needed. In this work, we report on the development and characterization of a novel TaCy process by atomic layer deposition (ALD). Detailed physical properties of TaCy films are studied using ellipsometry, a four-point probe, Rutherford backscattering spectrometry (RBS), x-ray photoelectron spectroscopy (XPS), and x-ray diffraction (XRD). RBS and XPS analysis indicate that TaCy films are near-stoichiometric, nitrogen free, and have low oxygen impurities. Powder XRD spectra showed that ALD films have a cubic microstructure. XPS carbon bonding studies revealed that little or no glassy carbon is present in the bulk of the film. Excellent electrical properties are obtained using ALD TaCy as a metal gate electrode. Well-behaved capacitance-voltage characteristics with ALD HfO2 gate dielectrics are demonstrated for TaCy thicknesses of 50, 100, and 250 Å. A low fixed charge (˜2-4×10-11 cm-2) is observed for all ALD HfO2/ALD TaCy devices. Increasing the thickness of ALD TaCy results in a decrease in work function (4.77 to 4.54 eV) and lower threshold voltages.

West Europe Report

DTIC Science & Technology

1987-01-14

Yet men are the same everywhere, intelli- gence functions in every individual according to the same principles. French philosopher Descartes , in...with Sunday work. Some 100, perhaps 200 would be affected by this, says Mega boss Friedrich. IG Metall works councilman Rene Kaufmann opines however...position of the industrial code: Sunday work only because of technical constraints or for service to the customer. 69 IG Metall works councilman Rene

Preparations and properties of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials.

PubMed

Watanabe, Shoji

2008-01-01

This short review describes various types of anti-corrosion additives of water-soluble metal working fluids for aluminum alloy materials. It is concerned with synthetic additives classified according to their functional groups; silicone compounds, carboxylic acids and dibasic acids, esters, Diels-Alder adducts, various polymers, nitrogen compounds, phosphoric esters, phosphonic acids, and others. Testing methods for water-soluble metal working fluids for aluminum alloy materials are described for a practical application in a laboratory.

Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality

PubMed Central

Patra, Abhirup; Bates, Jefferson E.; Sun, Jianwei; Perdew, John P.

2017-01-01

We have computed the surface energies, work functions, and interlayer surface relaxations of clean (111), (100), and (110) surfaces of Al, Cu, Ru, Rh, Pd, Ag, Pt, and Au. We interpret the surface energy from liquid metal measurements as the mean of the solid-state surface energies over these three lowest-index crystal faces. We compare experimental (and random phase approximation) reference values to those of a family of nonempirical semilocal density functionals, from the basic local density approximation (LDA) to our most advanced general purpose meta-generalized gradient approximation, strongly constrained and appropriately normed (SCAN). The closest agreement is achieved by the simplest density functional LDA, and by the most sophisticated one, SCAN+rVV10 (Vydrov–Van Voorhis 2010). The long-range van der Waals interaction, incorporated through rVV10, increases the surface energies by about 10%, and increases the work functions by about 3%. LDA works for metal surfaces through two known error cancellations. The Perdew–Burke–Ernzerhof generalized gradient approximation tends to underestimate both surface energies (by about 24%) and work functions (by about 4%), yielding the least-accurate results. The amount by which a functional underestimates these surface properties correlates with the extent to which it neglects van der Waals attraction at intermediate and long range. Qualitative arguments are given for the signs of the van der Waals contributions to the surface energy and work function. A standard expression for the work function in Kohn–Sham (KS) theory is shown to be valid in generalized KS theory. Interlayer relaxations from different functionals are in reasonable agreement with one another, and usually with experiment. PMID:29042509

Understanding the Effect of Plastic Deformation on Elastic Modulus of Metals Based on a Percolation Model with Electron Work Function

NASA Astrophysics Data System (ADS)

Li, Qingda; Hua, Guomin; Lu, Hao; Yu, Bin; Li, D. Y.

2018-05-01

The elastic modulus of materials is usually treated as a constant in engineering applications. However, plastic deformation may result in changes in the elastic modulus of metallic materials. Using brass, aluminum, and low-carbon steel as sample materials, it is demonstrated that plastic deformation decreased the elastic modulus of the materials by 10% to 20%. A percolation model incorporating the electron work function is proposed to correlate such plastic-strain-induced variations in the elastic modulus to corresponding changes in the electron work function. Efforts are made to understand the observed phenomenon on an electronic basis. The obtained experimental results are consistent with the theoretical analysis.

Thermoelectricity in fullerene-metal heterojunctions.

PubMed

Yee, Shannon K; Malen, Jonathan A; Majumdar, Arun; Segalman, Rachel A

2011-10-12

Thermoelectricty in heterojunctions, where a single-molecule is trapped between metal electrodes, has been used to understand transport properties at organic-inorganic interfaces. (1) The transport in these systems is highly dependent on the energy level alignment between the molecular orbitals and the Fermi level (or work function) of the metal contacts. To date, the majority of single-molecule measurements have focused on simple small molecules where transport is dominated through the highest occupied molecular orbital. (2, 3) In these systems, energy level alignment is limited by the absence of electrode materials with low Fermi levels (i.e., large work functions). Alternatively, more controllable alignment between molecular orbitals and the Fermi level can be achieved with molecules whose transport is dominated by the lowest unoccupied molecular orbital (LUMO) because of readily available metals with lower work functions. Herein, we report molecular junction thermoelectric measurements of fullerene molecules (i.e., C(60), PCBM, and C(70)) trapped between metallic electrodes (i.e., Pt, Au, Ag). Fullerene junctions demonstrate the first strongly n-type molecular thermopower corresponding to transport through the LUMO, and the highest measured magnitude of molecular thermopower to date. While the electronic conductance of fullerenes is highly variable, due to fullerene's variable bonding geometries with the electrodes, the thermopower shows predictable trends based on the alignment of the LUMO with the work function of the electrodes. Both the magnitude and trend of the thermopower suggest that heterostructuring organic and inorganic materials at the nanoscale can further enhance thermoelectric performance, therein providing a new pathway for designing thermoelectric materials.

Role of point defects and HfO2/TiN interface stoichiometry on effective work function modulation in ultra-scaled complementary metal-oxide-semiconductor devices

NASA Astrophysics Data System (ADS)

Pandey, R. K.; Sathiyanarayanan, Rajesh; Kwon, Unoh; Narayanan, Vijay; Murali, K. V. R. M.

2013-07-01

We investigate the physical properties of a portion of the gate stack of an ultra-scaled complementary metal-oxide-semiconductor (CMOS) device. The effects of point defects, such as oxygen vacancy, oxygen, and aluminum interstitials at the HfO2/TiN interface, on the effective work function of TiN are explored using density functional theory. We compute the diffusion barriers of such point defects in the bulk TiN and across the HfO2/TiN interface. Diffusion of these point defects across the HfO2/TiN interface occurs during the device integration process. This results in variation of the effective work function and hence in the threshold voltage variation in the devices. Further, we simulate the effects of varying the HfO2/TiN interface stoichiometry on the effective work function modulation in these extremely-scaled CMOS devices. Our results show that the interface rich in nitrogen gives higher effective work function, whereas the interface rich in titanium gives lower effective work function, compared to a stoichiometric HfO2/TiN interface. This theoretical prediction is confirmed by the experiment, demonstrating over 700 meV modulation in the effective work function.

Manipulating electronic and mechanical properties at metal-ceramic interfaces with a nanomolecular layer

NASA Astrophysics Data System (ADS)

Kwan, Matthew P.

This work demonstrates that inserting nanomolecular layers (NMLs) can profoundly change and/or lead to novel electronic and mechanical properties of metal-ceramic interfaces. The first set of results demonstrate that organophosphonate NMLs up to 1.8 nm thick can alter metal work functions by +/- 0.6 eV. This work function change is a strong function of the NML terminal groups (methyl, mercaptan, carboxylic acid, or phosphonic acid), morphology (up right, lying down, or mixed orientation), and the nature of the bonding (covalent, polar, or Van der Waals) between NML and the adjacent layers. Additionally, while NML-ceramic bond type and strength can influence and counteract the effect of NML morphology, the metal-NML bond appears to be independent of the morphology of the NML underlayer. The second set of results demonstrate that inserting an organosilane NML at a metal-ceramic interface can lead to multifold fracture toughening under both static (stress corrosion) and cyclic loads (fatigue) tested in four-point bend. Nanolayer-induced interface strengthening during static loading activates metal plasticity above the metal yield strength, leading to two-fold fracture toughening. Metal plasticity-induced toughening increases as temperature is increased up to 85 °C due to decreasing yield stress. In the fatigue fracture tests I report for the first time a loading-frequency-dependent tripling in fracture toughening in the 75-300 Hz range upon inserting a mercapto-silane NML at the weakest interface of a ceramic-polymer-metal-ceramic stack. This unusual behavior arises from the NML strengthened interface enabling load transfer to- and plasticity in the polymer layer, while the fatigue toughening magnitude and frequency range are determined by polymer rheology.

Toward control of the metal-organic interfacial electronic structure in molecular electronics: a first-principles study on self-assembled monolayers of pi-conjugated molecules on noble metals.

PubMed

Heimel, Georg; Romaner, Lorenz; Zojer, Egbert; Brédas, Jean-Luc

2007-04-01

Self-assembled monolayers (SAMs) of organic molecules provide an important tool to tune the work function of electrodes in plastic electronics and significantly improve device performance. Also, the energetic alignment of the frontier molecular orbitals in the SAM with the Fermi energy of a metal electrode dominates charge transport in single-molecule devices. On the basis of first-principles calculations on SAMs of pi-conjugated molecules on noble metals, we provide a detailed description of the mechanisms that give rise to and intrinsically link these interfacial phenomena at the atomic level. The docking chemistry on the metal side of the SAM determines the level alignment, while chemical modifications on the far side provide an additional, independent handle to modify the substrate work function; both aspects can be tuned over several eV. The comprehensive picture established in this work provides valuable guidelines for controlling charge-carrier injection in organic electronics and current-voltage characteristics in single-molecule devices.

Metal dust exposure and lung function deterioration among steel workers: an exposure-response relationship.

PubMed

Hamzah, Nurul Ainun; Mohd Tamrin, Shamsul Bahri; Ismail, Noor Hassim

2016-07-01

Metallic dust is a heterogeneous substance with respiratory sensitizing properties. Its long term exposure adversely affected lung function, thus may cause acute or chronic respiratory diseases. A cross-sectional study was conducted in a steel factory in Terengganu, Malaysia to assess the metal dust exposure and its relationship to lung function values among 184 workers. Metal dust concentrations values (Co, Cr, and Ni) for each worker were collected using air personal sampling. Lung function values (FEV 1 , FVC, and %FEV 1 /FVC) were determined using spirometer. Exposure to cobalt and chromium were 1-3 times higher than permissible exposure limit (PEL) while nickel was not exceeding the PEL. Cumulative of chromium was the predictor to all lung function values (FEV 1 , FVC, and %FEV 1 /FVC). Frequency of using mask was positively associated with FVC (Adj b = 0.263, P = 0.011) while past respiratory illnesses were negatively associated with %FEV 1 /FVC (Adj b = -1.452, P = 0.026). Only few workers (36.4%) were found to wear their masks all times during the working hours. There was an exposure-response relationship of cumulative metal dust exposure with the deterioration of lung function values. Improvement of control measures as well as proper and efficient use or personal protection equipment while at work could help to protect the respiratory health of workers.

Densification and Devitrification of Fused Silica Induced by Ballistic Impact: A Computational Investigation

DTIC Science & Technology

2015-03-25

lime glass, the polyhedron -center atoms are all silicon and each silicon atom is surrounded by four oxygen atoms (while each oxygen atom is connected...of metallic force-field functions (in the pure metallic environment) within the force-field function database used in the present work. Consequently

Development of a 3D origami multiplex electrochemical immunodevice using a nanoporous silver-paper electrode and metal ion functionalized nanoporous gold-chitosan.

PubMed

Li, Weiping; Li, Long; Li, Meng; Yu, Jinghua; Ge, Shenguang; Yan, Mei; Song, Xianrang

2013-10-25

A simple and sensitive 3D microfluidic origami multiplex electrochemical immunodevice was developed for the first time using a novel nanoporous silver modified paper working electrode as a sensor platform and different metal ion functionalized nanoporous gold-chitosan as a tracer.

Towards an optimal contact metal for CNTFETs.

PubMed

Fediai, Artem; Ryndyk, Dmitry A; Seifert, Gotthard; Mothes, Sven; Claus, Martin; Schröter, Michael; Cuniberti, Gianaurelio

2016-05-21

Downscaling of the contact length Lc of a side-contacted carbon nanotube field-effect transistor (CNTFET) is challenging because of the rapidly increasing contact resistance as Lc falls below 20-50 nm. If in agreement with existing experimental results, theoretical work might answer the question, which metals yield the lowest CNT-metal contact resistance and what physical mechanisms govern the geometry dependence of the contact resistance. However, at the scale of 10 nm, parameter-free models of electron transport become computationally prohibitively expensive. In our work we used a dedicated combination of the Green function formalism and density functional theory to perform an overall ab initio simulation of extended CNT-metal contacts of an arbitrary length (including infinite), a previously not achievable level of simulations. We provide a systematic and comprehensive discussion of metal-CNT contact properties as a function of the metal type and the contact length. We have found and been able to explain very uncommon relations between chemical, physical and electrical properties observed in CNT-metal contacts. The calculated electrical characteristics are in reasonable quantitative agreement and exhibit similar trends as the latest experimental data in terms of: (i) contact resistance for Lc = ∞, (ii) scaling of contact resistance Rc(Lc); (iii) metal-defined polarity of a CNTFET. Our results can guide technology development and contact material selection for downscaling the length of side-contacts below 10 nm.

Jacob's Ladder as Sketched by Escher: Assessing the Performance of Broadly Used Density Functionals on Transition Metal Surface Properties.

PubMed

Vega, Lorena; Ruvireta, Judit; Viñes, Francesc; Illas, Francesc

2018-01-09

The present work surveys the performance of various widely used density functional theory exchange-correlation (xc) functionals in describing observable surface properties of a total of 27 transition metals with face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp) crystallographic structures. A total of 81 low Miller index surfaces were considered employing slab models. Exemplary xc functionals within the three first rungs of Jacob's ladder were considered, including the Vosko-Wilk-Nusair xc functional within the local density approximation, the Perdew-Burke-Ernzerhof (PBE) functional within the generalized gradient approximation (GGA), and the Tao-Perdew-Staroverov-Scuseria functional as a meta-GGA functional. Hybrids were excluded in the survey because they are known to fail in properly describing metallic systems. In addition, two variants of PBE were considered, PBE adapted for solids (PBEsol) and revised PBE (RPBE), aimed at improving adsorption energies. Interlayer atomic distances, surface energies, and surface work functions were chosen as the scrutinized properties. A comparison with available experimental data, including single-crystal and polycrystalline values, shows that no xc functional is best at describing all of the surface properties. However, in statistical mean terms the PBEsol xc functional is advised, while PBE is recommended when considering both bulk and surface properties. On the basis of the present results, a discussion of adapting GGA functionals to the treatment of metallic surfaces in an alternative way to meta-GGA or hybrids is provided.

The cathode material for a plasma-arc heater

NASA Astrophysics Data System (ADS)

Yelyutin, A. V.; Berlin, I. K.; Averyanov, V. V.; Kadyshevskii, V. S.; Savchenko, A. A.; Putintseva, R. G.

1983-11-01

The cathode of a plasma arc heater experiences a large thermal load. The temperature of its working surface, which is in contact with the plasma, reaches high values, as a result of which the electrode material is subject to erosion. Refractory metals are usually employed for the cathode material, but because of the severe erosion do not usually have a long working life. The most important electrophysical characteristic of the electrode is the electron work function. The use of materials with a low electron work function allows a decrease in the heat flow to the cathode, and this leads to an increase in its erosion resistance and working life. The electroerosion of certain materials employed for the cathode in an electric arc plasma generator in the process of reduction smelting of refractory metals was studied.

Efficiency of Cs-free materials for negative ion production in H2 and D2 plasmas

NASA Astrophysics Data System (ADS)

Friedl, R.; Kurutz, U.; Fantz, U.

2017-08-01

High power negative ion sources use caesium to reduce the work function of the converter surface which significantly increases the negative ion yield. Caesium, however, is a very reactive alkali-metal and shows complex redistribution dynamics in consequence of plasma-surface-interaction. Thus, maintaining a stable and homogenous low work function surface is a demanding task, which is not easily compatible with the RAMI issues (reliability, availability, maintainability, inspectability) for a future DEMO fusion reactor. Hence, Cs-free alternative materials for efficient negative ion formation are desirable. At the laboratory experiment HOMER materials which are referred to as promising are investigated under identical and ion source relevant parameters: the refractory metals Ta and W, non-doped and boron-doped diamond as well as materials with inherent low work function (lanthanum-doped molybdenum, MoLa and lanthanum hexaboride, LaB6). The results are compared to the effect of in-situ caesiation, which at HOMER leads to a maximal increase of the negative ion density by a factor of 2.5. Among the examined samples low work function materials are most efficient. In particular, MoLa leads to an increase of almost 50 % compared to pure volume formation. The difference to a caesiated surface can be attributed to the still higher work function of MoLa, which is expected to be slightly below 3 eV. Using deuterium instead of hydrogen leads to increased atomic and positive ion densities, while comparable negative ion densities are achieved. In contrast to the low work function materials, bulk samples of the refractory metals as well as carbon based materials have no enhancing effect on H-, where the latter materials furthermore show severe erosion due to the hydrogen plasma.

Metal dust exposure and lung function deterioration among steel workers: an exposure-response relationship

PubMed Central

Hamzah, Nurul Ainun; Mohd Tamrin, Shamsul Bahri; Ismail, Noor Hassim

2016-01-01

Background Metallic dust is a heterogeneous substance with respiratory sensitizing properties. Its long term exposure adversely affected lung function, thus may cause acute or chronic respiratory diseases. Methods A cross-sectional study was conducted in a steel factory in Terengganu, Malaysia to assess the metal dust exposure and its relationship to lung function values among 184 workers. Metal dust concentrations values (Co, Cr, and Ni) for each worker were collected using air personal sampling. Lung function values (FEV1, FVC, and %FEV1/FVC) were determined using spirometer. Results Exposure to cobalt and chromium were 1–3 times higher than permissible exposure limit (PEL) while nickel was not exceeding the PEL. Cumulative of chromium was the predictor to all lung function values (FEV1, FVC, and %FEV1/FVC). Frequency of using mask was positively associated with FVC (Adj b = 0.263, P = 0.011) while past respiratory illnesses were negatively associated with %FEV1/FVC (Adj b = –1.452, P = 0.026). Only few workers (36.4%) were found to wear their masks all times during the working hours. Conclusions There was an exposure-response relationship of cumulative metal dust exposure with the deterioration of lung function values. Improvement of control measures as well as proper and efficient use or personal protection equipment while at work could help to protect the respiratory health of workers. PMID:27392157

Effect of molecular desorption on the electronic properties of self-assembled polarizable molecular monolayers.

PubMed

Wang, Gunuk; Jeong, Hyunhak; Ku, Jamin; Na, Seok-In; Kang, Hungu; Ito, Eisuke; Jang, Yun Hee; Noh, Jaegeun; Lee, Takhee

2014-04-01

We investigated the interfacial electronic properties of self-assembled monolayers (SAM)-modified Au metal surface at elevated temperatures. We observed that the work functions of the Au metal surfaces modified with SAMs changed differently under elevated-temperature conditions based on the type of SAMs categorized by three different features based on chemical anchoring group, molecular backbone structure, and the direction of the dipole moment. The temperature-dependent work function of the SAM-modified Au metal could be explained in terms of the molecular binding energy and the thermal stability of the SAMs, which were investigated with thermal desorption spectroscopic measurements and were explained with molecular modeling. Our study will aid in understanding the electronic properties at the interface between SAMs and metals in organic electronic devices if an annealing treatment is applied. Copyright © 2013 Elsevier Inc. All rights reserved.

Photo-Curable Metal-Chelating Coatings Offer a Scalable Approach to Production of Antioxidant Active Packaging.

PubMed

Lin, Zhuangsheng; Goddard, Julie

2018-02-01

Synthetic metal chelators (for example, ethylenediaminetetraacetic acid, EDTA) are widely used as additives to control trace transition metal induced oxidation in consumer products. To enable removal of synthetic chelators in response to increasing consumer demand for clean label products, metal-chelating active food packaging technologies have been developed with demonstrated antioxidant efficacy in simulated food systems. However, prior work in fabrication of metal-chelating materials leveraged batch chemical reactions to tether metal-chelating ligands, a process with limited industrial translatability for large-scale fabrication. To improve the industrial translatability, we have designed a 2-step laminated photo-grafting process to introduce metal chelating functionality onto common polymeric packaging materials. Iminodiacetic acid (IDA) functionalized materials were fabricated by photo-grafting poly(acrylic acid) onto polypropylene (PP) films, followed by a second photo-grafting process to graft-polymerize an IDA functionalized vinyl monomer (GMA-IDA). The photo-grafting was conducted under atmospheric conditions and was completed in 2 min. The resulting IDA functionalized metal-chelating material was able to chelate iron and copper, and showed antioxidant efficacy against ascorbic acid degradation, supporting its potential to be used synergistically with natural antioxidants for preservation of food and beverage products. The 2-step photo-grafting process improves the throughput of active packaging coatings, enabling potential roll-to-roll fabrication of metal-chelating active packaging materials for antioxidant food packaging applications. To address consumer and retail demands for "clean label" foods and beverages without a corresponding loss in product quality and shelf life, producers are seeking next generation technologies such as active packaging. In this work, we will report the synthesis of metal-chelating active packaging films, which enable removal of the synthetic additive, ethylenediamine tetraacetic acid. The new synthesis technique improves the throughput of metal-chelating active packaging coatings, enabling potential roll-to-roll fabrication of the materials for antioxidant food packaging applications. © 2018 Institute of Food Technologists®.

Transition metal oxide as anode interface buffer for impedance spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Hui; Tang, Chao; Wang, Xu-Liang; Zhai, Wen-Juan; Liu, Rui-Lan; Rong, Zhou; Pang, Zong-Qiang; Jiang, Bing; Fan, Qu-Li; Huang, Wei

2015-12-01

Impedance spectroscopy is a strong method in electric measurement, which also shows powerful function in research of carrier dynamics in organic semiconductors when suitable mathematical physical models are used. Apart from this, another requirement is that the contact interface between the electrode and materials should at least be quasi-ohmic contact. So in this report, three different transitional metal oxides, V2O5, MoO3 and WO3 were used as hole injection buffer for interface of ITO/NPB. Through the impedance spectroscopy and PSO algorithm, the carrier mobilities and I-V characteristics of the NPB in different devices were measured. Then the data curves were compared with the single layer device without the interface layer in order to investigate the influence of transitional metal oxides on the carrier mobility. The careful research showed that when the work function (WF) of the buffer material was just between the work function of anode and the HOMO of the organic material, such interface material could work as a good bridge for carrier injection. Under such condition, the carrier mobility measured through impedance spectroscopy should be close to the intrinsic value. Considering that the HOMO (or LUMO) of most organic semiconductors did not match with the work function of the electrode, this report also provides a method for wide application of impedance spectroscopy to the research of carrier dynamics.

Type-inversion as a working mechanism of high voltage MAPbBr3(Cl)-based halide perovskite solar cells.

PubMed

Kedem, Nir; Kulbak, Michael; Brenner, Thomas M; Hodes, Gary; Cahen, David

2017-02-22

Using several metals with different work functions as solar cell back contact we identify majority carrier type inversion in methylammonium lead bromide (MAPbBr3, without intentional doping) as the basis for the formation of a p-n junction. MAPbBr 3 films deposited on TiO 2 are slightly n-type, whereas in a full device they are strongly p-type. The charge transfer between the metal electrode and the halide perovskite (HaP) film is shown to determine the dominant charge carrier type of the HaP and, thus, also of the final cells. Usage of Pt, Au and Pb as metal electrodes shows the effects of metal work function on minority carrier diffusion length and majority carrier concentration in the HaP, as well as on built-in voltage, band bending, and open circuit voltage (V OC ) within a solar cell. V OC > 1.5 V is demonstrated. The higher the metal WF, the higher the carrier concentration induced in the HaP, as indicated by a narrower space charge region and a smaller minority carrier diffusion length. From the analysis of bias-dependent electron beam-induced currents, the HaP carrier concentrations are estimated to be ∼ 1 × 10 17 cm -3 with Au and 2-3 × 10 18 cm -3 with Pt. A model in which type-inversion stretches across the entire film width implies formation of the p-n junction away from the interface, near the back-contact metal electrode. This work highlights the importance of the contact metal on device performance in that contact engineering can also serve to control the carrier concentration in HaP.

Alleviation of Fermi level pinning at metal/n-Ge interface with lattice-matched Si x Ge1‑ x ‑ y Sn y ternary alloy interlayer on Ge

NASA Astrophysics Data System (ADS)

Suzuki, Akihiro; Nakatsuka, Osamu; Sakashita, Mitsuo; Zaima, Shigeaki

2018-06-01

The impact of a silicon germanium tin (Si x Ge1‑ x ‑ y Sn y ) ternary alloy interlayer on the Schottky barrier height (SBH) of metal/Ge contacts with various metal work functions has been investigated. Lattice matching at the Si x Ge1‑ x ‑ y Sn y /Ge heterointerface is a key factor for controlling Fermi level pinning (FLP) at the metal/Ge interface. The Si x Ge1‑ x ‑ y Sn y ternary alloy interlayer having a small lattice mismatch with the Ge substrate can alleviate FLP at the metal/Ge interface significantly. A Si0.11Ge0.86Sn0.03 interlayer increases the slope parameter for the work function dependence of the SBH to 0.4. An ohmic behavior with an SBH below 0.15 eV can be obtained with Zr and Al/Si0.11Ge0.86Sn0.03/n-Ge contacts at room temperature.

Metal contact engineering and registration-free fabrication of complementary metal-oxide semiconductor integrated circuits using aligned carbon nanotubes.

PubMed

Wang, Chuan; Ryu, Koungmin; Badmaev, Alexander; Zhang, Jialu; Zhou, Chongwu

2011-02-22

Complementary metal-oxide semiconductor (CMOS) operation is very desirable for logic circuit applications as it offers rail-to-rail swing, larger noise margin, and small static power consumption. However, it remains to be a challenging task for nanotube-based devices. Here in this paper, we report our progress on metal contact engineering for n-type nanotube transistors and CMOS integrated circuits using aligned carbon nanotubes. By using Pd as source/drain contacts for p-type transistors, small work function metal Gd as source/drain contacts for n-type transistors, and evaporated SiO(2) as a passivation layer, we have achieved n-type transistor, PN diode, and integrated CMOS inverter with an air-stable operation. Compared with other nanotube n-doping techniques, such as potassium doping, PEI doping, hydrazine doping, etc., using low work function metal contacts for n-type nanotube devices is not only air stable but also integrated circuit fabrication compatible. Moreover, our aligned nanotube platform for CMOS integrated circuits shows significant advantage over the previously reported individual nanotube platforms with respect to scalability and reproducibility and suggests a practical and realistic approach for nanotube-based CMOS integrated circuit applications.

Generalized formula for electron emission taking account of the polaron effect

NASA Astrophysics Data System (ADS)

Barengolts, Yu A.; Beril, S. I.; Barengolts, S. A.

2018-01-01

A generalized formula is derived for the electron emission current as a function of temperature, field, and electron work function in a metal-dielectric system that takes account of the quantum nature of the image forces. In deriving the formula, the Fermi-Dirac distribution for electrons in a metal and the quantum potential of the image obtained in the context of electron polaron theory are used.

Heavy metal pumps in plants. 1998 annual progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harper, J.F.

1998-06-01

'The purpose of the proposed DOE research is to determine the function of AMA1, a novel heavy metal pump identified in a model plant system, Arabidopsis. Heavy metal pumps belong to a superfamily of P-type ATPases which include the plasma membrane Na/K-ATPase in animals and the plasma membrane H + ATPase in plants and fungi. Heavy metal pumps have been implicated in heavy metal resistance (e.g., cadmium) and regulation of essential micronutrients (e.g., copper). Although several heavy metal pumps have now been identified in plants, their isoform specific functions have not been investigated. The results suggest that AMA1 is amore » molydenum uptake pump. The authors are exploring the possibility to engineer the ion specificity of these pumps to take up other heavy metals from the soil. This report summarizes work after 2 years of a 3 year project.'« less

Solid-State Diffusional Behaviors of Functional Metal Oxides at Atomic Scale.

PubMed

Chen, Jui-Yuan; Huang, Chun-Wei; Wu, Wen-Wei

2018-02-01

Metal/metal oxides have attracted extensive research interest because of their combination of functional properties and compatibility with industry. Diffusion and thermal reliability have become essential issues that require detailed study to develop atomic-scaled functional devices. In this work, the diffusional reaction behavior that transforms piezoelectric ZnO into magnetic Fe 3 O 4 is investigated at the atomic scale. The growth kinetics of metal oxides are systematically studied through macro- and microanalyses. The growth rates are evaluated by morphology changes, which determine whether the growth behavior was a diffusion- or reaction-controlled process. Furthermore, atom attachment on the kink step is observed at the atomic scale, which has important implications for the thermodynamics of functional metal oxides. Faster growth planes simultaneously decrease, which result in the predominance of low surface energy planes. These results directly reveal the atomic formation process of metal oxide via solid-state diffusion. In addition, the nanofabricated method provides a novel approach to investigate metal oxide evolution and sheds light on diffusional reaction behavior. More importantly, the results and phenomena of this study provide considerable inspiration to enhance the material stability and reliability of metal/oxide-based devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrical characteristics of n-GaN Schottky contacts on cleaved surfaces of free-standing substrates: Metal work function dependence of Schottky barrier height

NASA Astrophysics Data System (ADS)

Imadate, Hiroyoshi; Mishima, Tomoyoshi; Shiojima, Kenji

2018-04-01

We report the electrical characteristics of Schottky contacts with nine different metals (Ag, Ti, Cr, W, Mo, Au, Pd, Ni, and Pt) formed on clean m-plane surfaces by cleaving freestanding GaN substrates, compared with these of contacts on Ga-polar c-plane n-GaN surfaces grown on GaN substrates. The n-values from the forward current–voltage (I–V) characteristics are as good as 1.02–1.18 and 1.02–1.09 for the m- and c-plane samples, respectively. We found that the reverse I–V curves of both samples can be explained by the thermionic field emission theory, and that the Schottky barrier height of the cleaved m-plane contacts shows a metal work function dependence.

Hartree-Fock theory of the inhomogeneous electron gas at a jellium metal surface: Rigorous upper bounds to the surface energy and accurate work functions

NASA Astrophysics Data System (ADS)

Sahni, V.; Ma, C. Q.

1980-12-01

The inhomogeneous electron gas at a jellium metal surface is studied in the Hartree-Fock approximation by Kohn-Sham density functional theory. Rigorous upper bounds to the surface energy are derived by application of the Rayleigh-Ritz variational principle for the energy, the surface kinetic, electrostatic, and nonlocal exchange energy functionals being determined exactly for the accurate linear-potential model electronic wave functions. The densities obtained by the energy minimization constraint are then employed to determine work-function results via the variationally accurate "displaced-profile change-in-self-consistent-field" expression. The theoretical basis of this non-self-consistent procedure and its demonstrated accuracy for the fully correlated system (as treated within the local-density approximation for exchange and correlation) leads us to conclude these results for the surface energies and work functions to be essentially exact. Work-function values are also determined by the Koopmans'-theorem expression, both for these densities as well as for those obtained by satisfaction of the constraint set on the electrostatic potential by the Budd-Vannimenus theorem. The use of the Hartree-Fock results in the accurate estimation of correlation-effect contributions to these surface properties of the nonuniform electron gas is also indicated. In addition, the original work and approximations made by Bardeen in this attempt at a solution of the Hartree-Fock problem are briefly reviewed in order to contrast with the present work.

Controlled modification of resonant tunneling in metal-insulator-insulator-metal structures

NASA Astrophysics Data System (ADS)

Mitrovic, I. Z.; Weerakkody, A. D.; Sedghi, N.; Ralph, J. F.; Hall, S.; Dhanak, V. R.; Luo, Z.; Beeby, S.

2018-01-01

We present comprehensive experimental and theoretical work on tunnel-barrier rectifiers comprising bilayer (Nb2O5/Al2O3) insulator configurations with similar (Nb/Nb) and dissimilar (Nb/Ag) metal electrodes. The electron affinity, valence band offset, and metal work function were ascertained by X-ray photoelectron spectroscopy, variable angle spectroscopic ellipsometry, and electrical measurements on fabricated reference structures. The experimental band line-up parameters were fed into a theoretical model to predict available bound states in the Nb2O5/Al2O3 quantum well and generate tunneling probability and transmittance curves under applied bias. The onset of strong resonance in the sub-V regime was found to be controlled by a work function difference of Nb/Ag electrodes in agreement with the experimental band alignment and theoretical model. A superior low-bias asymmetry of 35 at 0.1 V and a responsivity of 5 A/W at 0.25 V were observed for the Nb/4 nm Nb2O5/1 nm Al2O3/Ag structure, sufficient to achieve a rectification of over 90% of the input alternate current terahertz signal in a rectenna device.

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

DOE PAGES

Liu, Zhen-Fei; Egger, David A.; Refaely-Abramson, Sivan; ...

2017-02-21

The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density functional theory calculations, especially those using local and semi-local functionals, often underestimate level alignment leading to inaccurate electronic structure and charge transport properties. Here, we develop a new fully self-consistent predictive scheme to accurately compute level alignment at certain classes of complex heterogeneous molecule-metal interfaces based on optimally tuned range-separated hybrid functionals. Starting from a highly accurate description of the gas-phase electronic structure, our method by constructionmore » captures important nonlocal surface polarization effects via tuning of the long-range screened exchange in a range-separated hybrid in a non-empirical and system-specific manner. We implement this functional in a plane-wave code and apply it to several physisorbed and chemisorbed molecule-metal interface systems. Our results are in quantitative agreement with experiments, the both the level alignment and work function changes. This approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.« less

To what extent do structural changes in catalytic metal sites affect enzyme function?

PubMed

Valasatava, Yana; Rosato, Antonio; Furnham, Nicholas; Thornton, Janet M; Andreini, Claudia

2018-02-01

About half of known enzymatic reactions involve metals. Enzymes belonging to the same superfamily often evolve to catalyze different reactions on the same structural scaffold. The work presented here investigates how functional differentiation, within superfamilies that contain metalloenzymes, relates to structural changes at the catalytic metal site. In general, when the catalytic metal site is unchanged across the enzymes of a superfamily, the functional differentiation within the superfamily tends to be low and the mechanism conserved. Conversely, all types of structural changes in the metal binding site are observed for superfamilies with high functional differentiation. Overall, the catalytic role of the metal ions appears to be one of the most conserved features of the enzyme mechanism within metalloenzyme superfamilies. In particular, when the catalytic role of the metal ion does not involve a redox reaction (i.e. there is no exchange of electrons with the substrate), this role is almost always maintained even when the site undergoes significant structural changes. In these enzymes, functional diversification is most often associated with modifications in the surrounding protein matrix, which has changed so much that the enzyme chemistry is significantly altered. On the other hand, in more than 50% of the examples where the metal has a redox role in catalysis, changes at the metal site modify its catalytic role. Further, we find that there are no examples in our dataset where metal sites with a redox role are lost during evolution. In this paper we investigate how functional diversity within superfamilies of metalloenzymes relates to structural changes at the catalytic metal site. Evolution tends to strictly conserve the metal site. When changes occur, they do not modify the catalytic role of non-redox metals whereas they affect the role of redox-active metals. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Application of Density Functional Theory to Systems Containing Metal Atoms

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.

2006-01-01

The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+n, MNO+, and MCO+2. The DFT works well for frequencies and geometries, even in case with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of successes as well as failures of DFT will be given.

Work function of few layer graphene covered nickel thin films measured with Kelvin probe force microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eren, B.; Material Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720; Gysin, U.

2016-01-25

Few layer graphene and graphite are simultaneously grown on a ∼100 nm thick polycrystalline nickel film. The work function of few layer graphene/Ni is found to be 4.15 eV with a variation of 50 meV by local measurements with Kelvin probe force microscopy. This value is lower than the work function of free standing graphene due to peculiar electronic structure resulting from metal 3d-carbon 2p(π) hybridization.

Quantum and conversion efficiencies optimization of superstrate CIGS thin-films solar cells using In2Se3 buffer layer

NASA Astrophysics Data System (ADS)

Bouchama, Idris; Boudour, Samah; Bouarissa, Nadir; Rouabah, Zahir

2017-10-01

In this present contribution, AMPS-1D device simulator is employed to study the performances of superstrate SLG/TCO/p-Cu(In,Ga)Se2(CIGS)/n-ODC/n-In2Se3/Metal thin film solar cells. The impact of the TCO and Metal work functions on the cell performance has been investigated. The combination of optical transparency and electrical property for TCO front contact layer is found to yield high efficiency. The obtained results show that the TCO work function should be large enough to achieve high conversion efficiency for superstrate CIGS solar cell. Nevertheless, it is desirable for Metal back contact layer to have low work function to prevent the effect of band bending in the n-In2Se3/Metal interface. Several TCOs materials and metals have been tested respectively as a front and back contact layers for superstrate CIGS solar cells. An efficiency of 20.18%, with Voc ≈ 0.71 V, Jsc ≈ 35.36 mA/cm2 and FF ≈ 80.42%, has been achieved with ZnSn2O3-based as TCO front contact layer. In the case of SnO2:F front contact and indium back contact layers, an efficiency of 16.31%, with Voc ≈ 0.64 V, Jsc ≈ 31.4 mA/cm2 and FF ≈ 79.4%, has been obtained. The present results of simulation suggest an improvement of superstrate CIGS solar cells efficiency for feasible fabrication.

Charge injection in thin dielectric layers by atomic force microscopy: influence of geometry and material work function of the AFM tip on the injection process

NASA Astrophysics Data System (ADS)

Villeneuve-Faure, C.; Makasheva, K.; Boudou, L.; Teyssedre, G.

2016-06-01

Charge injection and retention in thin dielectric layers remain critical issues for the reliability of many electronic devices because of their association with a large number of failure mechanisms. To overcome this drawback, a deep understanding of the mechanisms leading to charge injection close to the injection area is needed. Even though the charge injection is extensively studied and reported in the literature to characterize the charge storage capability of dielectric materials, questions about charge injection mechanisms when using atomic force microscopy (AFM) remain open. In this paper, a thorough study of charge injection by using AFM in thin plasma-processed amorphous silicon oxynitride layers with properties close to that of thermal silica layers is presented. The study considers the impact of applied voltage polarity, work function of the AFM tip coating and tip curvature radius. A simple theoretical model was developed and used to analyze the obtained experimental results. The electric field distribution is computed as a function of tip geometry. The obtained experimental results highlight that after injection in the dielectric layer the charge lateral spreading is mainly controlled by the radial electric field component independently of the carrier polarity. The injected charge density is influenced by the nature of electrode metal coating (work function) and its geometry (tip curvature radius). The electron injection is mainly ruled by the Schottky injection barrier through the field electron emission mechanism enhanced by thermionic electron emission. The hole injection mechanism seems to differ from the electron one depending on the work function of the metal coating. Based on the performed analysis, it is suggested that for hole injection by AFM, pinning of the metal Fermi level with the metal-induced gap states in the studied silicon oxynitride layers starts playing a role in the injection mechanisms.

Prospects of zero Schottky barrier height in a graphene-inserted MoS2-metal interface

NASA Astrophysics Data System (ADS)

Chanana, Anuja; Mahapatra, Santanu

2016-01-01

A low Schottky barrier height (SBH) at source/drain contact is essential for achieving high drive current in atomic layer MoS2-channel-based field effect transistors. Approaches such as choosing metals with appropriate work functions and chemical doping are employed previously to improve the carrier injection from the contact electrodes to the channel and to mitigate the SBH between the MoS2 and metal. Recent experiments demonstrate significant SBH reduction when graphene layer is inserted between metal slab (Ti and Ni) and MoS2. However, the physical or chemical origin of this phenomenon is not yet clearly understood. In this work, density functional theory simulations are performed, employing pseudopotentials with very high basis sets to get insights of the charge transfer between metal and monolayer MoS2 through the inserted graphene layer. Our atomistic simulations on 16 different interfaces involving five different metals (Ti, Ag, Ru, Au, and Pt) reveal that (i) such a decrease in SBH is not consistent among various metals, rather an increase in SBH is observed in case of Au and Pt; (ii) unlike MoS2-metal interface, the projected dispersion of MoS2 remains preserved in any MoS2-graphene-metal system with shift in the bands on the energy axis. (iii) A proper choice of metal (e.g., Ru) may exhibit ohmic nature in a graphene-inserted MoS2-metal contact. These understandings would provide a direction in developing high-performance transistors involving heteroatomic layers as contact electrodes.

Progress of Application Researches of Porous Fiber Metals

PubMed Central

Xi, Zhengping; Zhu, Jilei; Tang, Huiping; Ao, Qingbo; Zhi, Hao; Wang, Jianyong; Li, Cheng

2011-01-01

Metal fiber porous materials with intrinsic properties of metal and functional properties of porous materials have received a great deal of attention in the fundamental research and industry applications. With developments of the preparation technologies and industrial requirements, porous fiber metals with excellent properties are developed and applied in many industry areas, e.g., sound absorption, heat transfer, energy absorption and lightweight structures. The applied research progress of the metal fiber porous materials in such application areas based on the recent work in our group was reviewed in this paper. PMID:28879952

Biomolecules for Removal of Heavy Metal.

PubMed

Singh, Namita Ashish

2017-01-01

Patents reveal that heavy metals are natural constituents of the earth's crust, but some heavy metals like cadmium, lead, mercury, arsenic etc. are injurious to living organisms at higher concentration. Nowadays, anthropogenic activities have altered geochemical cycles and biochemical balance of heavy metals. Biomolecules are used nowadays for removal of heavy metals compared to other synthetic biosorbents due to their environmental friendly nature and cost effectiveness. The goal of this work is to identify the role of biomolecules like polysaccharides, polypeptides, natural compounds containing aromatic acid etc. for heavy metal removal by bio sorption. It has been observed that efficiency of biomolecules can be increased by functionalization e.g. cellulose functionalization with EDTA, chitosan with sulphur groups, alginate with carboxyl/ hydroxyl group etc. It was found that the porous structure of aerogel beads improves both sorption and kinetic properties of the material. Out of polypeptides metallothionein has been widely used for removal of heavy metal up to 88% from seawater after a single centrifugation. These cost effective functionalized biomolecules are significantly used for remediation of heavy metals by immobilizing these biomolecules onto materials. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Transmissive metallic contact for amorphous silicon solar cells

DOEpatents

Madan, A.

1984-11-29

A transmissive metallic contact for amorphous silicon semiconductors includes a thin layer of metal, such as aluminum or other low work function metal, coated on the amorphous silicon with an antireflective layer coated on the metal. A transparent substrate, such as glass, is positioned on the light reflective layer. The metallic layer is preferably thin enough to transmit at least 50% of light incident thereon, yet thick enough to conduct electricity. The antireflection layer is preferably a transparent material that has a refractive index in the range of 1.8 to 2.2 and is approximately 550A to 600A thick.

Electron Thermionic Emission from Graphene and a Thermionic Energy Converter

NASA Astrophysics Data System (ADS)

Liang, Shi-Jun; Ang, L. K.

2015-01-01

In this paper, we propose a model to investigate the electron thermionic emission from single-layer graphene (ignoring the effects of the substrate) and to explore its application as the emitter of a thermionic energy converter (TIC). An analytical formula is derived, which is a function of the temperature, work function, and Fermi energy level. The formula is significantly different from the traditional Richardson-Dushman (RD) law for which it is independent of mass to account for the supply function of the electrons in the graphene behaving like massless fermion quasiparticles. By comparing with a recent experiment [K. Jiang et al., Nano Res. 7, 553 (2014)] measuring electron thermionic emission from suspended single-layer graphene, our model predicts that the intrinsic work function of single-layer graphene is about 4.514 eV with a Fermi energy level of 0.083 eV. For a given work function, a scaling of T3 is predicted, which is different from the traditional RD scaling of T2. If the work function of the graphene is lowered to 2.5-3 eV and the Fermi energy level is increased to 0.8-0.9 eV, it is possible to design a graphene-cathode-based TIC operating at around 900 K or lower, as compared with the metal-based cathode TIC (operating at about 1500 K). With a graphene-based cathode (work function=4.514 eV ) at 900 K and a metallic-based anode (work function=2.5 eV ) like LaB6 at 425 K, the efficiency of our proposed TIC is about 45%.

Metal electrode for amorphous silicon solar cells

DOEpatents

Williams, Richard

1983-01-01

An amorphous silicon solar cell having an N-type region wherein the contact to the N-type region is composed of a material having a work function of about 3.7 electron volts or less. Suitable materials include strontium, barium and magnesium and rare earth metals such as gadolinium and yttrium.

Heavy Metal Adsorption onto Kappaphycus sp. from Aqueous Solutions: The Use of Error Functions for Validation of Isotherm and Kinetics Models

PubMed Central

Rahman, Md. Sayedur; Sathasivam, Kathiresan V.

2015-01-01

Biosorption process is a promising technology for the removal of heavy metals from industrial wastes and effluents using low-cost and effective biosorbents. In the present study, adsorption of Pb2+, Cu2+, Fe2+, and Zn2+ onto dried biomass of red seaweed Kappaphycus sp. was investigated as a function of pH, contact time, initial metal ion concentration, and temperature. The experimental data were evaluated by four isotherm models (Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich) and four kinetic models (pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion models). The adsorption process was feasible, spontaneous, and endothermic in nature. Functional groups in the biomass involved in metal adsorption process were revealed as carboxylic and sulfonic acids and sulfonate by Fourier transform infrared analysis. A total of nine error functions were applied to validate the models. We strongly suggest the analysis of error functions for validating adsorption isotherm and kinetic models using linear methods. The present work shows that the red seaweed Kappaphycus sp. can be used as a potentially low-cost biosorbent for the removal of heavy metal ions from aqueous solutions. Further study is warranted to evaluate its feasibility for the removal of heavy metals from the real environment. PMID:26295032

Heavy Metal Adsorption onto Kappaphycus sp. from Aqueous Solutions: The Use of Error Functions for Validation of Isotherm and Kinetics Models.

PubMed

Rahman, Md Sayedur; Sathasivam, Kathiresan V

2015-01-01

Biosorption process is a promising technology for the removal of heavy metals from industrial wastes and effluents using low-cost and effective biosorbents. In the present study, adsorption of Pb(2+), Cu(2+), Fe(2+), and Zn(2+) onto dried biomass of red seaweed Kappaphycus sp. was investigated as a function of pH, contact time, initial metal ion concentration, and temperature. The experimental data were evaluated by four isotherm models (Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich) and four kinetic models (pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion models). The adsorption process was feasible, spontaneous, and endothermic in nature. Functional groups in the biomass involved in metal adsorption process were revealed as carboxylic and sulfonic acids and sulfonate by Fourier transform infrared analysis. A total of nine error functions were applied to validate the models. We strongly suggest the analysis of error functions for validating adsorption isotherm and kinetic models using linear methods. The present work shows that the red seaweed Kappaphycus sp. can be used as a potentially low-cost biosorbent for the removal of heavy metal ions from aqueous solutions. Further study is warranted to evaluate its feasibility for the removal of heavy metals from the real environment.

SDSS-IV MaNGA: modelling the metallicity gradients of gas and stars - radially dependent metal outflow versus IMF

NASA Astrophysics Data System (ADS)

Lian, Jianhui; Thomas, Daniel; Maraston, Claudia; Goddard, Daniel; Parikh, Taniya; Fernández-Trincado, J. G.; Roman-Lopes, Alexandre; Rong, Yu; Tang, Baitian; Yan, Renbin

2018-05-01

In our previous work, we found that only two scenarios are capable of reproducing the observed integrated mass-metallicity relations for the gas and stellar components of local star-forming galaxies simultaneously. One scenario invokes a time-dependent metal outflow loading factor with stronger outflows at early times. The other scenario uses a time-dependent initial mass function (IMF) slope with a steeper IMF at early times. In this work, we extend our study to investigate the radial profile of gas and stellar metallicity in local star-forming galaxies using spatially resolved spectroscopic data from the SDSS-IV MaNGA survey. We find that most galaxies show negative gradients in both gas and stellar metallicity with steeper gradients in stellar metallicity. The stellar metallicity gradients tend to be mass dependent with steeper gradients in more massive galaxies while no clear mass dependence is found for the gas metallicity gradient. Then we compare the observations with the predictions from a chemical evolution model of the radial profiles of gas and stellar metallicities. We confirm that the two scenarios proposed in our previous work are also required to explain the metallicity gradients. Based on these two scenarios, we successfully reproduce the radial profiles of gas metallicity, stellar metallicity, stellar mass surface density, and star formation rate surface density simultaneously. The origin of the negative gradient in stellar metallicity turns out to be driven by either radially dependent metal outflow or IMF slope. In contrast, the radial dependence of the gas metallicity is less constrained because of the degeneracy in model parameters.

Work function and quantum efficiency study of metal oxide thin films on Ag(100)

NASA Astrophysics Data System (ADS)

Chang, V.; Noakes, T. C. Q.; Harrison, N. M.

2018-04-01

Increasing the quantum efficiency (QE) of metal photocathodes is in the design and development of photocathodes for free-electron laser applications. The growth of metal oxide thin films on certain metal surfaces has previously been shown to reduce the work function (WF). Using a photoemission model B. Camino et al. [Comput. Mater. Sci. 122, 331 (2016), 10.1016/j.commatsci.2016.05.025] based on the three-step model combined with density functional theory calculations we predict that the growth of a finite number of MgO(100) or BaO(100) layers on the Ag(100) surface increases significantly the QE compared with the clean Ag(100) surface for a photon energy of 4.7 eV. Different mechanisms for affecting the QE are identified for the different metal oxide thin films. The addition of MgO(100) increases the QE due to the reduction of the WF and the direct excitation of electrons from the Ag surface to the MgO conduction band. For BaO(100) thin films, an additional mechanism is in operation as the oxide film also photoemits at this energy. We also note that a significant increase in the QE for photons with an energy of a few eV above the WF is achieved due to an increase in the inelastic mean-free path of the electrons.

Electronic states of Ca/PC61BM: Mechanism of low work function metal as interfacial material

NASA Astrophysics Data System (ADS)

Du, Ying-Ying; Chen, Guang-Hua; Li, Wen-Jie; Bai, Xin-Yuan; Lin, De-Qu; Ju, Huanxin; Hu, Shanwei; Xu, Qian; Wang, Yan; Li, Xiong; Zhu, Junfa; Li, Hong-Nian

2018-03-01

We have studied the electronic states at Ca/PC61BM interface using photoemission spectroscopy. It is found that the state of unoccupied molecular orbitals of the top molecular layer (TML) becomes occupied by the electrons transferred from the Ca atoms. The work function of the heavily doped TML of PC61BM film is smaller than that of metal Ca, and thus the contact between the TML and metal Ca is Ohmic. A transition layer (TL) of several molecular layers forms beneath the TML due to the diffusion of the Ca atoms. The TL is conductive and aligns its Fermi level with the negative integer charge transfer level of the interior PC61BM. The built-in electric field in the TL facilitates the electron transport from the interior of the PC61BM film to the TML.

ITO Modification for Efficient Inverted Organic Solar Cells.

PubMed

Susarova, Diana K; Akkuratov, Alexander V; Kukharenko, Andrey I; Cholakh, Seif O; Kurmaev, Ernst Z; Troshin, Pavel A

2017-10-03

We demonstrate a facile approach to designing transparent electron-collecting electrodes by depositing thin layers of medium and low work function metals on top of transparent conductive metal oxides (TCOs) such as ITO and FTO. The modified electrodes were fairly stable for months under ambient conditions and maintained their electrical characteristics. XPS spectroscopy data strongly suggested integration of the deposited metal in the TCO structure resulting in additional doping of the conducting oxide at the interface. Kelvin probe microscopy measurements revealed a significant decrease in the ITO work function after modification. Organic solar cells based on three different conjugated polymers have demonstrated state of the art performances in inverted device geometry using Mg- or Yb-modified ITO as electron collecting electrode. The simplicity of the proposed approach and the excellent ambient stability of the modified ITO electrodes allows one to expect their wide utilization in research laboratories and electronic industry.

Enlarging photovoltaic effect: combination of classic photoelectric and ferroelectric photovoltaic effects.

PubMed

Zhang, Jingjiao; Su, Xiaodong; Shen, Mingrong; Dai, Zhihua; Zhang, Lingjun; He, Xiyun; Cheng, Wenxiu; Cao, Mengyu; Zou, Guifu

2013-01-01

Converting light energy to electrical energy in photovoltaic devices relies on the photogenerated electrons and holes separated by the built-in potential in semiconductors. Photo-excited electrons in metal electrodes are usually not considered in this process. Here, we report an enhanced photovoltaic effect in the ferroelectric lanthanum-modified lead zirconate titanate (PLZT) by using low work function metals as the electrodes. We believe that electrons in the metal with low work function could be photo-emitted into PLZT and form the dominant photocurrent in our devices. Under AM1.5 (100 mW/cm²) illumination, the short-circuit current and open-circuit voltage of Mg/PLZT/ITO are about 150 and 2 times of those of Pt/PLZT/ITO, respectively. The photovoltaic response of PLZT capacitor was expanded from ultraviolet to visible spectra, and it may have important impact on design and fabrication of high performance photovoltaic devices based on ferroelectric materials.

Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

NASA Astrophysics Data System (ADS)

Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-03-01

The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

Electrode influence on the number of oxygen vacancies at the gate/high-κ dielectric interface in nanoscale MIM capacitors

NASA Astrophysics Data System (ADS)

Stojanovska-Georgievska, Lihnida

2015-02-01

In this paper, a particular attention has been paid in determining the impact of the type of top electrode (the gate), on the overall characteristics of the examined metal-insulator-metal structures, that contain doped Ta2O5:Hf high-κ dielectric as an insulator. For that purpose MIM capacitors with different metal gates (conventional Al and also W, Au, Pt, Mo, TiN, Ta) were formed. The results obtained, consider both the influence of metal work function and oxygen affinity, as possible reasons for increasing of number of oxygen vacancies at the gate/dielectric interface. Here we use capacitance-voltage alteration (C-V measurements) under constant current stress (CCS) conditions as characterization technique. The measurements show grater creation of positive oxygen vacancies in the case of metal electrodes with high work function, like Au and Pt, for almost one order of magnitude. It is also indicative that these metals have also the lowest values of heat of oxygen formation, which also favors the creation of oxygen vacancies. All results are discussed taking into consideration the nanoscale thickness of the dielectric layer (of the order of 8 nm), implicating the stronger effect of interface properties on the overall behavior rather than the one originating from the bulk of material.

Charge transfer and injection barrier at the metal-organic interfaces

NASA Astrophysics Data System (ADS)

Yan, Li

2002-09-01

The metal-organic interface plays a critical role in determining the functionality and performance of many innovative organic based devices. It has attracted extensive research interests in recent years. This thesis presents investigations of the electronic structures of organic materials, such as tris-(8-hydroxyquinoline) aluminum (Alq3) and copper phthalocyanine (CuPc), during their interface formation with metals. The characterization is accomplished by X-ray and ultraviolet photoelectron spectroscopes (XPS and UPS) and inverse photoelectron spectroscopy (IPES). As discussed herein, both occupied and unoccupied electronic states at the interfaces are carefully examined in different aspects. In Chapter 4, the charge transfer and chemical reaction at various metal/Alq3 interfaces are investigated using XPS and UPS to study the electron injection into the Alga film. Electron transfer from the low work function metal and Al/LiF(CsF) bilayer to the Alga has been observed. The role of the dielectric and possible chemistry at the interface are discussed in comparison of the low work function metals. Further in Chapter 5, the origin of the metal-interface dipole and the estimation of charge injection barrier is explored using several organic materials. A thermodynamic equilibrium model is extended to explain the relation between the charge transfer process ad the interface dipole. Further, in Chapter 6 the combination of XPS, UPS and IPES detailed the evolution of both occupied and unoccupied energy states during the alkali metal doping. The energy gap modification in organic due to metal doping is observed directly for the spectra. Chapter 7 provides stability study of the organic thin films under x-ray and UV light. The results verify the usability of UPS and XPS for the organic materials used in the thesis. Chapter 7 also shows the secondary ion mass spectroscopy results of metal diffusion in organic thin films.

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

PubMed

Lennon, David; Winfield, John M

2017-01-28

Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

Quasi-static Tensile and Compressive Behavior of Nanocrystalline Tantalum based on Miniature Specimen Testing—Part I: Materials Processing and Microstructure

NASA Astrophysics Data System (ADS)

Ligda, J.; Scotto D'Antuono, D.; Taheri, M. L.; Schuster, B. E.; Wei, Q.

2016-11-01

Grain size reduction of metals into ultrafine-grained (UFG, grain size 100 nm < d < 1000 nm) and nanocrystalline (NC, d < 100 nm) regimes results in considerable increase in strength along with other changes in mechanical behavior such as vanishing strain hardening and limited ductility. Severe plastic deformation (SPD) has been among the favored technologies for the fabrication of UFG/NC metals. Primary past research efforts on SPD UFG/NC metals have been focused on easy-to-work metals, especially face-centered cubic metals such as copper, nickel, etc., and the limited efforts on body-centered cubic metals have mainly focused on high strain rate behavior where these metals are shown to deform via adiabatic shear bands. Except for the work on Fe, only a few papers can be found associated with UFG/NC refractory metals. In the first part of the present work (Part I), high-pressure torsion (HPT) is used to process UFG/NC tantalum, a typical refractory metal. The microstructure of the HPT disk as a function of radial location as well as orientation will be examined. In the subsequent part (Part II), the location-specific mechanical behavior will be presented and discussed. It is suggested that refractory metals such as Ta are ideal to employ SPD technology for microstructure refinement because of the extremely high melting point and relatively good workability.

Exploring the charge localization and band gap opening of borophene: a first-principles study.

PubMed

Kistanov, Andrey A; Cai, Yongqing; Zhou, Kun; Srikanth, Narasimalu; Dmitriev, Sergey V; Zhang, Yong-Wei

2018-01-18

Recently synthesized two-dimensional (2D) boron, borophene, exhibits a novel metallic behavior rooted in the s-p orbital hybridization, distinctively different from other 2D materials such as sulfides/selenides and semi-metallic graphene. This unique feature of borophene implies new routes for charge delocalization and band gap opening. Herein, using first-principles calculations, we explore the routes to localize the carriers and open the band gap of borophene via chemical functionalization, ribbon construction, and defect engineering. The metallicity of borophene is found to be remarkably robust against H- and F-functionalization and the presence of vacancies. Interestingly, a strong odd-even oscillation of the electronic structure with width is revealed for H-functionalized borophene nanoribbons, while an ultra-high work function (∼7.83 eV) is found for the F-functionalized borophene due to its strong charge transfer to the atomic adsorbates.

Application of Density Functional Theory to Systems Containing Metal Atoms

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

1997-01-01

The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+(sub n), MNO+, and MCO+(sub 2). The DFT works well for frequencies and geometries, even in cases with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of the successes as well as failures of DFT will be given.

Optimization of the Negative Electrode in Organic Photovoltaic Devices

NASA Astrophysics Data System (ADS)

Reese, Matthew; White, Matthew; Rumbles, Garry; Ginley, David; Shaheen, Sean

2007-03-01

A blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) is used as the active layer in a series of bulk heterojunction organic solar cells. This polymer blend serves as a test-bed to explore the significant effects on device performance of using low work function metals and/or alkali metal halides as the top, negative electrode. Work function values reported in the literature are compared with those measured for our thin films. A series of contact materials are investigated including Al, Ca/Al, Ba/Al, LiF/Al; many devices are prepared with each contact type to validate the statistical significance of the results.

Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

PubMed

Benson, Oguarabau; da Silva, Ivan; Argent, Stephen P; Cabot, Rafel; Savage, Mathew; Godfrey, Harry G W; Yan, Yong; Parker, Stewart F; Manuel, Pascal; Lennox, Matthew J; Mitra, Tamoghna; Easun, Timothy L; Lewis, William; Blake, Alexander J; Besley, Elena; Yang, Sihai; Schröder, Martin

2016-11-16

An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO 2 uptake of 12.6 mmol g -1 at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffraction reveals that, surprisingly, there is no direct binding between the adsorbed CO 2 /CH 4 molecules and the pendant amide group in the pore. This observation has been confirmed unambiguously by inelastic neutron spectroscopy. This suggests that introduction of functional groups solely may not necessarily induce specific guest-host binding in porous materials, but it is a combination of pore size, geometry, and functional group that leads to enhanced gas adsorption properties.

Controlled Fabrication of Functional Capsules Based on the Synergistic Interaction between Polyphenols and MOFs under Weak Basic Condition.

PubMed

Wang, Hui; Zhu, Wei; Ping, Yuan; Wang, Chen; Gao, Ning; Yin, Xianpeng; Gu, Chen; Ding, Dan; Brinker, C Jeffrey; Li, Guangtao

2017-04-26

Metal-organic coordination materials with controllable nanostructures are of widespread interest due to the coupled benefits of inorganic/organic building blocks and desired architectures. In this work, based on the finding of a synergistic interaction between metal-organic frameworks (MOFs) and natural polyphenols under weak basic condition, a facile strategy has been developed for directly fabricating diverse phenolic-inspired functional materials or metal-phenolic frameworks (MPFs) with controlled hollow nanostructures (polyhedral core-shell, rattle-like, hollow cage, etc.) and controllable size, morphology, and roughness, as well as composition. By further incorporating the diverse functionalities of polyphenols such as low toxicity and therapeutic properties, catalytic activity, and ability to serve as carbon precursors, into the novel assemblies, diverse artificially designed nanoarchitectures with target functionalities have been generated for an array of applications.

Prospects of zero Schottky barrier height in a graphene-inserted MoS{sub 2}-metal interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chanana, Anuja; Mahapatra, Santanu

2016-01-07

A low Schottky barrier height (SBH) at source/drain contact is essential for achieving high drive current in atomic layer MoS{sub 2}-channel-based field effect transistors. Approaches such as choosing metals with appropriate work functions and chemical doping are employed previously to improve the carrier injection from the contact electrodes to the channel and to mitigate the SBH between the MoS{sub 2} and metal. Recent experiments demonstrate significant SBH reduction when graphene layer is inserted between metal slab (Ti and Ni) and MoS{sub 2}. However, the physical or chemical origin of this phenomenon is not yet clearly understood. In this work, densitymore » functional theory simulations are performed, employing pseudopotentials with very high basis sets to get insights of the charge transfer between metal and monolayer MoS{sub 2} through the inserted graphene layer. Our atomistic simulations on 16 different interfaces involving five different metals (Ti, Ag, Ru, Au, and Pt) reveal that (i) such a decrease in SBH is not consistent among various metals, rather an increase in SBH is observed in case of Au and Pt; (ii) unlike MoS{sub 2}-metal interface, the projected dispersion of MoS{sub 2} remains preserved in any MoS{sub 2}-graphene-metal system with shift in the bands on the energy axis. (iii) A proper choice of metal (e.g., Ru) may exhibit ohmic nature in a graphene-inserted MoS{sub 2}-metal contact. These understandings would provide a direction in developing high-performance transistors involving heteroatomic layers as contact electrodes.« less

Impact of high-κ dielectric and metal nanoparticles in simultaneous enhancement of programming speed and retention time of nano-flash memory

NASA Astrophysics Data System (ADS)

Pavel, Akeed A.; Khan, Mehjabeen A.; Kirawanich, Phumin; Islam, N. E.

2008-10-01

A methodology to simulate memory structures with metal nanocrystal islands embedded as floating gate in a high-κ dielectric material for simultaneous enhancement of programming speed and retention time is presented. The computational concept is based on a model for charge transport in nano-scaled structures presented earlier, where quantum mechanical tunneling is defined through the wave impedance that is analogous to the transmission line theory. The effects of substrate-tunnel dielectric conduction band offset and metal work function on the tunneling current that determines the programming speed and retention time is demonstrated. Simulation results confirm that a high-κ dielectric material can increase programming current due to its lower conduction band offset with the substrate and also can be effectively integrated with suitable embedded metal nanocrystals having high work function for efficient data retention. A nano-memory cell designed with silver (Ag) nanocrystals embedded in Al 2O 3 has been compared with similar structure consisting of Si nanocrystals in SiO 2 to validate the concept.

Thermal transport across metal silicide-silicon interfaces: First-principles calculations and Green's function transport simulations

NASA Astrophysics Data System (ADS)

Sadasivam, Sridhar; Ye, Ning; Feser, Joseph P.; Charles, James; Miao, Kai; Kubis, Tillmann; Fisher, Timothy S.

2017-02-01

Heat transfer across metal-semiconductor interfaces involves multiple fundamental transport mechanisms such as elastic and inelastic phonon scattering, and electron-phonon coupling within the metal and across the interface. The relative contributions of these different transport mechanisms to the interface conductance remains unclear in the current literature. In this work, we use a combination of first-principles calculations under the density functional theory framework and heat transport simulations using the atomistic Green's function (AGF) method to quantitatively predict the contribution of the different scattering mechanisms to the thermal interface conductance of epitaxial CoSi2-Si interfaces. An important development in the present work is the direct computation of interfacial bonding from density functional perturbation theory (DFPT) and hence the avoidance of commonly used "mixing rules" to obtain the cross-interface force constants from bulk material force constants. Another important algorithmic development is the integration of the recursive Green's function (RGF) method with Büttiker probe scattering that enables computationally efficient simulations of inelastic phonon scattering and its contribution to the thermal interface conductance. First-principles calculations of electron-phonon coupling reveal that cross-interface energy transfer between metal electrons and atomic vibrations in the semiconductor is mediated by delocalized acoustic phonon modes that extend on both sides of the interface, and phonon modes that are localized inside the semiconductor region of the interface exhibit negligible coupling with electrons in the metal. We also provide a direct comparison between simulation predictions and experimental measurements of thermal interface conductance of epitaxial CoSi2-Si interfaces using the time-domain thermoreflectance technique. Importantly, the experimental results, performed across a wide temperature range, only agree well with predictions that include all transport processes: elastic and inelastic phonon scattering, electron-phonon coupling in the metal, and electron-phonon coupling across the interface.

Surface properties of thermionic electrodes

NASA Technical Reports Server (NTRS)

Stickney, R. E.

1972-01-01

A quasi-equilibrium model which provides semiquantitative predictions of the oxygen reaction with refractory metals was developed at high temperature and low pressure. Extensive experimental data was obtained on adsorption and work function properties for a wide variety of adsorbates (Cs, K, Na, I, Br, Cl, and O) on several refractory metals (W, Ta, Mo, and Re). Conclusions and recommendations for research on alkali metal adsorption, oxygen adsorption, and adsorption of cesium - oxygen mixtures are included.

Spectral observations of hole injection with transition metal oxides for an efficient organic light-emitting diode

NASA Astrophysics Data System (ADS)

Chiu, Tien-Lung; Chuang, Ya-Ting

2015-02-01

Transition metal oxides, such as molybdenum trioxide (MoO3), tungsten trioxide (WO3) and vanadium pent-oxide (V2O5), are well-known hole injection materials used for organic electronic devices. These materials promote work functions of anodes, reduce energy barriers, and facilitate hole transport at the interface between the inorganic anode and organic hole-transporting layer (HTL). In this study, we characterized the transmittance spectra and work function of these materials. Furthermore, we employed a hole-injection layer (HIL) in a blue phosphorescent organic light-emitting diode (OLED) to evaluate their hole-injection capacity by detecting the variation in the emission spectra. Thus, we utilized an OLED structure that has fast electron transporting dynamics to establish the recombination zone located at emitting layer and a partial HTL close to the anode. We used these three transition metal oxides individually as HILs sandwiched between the ITO anode and HTL and concluded that the strength of emissive light from the HTL was determined by their hole-injection capacity, depending on work function. The small amount of HTL emission light of the V2O5 OLED was explained by the high work function of 5.8 eV for the V2O5 film. However, the V2O5 OLED demonstrated the least favorable optoelectrical performance because of its low transmittance and high resistance of the V2O5 film. Ultimately, the 5 nm-MoO3 OLED exhibited the highest device performance because of its high material conductivity and transparency in the visible band.

Electronic energy level alignment at metal-molecule interfaces with a GW approach

NASA Astrophysics Data System (ADS)

Tamblyn, Isaac; Darancet, Pierre; Quek, Su Ying; Bonev, Stanimir A.; Neaton, Jeffrey B.

2011-11-01

Using density functional theory and many-body perturbation theory within a GW approximation, we calculate the electronic structure of a metal-molecule interface consisting of benzene diamine (BDA) adsorbed on Au(111). Through direct comparison with photoemission data, we show that a conventional G0W0 approach can underestimate the energy of the adsorbed molecular resonance relative to the Au Fermi level by up to 0.8 eV. The source of this discrepancy is twofold: a 0.7 eV underestimate of the gas phase ionization energy (IE), and a 0.2 eV overestimate of the Au work function. Refinements to self-energy calculations within the GW framework that account for deviations in both the Au work function and BDA gas-phase IE can result in an interfacial electronic level alignment in quantitative agreement with experiment.

The effect of Al segregation on Schottky barrier height and effective work function in TiAl/TiN/HfO2 gate stacks

NASA Astrophysics Data System (ADS)

Kim, Geun-Myeong; Oh, Young Jun; Chang, K. J.

2016-07-01

We perform first-principles density functional calculations to investigate the effects of Al incorporation on the p-type Schottky barrier height ≤ft({φ\\text{p}}\\right) and the effective work function for various high-k/metal gate stacks, such as TiN/HfO2 with interface Al impurities, Ti1-x Al x N/HfO2, and TiAl/TiN/HfO2. When Al atoms substitute for the interface Ti atoms at TiN/HfO2 interface, interface dipole fields become stronger, leading to the increase of {φ\\text{p}} and thereby the n-type shift of effective work function. In Ti1-x Al x N/HfO2 interface, {φ\\text{p}} linearly increases with the Al content, attributed to the presence of interface Al atoms. On the other hand, in TiAl/TiN/HfO2 interface, where Al is assumed not to segregate from TiAl to TiN, {φ\\text{p}} is nearly independent of the thickness of TiAl. Our results indicate that Al impurities at the metal/dielectric interface play an important role in controlling the effective work function, and provide a clue to understanding the n-type shift of the effective work function observed in TiAl/TiN/HfO2 gate stacks fabricated by using thegate-last process.

Emission properties of body-centered cubic elemental metal photocathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Tuo; Rickman, Benjamin L., E-mail: brickm2@uic.edu; Schroeder, W. Andreas

2015-04-07

A first principles analysis of photoemission is developed to explain the lower than expected rms transverse electron momentum measured using the solenoid scan technique for the body-centered cubic Group Vb (V, Nb, and Ta) and Group VIb (Cr, Mo, and W) metallic photocathodes. The density functional theory based analysis elucidates the fundamental role that the electronic band structure (and its dispersion) plays in determining the emission properties of solid-state photocathodes and includes evaluation of work function anisotropy using a thin-slab method.

Lung function and functional capacity among foundry workers using effective risk control measures.

PubMed

Bernardes, Rosane Andrea Bretas; Chiavegato, Luciana Dias; de Moraes, Mônica Vasconcelos; Negreiros, Alexandher; Padula, Rosimeire Simprini

2015-01-01

Inhaled dust in the environment can trigger specific reactions in the airways and cause various respiratory diseases. Evaluate the lung function and functional capacity of foundry workers who are exposed to metals and use effective control measures. A cross-sectional study was realized with 108 workers at a bronze foundry and machining plant and in maintenance at a private university, both in Brazil. The workers were divided into two groups: the study group exposed to metals but using risk control measues and a control group not exposed to metal work. The Medical Research Council Questionnaire on Respiratory Symptoms and the International Physical Activity Questionnaire were administered, and lung function and functional capacity were evaluated. Comparative statistics were used to identify differences in the outcome measures between the two groups. The groups had similar personal and anthropometric characteristics and time on the job. Spirometry and peak expiratory flow presented no significant differences between the groups. And there was also no statistically significant difference between groups in functional capacity as assessed by performance on the six-minute walk test. Foundry industry workers in Brazil who were exposed to metal but used risk control measures had similar lung function and functional capacity when compared to the control group who were not exposed to metal. This is a positive results and maybe related to age, time exposure and control of occupational hazards. However, these workers need to continue being monitored in longitudinal studies.

Electron work function-a promising guiding parameter for material design.

PubMed

Lu, Hao; Liu, Ziran; Yan, Xianguo; Li, Dongyang; Parent, Leo; Tian, Harry

2016-04-14

Using nickel added X70 steel as a sample material, we demonstrate that electron work function (EWF), which largely reflects the electron behavior of materials, could be used as a guide parameter for material modification or design. Adding Ni having a higher electron work function to X70 steel brings more "free" electrons to the steel, leading to increased overall work function, accompanied with enhanced e(-)-nuclei interactions or higher atomic bond strength. Young's modulus and hardness increase correspondingly. However, the free electron density and work function decrease as the Ni content is continuously increased, accompanied with the formation of a second phase, FeNi3, which is softer with a lower work function. The decrease in the overall work function corresponds to deterioration of the mechanical strength of the steel. It is expected that EWF, a simple but fundamental parameter, may lead to new methodologies or supplementary approaches for metallic materials design or tailoring on a feasible electronic base.

Effects of coating thickness on high power metal coated fibre lasers

NASA Astrophysics Data System (ADS)

Daniel, Jae M. O.; Simakov, Nikita; Hemming, Alexander; Clarkson, W. Andrew; Haub, John

2017-03-01

We investigate the effects of coating thickness on the scattering losses of metal coated active fibre. A range of low numerical aperture metal coated optical fibres are placed in etchant solutions whilst measuring propagation loss as a function of time. By utilising concurrent coating diameter measurements, we are able to correlate propagation losses with coating thickness. Experimentally we find a monotonic dependence on coating thickness and scattering loss. We present the results of this work, providing useful parameters for high power metal coated fibre laser designs.

Spin doping using transition metal phthalocyanine molecules

PubMed Central

Atxabal, A.; Ribeiro, M.; Parui, S.; Urreta, L.; Sagasta, E.; Sun, X.; Llopis, R.; Casanova, F.; Hueso, L. E.

2016-01-01

Molecular spins have become key enablers for exploring magnetic interactions, quantum information processes and many-body effects in metals. Metal-organic molecules, in particular, let the spin state of the core metal ion to be modified according to its organic environment, allowing localized magnetic moments to emerge as functional entities with radically different properties from its simple atomic counterparts. Here, using and preserving the integrity of transition metal phthalocyanine high-spin complexes, we demonstrate the magnetic doping of gold thin films, effectively creating a new ground state. We demonstrate it by electrical transport measurements that are sensitive to the scattering of itinerant electrons with magnetic impurities, such as Kondo effect and weak antilocalization. Our work expands in a simple and powerful way the classes of materials that can be used as magnetic dopants, opening a new channel to couple the wide range of molecular properties with spin phenomena at a functional scale. PMID:27941810

Development of JSTAMP-Works/NV and HYSTAMP for Multipurpose Multistage Sheet Metal Forming Simulation

NASA Astrophysics Data System (ADS)

Umezu, Yasuyoshi; Watanabe, Yuko; Ma, Ninshu

2005-08-01

Since 1996, Japan Research Institute Limited (JRI) has been providing a sheet metal forming simulation system called JSTAMP-Works packaged the FEM solvers of LS-DYNA and JOH/NIKE, which might be the first multistage system at that time and has been enjoying good reputation among users in Japan. To match the recent needs, "faster, more accurate and easier", of process designers and CAE engineers, a new metal forming simulation system JSTAMP-Works/NV is developed. The JSTAMP-Works/NV packaged the automatic healing function of CAD and had much more new capabilities such as prediction of 3D trimming lines for flanging or hemming, remote control of solver execution for multi-stage forming processes and shape evaluation between FEM and CAD. On the other way, a multi-stage multi-purpose inverse FEM solver HYSTAMP is developed and will be soon put into market, which is approved to be very fast, quite accurate and robust. Lastly, authors will give some application examples of user defined ductile damage subroutine in LS-DYNA for the estimation of material failure and springback in metal forming simulation.

DNAzyme sensors for detection of metal ions in the environment and imaging them in living cells

PubMed Central

McGhee, Claire E.; Loh, Kang Yong

2017-01-01

The on-site and real-time detection of metal ions is important for environmental monitoring and for understanding the impact of metal ions on human health. However, developing sensors selective for a wide range of metal ions that can work in the complex matrices of untreated samples and cells presents significant challenges. To meet these challenges, DNAzymes, an emerging class of metal ion-dependent enzymes selective for almost any metal ion, have been functionalized with fluorophores, nanoparticles and other imaging agents and incorporated into sensors for the detection of metal ions in environmental samples and for imaging the metal ions in living cells. Herein, we highlight the recent developments of DNAzyme-based fluorescent, colorimetric, SERS, electrochemical and electrochemiluminscent sensors for metal ions for these applications. PMID:28458112

Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water.

PubMed

Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

2011-11-30

The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu(3)(BTC)(2)(H(2)O)(3)](n) (HKUST-1, BTC=benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu(3)(BTC)(2)](n) samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N(2) sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu(3)(BTC)(2)](n) exhibited remarkably high adsorption affinity (K(d)=4.73 × 10(5)mL g(-1)) and high adsorption capacity (714.29 mg g(-1)) for Hg(2+) adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg(2+) under the same condition. Copyright © 2011 Elsevier B.V. All rights reserved.

Electric field effects on the optical properties of buckled GaAs monolayer

NASA Astrophysics Data System (ADS)

Bahuguna, Bhagwati Prasad; Saini, L. K.; Sharma, Rajesh O.

2018-04-01

Buckled GaAs monolayer has a direct band gap semiconductor with energy gap of 1.31 eV in the absence of electric field. When we applied transverse electric field, the value of band gap decreases with increasing of electric field strength. In our previous work [1], it is observed that the buckled GaAs monolayer becomes metallic at 1.3 V/Å. In the present work, we investigate the optical properties such as photon energy-dependent dielectric functions, extinction coefficient, refractive index, absorption spectrum and reflectivity of buckled GaAs monolayer in the semiconducting phase i.e. absence of external electric field and metallic phase i.e. presence of external electric field using density functional theory.

Highly selective removal of Hg2+ and Pb2+ by thiol-functionalized Fe3O4@metal-organic framework core-shell magnetic microspheres

NASA Astrophysics Data System (ADS)

Ke, Fei; Jiang, Jing; Li, Yizhi; Liang, Jing; Wan, Xiaochun; Ko, Sanghoon

2017-08-01

In this work, we report a novel type of thiol-functionalized magnetic core-shell metal-organic framework (MOF) microspheres that can be potentially used for selective removal of Hg2+ and Pb2+ in the presence of other background ions from wastewater. The monodisperse Fe3O4@Cu3(btc)2 core-shell magnetic microspheres have been fabricated by a versatile step-by-step assembly strategy. Further, the thiol-functionalized Fe3O4@Cu3(btc)2 magnetic microspheres were successfully synthesized by utilizing a facile postsynthetic strategy. Significantly, the thiol-functionalized Fe3O4@Cu3(btc)2 magnetic microspheres exhibit remarkably selective adsorption affinity for Hg2+ (Kd = 5.98 × 104 mL g-1) and Pb2+ (Kd = 1.23 × 104 mL g-1), while a weaker binding affinity occurred for the other background ions such as Ni2+, Na+, Mg2+, Ca2+, Zn2+ and Cd2+. The adsorption kinetics follow the pseudo-second-order rate equation and with an almost complete removal of Hg2+ and Pb2+ from the mixed heavy metal ions wastewater (0.5 mM) within 120 min. Moreover, this adsorbent can be easily recycled because of the presence of the magnetic Fe3O4 core. This work provides a promising functionalized porous magnetic Fe3O4@MOF-based adsorbent with easy recycling property for the selective removal of heavy metal ions from wastewater.

Photochemical Fabrication of Transition Metal Nanoparticles Using CdS Template and Their Co-Catalysis Effects for TiO2 Photocatalysis

NASA Astrophysics Data System (ADS)

Badhwar, Nidhi; Gupta, Nidhi; Pal, Bonamali

2013-09-01

Transition metal nanoparticles were prepared by chemical dissolution of CdS template from metal photodeposited CdS nanorod (length = 70-85 nm and width = 5-6 nm) heterocomposites. Size (9-10 nm) of metal nanoparticles obtained after CdS removal was larger than the size (4-6 nm) of metal nanodeposits over CdS template. The obtained Au nanoparticles displayed a broad red shifted absorption band at 660 nm, whereas Pt, Pd and Rh nanoparticles exhibit featureless absorption spectra. Elemental analysis confirms the complete removal of CdS template from Au-CdS (Au — 2.65 at.%) and Ag-CdS (Ag — 2.06 at.%) composites showing no Cd peak. These metal nanoparticles imparted dissimilar co-catalytic activity of TiO2 for photocatalytic degradation of salicylic acid in the order Au > Pt > Pd > Ag > Rh as a function of their nature, electronegativity, redox potential and work function.

Processing and Prolonged 500 C Testing of 4H-SiC JFET Integrated Circuits with Two Levels of Metal Interconnect

NASA Technical Reports Server (NTRS)

Spry, David J.; Neudeck, Philip G.; Chen, Liangyu; Lukco, Dorothy; Chang, Carl W.; Beheim, Glenn M.; Krasowski, Michael J.; Prokop, Norman F.

2015-01-01

Complex integrated circuit (IC) chips rely on more than one level of interconnect metallization for routing of electrical power and signals. This work reports the processing and testing of 4H-SiC junction field effect transistor (JFET) prototype ICs with two levels of metal interconnect capable of prolonged operation at 500 C. Packaged functional circuits including 3-and 11-stage ring oscillators, a 4-bit digital to analog converter, and a 4-bit address decoder and random access memory cell have been demonstrated at 500 C. A 3-stage oscillator functioned for over 3000 hours at 500 C in air ambient.

Effect of nanoscale size and medium on metal work function in oleylamine-capped gold nanocrystals

NASA Astrophysics Data System (ADS)

Abdellatif, M. H.; Ghosh, S.; Liakos, I.; Scarpellini, A.; Marras, S.; Diaspro, A.; Salerno, M.

2016-02-01

The work function is an important material property with several applications in photonics and optoelectronics. We aimed to characterize the work function of clusters resulting from gold nanocrystals capped with oleylamine surfactant and drop-casted onto gold substrate. We used scanning Kelvin probe microscopy to investigate the work function, and complemented our study mainly with X-ray diffraction and X-ray photoelectron spectroscopy. The oleylamine works as an electron blocking layer through which the electrical conduction takes place by tunneling effect. The surface potential appears to depend on the size of the clusters, which can be ascribed to their difference in effective work function with the substrate. The charge state of gold clusters is discussed in comparison with theory, and their capacitance is calculated from a semi-analytical equation. The results suggest that at the nanoscale the work function is not an intrinsic property of a material but rather depends on the size and morphology of the clusters, including also effects of the surrounding materials.

Electron work function–a promising guiding parameter for material design

PubMed Central

Lu, Hao; Liu, Ziran; Yan, Xianguo; Li, Dongyang; Parent, Leo; Tian, Harry

2016-01-01

Using nickel added X70 steel as a sample material, we demonstrate that electron work function (EWF), which largely reflects the electron behavior of materials, could be used as a guide parameter for material modification or design. Adding Ni having a higher electron work function to X70 steel brings more “free” electrons to the steel, leading to increased overall work function, accompanied with enhanced e−–nuclei interactions or higher atomic bond strength. Young’s modulus and hardness increase correspondingly. However, the free electron density and work function decrease as the Ni content is continuously increased, accompanied with the formation of a second phase, FeNi3, which is softer with a lower work function. The decrease in the overall work function corresponds to deterioration of the mechanical strength of the steel. It is expected that EWF, a simple but fundamental parameter, may lead to new methodologies or supplementary approaches for metallic materials design or tailoring on a feasible electronic base. PMID:27074974

Pseudopotential theoretical study of the alkali metals under arbitrary pressure: Density, bulk modulus, and shear moduli

NASA Astrophysics Data System (ADS)

Rasky, Daniel J.; Milstein, Frederick

1986-02-01

Milstein and Hill previously derived formulas for computing the bulk and shear moduli, κ, μ, and μ', at arbitrary pressures, for cubic crystals in which interatomic interaction energies are modeled by pairwise functions, and they carried out the moduli computations using the complete family of Morse functions. The present study extends their work to a pseudopotential description of atomic binding. Specifically: (1) General formulas are derived for determining these moduli under hydrostatic loading within the framework of a pseudopotential model. (2) A two-parameter pseudopotential model is used to describe atomic binding of the alkali metals, and the two parameters are determined from experimental data (the model employs the Heine-Abarenkov potential with the Taylor dielectric function). (3) For each alkali metal (Li, Na, K, Rb, and Cs), the model is used to compute the pressure-versus-volume behavior and, at zero pressure, the binding energy, the density, and the elastic moduli and their pressure derivatives; the theoretical behavior is found to be in excellent agreement with experiment. (4) Calculations are made of κ, μ, and μ' of the bcc alkali metals over wide ranges of hydrostatic compression and expansion. (5) The pseudopotential results are compared with those of arbitrary-central-force models (wherein κ-(2/3)μ=μ'+2P) and with the specific Morse-function results. The pressures, bulk moduli, and zero-pressure shear moduli (as determined for the Morse and pseudopotential models) are in excellent agreement, but important differences appear in the shear moduli under high compressions. The computations in the present paper are for the bcc metals; a subsequent paper will extend this work to include both the bcc and fcc structures, at compressions and expansions where elastic stability or lattice cohesion is, in practice, lost.

Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

2012-02-01

The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

More accurate depiction of adsorption energy on transition metals using work function as one additional descriptor.

PubMed

Shen, Xiaochen; Pan, Yanbo; Liu, Bin; Yang, Jinlong; Zeng, Jie; Peng, Zhenmeng

2017-05-24

The reaction mechanism and properties of a catalytic process are primarily determined by the interactions between reacting species and catalysts. However, the interactions are often challenging to be experimentally measured, especially for unstable intermediates. Therefore, it is of significant importance to establish an exact relationship between chemical-catalyst interactions and catalyst parameters, which will allow calculation of these interactions and thus advance their mechanistic understanding. Herein we report the description of adsorption energy on transition metals by considering both ionic bonding and covalent bonding contributions and introduce the work function as one additional responsible parameter. We find that the adsorption energy can be more accurately described using a two-dimensional (2D) polynomial model, which shows a significant improvement compared with the current adsorption energy-d-band center linear correlation. We also demonstrate the utilization of this new 2D polynomial model to calculate oxygen binding energy of different transition metals to help understand their catalytic properties in oxygen reduction reactions.

Manipulating the dipole layer of polar organic molecules on metal surfaces via different charge-transfer channels

NASA Astrophysics Data System (ADS)

Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Wang, Chin-Yung; Pi, Tun-Wen; Ishii, Hisao; Tang, S.-J.

The key properties of organic films such as energy level alignment (ELA), work functions, and injection barriers are closely linked to this dipole layer. Using angle resolved photoemission spectroscopy (ARPES), we systemically investigate the coverage-dependent work functions and spectra line shapes of occupied molecular orbital states of a polar molecule, chloroaluminium phthalocyanine (ClAlPc), grown on Ag(111) to show that the orientations of the first ClAlPc layer can be manipulated via the molecule deposition rate and post annealing, causing ELA at organic-metal interface to differ for about 0.3 eV between Cl-up and Cl-down configuration. Moreover, by comparing the experimental results with the calculations based on both gas-phase model and realistic model of ClAlPc on Ag(111) , we evidence that the different orientations of ClAlPc dipole layers lead to different charge-transfer channels between ClAlPc and Ag, a key factor that controls the ELA at organic-metal interface.

Enlarging photovoltaic effect: combination of classic photoelectric and ferroelectric photovoltaic effects

PubMed Central

Zhang, Jingjiao; Su, Xiaodong; Shen, Mingrong; Dai, Zhihua; Zhang, Lingjun; He, Xiyun; Cheng, Wenxiu; Cao, Mengyu; Zou, Guifu

2013-01-01

Converting light energy to electrical energy in photovoltaic devices relies on the photogenerated electrons and holes separated by the built-in potential in semiconductors. Photo-excited electrons in metal electrodes are usually not considered in this process. Here, we report an enhanced photovoltaic effect in the ferroelectric lanthanum-modified lead zirconate titanate (PLZT) by using low work function metals as the electrodes. We believe that electrons in the metal with low work function could be photo-emitted into PLZT and form the dominant photocurrent in our devices. Under AM1.5 (100 mW/cm2) illumination, the short-circuit current and open-circuit voltage of Mg/PLZT/ITO are about 150 and 2 times of those of Pt/PLZT/ITO, respectively. The photovoltaic response of PLZT capacitor was expanded from ultraviolet to visible spectra, and it may have important impact on design and fabrication of high performance photovoltaic devices based on ferroelectric materials. PMID:23811832

Heavy metals found in the breathing zone, toenails and lung function of welders working in an air-conditioned welding workplace.

PubMed

Hariri, Azian; Mohamad Noor, Noraishah; Paiman, Nuur Azreen; Ahmad Zaidi, Ahmad Mujahid; Zainal Bakri, Siti Farhana

2017-09-22

Welding operations are rarely conducted in an air-conditioned room. However, a company would set its welding operations in an air-conditioned room to maintain the humidity level needed to reduce hydrogen cracks in the specimen being welded. This study intended to assess the exposure to metal elements in the welders' breathing zone and toenail samples. Heavy metal concentration was analysed using inductively coupled plasma mass spectrometry. The lung function test was also conducted and analysed using statistical approaches. Chromium and manganese concentrations in the breathing zone exceeded the permissible exposure limit stipulated by Malaysian regulations. A similar trend was obtained in the concentration of heavy metals in the breathing zone air sampling and in the welders' toenails. Although there was no statistically significant decrease in the lung function of welders, it is suggested that exposure control through engineering and administrative approaches should be considered for workplace safety and health improvement.

[Influence of work intensity on development of arterial hypertension in metal-mining workers].

PubMed

Ustinova, O Iu; Alekseev, V B; Rumiantseva, A N; Orehova, Ia V

2013-01-01

The article covers data on influence of working shifts duration and shift work intensity on cardiovascular system functioning in operators of mining excavators. Findings are that 8 hours shift with regular shift schedule (40 working hours per week) gives significant load on cardiovascular system of workers engaged into underground activities. 50% of mining excavator operators following this working schedule develop transitory arterial hypertension within 10 years. Longer work shift over 8 hours and more intensive shifting schedule over 40 hours per week causes stable arterial hypertension within 3 months in 60% of workers, in 10% of cases associated with lower functioning of sinus node.

Functional metasurfaces based on metallic and dielectric subwavelength slits and stripes array

NASA Astrophysics Data System (ADS)

Guo, Yinghui; Pu, Mingbo; Li, Xiong; Ma, Xiaoliang; Gao, Ping; Wang, Yanqin; Luo, Xiangang

2018-04-01

Starting with the early works of extraordinary optical transmission and extraordinary Young’s interference, researchers have been fascinated by the unusual optical properties displayed by metallic holes/slits and subsequently found similar abnormities in dielectric counterparts. Benefiting from the shrinking wavelength of surface plasmon polaritons excited in metallic slits and high refractive index of dielectric stripes, one can realize local phase modulation and approach desired dispersion by engineering the geometries of a slits and stripes array. In this review, we review recent developments in functional metasurfaces composed of various metallic and dielectric subwavelength slits and stripes arrays, with special emphasis on achromatic, ultra-broadband, quasi-continuous, multifunctional and reconfigurable metasurfaces. Particular attention is paid to provide insight into the design strategies for these devices. Finally, we give an outlook of the development in this fascinating area.

Pressure-enabled phonon engineering in metals

PubMed Central

Lanzillo, Nicholas A.; Thomas, Jay B.; Watson, Bruce; Washington, Morris; Nayak, Saroj K.

2014-01-01

We present a combined first-principles and experimental study of the electrical resistivity in aluminum and copper samples under pressures up to 2 GPa. The calculations are based on first-principles density functional perturbation theory, whereas the experimental setup uses a solid media piston–cylinder apparatus at room temperature. We find that upon pressurizing each metal, the phonon spectra are blue-shifted and the net electron–phonon interaction is suppressed relative to the unstrained crystal. This reduction in electron–phonon scattering results in a decrease in the electrical resistivity under pressure, which is more pronounced for aluminum than for copper. We show that density functional perturbation theory can be used to accurately predict the pressure response of the electrical resistivity in these metals. This work demonstrates how the phonon spectra in metals can be engineered through pressure to achieve more attractive electrical properties. PMID:24889627

Respiratory symptoms and lung function change in welders: are they associated with workplace exposures?

PubMed

Fishwick, David; Bradshaw, Lisa; Slater, Tania; Curran, Andrew; Pearce, Neil

2004-05-07

This study investigates whether work-related respiratory symptoms and acute falls in forced expiratory volume in 1 second (FEV1), previously observed in current welders, are related to measured workplace exposures to total fume and metals. At four work sites in New Zealand, changes in pulmonary function (and reported respiratory symptoms) were recorded in 49 welding workers (and 26 non-welders) exposed to welding fume. We also determined the personal breathing zone levels of total fume and various metals. Work-related respiratory symptoms were reported by 26.5% of welders and 11.5% of non-welders. These symptoms were related significantly to their personal breathing zone nickel exposure--with an adjusted odds ratio (OR) and 95% confidence interval [CI] of the high exposure group (compared to a low exposure group of 7.0 [1.3-36.6]). There were non-significant associations with total fume exposure (OR = 2.6, 95% CI 0.6-12.2), and exposure index of greater than 10 years (OR=2.8, 95% CI 0.5-15.0). A fall in FEV1 of at least 5% after 15 minutes of work was significantly associated with aluminium exposure (OR=5.8, 95% CI 1.7-20.6). Nickel exposure from metal inert gas (MIG) and tungsten inert gas (TIG) welding is associated with work-related respiratory symptoms and aluminium exposure from welding is associated with a fall in FEV1 of at least 5 % after 15 minutes of work.

Insights into the Influence of Work Functions of Cathodes on Efficiencies of Perovskite Solar Cells.

PubMed

Yue, Shizhong; Lu, Shudi; Ren, Kuankuan; Liu, Kong; Azam, Muhammad; Cao, Dawei; Wang, Zhijie; Lei, Yong; Qu, Shengchun; Wang, Zhanguo

2017-05-01

Though various efforts on modification of electrodes are still undertaken to improve the efficiency of perovskite solar cells, attributing to the large scope of these methods, it is of significance to unveil the working principle systematically. Herein, inverted perovskite solar cells based on indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)/CH 3 NH 3 PbI 3 /phenyl-C61-butyric acid methyl ester (PC 61 BM)/buffer metal/Al are constructed. Through the choice of different buffer metals to tune work function of the cathode, the contact nature of the active layer with the cathode could be manipulated well. In comparison with the device using Au/Al as the electrode that shows an unfavorable band bending for conducting the excited electrons to the cathode, the one with Ca/Al presents a dramatically improved efficiency over 17.1%, ascribed to the favorable band bending at the interface of the cathode with the active layer. Details for tuning the band bending and the corresponding charge transfer mechanism are given in a systematic manner. Thus, a general guideline for constructing perovskite photovoltaic devices efficiently is provided. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced electron emission from coated metal targets: Effect of surface thickness on performance

NASA Astrophysics Data System (ADS)

Madas, Saibabu; Mishra, S. K.; Upadhyay Kahaly, Mousumi

2018-03-01

In this work, we establish an analytical formalism to address the temperature dependent electron emission from a metallic target with thin coating, operating at a finite temperature. Taking into account three dimensional parabolic energy dispersion for the target (base) material and suitable thickness dependent energy dispersion for the coating layer, Fermi Dirac statistics of electron energy distribution and Fowler's mechanism of the electron emission, we discuss the dependence of the emission flux on the physical properties such as the Fermi level, work function, thickness of the coating material, and operating temperature. Our systematic estimation of how the thickness of coating affects the emission current demonstrates superior emission characteristics for thin coating layer at high temperature (above 1000 K), whereas in low temperature regime, a better response is expected from thicker coating layer. This underlying fundamental behavior appears to be essentially identical for all configurations when work function of the coating layer is lower than that of the bulk target work function. The analysis and predictions could be useful in designing new coated materials with suitable thickness for applications in the field of thin film devices and field emitters.

Charge injection and transport in regioregular poly(3-hexylthiophene)-based field-effect transistors

NASA Astrophysics Data System (ADS)

Singh, Kumar Abhishek

Organic (semi)conductors are poised as never before to transform the electronics industry towards unprecedented versatility. In this thesis, we have taken an experimental approach to address the effect of nanostructure and the energy-level alignment at the metal/polymer interface on charge injection and transport in regioregular poly(3-hexylthiophene) (rr-P3HT) based field-effect transistors (FETs). We found that the mobility and contact resistance in rr-P3HT based FETs show an inverse relationship, and that both properties were affected by the nanostructure of the polymer proving that that charge injection, in addition to charge transport, is significantly affected by the bulk-transport properties of rr-P3HT. Thereafter we successfully recessed the contacts into the SiO 2 dielectric to minimize the effect of the step between the metal contacts and the dielectric on the polymer nanomorphology. The planarization of the devices resulted in a dramatic improvement of the nanomorphology of rr-P3HT reflected as an improvement in charge injection as evident from the decrease in contact resistance values. Gold contacts were also modified by treating them with self-assembled monolayers (SAMs) of aromatic thiols. Electron-poor (electron-rich) SAMs resulted in an increase (decrease) in the Au work function because of the electron-withdrawing (-donating) tendency of the polar molecules. The change in metal work-function by SAM modification also resulted in a modulation of the contact resistance. While there was a clear effect on charge injection upon modification of the contacts, either by SAMs or planarization, the mobility values improved only in the short-channel devices indicating that at longer channels the OFETs are channel-limited because of grain-boundary limited charge transport. Photoemission spectroscopy was also conducted to investigate the energy level alignment at bottom-contact (polymer-on-metal) and top-contact (metal-on-polymer) geometries for high work function metals (Au, Pt) and rr-P3HT. The Fermi energy level was found to be pinned at the polaronic energy level within the band gap of rr-P3HT resulting in barrier-less interfaces for charge injection. Photoemission spectroscopy studies of the metal-on-polymer configuration also provided insight into the chemical structure of the metal/polymer interface. Platinum was found to react with sulfur from the thiophene ring whereas Au was found to be relatively unreactive.

Metal Sulfides as Sensing Materials for Chemoresistive Gas Sensors

PubMed Central

Gaiardo, Andrea; Fabbri, Barbara; Guidi, Vincenzo; Bellutti, Pierluigi; Giberti, Alessio; Gherardi, Sandro; Vanzetti, Lia; Malagù, Cesare; Zonta, Giulia

2016-01-01

This work aims at a broad overview of the results obtained with metal-sulfide materials in the field of chemoresistive gas sensing. Indeed, despite the well-known electrical, optical, structural and morphological features previously described in the literature, metal sulfides present lack of investigation for gas sensing applications, a field in which the metal oxides still maintain a leading role owing to their high sensitivity, low cost, small dimensions and simple integration, in spite of the wide assortment of sensing materials. However, despite their great advantages, metal oxides have shown significant drawbacks, which have led to the search for new materials for gas sensing devices. In this work, Cadmium Sulfide and Tin (IV) Sulfide were investigated as functional materials for thick-film chemoresistive gas-sensors fabrication and they were tested both in thermo- and in photo-activation modes. Furthermore, electrical characterization was carried out in order to verify their gas sensing properties and material stability, by comparing the results obtained with metal sulfides to those obtained by using their metal-oxides counterparts. The results highlighted the possibility to use metal sulfides as a novel class of sensing materials, owing to their selectivity to specific compounds, stability, and the possibility to operate at room temperature. PMID:26927120

Calibrated work function mapping by Kelvin probe force microscopy

NASA Astrophysics Data System (ADS)

Fernández Garrillo, Pablo A.; Grévin, Benjamin; Chevalier, Nicolas; Borowik, Łukasz

2018-04-01

We propose and demonstrate the implementation of an alternative work function tip calibration procedure for Kelvin probe force microscopy under ultrahigh vacuum, using monocrystalline metallic materials with known crystallographic orientation as reference samples, instead of the often used highly oriented pyrolytic graphite calibration sample. The implementation of this protocol allows the acquisition of absolute and reproducible work function values, with an improved uncertainty with respect to unprepared highly oriented pyrolytic graphite-based protocols. The developed protocol allows the local investigation of absolute work function values over nanostructured samples and can be implemented in electronic structures and devices characterization as demonstrated over a nanostructured semiconductor sample presenting Al0.7Ga0.3As and GaAs layers with variable thickness. Additionally, using our protocol we find that the work function of annealed highly oriented pyrolytic graphite is equal to 4.6 ± 0.03 eV.

Metals in proteins: correlation between the metal-ion type, coordination number and the amino-acid residues involved in the coordination.

PubMed

Dokmanić, Ivan; Sikić, Mile; Tomić, Sanja

2008-03-01

Metal ions are constituents of many metalloproteins, in which they have either catalytic (metalloenzymes) or structural functions. In this work, the characteristics of various metals were studied (Cu, Zn, Mg, Mn, Fe, Co, Ni, Cd and Ca in proteins with known crystal structure) as well as the specificity of their environments. The analysis was performed on two data sets: the set of protein structures in the Protein Data Bank (PDB) determined with resolution <1.5 A and the set of nonredundant protein structures from the PDB. The former was used to determine the distances between each metal ion and its electron donors and the latter was used to assess the preferred coordination numbers and common combinations of amino-acid residues in the neighbourhood of each metal. Although the metal ions considered predominantly had a valence of two, their preferred coordination number and the type of amino-acid residues that participate in the coordination differed significantly from one metal ion to the next. This study concentrates on finding the specificities of a metal-ion environment, namely the distribution of coordination numbers and the amino-acid residue types that frequently take part in coordination. Furthermore, the correlation between the coordination number and the occurrence of certain amino-acid residues (quartets and triplets) in a metal-ion coordination sphere was analysed. The results obtained are of particular value for the identification and modelling of metal-binding sites in protein structures derived by homology modelling. Knowledge of the geometry and characteristics of the metal-binding sites in metalloproteins of known function can help to more closely determine the biological activity of proteins of unknown function and to aid in design of proteins with specific affinity for certain metals.

Does Variation of the Inter-Domain Linker Sequence Modulate the Metal Binding Behaviour of Helix pomatia Cd-Metallothionein?

PubMed Central

Gil-Moreno, Selene; Jiménez-Martí, Elena; Palacios, Òscar; Zerbe, Oliver; Dallinger, Reinhard; Capdevila, Mercè; Atrian, Sílvia

2015-01-01

Snail metallothioneins (MTs) constitute an ideal model to study structure/function relationships in these metal-binding polypeptides. Helix pomatia harbours three MT isoforms: the highly specific CdMT and CuMT, and an unspecific Cd/CuMT, which represent paralogous proteins with extremely different metal binding preferences while sharing high sequence similarity. Preceding work allowed assessing that, although, the Cys residues are responsible for metal ion coordination, metal specificity or preference is achieved by diversification of the amino acids interspersed between them. The metal-specific MT polypeptides fold into unique, energetically-optimized complexes of defined metal content, when binding their cognate metal ions, while they produce a mixture of complexes, none of them representing a clear energy minimum, with non-cognate metal ions. Another critical, and so far mostly unexplored, region is the stretch linking the individual MT domains, each of which represents an independent metal cluster. In this work, we have designed and analyzed two HpCdMT constructs with substituted linker segments, and determined their coordination behavior when exposed to both cognate and non-cognate metal ions. Results unequivocally show that neither length nor composition of the inter-domain linker alter the features of the Zn(II)- and Cd(II)-complexes, but surprisingly that they influence their ability to bind Cu(I), the non-cognate metal ion. PMID:26703589

Predicting Bond Dissociation Energies of Transition-Metal Compounds by Multiconfiguration Pair-Density Functional Theory and Second-Order Perturbation Theory Based on Correlated Participating Orbitals and Separated Pairs.

PubMed

Bao, Junwei Lucas; Odoh, Samuel O; Gagliardi, Laura; Truhlar, Donald G

2017-02-14

We study the performance of multiconfiguration pair-density functional theory (MC-PDFT) and multireference perturbation theory for the computation of the bond dissociation energies in 12 transition-metal-containing diatomic molecules and three small transition-metal-containing polyatomic molecules and in two transition-metal dimers. The first step is a multiconfiguration self-consistent-field calculation, for which two choices must be made: (i) the active space and (ii) its partition into subspaces, if the generalized active space formulation is used. In the present work, the active space is chosen systematically by using three correlated-participating-orbitals (CPO) schemes, and the partition is chosen by using the separated-pair (SP) approximation. Our calculations show that MC-PDFT generally has similar accuracy to CASPT2, and the active-space dependence of MC-PDFT is not very great for transition-metal-ligand bond dissociation energies. We also find that the SP approximation works very well, and in particular SP with the fully translated BLYP functional SP-ftBLYP is more accurate than CASPT2. SP greatly reduces the number of configuration state functions relative to CASSCF. For the cases of FeO and NiO with extended-CPO active space, for which complete active space calculations are unaffordable, SP calculations are not only affordable but also of satisfactory accuracy. All of the MC-PDFT results are significantly better than the corresponding results with broken-symmetry spin-unrestricted Kohn-Sham density functional theory. Finally we test a perturbation theory method based on the SP reference and find that it performs slightly worse than CASPT2 calculations, and for most cases of the nominal-CPO active space, the approximate SP perturbation theory calculations are less accurate than the much less expensive SP-PDFT calculations.

Emerging Novel Metal Electrodes for Photovoltaic Applications.

PubMed

Lu, Haifei; Ren, Xingang; Ouyang, Dan; Choy, Wallace C H

2018-04-01

Emerging novel metal electrodes not only serve as the collector of free charge carriers, but also function as light trapping designs in photovoltaics. As a potential alternative to commercial indium tin oxide, transparent electrodes composed of metal nanowire, metal mesh, and ultrathin metal film are intensively investigated and developed for achieving high optical transmittance and electrical conductivity. Moreover, light trapping designs via patterning of the back thick metal electrode into different nanostructures, which can deliver a considerable efficiency improvement of photovoltaic devices, contribute by the plasmon-enhanced light-mattering interactions. Therefore, here the recent works of metal-based transparent electrodes and patterned back electrodes in photovoltaics are reviewed, which may push the future development of this exciting field. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On Practical Charge Injection at the Metal/Organic Semiconductor Interface

PubMed Central

Kumatani, Akichika; Li, Yun; Darmawan, Peter; Minari, Takeo; Tsukagoshi, Kazuhito

2013-01-01

We have revealed practical charge injection at metal and organic semiconductor interface in organic field effect transistor configurations. We have developed a facile interface structure that consisted of double-layer electrodes in order to investigate the efficiency through contact metal dependence. The metal interlayer with few nanometers thickness between electrode and organic semiconductor drastically reduces the contact resistance at the interface. The improvement has clearly obtained when the interlayer is a metal with lower standard electrode potential of contact metals than large work function of the contact metals. The electrode potential also implies that the most dominant effect on the mechanism at the contact interface is induced by charge transfer. This mechanism represents a step forward towards understanding the fundamental physics of intrinsic charge injection in all organic devices. PMID:23293741

Cotransport of Herbaspirillum chlorophenolicum FA1 and heavy metals in saturated porous media: column studies and modeling approaches

NASA Astrophysics Data System (ADS)

Li, X.; Xu, H.; Wu, J.

2017-12-01

For in situ biodegradation of organic contaminants in soil and groundwater, precise prediction and monitoring of the movement of the bio-agent is vital for the effectiveness of the subsurface bioremediation technologies. Therefore, the fate and transport of functional microorganisms in porous media has been extensively investigated in the literature, and the effects of a number of physical and chemical factors have been explored. During the bioremediation of contaminated sites, it is highly likely that functional bacteria and heavy metals would be simultaneously present for heavy metals often co-exist with organic contaminants like polycyclic aromatic hydrocarbons (PAHs) in polluted environment. To date, relevant studies on the interactions between heavy metals and functional agents such as PAHs-degrading bacteria are lacking and thus require investigation. In this study, the cotransport of bioremediation agents and heavy metals were evaluated through batch and column experiments. Herbaspirillum chlorophenolicum FA1, a pure bacterial strain capable of absorbing heavy metals and degrading polycyclic aromatic hydrocarbons (PAHs), was used as the model remediation agent, and metal ions of Pb(Ⅱ) and Cd(Ⅱ) were used as the representative heavy metals. Effects of metal species, the concentration of heavy metals, the sequence of entering the media, and the activity of biomass were investigated in detail. In addition, numerical simulations of breakthrough curves (BTC) data were also performed for information gathering. Results of this study could advance our understanding of interactions between functional bacteria and heavy metals during bioremediation process and help to develop successful bioremediation strategies.This work was financially supported by the National Natural Science Foundation of China -Xinjiang Project (U1503282), the National Natural Science Foundation of China (41030746, 41102148), and the Natural Science Foundation of Jiangsu Province (BK20151385). Keywords: Herbaspirillum chlorophenolicum FA1, heavy metal, porous media, cotransport, modeling

Potential barrier heights at metal on oxygen-terminated diamond interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muret, P., E-mail: pierre.muret@neel.cnrs.fr; Traoré, A.; Maréchal, A.

2015-11-28

Electrical properties of metal-semiconductor (M/SC) and metal/oxide/SC structures built with Zr or ZrO{sub 2} deposited on oxygen-terminated surfaces of (001)-oriented diamond films, comprised of a stack of lightly p-doped diamond on a heavily doped layer itself homoepitaxially grown on an Ib substrate, are investigated experimentally and compared to different models. In Schottky barrier diodes, the interfacial oxide layer evidenced by high resolution transmission electron microscopy and electron energy losses spectroscopy before and after annealing, and barrier height inhomogeneities accounts for the measured electrical characteristics until flat bands are reached, in accordance with a model which generalizes that by Tung [Phys.more » Rev. B 45, 13509 (1992)] and permits to extract physically meaningful parameters of the three kinds of interface: (a) unannealed ones, (b) annealed at 350 °C, (c) annealed at 450 °C with the characteristic barrier heights of 2.2–2.5 V in case (a) while as low as 0.96 V in case (c). Possible models of potential barriers for several metals deposited on well defined oxygen-terminated diamond surfaces are discussed and compared to experimental data. It is concluded that interface dipoles of several kinds present at these compound interfaces and their chemical evolution due to annealing are the suitable ingredients that are able to account for the Mott-Schottky behavior when the effect of the metal work function is ignored, and to justify the reverted slope observed regarding metal work function, in contrast to the trend always reported for all other metal-semiconductor interfaces.« less

Metal adsorption on monolayer blue phosphorene: A first principles study

NASA Astrophysics Data System (ADS)

Khan, Imran; Son, Jicheol; Hong, Jisang

2018-01-01

We investigated the electronic structure, adsorption energies, magnetic properties, dipole moment and work function of metal adatoms (Mg, Cr, Mo, Pd, Pt, and Au) adsorption on a blue phosphorene monolayer. For Mg, Pt and Au metals, the most stable state was found in hollow site while for Cr, Mo and Pd metals we found an adsorption in valley site. We suggest that the Pd and Pt atoms prefer 2D growth mode while the Mg, Cr, Mo and Au atoms prefer 3D island growth mode on monolayer phosphorene. The electronic band structures and magnetic properties were dependent on the doping site and dopant materials. For instance, the semiconducting features were preserved in Mg, Pd, Pt, and Au doped systems. However, the Cr and Mo doped systems displayed half-metallic band structures. The total magnetic moment of 4.05, 2.0 and 0.77 μB /impurity atom were obtained in Cr, Mo and Au doped systems whereas the Mg, Pd and Pt doped systems remained nonmagnetic. We also investigated the magnetic interaction between two transition metal impurities. We observed ferromagnetic coupling between two transition metal impurities in Cr and Mo doped systems while the Au doped system displayed almost degenerated magnetic state. For Mg, Cr, and Mo adsorptions, we found relatively large values of dipole moments compared to those in the Pd, Pt and Au adsorptions. This resulted in a significant suppression of the work function in Mg, Cr and Mo adsorptions. Overall, adsorption can tune the physical and magnetic properties of phosphorene monolayer.

Processing and Prolonged 500 C Testing of 4H-SiC JFET Integrated Circuits with Two Levels of Metal Interconnect

NASA Technical Reports Server (NTRS)

Spry, David J.; Neudeck, Philip G.; Chen, Liangyu; Lukco, Dorothy; Chang, Carl W.; Beheim, Glenn M.; Krasowski, Michael J.; Prokop, Norman F.

2015-01-01

Complex integrated circuit (IC) chips rely on more than one level of interconnect metallization for routing of electrical power and signals. This work reports the processing and testing of 4H-SiC junction field effect transistor (JFET) prototype IC's with two levels of metal interconnect capable of prolonged operation at 500 C. Packaged functional circuits including 3- and 11-stage ring oscillators, a 4-bit digital to analog converter, and a 4-bit address decoder and random access memory cell have been demonstrated at 500 C. A 3-stage oscillator functioned for over 3000 hours at 500 C in air ambient. Improved reproducibility remains to be accomplished.

Nonequilibrium approach regarding metals from a linearised kappa distribution

NASA Astrophysics Data System (ADS)

Domenech-Garret, J. L.

2017-10-01

The widely used kappa distribution functions develop high-energy tails through an adjustable kappa parameter. The aim of this work is to show that such a parameter can itself be regarded as a function, which entangles information about the sources of disequilibrium. We first derive and analyse an expanded Fermi-Dirac kappa distribution. Later, we use this expanded form to obtain an explicit analytical expression for the kappa parameter of a heated metal on which an external electric field is applied. We show that such a kappa index causes departures from equilibrium depending on the physical magnitudes. Finally, we study the role of temperature and electric field on such a parameter, which characterises the electron population of a metal out of equilibrium.

A self-healing PDMS polymer with solvatochromic properties.

PubMed

Jia, Xiao-Yong; Mei, Jin-Feng; Lai, Jian-Cheng; Li, Cheng-Hui; You, Xiao-Zeng

2015-05-28

Coordination bonds are effective for constructing functional self-healing materials due to their tunable bond strength and metal-ion-induced functionalities. In this work, we incorporate a cobalt(II) triazole complex into a polydimethylsiloxane (PDMS) matrix. The resulting polymers show solvatochromic behaviour as well as self-healing properties.

Seasonal Drivers of Dissolved Metal Transport During Infiltration of Road Runoff in an Urban Roadside Environment

NASA Astrophysics Data System (ADS)

Mullins, A.; Bain, D.

2017-12-01

Infiltration-based green infrastructure (GI) is being increasingly applied in urban areas, systems characterized by substantial legacy contamination and complicated hydrology. However, it is not clear how the application of green infrastructure changes the geochemistry of urban roadside environments. Most current research on GI focuses on small sets of chemical parameters (e.g. road salt, nitrogen and phosphorous species) over relatively short time periods, limiting comprehensive understanding of geochemical function. This work measures changes in groundwater infiltration rate and dissolved metal concentrations in two infiltration trenches in Pittsburgh, PA to evaluate function and measure dissolved metal transport from the system over time. Two distinct geochemical regimes seem to be driven by seasonality: road de-icer exchange and microbial driven summer reducing conditions. Interactions between these geochemical regimes and variability in infiltration rate control the flux of different metals, varying with metal chemistry. These findings suggest the adoption of infiltration based green infrastructure will likely create complicated patterns of legacy contamination transport to downstream receptors.

Results of Microbiologic Investigations of Water-Development Works

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durcheva, V. N., E-mail: durchevavn@vniig.ru; Izmailova, R. A., E-mail: izmailovara@vniig.ru; Legina, E. E., E-mail: leginaee@vniig.ru

2015-03-15

Results are presented for multiyear field investigations of the effect of microbe colonies on components of water-development works. Concrete, metal, and geologic rocks were studied as component parts of the bed of concrete dams functioning in various climatic zones. The participation of lithotrophic bacteria in processes involving corrosion failure of the metal, concrete, and rock beds of dams is established, and causes of intensification of microbe activity are exposed. The need for monitoring the composition and number of microorganisms-biodestructors is substantiated in the water of a reservoir and observation wells, as well as on the surfaces of structural components ofmore » water-development works for monitoring of the safety of the concrete dams.« less

Silver metal nano-matrixes as high efficiency and versatile catalytic reactors for environmental remediation

NASA Astrophysics Data System (ADS)

Dumée, Ludovic F.; Yi, Zhifeng; Tardy, Blaise; Merenda, Andrea; Des Ligneris, Elise; Dagastine, Ray R.; Kong, Lingxue

2017-03-01

Nano-porous metallic matrixes (NMMs) offer superior surface to volume ratios as well as enhanced optical, photonic, and electronic properties to bulk metallic materials. Such behaviours are correlated to the nano-scale inter-grain metal domains that favour the presence of electronic vacancies. In this work, continuous 3D NMMs were synthesized for the first time through a simple diffusion-reduction process whereby the aerogel matrix was functionalized with (3-Mercaptopropyl)trimethoxysilane. The surface energy of the silica monolith templates was tuned to improve the homogeneity of the reduction process while thiol functionalization facilitated the formation of a high density of seeding points for metal ions to reduce. The diameter of NMMs was between 2 and 1000 nm, corresponding to a silver loading between 1.23 and 41.16 at.%. A rates of catalytic degradation kinetics of these NMMS which is three orders of magnitude higher than those of the non-functionalized silver-silica structures. Furthermore, the enhancement in mechanical stability at nanoscale which was evaluated by Atomic Force Microscopy force measurements, electronic density and chemical inertness was assessed and critically correlated to their catalytic potential. This strategy opens up new avenues for design of complex architectures of either single or multi-metal alloy NMMs with enhanced surface properties for various applications.

Silver metal nano-matrixes as high efficiency and versatile catalytic reactors for environmental remediation

PubMed Central

Dumée, Ludovic F.; Yi, Zhifeng; Tardy, Blaise; Merenda, Andrea; des Ligneris, Elise; Dagastine, Ray R.; Kong, Lingxue

2017-01-01

Nano-porous metallic matrixes (NMMs) offer superior surface to volume ratios as well as enhanced optical, photonic, and electronic properties to bulk metallic materials. Such behaviours are correlated to the nano-scale inter-grain metal domains that favour the presence of electronic vacancies. In this work, continuous 3D NMMs were synthesized for the first time through a simple diffusion-reduction process whereby the aerogel matrix was functionalized with (3-Mercaptopropyl)trimethoxysilane. The surface energy of the silica monolith templates was tuned to improve the homogeneity of the reduction process while thiol functionalization facilitated the formation of a high density of seeding points for metal ions to reduce. The diameter of NMMs was between 2 and 1000 nm, corresponding to a silver loading between 1.23 and 41.16 at.%. A rates of catalytic degradation kinetics of these NMMS which is three orders of magnitude higher than those of the non-functionalized silver-silica structures. Furthermore, the enhancement in mechanical stability at nanoscale which was evaluated by Atomic Force Microscopy force measurements, electronic density and chemical inertness was assessed and critically correlated to their catalytic potential. This strategy opens up new avenues for design of complex architectures of either single or multi-metal alloy NMMs with enhanced surface properties for various applications. PMID:28332602

Magnetic behavior study of samarium nitride using density functional theory

NASA Astrophysics Data System (ADS)

Som, Narayan N.; Mankad, Venu H.; Dabhi, Shweta D.; Patel, Anjali; Jha, Prafulla K.

2018-02-01

In this work, the state-of-art density functional theory is employed to study the structural, electronic and magnetic properties of samarium nitride (SmN). We have performed calculation for both ferromagnetic and antiferromagnetic states in rock-salt phase. The calculated results of optimized lattice parameter and magnetic moment agree well with the available experimental and theoretical values. From energy band diagram and electronic density of states, we observe a half-metallic behaviour in FM phase of rock salt SmN in while metallicity in AFM I and AFM III phases. We present and discuss our current understanding of the possible half-metallicity together with the magnetic ordering in SmN. The calculated phonon dispersion curves shows dynamical stability of the considered structures. The phonon density of states and Eliashberg functional have also been analysed to understand the superconductivity in SmN.

Enantioselective C(sp3)‒H bond activation by chiral transition metal catalysts.

PubMed

Saint-Denis, Tyler G; Zhu, Ru-Yi; Chen, Gang; Wu, Qing-Feng; Yu, Jin-Quan

2018-02-16

Organic molecules are rich in carbon-hydrogen bonds; consequently, the transformation of C-H bonds to new functionalities (such as C-C, C-N, and C-O bonds) has garnered much attention by the synthetic chemistry community. The utility of C-H activation in organic synthesis, however, cannot be fully realized until chemists achieve stereocontrol in the modification of C-H bonds. This Review highlights recent efforts to enantioselectively functionalize C(sp 3 )-H bonds via transition metal catalysis, with an emphasis on key principles for both the development of chiral ligand scaffolds that can accelerate metalation of C(sp 3 )-H bonds and stereomodels for asymmetric metalation of prochiral C-H bonds by these catalysts. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Effect of sputtered lanthanum hexaboride film thickness on field emission from metallic knife edge cathodes

NASA Astrophysics Data System (ADS)

Kirley, M. P.; Novakovic, B.; Sule, N.; Weber, M. J.; Knezevic, I.; Booske, J. H.

2012-03-01

We report experiments and analysis of field emission from metallic knife-edge cathodes, which are sputter-coated with thin films of lanthanum hexaboride (LaB6), a low-work function material. The emission current is found to depend sensitively on the thickness of the LaB6 layer. We find that films thinner than 10 nm greatly enhance the emitted current. However, cathodes coated with a thicker layer of LaB6 are observed to emit less current than the uncoated metallic cathode. This result is unexpected due to the higher work function of the bare metal cathode. We show, based on numerical calculation of the electrostatic potential throughout the structure, that the external (LaB6/vacuum) barrier is reduced with respect to uncoated samples for both thin and thick coatings. However, this behavior is not exhibited at the internal (metal/LaB6) barrier. In thinly coated samples, electrons tunnel efficiently through both the internal and external barrier, resulting in current enhancement with respect to the uncoated case. In contrast, the thick internal barrier in thickly coated samples suppresses current below the value for uncoated samples in spite of the lowered external barrier. We argue that this coating thickness variation stems from a relatively low (no higher than 1018 cm-3) free carrier density in the sputtered polycrystalline LaB6.

Rectified tunneling current response of bio-functionalized metal-bridge-metal junctions.

PubMed

Liu, Yaqing; Offenhäusser, Andreas; Mayer, Dirk

2010-01-15

Biomolecular bridged nanostructures allow direct electrical addressing of electroactive biomolecules, which is of interest for the development of bioelectronic and biosensing hybrid junctions. In the present paper, the electroactive biomolecule microperoxidase-11 (MP-11) was integrated into metal-bridge-metal (MBM) junctions assembled from a scanning tunneling microscope (STM) setup. Before immobilization of MP-11, the Au working electrode was first modified by a self-assembled monolayer of 1-undecanethiol (UDT). A symmetric and potential independent response of current-bias voltage (I(t)/V(b)) was observed for the Au (substrate)/UDT/Au (tip) junction. However, the I(t)/V(b) characteristics became potential dependent and asymmetrical after binding of MP-11 between the electrodes of the junction. The rectification ratio of the asymmetric current response varies with gate electrode modulation. A resonant tunneling process between metal electrode and MP-11 enhances the tunneling current and is responsible for the observed rectification. Our investigations demonstrated that functional building blocks of proteins can be reassembled into new conceptual devices with operation modes deviating from their native function, which could prove highly useful in the design of future biosensors and bioelectronic devices. Copyright 2009 Elsevier B.V. All rights reserved.

Transition-Metal-Catalyzed Selective Cage B-H Functionalization of o-Carboranes.

PubMed

Quan, Yangjian; Qiu, Zaozao; Xie, Zuowei

2018-02-26

Carboranes are a class of carbon-boron molecular clusters with unusual thermal and chemical stabilities. They have been proved as very useful building blocks in supramolecular design, optoelectronics, nanomaterials, boron neutron capture therapy agents and organometallic/coordination chemistry. Thus, the functionalization of o-carboranes has received growing interests. Over the past decades, most of the works in this area have been focused on cage carbon functionalization as the weakly acidic cage C-H proton can be readily deprotonated by strong bases. In sharp contrast, selective cage B-H activation/functionalization among chemically very similar ten B-H vertices is very challenging. Considering the differences in electron density of ten cage B-H bonds in o-carborane and the nature of transition metal complexes, we have tackled this selectivity issue by means of organometallic chemistry. Our strategy is as follows: using electron-rich transition metal catalysts for the functionalization of the most electron-deficient B(3,6)-H vertices (bonded to both cage CH vertices); using electron-deficient transition-metal catalysts for the functionalization of relatively electron-rich B(8,9,10,12)-H vertices (with no bonding to both cage CH vertices); and using the combination of directing groups and electrophilic transition metal catalysts for the functionalization of B(4,5,7,11)-H vertices (bonded to only one cage CH vertex). Successful applications of such a strategy result in the preparation of a large variety of cage B-functionalized carboranes in a regioselective and catalytic manner, which are inaccessible by other means. It is believed that as this field progresses, other cage B-functionalized carboranes are expected to be synthesized, and the results detailed in this concept article will further these efforts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inverted amorphous silicon solar cell utilizing cermet layers

DOEpatents

Hanak, Joseph J.

1979-01-01

An amorphous silicon solar cell incorporating a transparent high work function metal cermet incident to solar radiation and a thick film cermet contacting the amorphous silicon opposite to said incident surface.

Theory of the dynamical thermal conductivity of metals

NASA Astrophysics Data System (ADS)

Bhalla, Pankaj; Kumar, Pradeep; Das, Nabyendu; Singh, Navinder

2016-09-01

The Mori's projection method, known as the memory function method, is an important theoretical formalism to study various transport coefficients. In the present work, we calculate the dynamical thermal conductivity in the case of metals using the memory function formalism. We introduce thermal memory functions for the first time and discuss the behavior of thermal conductivity in both the zero frequency limit and in the case of nonzero frequencies. We compare our results for the zero frequency case with the results obtained by the Bloch-Boltzmann kinetic approach and find that both approaches agree with each other. Motivated by some recent experimental advancements, we obtain several new results for the ac or the dynamical thermal conductivity.

General and Direct Method for Preparing Oligonucleotide-Functionalized Metal-Organic Framework Nanoparticles.

PubMed

Wang, Shunzhi; McGuirk, C Michael; Ross, Michael B; Wang, Shuya; Chen, Pengcheng; Xing, Hang; Liu, Yuan; Mirkin, Chad A

2017-07-26

Metal-organic frameworks (MOFs) are a class of modular, crystalline, and porous materials that hold promise for storage and transport of chemical cargoes. Though MOFs have been studied in bulk forms, ways of deliberately manipulating the external surface functionality of MOF nanoparticles are less developed. A generalizable approach to modify their surfaces would allow one to impart chemical functionality onto the particle surface that is independent of the bulk MOF structure. Moreover, the use of a chemically programmable ligand, such as DNA, would allow for the manipulation of interparticle interactions. Herein, we report a coordination chemistry-based strategy for the surface functionalization of the external metal nodes of MOF nanoparticles with terminal phosphate-modified oligonucleotides. The external surfaces of nine distinct archetypical MOF particles containing four different metal species (Zr, Cr, Fe, and Al) were successfully functionalized with oligonucleotides, illustrating the generality of this strategy. By taking advantage of the programmable and specific interactions of DNA, 11 distinct MOF particle-inorganic particle core-satellite clusters were synthesized. In these hybrid nanoclusters, the relative stoichiometry, size, shape, and composition of the building blocks can all be independently controlled. This work provides access to a new set of nucleic acid-nanoparticle conjugates, which may be useful as programmable material building blocks and as probes for measuring and manipulating intracellular processes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Young Ki; Kwon, Junyeon; Hong, Seongin

Various strategies and mechanisms have been suggested for investigating a Schottky contact behavior in molybdenum disulfide (MoS{sub 2}) thin-film transistor (TFT), which are still in much debate and controversy. As one of promising breakthrough for transparent electronics with a high device performance, we have realized MoS{sub 2} TFTs with source/drain electrodes consisting of transparent bi-layers of a conducting oxide over a thin film of low work function metal. Intercalation of a low work function metal layer, such as aluminum, between MoS{sub 2} and transparent source/drain electrodes makes it possible to optimize the Schottky contact characteristics, resulting in about 24-fold andmore » 3 orders of magnitude enhancement of the field-effect mobility and on-off current ratio, respectively, as well as transmittance of 87.4 % in the visible wavelength range.« less

Examining changes in cellular communication in neuroendocrine cells after noble metal nanoparticle exposure.

PubMed

Love, Sara A; Liu, Zhen; Haynes, Christy L

2012-07-07

As nanoparticles enjoy increasingly widespread use in commercial applications, the potential for unintentional exposure has become much more likely during any given day. Researchers in the field of nanotoxicity are working to determine the physicochemical nanoparticle properties that lead to toxicity in an effort to establish safe design rules. This work explores the effects of noble metal nanoparticle exposure in murine chromaffin cells, focusing on examining the effects of size and surface functionality (coating) in silver and gold, respectively. Carbon-fibre microelectrode amperometry was utilized to examine the effect of exposure on exocytosis function, at the single cell level, and provided new insights into the compromised functions of cells. Silver nanoparticles of varied size, between 15 and 60 nm diameter, were exposed to cells and found to alter the release kinetics of exocytosis for those cells exposed to the smallest examined size. Effects of gold were examined after modification with two commonly used 'bio-friendly' polymers, either heparin or poly (ethylene glycol), and gold nanoparticles were found to induce altered cellular adhesion or the number of chemical messenger molecules released, respectively. These results support the body of work suggesting that noble metal nanoparticles perturb exocytosis, typically altering the number of molecules and kinetics of release, and supports a direct disruption of the vesicle matrix by the nanoparticle. Overall, it is clear that various nanoparticle physicochemical properties, including size and surface coating, do modulate changes in cellular communication via exocytosis.

Understanding the Reaction Chemistry of 2,2':5',2''-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Understanding the Reaction Chemistry of 2,2':5',2"-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Understanding charge transfer of Li+ and Na+ ions scattered from metal surfaces with high work function

NASA Astrophysics Data System (ADS)

Chen, Lin; Wu, Wen-Bin; Liu, Pin-Yang; Xiao, Yun-Qing; Li, Guo-Peng; Liu, Yi-Ran; Jiang, Hao-Yu; Guo, Yan-Ling; Chen, Xi-Meng

2016-08-01

For Li+ and Na+ ions scattered from high work function metal surfaces, efficient neutralization is observed, and it cannot be explained by the conventional free electron model. In order to explain these experimental data, we investigate the velocity-dependent neutral fraction with the modified Brako-Newns (BN) model. The calculated results are in agreement with the experimental data. We find that the parallel velocity effect plays an important role in neutralizing the Li+ and Na+ ions for large angle scattering. The nonmonotonic velocity behavior of neutral fraction is strongly related to the distance-dependent coupling strength between the atomic level and metal states. Project supported by the National Natural Science Foundation of China (Grant Nos. 11405078 and 11474140), the Fundamental Research Funds for the Central Universities, China (Grant Nos. lzujbky-2014-169 and lzujbky-2015-244), the Project sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, the State Education Ministry, and the National Students’ Innovation and Entrepreneurship Training Program (Grant Nos. 201410730069 and 201510730078).

Transition metal doped (X = V, Cr) CdS monolayer: A DFT study

NASA Astrophysics Data System (ADS)

Deb, Jyotirmoy; Paul, Debolina; Sarkar, Utpal

2018-05-01

In this work based on density functional theory approach with generalized gradient approximation we have investigated the effect doping and co-doping of transition metal atoms in CdS monolayer sheet. On the basis cohesive energy, we have determined the stability of all the transition metal doped systems. CdS monolayer is of nonmagnetic character but the insertion of transition metal atoms introduces the spontaneous spin polarization which results in a significant value of magnetic moment. The band structure analysis reveals that three different types of conducting nature such as spin-select-half-semiconductor, half metallic and metallic nature with total spin polarization has also been observed. The versatile conducting nature of the transition metal doped CdS monolayer predicts the possibility of using these systems in spintronics mainly as a spin filter and also to form metal-semiconductor interface etc. at nanoscale level.

Switching Hole and Electron Transports of Molecules on Metal Oxides by Energy Level Alignment Tuning.

PubMed

Bao, Zhong-Min; Xu, Rui-Peng; Li, Chi; Xie, Zhong-Zhi; Zhao, Xin-Dong; Zhang, Yi-Bo; Li, Yan-Qing; Tang, Jian-Xin

2016-08-31

Charge transport at organic/inorganic hybrid contacts significantly affects the performance of organic optoelectronic devices because the unfavorable energy level offsets at these interfaces can hinder charge injection or extraction due to large barrier heights. Herein, we report a technologically relevant method to functionalize a traditional hole-transport layer of solution-processed nickel oxide (NiOx) with various interlayers. The photoemission spectroscopy measurements reveal the continuous tuning of the NiOx substrate work function ranging from 2.5 to 6.6 eV, enabling the alignment transition of energy levels between the Schottky-Mott limit and Fermi level pinning at the organic/composite NiOx interface. As a result, switching hole and electron transport for the active organic material on the composite NiOx layer is achieved due to the controlled carrier injection/extraction barriers. The experimental findings indicate that tuning the work function of metal oxides with optimum energy level offsets can facilitate the charge transport at organic/electrode contacts.

Stress Intensity Factors for Cracking Metal Structures under Rapid Thermal Loading. Volume 2. Theoretical Background

DTIC Science & Technology

1989-08-01

thermal pulse loadings. The work couples a Green’s function integration technique for transient thermal stresses with the well-known influence ... function approach for calculating stress intensity factors. A total of seven most commonly used crack models were investigated in this study. A computer

Analytical model of threshold voltage degradation due to localized charges in gate material engineered Schottky barrier cylindrical GAA MOSFETs

NASA Astrophysics Data System (ADS)

Kumar, Manoj; Haldar, Subhasis; Gupta, Mridula; Gupta, R. S.

2016-10-01

The threshold voltage degradation due to the hot carrier induced localized charges (LC) is a major reliability concern for nanoscale Schottky barrier (SB) cylindrical gate all around (GAA) metal-oxide-semiconductor field-effect transistors (MOSFETs). The degradation physics of gate material engineered (GME)-SB-GAA MOSFETs due to LC is still unexplored. An explicit threshold voltage degradation model for GME-SB-GAA-MOSFETs with the incorporation of localized charges (N it) is developed. To accurately model the threshold voltage the minimum channel carrier density has been taken into account. The model renders how +/- LC affects the device subthreshold performance. One-dimensional (1D) Poisson’s and 2D Laplace equations have been solved for two different regions (fresh and damaged) with two different gate metal work-functions. LCs are considered at the drain side with low gate metal work-function as N it is more vulnerable towards the drain. For the reduction of carrier mobility degradation, a lightly doped channel has been considered. The proposed model also includes the effect of barrier height lowering at the metal-semiconductor interface. The developed model results have been verified using numerical simulation data obtained by the ATLAS-3D device simulator and excellent agreement is observed between analytical and simulation results.

Metal-dielectric metamaterials for guided wave silicon photonics.

PubMed

Lupu, A; Dubrovina, N; Ghasemi, R; Degiron, A; de Lustrac, A

2011-11-21

The aim of the present paper is to investigate the potential of metallic metamaterials for building optical functions in guided wave optics at 1.5 µm. A significant part of this work is focused on the optimization of the refractive index variation associated with localized plasmon resonances. The minimization of metal related losses is specifically addressed as well as the engineering of the resonance frequency of the localized plasmons. Our numerical modeling results show that a periodic chain of gold cut wires placed on the top of a 100 nm silicon waveguide makes it possible to achieve a significant index variation in the vicinity of the metamaterial resonance and serve as building blocks for implementing optical functions. The considered solutions are compatible with current nano-fabrication technologies. © 2011 Optical Society of America

Strong Fermi-Level Pinning at Metal/n-Si(001) Interface Ensured by Forming an Intact Schottky Contact with a Graphene Insertion Layer.

PubMed

Yoon, Hoon Hahn; Jung, Sungchul; Choi, Gahyun; Kim, Junhyung; Jeon, Youngeun; Kim, Yong Soo; Jeong, Hu Young; Kim, Kwanpyo; Kwon, Soon-Yong; Park, Kibog

2017-01-11

We report the systematic experimental studies demonstrating that a graphene layer inserted at metal/n-Si(001) interface is efficient to explore interface Fermi-level pinning effect. It is confirmed that an inserted graphene layer prevents atomic interdiffusion to form an atomically abrupt Schottky contact. The Schottky barriers of metal/graphene/n-Si(001) junctions show a very weak dependence on metal work-function, implying that the metal Fermi-level is almost completely pinned at charge neutrality level close to the valence band edge of Si. The atomically impermeable and electronically transparent properties of graphene can be used generally to form an intact Schottky contact for all semiconductors.

Infrared photoemitting diode having reduced work function

DOEpatents

Hirschfeld, T.B.

1982-05-06

In electro-optical detectors which include as elements a photoemitting photocathode and anode, a photoemitting diode is fabricated which lowers the diode's work function, thus reducing the cooling requirement typically needed for this type of device. The work function is reduced by sandwiching between the photocathode and anode a liquid meidum of the formula NR/sub 3/ and having an electron affinity for the electrons of the photocathode, which liquid medium permits free electrons leaving the photocathode to remain as stable solvated species in the liquid medium. Thus, highly light-absorbent, and therefore thin, metallic layers can be used for detection, thereby reducing dark current at a given temperature, with a consequent reduction in cooling requirements at constant detector performance.

Infrared photoemitting diode having reduced work function

DOEpatents

Hirschfeld, Tomas B.

1984-01-01

In electro-optical detectors which include as elements a photoemitting photocathode and anode, a photoemitting diode is fabricated which lowers the diode's work function, thus reducing the cooling requirement typically needed for this type of device. The work function is reduced by sandwiching between the photocathode and anode a liquid medium of the formula NR.sub.3 and having an electron affinity for the electrons of the photocathode, which liquid medium permits free electrons leaving the photocathode to remain as stable solvated species in the liquid medium. Thus, highly light-absorbent, and therefore thin, metallic layers can be used for detection, thereby reducing dark current at a given temperature, with a consequent reduction in cooling requirements at constant detector performance.

Sintered wire cesium dispenser photocathode

DOEpatents

Montgomery, Eric J; Ives, R. Lawrence; Falce, Louis R

2014-03-04

A photoelectric cathode has a work function lowering material such as cesium placed into an enclosure which couples a thermal energy from a heater to the work function lowering material. The enclosure directs the work function lowering material in vapor form through a low diffusion layer, through a free space layer, and through a uniform porosity layer, one side of which also forms a photoelectric cathode surface. The low diffusion layer may be formed from sintered powdered metal, such as tungsten, and the uniform porosity layer may be formed from wires which are sintered together to form pores between the wires which are continuous from the a back surface to a front surface which is also the photoelectric surface.

Functionalized graphene-based cathode for highly reversible lithium-sulfur batteries.

PubMed

Kim, Jin Won; Ocon, Joey D; Park, Dong-Won; Lee, Jaeyoung

2014-05-01

In this article, we highlight the salient issues in the development of lithium-sulfur battery (LSB) cathodes, present different points of view in solving them, and argue, why in the future, functionalized graphene or graphene oxide might be the ultimate solution towards LSB commercialization. As shown by previous studies and also in our recent work, functionalized graphene and graphene oxide enhance the reversibility of the charge-discharge process by trapping polysulfides in the oxygen functional groups on the graphene surface, thus minimizing polysulfide dissolution. This will be helpful for the rational design of new cathode structures based on graphene for LSBs with minimal capacity fading, low extra cost, and without the unnecessary weight increase caused by metal/metal oxide additives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integration of an Anti-parallel Pair of Planar Schottky Barrier Diodes for Millimeter and Submillimeter Wavelengths

DTIC Science & Technology

1991-08-01

built in potential OB - barrier potential Om - metal work function Os - semiconductor work function Xs semiconductor electron affinity (tOF...undoped Si0 2 (grown at 350 ’C) at a rate of 35 A/sec. The etch is isotropic, with 75 a lateral etch rate equal to the vertical etch rate. Agitation...the chromium to the atmosphere when the target is changed. The samples must therefore be allowed to outgas in a vacuum for several hours before the

Metal Based Synthetic Strategies and the Examination of Structure Determining Factors in Alkaline Earth Metal Compounds

NASA Astrophysics Data System (ADS)

Takahashi, Yuriko

Last decades have witnessed a large expansion of the organometallic heavier alkaline earth metal species. However, continued growth of this promising area of chemistry has been slowed by severe restrictions and limitations in viable synthetic methodologies leading to difficulties in preparing and characterizing the target compounds. There is clearly a need for the further development of synthetic methodologies and detailed structure function analysis that will promote the further advancement of organoalkaline earth metal chemistry in applications as diverse as materials chemistry and catalysis. This thesis work greatly extends the synthetic options currently available towards organoalkaline earth metal species by introducing redox transmetallation protolysis (RTP), a reaction based on the readily available Ph3Bi as a non-toxic transmetallation agent. Based on a straightforward one-pot procedure and work-up, Ph3Bi based RTP presents a powerful synthetic alternative for the facile preparation of a large variety of heavy alkaline earth metal compounds. The second part of the thesis explores the effect of secondary non covalent interactions on the coordination chemistry as well as thermal properties of a series of novel alkali, alkaline earth, rare earth as well as heterobimetallic alkali/alkaline earth fluoroalkoxides. These compounds showcase the significance of non-covalent M···F-C and agostic interactions on metal stabilization and structural features, providing critical input on ligand design for the design of advanced metal organic vapor deposition (MOCVD) precursor materials. This work also showcases the impact of M···F-C interactions over M---co-ligand coordination, a critical precursor design element as well.

Conjugated Polymer Zwitterions: Efficient Interlayer Materials in Organic Electronics.

PubMed

Liu, Yao; Duzhko, Volodimyr V; Page, Zachariah A; Emrick, Todd; Russell, Thomas P

2016-11-15

Conjugated polymer zwitterions (CPZs) are neutral, hydrophilic, polymer semiconductors. The pendent zwitterions, viewed as side chain dipoles, impart solubility in polar solvents for solution processing, and open opportunities as interfacial components of optoelectronic devices, for example, between metal electrodes and organic semiconductor active layers. Such interlayers are crucial for defining the performance of organic electronic devices, e.g., field-effect transistors (OFETs), light-emitting diodes (OLEDs), and photovoltaics (OPVs), all of which consist of multilayer structures. The interlayers reduce the Schottky barrier height and thus improve charge injection in OFETs and OLEDs. In OPVs, the interlayers serve to increase the built-in electric potential difference (V bi ) across the active layer, ensuring efficient extraction of photogenerated charge carriers. In general, polar and even charged electronically active polymers have gained recognition for their ability to modify metal/semiconductor interfaces to the benefit of organic electronics. While conjugated polyelectrolytes (CPEs) as interlayer materials are well-documented, open questions remain about the role of mobile counterions in CPE-containing devices. CPZs possess the processing advantages of CPEs, but as neutral molecules lack any potential complications associated with counterions. The electronic implications of CPZs on metal electrodes stem from the orientation of the zwitterion dipole moment in close proximity to the metal surface, and the resultant surface-induced polarization. This generates an interfacial dipole (Δ) at the CPZ/metal interface, altering the work function of the electrode, as confirmed by ultraviolet photoelectron spectroscopy (UPS), and improving device performance. An ideal cathode interlayer would reduce electrode work function, have orthogonal processability to the active layer, exhibit good film forming properties (i.e., wettability/uniformity), prevent exciton quenching, possess optimal electron affinity that neither limits the work function reduction nor impedes the charge extraction, transport electrons selectively, and exhibit long-term stability. Our recent discoveries show that CPZs achieve many of these attributes, and are poised for further expansion and development in the interfacial science of organic electronics. This Account reviews a recent collaboration that began with the synthesis of CPZs and a study of their structural and electronic properties on metals, then extended to their application as interlayer materials for OPVs. We discuss CPZ structure-property relationships based on several material platforms, ranging from homopolymers to copolymers, and from materials with intrinsic p-type conjugated backbones to those with intrinsic n-type conjugated backbones. We discuss key components of such interlayers, including (i) the origin of work function reduction of CPZ interlayers on metals; (ii) the role of the frontier molecular orbital energy levels and their trade-offs in optimizing electronic and device properties; and (iii) the role of polymer conductivity type and the magnitude of charge carrier mobility. Our motivation is to present our prior use and current understanding of CPZs as interlayer materials in organic electronics, and describe outstanding issues and future potential directions.

Large Work Function Modulation of Monolayer MoS2 by Ambient Gases.

PubMed

Lee, Si Young; Kim, Un Jeong; Chung, JaeGwan; Nam, Honggi; Jeong, Hye Yun; Han, Gang Hee; Kim, Hyun; Oh, Hye Min; Lee, Hyangsook; Kim, Hyochul; Roh, Young-Geun; Kim, Jineun; Hwang, Sung Woo; Park, Yeonsang; Lee, Young Hee

2016-06-28

Although two-dimensional monolayer transition-metal dichalcogenides reveal numerous unique features that are inaccessible in bulk materials, their intrinsic properties are often obscured by environmental effects. Among them, work function, which is the energy required to extract an electron from a material to vacuum, is one critical parameter in electronic/optoelectronic devices. Here, we report a large work function modulation in MoS2 via ambient gases. The work function was measured by an in situ Kelvin probe technique and further confirmed by ultraviolet photoemission spectroscopy and theoretical calculations. A measured work function of 4.04 eV in vacuum was converted to 4.47 eV with O2 exposure, which is comparable with a large variation in graphene. The homojunction diode by partially passivating a transistor reveals an ideal junction with an ideality factor of almost one and perfect electrical reversibility. The estimated depletion width obtained from photocurrent mapping was ∼200 nm, which is much narrower than bulk semiconductors.

Postadsorption Work Function Tuning via Hydrogen Pressure Control

PubMed Central

2015-01-01

The work function of metal substrates can be easily tuned, for instance, by adsorbing layers of molecular electron donors and acceptors. In this work, we discuss the possibility of changing the donor/acceptor mixing ratio reversibly after adsorption by choosing a donor/acceptor pair that is coupled via a redox reaction and that is in equilibrium with a surrounding gas phase. We discuss such a situation for the example of tetrafluoro-1,4-benzenediol (TFBD)/tetrafluoro-1,4-benzoquinone (TFBQ), adsorbed on Cu(111) and Ag(111) surfaces. We use density functional theory and ab initio thermodynamics to show that arbitrary TFBD/TFBQ mixing ratios can be set using hydrogen pressures attainable in low to ultrahigh vacuum. Adjusting the mixing ratio allows modifying the work function over a range of about 1 eV. Finally, we contrast single-species submonolayers with mixed layers to discuss why the resulting inhomogeneities in the electrostatic energy above the surface have different impacts on the interfacial level alignment and the work function. PMID:26692915

Positron states and annihilation characteristics of surface-trapped positrons at the oxidized Cu(110) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Olenga, Antoine; Weiss, A. H.

2013-03-01

The process by which oxide layers are formed on metal surfaces is still not well understood. In this work we present the results of theoretical studies of positron states and annihilation characteristics of surface-trapped positrons at the oxidized Cu(110) surface. An ab-initio investigation of stability and associated electronic properties of different adsorption phases of oxygen on Cu(110) has been performed on the basis of density functional theory and using DMOl3 code. The changes in the positron work function and the surface dipole moment when oxygen atoms occupy on-surface and sub-surface sites have been attributed to charge redistribution within the first two layers, buckling effects within each layer and interlayer expansion. The computed positron binding energy, positron surface state wave function, and annihilation probabilities of surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, elemental content, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data obtained from studies of oxidized transition metal surfaces using positron annihilation induced Auger electron spectroscopy. This work was supported in part by the National Science Foundation Grant DMR-0907679.

Optical and electronic structure description of metal-doped phthalocyanines.

PubMed

Leal, Luciano Almeida; da Cunha, Wiliam Ferreira; Ribeiro Junior, Luiz Antonio; Pereira, Tamires Lima; Blawid, Stefan Michael; de Sousa Junior, Rafael Timóteo; da Silva Filho, Demétrio Antonio

2017-05-01

Phthalocyanines represent a crucial class of organic compounds with high technological appeal. By doping the center of these systems with metals, one obtains the so-called metal-phthalocyanines, whose property of being an effective electron donor allows for potentially interesting uses in organic electronics. In this sense, investigating optical and electronic structure changes in the phthalocyanine profiles in the presence of different metals is of fundamental importance for evaluating the appropriateness of the resulting system as far as these uses are concerned. In the present work, we carry out this kind of effort for phthalocyanines doped with different metals, namely, copper, nickel, and magnesium. Density functional theory was applied to obtain the absorption spectra, and electronic and structural properties of the complexes. Our results suggest that depending on the dopant, a different level of change is achieved. Moreover, electrostatic potential energy mapping shows how the charge distribution can be affected by solar radiation. Our contribution is crucial in describing the best possible candidates for use in different organic photovoltaic applications. Graphical Abstract Representation of meta-phthalocyanine systems. All calculations of this work are based on varying metal position along z axis, considering the z-axis has its zero point matching with the center of phthalocyanine cavityconsidering.

Band structure and spin texture of Bi2Se3 3 d ferromagnetic metal interface

NASA Astrophysics Data System (ADS)

Zhang, Jia; Velev, Julian P.; Dang, Xiaoqian; Tsymbal, Evgeny Y.

2016-07-01

The spin-helical surface states in a three-dimensional topological insulator (TI), such as Bi2Se3 , are predicted to have superior efficiency in converting charge current into spin polarization. This property is said to be responsible for the giant spin-orbit torques observed in ferromagnetic metal/TI structures. In this work, using first-principles and model tight-binding calculations, we investigate the interface between the topological insulator Bi2Se3 and 3 d -transition ferromagnetic metals Ni and Co. We find that the difference in the work functions of the topological insulator and the ferromagnetic metals shift the topological surface states down about 0.5 eV below the Fermi energy where the hybridization of these surface states with the metal bands destroys their helical spin structure. The band alignment of Bi2Se3 and Ni (Co) places the Fermi energy far in the conduction band of bulk Bi2Se3 , where the spin of the carriers is aligned with the magnetization in the metal. Our results indicate that the topological surface states are unlikely to be responsible for the huge spin-orbit torque effect observed experimentally in these systems.

Clean thermal decomposition of tertiary-alkyl metal thiolates to metal sulfides: environmentally-benign, non-polar inks for solution-processed chalcopyrite solar cells.

PubMed

Heo, Jungwoo; Kim, Gi-Hwan; Jeong, Jaeki; Yoon, Yung Jin; Seo, Jung Hwa; Walker, Bright; Kim, Jin Young

2016-11-09

We report the preparation of Cu 2 S, In 2 S 3 , CuInS 2 and Cu(In,Ga)S 2 semiconducting films via the spin coating and annealing of soluble tertiary-alkyl thiolate complexes. The thiolate compounds are readily prepared via the reaction of metal bases and tertiary-alkyl thiols. The thiolate complexes are soluble in common organic solvents and can be solution processed by spin coating to yield thin films. Upon thermal annealing in the range of 200-400 °C, the tertiary-alkyl thiolates decompose cleanly to yield volatile dialkyl sulfides and metal sulfide films which are free of organic residue. Analysis of the reaction byproducts strongly suggests that the decomposition proceeds via an SN 1 mechanism. The composition of the films can be controlled by adjusting the amount of each metal thiolate used in the precursor solution yielding bandgaps in the range of 1.2 to 3.3 eV. The films form functioning p-n junctions when deposited in contact with CdS films prepared by the same method. Functioning solar cells are observed when such p-n junctions are prepared on transparent conducting substrates and finished by depositing electrodes with appropriate work functions. This method enables the fabrication of metal chalcogenide films on a large scale via a simple and chemically clear process.

Clean thermal decomposition of tertiary-alkyl metal thiolates to metal sulfides: environmentally-benign, non-polar inks for solution-processed chalcopyrite solar cells

NASA Astrophysics Data System (ADS)

Heo, Jungwoo; Kim, Gi-Hwan; Jeong, Jaeki; Yoon, Yung Jin; Seo, Jung Hwa; Walker, Bright; Kim, Jin Young

2016-11-01

We report the preparation of Cu2S, In2S3, CuInS2 and Cu(In,Ga)S2 semiconducting films via the spin coating and annealing of soluble tertiary-alkyl thiolate complexes. The thiolate compounds are readily prepared via the reaction of metal bases and tertiary-alkyl thiols. The thiolate complexes are soluble in common organic solvents and can be solution processed by spin coating to yield thin films. Upon thermal annealing in the range of 200-400 °C, the tertiary-alkyl thiolates decompose cleanly to yield volatile dialkyl sulfides and metal sulfide films which are free of organic residue. Analysis of the reaction byproducts strongly suggests that the decomposition proceeds via an SN1 mechanism. The composition of the films can be controlled by adjusting the amount of each metal thiolate used in the precursor solution yielding bandgaps in the range of 1.2 to 3.3 eV. The films form functioning p-n junctions when deposited in contact with CdS films prepared by the same method. Functioning solar cells are observed when such p-n junctions are prepared on transparent conducting substrates and finished by depositing electrodes with appropriate work functions. This method enables the fabrication of metal chalcogenide films on a large scale via a simple and chemically clear process.

A Review on the Synthesis and Applications of Mesostructured Transition Metal Phosphates

PubMed Central

Lin, Ronghe; Ding, Yunjie

2013-01-01

Considerable efforts have been devoted to extending the range of the elemental composition of mesoporous materials since the pioneering work of the M41S family of ordered mesoporous silica by Mobil researchers. The synthesis of transition metal-containing mesostructured materials with large surface area and high porosity has drawn great attention for its potential applications in acid and redox catalysis, photocatalysis, proton conducting devices, environmental restoration and so on. Thus, various transition metals-containing mesoporous materials, including transition metal-substituted mesoporous silicates, mesostructured transition metal oxides and transition metal phosphates (TMP), have been documented in the literature. Among these, mesostructured TMP materials are less studied, but possess some unique features, partly because of the easy and facile functionalization of PO4 and/or P–OH groups, rendering them interesting functional materials. This review first introduced the general synthesis strategies for manufacturing mesostructured TMP materials, as well as advantages and disadvantages of the respective method; then, we surveyed the ongoing developments of fabrication and application of the TMP materials in three groups on the basis of their components and application fields. Future perspectives on existing problems related to the present synthesis routes and further modifying of the functional groups for the purpose of tailoring special physical-chemical properties to meet wide application requirements were also provided in the last part. PMID:28809304

Metal-organometallic polymers and frameworks derived from facially metalated arylcarboxylates

NASA Astrophysics Data System (ADS)

Kumalah Robinson, Sayon A.

The interest in coordination polymers, also known as metal-organic frameworks, has risen drastically over the past 2 decades. In this time, the field has matured and given rise to a diverse range of crystalline structures possessing various functionalities. Coordination polymers are typically formed from the self assembly of metal ions which serve as nodes and organic ligands which act as bridges. By the careful selection of the organic ligand and the metal ion, the overall physical properties of the material may be tuned. In this work, the use of organometallic bridging ligands are explored using facially metalated aryl carboxylates ligands to synthesize metal-organometallic frameworks (MOMFs). Therefore, with the aim of synthesizing [CpM]+-functionalized (M = FeII, RuII; Cp = cyclopentadienyl) coordination polymers and metal organic frameworks, various [CpFe]+and [CpRu] + functionalized aryl carboxylates were synthesized and characterized. In particular, the [CpFe]+-functionalized benzoic, terephthalic and trimesic acids as well as the [CpRu]+-functionalized terephthalic acid were made. Using the [CpFe]+ complexes of the benzoic and terephthalic acid as bridging ligands, a number of 1D and 2D coordination polymers were synthesized. For instance, the reaction of [CpFe]+-functionalized benzoic acid with CdCl2 yielded the 1D chain of [Cd(benzoate)Cl 2]˙H2O whilst the reaction of [CpFe]+-functionalized terephthalic acid with Cu(NO3)2˙6H2O yielded a 2D square grid sheet. Using the [CpFe]+-functionalized terephthalic acid, a series of polymorphic, 3D metal-organometallic frameworks of the general formula [M3(terephthalate)4(mu-H2O)2(H 2O)2][NO3]2˙xsolvent (M = Co II, NiII ; solvent = EtOH, DMF, H2O) were synthesized and fully characterized. The polymorphic nature of these frameworks may be attributed to the different orientations that the [CpFe]+ moiety may adapt within the cavities in the 3D frameworks. The selectivity of the desolvated forms of the polymorphs for various alcohols was also probed. A framework having the same 3D topology but slightly different composition as the polymorphic frameworks of [M3(terephthalate)4(mu-H 2O)2(H2O)2][NO3]2˙ xsolvent was obtained using MnBr2˙4H2O. The solvothermal reaction of [CpFe]+-functionalized terephthalic acid and Co(NO3)2˙6H2O afforded the first microporous metal-organometallic phosphate. This 3D framework formed a cubic, 12-connected face centered net featuring a novel dodecanuclear truncated tetrahedral node consisting of [CpFe(terephthalate)]+, CoII, F- and phosphate ions. Lastly, the [CpFe]+-functionalized terephthalic acid was successfully reticulated into the MIL-88 and MIL 53 framework topologies indicating that the metalated ligand may be used to synthesis both known and novel 3D metal organic frameworks.

Influence of surface topology and electrostatic potential on water/electrode systems

NASA Astrophysics Data System (ADS)

Siepmann, J. Ilja; Sprik, Michiel

1995-01-01

We have used the classical molecular dynamics technique to simulate the ordering of a water film adsorbed on an atomic model of a tip of a scanning tunneling microscope approaching a planar metal surface. For this purpose, we have developed a classical model for the water-substrate interactions that solely depends on the coordinates of the particles and does not require the definition of geometrically smooth boundary surfaces or image planes. The model includes both an electrostatic induction for the metal atoms (determined by means of an extended Lagrangian technique) and a site-specific treatment of the water-metal chemisorption. As a validation of the model we have investigated the structure of water monolayers on metal substrates of various topology [the (111), (110), and (100) crystallographic faces] and composition (Pt, Ag, Cu, and Ni), and compared the results to experiments. The modeling of the electrostatic induction is compatible with a finite external potential imposed on the metal. This feature is used to investigate the structural rearrangements of the water bilayer between the pair of scanning tunneling microscope electrodes in response to an applied external voltage difference. We find significant asymmetry in the dependence on the sign of the applied voltage. Another result of the calculation is an estimate of the perturbation to the work function caused by the wetting film. For the conditions typical for operation of a scanning tunneling microscope probe, the change in the work function is found to be comparable to the applied voltage (a few hundred millivolts).

Investigation of thermally evaporated high resistive B-doped amorphous selenium alloy films and metal contact studies

NASA Astrophysics Data System (ADS)

Oner, Cihan; Nguyen, Khai V.; Pak, Rahmi O.; Mannan, Mohammad A.; Mandal, Krishna C.

2015-08-01

Amorphous selenium (a-Se) alloy materials with arsenic, chlorine, boron, and lithium doping were synthesized for room temperature nuclear radiation detector applications using an optimized alloy composition for enhanced charge transport properties. A multi-step synthetic process has been implemented to first synthesize Se-As and Se-Cl master alloys from zone-refined Se (~ 7N), and then synthesized the final alloys for thermally evaporated large-area thin-film deposition on oxidized aluminum (Al/Al2O3) and indium tin oxide (ITO) coated glass substrates. Material purity, morphology, and compositional characteristics of the alloy materials and films were examined using glow discharge mass spectroscopy (GDMS), inductively coupled plasma mass spectroscopy (ICP-MS), differential scanning calorimetry (DSC), x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive analysis by x-rays (EDAX). Current-Voltage (I-V) measurements were carried out to confirm very high resistivity of the alloy thin-films. We have further investigated the junction properties of the alloy films with a wide variety of metals with different work functions (Au, Ni, W, Pd, Cu, Mo, In, and Sn). The aim was to investigate whether the choice of metal can improve the performance of fabricated detectors by minimizing the dark leakage current. For various metal contacts, we have found significant dependencies of metal work functions on current transients by applying voltages from -800 V to +1000 V.

Environment-dependent interfacial strength using first principles thermodynamics: The example of the Pt-HfO2 interface

NASA Astrophysics Data System (ADS)

Cardona Quintero, Y.; Ramanath, Ganpati; Ramprasad, R.

2013-10-01

A parameter-free, quantitative, first-principles methodology to determine the environment-dependent interfacial strength of metal-metal oxide interfaces is presented. This approach uses the notion of the weakest link to identify the most likely cleavage plane, and first principles thermodynamics to calculate the average work of separation as a function of the environment (in this case, temperature and oxygen pressure). The method is applied to the case of the Pt-HfO2 interface, and it is shown that the computed environment-dependent work of separation is in quantitative agreement with available experimental data.

Stabilized metal nanoparticles from organometallic precursors for low temperature fuel cells.

PubMed

Ramirez-Meneses, E; Dominguez-Crespo, M A; Torres-Huerta, A M

2013-01-01

In this work, a review of articles and patents related to the utilization of colloidal metal nanoparticles produced by the decomposition of organometallic precursors as supported electrocatalysts in different electrochemical reactions including hydrogen evolution reaction (HER), oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) is discussed. In the case of stabilized metal nanoparticles, the kind of functional group contained in the stabilizer as well as the metal/stabilizer ratio, to evaluate the effect of particle size on the electrochemical performance, were also debated. Potential applications and perspectives of these electrocatalysts in proton exchange membrane fuel cells (PEMFC) are contended with reference to the role played by the coordination compounds and costs.

Thermodynamic Investigation of the Reduction-Distillation Process for Rare Earth Metals Production

NASA Astrophysics Data System (ADS)

Judge, W. D.; Azimi, G.

2017-10-01

Owing to their high vapor pressure, the four rare earth metals samarium, europium, thulium, and ytterbium are produced by reduction-distillation whereby their oxides are reduced with metallic lanthanum in vacuo, and the produced metal is subsequently vaporized off. Here, we performed a thorough thermodynamic investigation to establish a fundamental understanding of the reduction-distillation process. Thermodynamic functions including vapor pressures, Gibbs free energies, and enthalpies of reaction were calculated and compared with available experimental data. Furthermore, the kinetics of the process was explored and theoretical evaporation rates were calculated from thermodynamic data. The thermodynamic model developed in this work can help optimize processing conditions to maximize the yield and improve the overall process.

Sequential chemical extraction for a phosphogypsum environmental impact evaluation

NASA Astrophysics Data System (ADS)

Gennari, R. F.; Garcia, I.; Medina, N. H.; Silveira, M. A. G.

2013-05-01

Phosphogypsum (PG) is gypsum generated during phosphoric acid production. PG is stocked in large stacks or accumulated in lakes; it contains heavy metals and naturally occurring radioactive elements. The metal contamination may affect the functionality, sustainability and biodiversity of ecosystems. In this work, PG samples were analyzed by Plasma Spectrometry. Total metal content and in the extractable fraction of chemical elements were determined. For K, Ni, Zn, Cr, Cd, Ba, Pb and U, the results obtained are lower than those obtained in a Idaho plant are including and also lower than those found in the soil, indicating this PG sample analyzed probably will not cause any additional metal neither natural radiation contamination.

Assembly, Structure, and Functionality of Metal-Organic Networks and Organic Semiconductor Layers at Surfaces

NASA Astrophysics Data System (ADS)

Tempas, Christopher D.

Self-assembled nanostructures at surfaces show promise for the development of next generation technologies including organic electronic devices and heterogeneous catalysis. In many cases, the functionality of these nanostructures is not well understood. This thesis presents strategies for the structural design of new on-surface metal-organic networks and probes their chemical reactivity. It is shown that creating uniform metal sites greatly increases selectivity when compared to ligand-free metal islands. When O2 reacts with single-site vanadium centers, in redox-active self-assembled coordination networks on the Au(100) surface, it forms one product. When O2 reacts with vanadium metal islands on the same surface, multiple products are formed. Other metal-organic networks described in this thesis include a mixed valence network containing Pt0 and PtII and a network where two Fe centers reside in close proximity. This structure is stable to temperatures >450 °C. These new on-surface assemblies may offer the ability to perform reactions of increasing complexity as future heterogeneous catalysts. The functionalization of organic semiconductor molecules is also shown. When a few molecular layers are grown on the surface, it is seen that the addition of functional groups changes both the film's structure and charge transport properties. This is due to changes in both first layer packing structure and the pi-electron distribution in the functionalized molecules compared to the original molecule. The systems described in this thesis were studied using high-resolution scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy. Overall, this work provides strategies for the creation of new, well-defined on-surface nanostructures and adds additional chemical insight into their properties.

Use of Metallic Endosseous Implants as a Tooth Substitute

DTIC Science & Technology

1975-11-25

is exposed in the oral cavity and placed in function with the opposing dentition. BACKGROUND An appraisal of published work in the field of dental ...implant reveals that the dental literature abounds with articles concerned with the use of implants. The reports are mainly of clinical procedures and...metallic blades driven into the bone to become an anchor for prosthetic appliances. A complete critical review of the literature on dental implants was

Perturbation theory of structure in classical liquid mixtures: Application to metallic systems near phase separation. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Henderson, R. L.

1974-01-01

The partial structure factors of classical simple liquid mixtures near phase separation are dicussed. The theory is developed for particles interacting through pair potentials, and is thus appropriate both to insulating fluids, and also to metallic systems if these may be described by an effective ion-ion pair interaction. The motivation arose from consideration of metallic liquid mixtures, in which resistive anomalies have been observed near phase separation. A mean field theory correction appropriate to 3 pair potential for the effects of correlated motions in the reference fluid is studied. The work is cast in terms of functions which are closely related to the direct correlation functions of Ornstein and Zernike. The results are qualitatively in accord with physical expectations. Quantitative agreement with experiment seems to turn on the selection of the hard core reference potential in terms of the metallic effective pair potential. It is suggested that the present effective pair potentials are perhaps not properly used to calculate the metallic structure factors at long wavelength.

Resilience of Soil Microbial Communities to Metals and Additional Stressors: DNA-Based Approaches for Assessing “Stress-on-Stress” Responses

PubMed Central

Azarbad, Hamed; van Gestel, Cornelis A. M.; Niklińska, Maria; Laskowski, Ryszard; Röling, Wilfred F. M.; van Straalen, Nico M.

2016-01-01

Many microbial ecology studies have demonstrated profound changes in community composition caused by environmental pollution, as well as adaptation processes allowing survival of microbes in polluted ecosystems. Soil microbial communities in polluted areas with a long-term history of contamination have been shown to maintain their function by developing metal-tolerance mechanisms. In the present work, we review recent experiments, with specific emphasis on studies that have been conducted in polluted areas with a long-term history of contamination that also applied DNA-based approaches. We evaluate how the “costs” of adaptation to metals affect the responses of metal-tolerant communities to other stress factors (“stress-on-stress”). We discuss recent studies on the stability of microbial communities, in terms of resistance and resilience to additional stressors, focusing on metal pollution as the initial stress, and discuss possible factors influencing the functional and structural stability of microbial communities towards secondary stressors. There is increasing evidence that the history of environmental conditions and disturbance regimes play central roles in responses of microbial communities towards secondary stressors. PMID:27314330

Dynamics of metal-induced crystallization of ultrathin Ge films by rapid thermal annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liao, Yuanxun; Huang, Shujuan; Shrestha, Santosh

2015-12-07

Though Ge crystallization has been widely studied, few works investigate metal-induced crystallization of ultrathin Ge films. For 2 nm Ge films in oxide matrix, crystallization becomes challenging due to easy oxidation and low mobility of Ge atoms. Introducing metal atoms may alleviate these problems, but the functions and the behaviours of metal atoms need to be clarified. This paper investigates the crystallization dynamics of a multilayer structure 1.9 nm Ge/0.5 nm Al/1.5 nm Al{sub 2}O{sub 3} under rapid thermal annealing (RTA). The functions of metal atoms, like effective anti-oxidation, downshifting Raman peaks, and incapability to decrease crystallization temperature, are found and explained. The metalmore » behaviours, such as inter-diffusion and defect generation, are supported with direct evidences, Al-Ge nanobicrystals, and Al cluster in Ge atoms. With these understandings, a two-step RTA process achieves high-quality 2 nm nanocrystal Ge films with Raman peak at 298 cm{sup −1} of FWHM 10.3 cm{sup −1} and atomic smooth interfaces.« less

Rapid, sensitive, and selective fluorescent DNA detection using iron-based metal-organic framework nanorods: Synergies of the metal center and organic linker.

PubMed

Tian, Jingqi; Liu, Qian; Shi, Jinle; Hu, Jianming; Asiri, Abdullah M; Sun, Xuping; He, Yuquan

2015-09-15

Considerable recent attention has been paid to homogeneous fluorescent DNA detection with the use of nanostructures as a universal "quencher", but it still remains a great challenge to develop such nanosensor with the benefits of low cost, high speed, sensitivity, and selectivity. In this work, we report the use of iron-based metal-organic framework nanorods as a high-efficient sensing platform for fluorescent DNA detection. It only takes about 4 min to complete the whole "mix-and-detect" process with a low detection limit of 10 pM and a strong discrimination of single point mutation. Control experiments reveal the remarkable sensing behavior is a consequence of the synergies of the metal center and organic linker. This work elucidates how composition control of nanostructures can significantly impact their sensing properties, enabling new opportunities for the rational design of functional materials for analytical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Schottky Barrier Height of Pd/MoS2 Contact by Large Area Photoemission Spectroscopy.

PubMed

Dong, Hong; Gong, Cheng; Addou, Rafik; McDonnell, Stephen; Azcatl, Angelica; Qin, Xiaoye; Wang, Weichao; Wang, Weihua; Hinkle, Christopher L; Wallace, Robert M

2017-11-08

MoS 2 , as a model transition metal dichalcogenide, is viewed as a potential channel material in future nanoelectronic and optoelectronic devices. Minimizing the contact resistance of the metal/MoS 2 junction is critical to realizing the potential of MoS 2 -based devices. In this work, the Schottky barrier height (SBH) and the band structure of high work function Pd metal on MoS 2 have been studied by in situ X-ray photoelectron spectroscopy (XPS). The analytical spot diameter of the XPS spectrometer is about 400 μm, and the XPS signal is proportional to the detection area, so the influence of defect-mediated parallel conduction paths on the SBH does not affect the measurement. The charge redistribution by Pd on MoS 2 is detected by XPS characterization, which gives insight into metal contact physics to MoS 2 and suggests that interface engineering is necessary to lower the contact resistance for the future generation electronic applications.

Modeling FBG sensors sensitivity from cryogenic temperatures to room temperature as a function of metal coating thickness

NASA Astrophysics Data System (ADS)

Vendittozzi, Cristian; Felli, Ferdinando; Lupi, Carla

2018-05-01

Fiber optics with photo-imprinted Bragg grating have been studied in order to be used as temperature sensors in cryogenic applications. The main disadvantage presented by Fiber Bragg Grating (FBG) sensors is the significant drop in sensitivity as temperature decreases, mainly due to the critical lowering of the thermo-optic coefficient of the fiber and the very low thermal expansion coefficient (CTE) of fused silica at cryogenic temperatures. Thus, especially for the latter, it is important to enhance sensitivity to temperature by depositing a metal coating presenting higher CTE. In this work the thermal sensitivity of metal-coated FBG sensors has been evaluated by considering their elongation within temperature variations in the cryogenic range, as compared to bare fiber sensors. To this purpose, a theoretical model simulating elongation of metal-coated sensors has been developed. The model has been used to evaluate the behaviour of different metals which can be used as coating (Ni, Cu, Al, Zn, Pb and In). The optimal coating thickness has been calculated at different fixed temperature (from 5 K to 100 K) for each metal. It has been found that the metal coating effectiveness depends on thickness and operating temperature in accordance to our previous experimental work and theory suggest.

Shape Evolution of Metal Nanoparticles in Water Vapor Environment.

PubMed

Zhu, Beien; Xu, Zhen; Wang, Chunlei; Gao, Yi

2016-04-13

The structures of the metal nanoparticles are crucial for their catalytic activities. How to understand and even control the shape evolution of nanoparticles under reaction condition is a big challenge in heterogeneous catalysis. It has been proved that many reactive gases hold the capability of changing the structures and properties of metal nanoparticles. One interesting question is whether water vapor, such a ubiquitous environment, could induce the shape evolution of metal nanoparticles. So far this question has not received enough attention yet. In this work, we developed a model based on the density functional theory, the Wulff construction, and the Langmuir adsorption isotherm to explore the shape of metal nanoparticle at given temperature and water vapor pressure. By this model, we show clearly that water vapor could notably increase the fraction of (110) facets and decrease that of (111) facets for 3-8 nm Cu nanoparticles, which is perfectly consistent with the experimental observations. Further investigations indicate the water vapor has different effects on the different metal species (Cu, Au, Pt, and Pd). This work not only helps to understand the water vapor effect on the structures of metal nanoparticles but also proposes a simple but effective model to predict the shape of nanoparticles in certain environment.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces.

PubMed

Crawford, Paul; Hu, P

2006-12-14

The dissociative adsorption of N2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Contact-metal dependent current injection in pentacene thin-film transistors

NASA Astrophysics Data System (ADS)

Wang, S. D.; Minari, T.; Miyadera, T.; Tsukagoshi, K.; Aoyagi, Y.

2007-11-01

Contact-metal dependent current injection in top-contact pentacene thin-film transistors is analyzed, and the local mobility in the contact region was found to follow the Meyer-Neldel rule. An exponential trap distribution, rather than the metal/organic hole injection barrier, is proposed to be the dominant factor of the contact resistance in pentacene thin-film transistors. The variable temperature measurements revealed a much narrower trap distribution in the copper contact compared with the corresponding gold contact, and this is the origin of the smaller contact resistance for copper despite a lower work function.

Analysis of non-fatal and fatal injury rates for mine operator and contractor employees and the influence of work location.

PubMed

Karra, Vijia K

2005-01-01

Mining injury surveillance data are used as the basis for assessing the severity of injuries among operator and contractor employees in the underground and surface mining of various minerals. Injury rates during 1983-2002 derived from Mine Safety and Health Administration (MSHA) database are analyzed using the negative binomial regression model. The logarithmic mean injury rate is expressed as a linear function of seven indicator variables representing Non-Coal Contractor, Metal Operator, Non Metal Operator, Stone Operator, Sand and Gravel Operator, Coal Contractor, and Work Location, and a continuous variable, RelYear, representing the relative year starting with 1983 as the base year. Based on the model, the mean injury rate declined at a 1.69% annual rate, and the mean injury rate for work on the surface is 52.53% lower compared to the rate for work in the underground. With reference to the Coal Operator mean injury rate: the Non-Coal Contractor rate is 30.34% lower, the Metal Operator rate is 27.18% lower, the Non-Metal Operator rate is 37.51% lower, the Stone Operator rate is 23.44% lower, the Sand and Gravel Operator rate is 16.45% lower, and the Coal Contractor rate is 1.41% lower. Fatality rates during the same 20 year period are analyzed similarly using Poisson regression model. Based on this model, the mean fatality rate declined at a 3.17% annual rate, and the rate for work on the surface is 64.3% lower compared to the rate for work in the underground. With reference to the Coal Operator mean fatality rate: the Non-Coal Contractor rate is 234.81% higher, the Metal Operator rate is 5.79% lower, the Non-Metal Operator rate is 47.36% lower, the Stone Operator rate is 8.29% higher, the Sand and Gravel Operator rate is 60.32% higher, and the Coal Contractor rate is 129.54% higher.

Quasi-2D Liquid State at Metal-Organic Interface and Adsorption State Manipulation

NASA Astrophysics Data System (ADS)

Mehdizadeh, Masih

The metal/organic interface between noble metal close-packed (111) surfaces and organic semiconducting molecules is studied using Scanning tunneling microscopy and Photoelectron Spectroscopy, supplemented by first principles density functional theory calculations and Markov Chain Monte Carlo simulations. Copper Phthalocyanine molecules were shown to have dual adsorption states: a liquid state where intermolecular interactions were shown to be repulsive in nature and largely due to entropic effects, and a disordered immobilized state triggered by annealing or applying a tip-sample bias larger than a certain temperature or voltage respectively where intermolecular forces were demonstrated to be attractive. A methodology for altering molecular orientation on the aforementioned surfaces is also proposed through introduction of a Fullerene C60 buffer layer. Density functional theory calculations demonstrate orientation-switching of Copper Phthalocyanine molecules based on the amount of charges transferred to/from the substrate to the C60-CuPc layers; suggesting existence of critical substrate work functions that cause reorientation.

Influence of the Substrate on the Formation of Metallic Glass Coatings by Cold Gas Spraying

NASA Astrophysics Data System (ADS)

Henao, John; Concustell, Amadeu; Dosta, Sergi; Cinca, Núria; Cano, Irene G.; Guilemany, Josep M.

2016-06-01

Cold gas spray technology has been used to build up coatings of Fe-base metallic glass onto different metallic substrates. In this work, the effect of the substrate properties on the viscoplastic response of metallic glass particles during their impact has been studied. Thick coatings with high deposition efficiencies have been built-up in conditions of homogeneous flow on substrates such as Mild Steel AISI 1040, Stainless Steel 316L, Inconel 625, Aluminum 7075-T6, and Copper (99.9%). Properties of the substrate have been identified to play an important role in the viscoplastic response of the metallic glass particles at impact. Depending on the process gas conditions, the impact morphologies show not only inhomogeneous deformation but also homogeneous plastic flow despite the high strain rates, 108 to 109 s-1, involved in the technique. Interestingly, homogenous deformation of metallic glass particles is promoted depending on the hardness and the thermal diffusivity of the substrate and it is not exclusively a function of the kinetic energy and the temperature of the particle at impact. Coating formation is discussed in terms of fundamentals of dynamics of undercooled liquids, viscoplastic flow mechanisms of metallic glasses, and substrate properties. The findings presented in this work have been used to build up a detailed scheme of the deposition mechanism of metallic glass coatings by the cold gas spraying technology.

A study on morbidity among automobile service and repair workers in an urban area of South India

PubMed Central

Philip, Mathew; Alex, Reginald G.; Sunny, Soumya S.; Alwan, Anand; Guzzula, Deepak; Srinivasan, Rajan

2014-01-01

Introduction: Service sector in Indian industrial growth has obtained significant numbers. Automobile service industry is one of the largest in the world with a majority of the workers in unorganized sector of the industry. This study was carried out among auto service industry workers in Vellore urban area to assess possible occupation related morbidity. Materials and Methods: A cross-sectional observation study was carried out among 106 automobile repair shop workers. Results: Half (47%) suffered work related stress, 32 (30.2%) reported exposure to dust, 81 (76%) to heat, and 50 (17%) to hazardous chemicals and heavy metals. More than 90% reported over exposure to petroleum products. A third reported cough for more than 2 weeks, more than a quarter reported gastrointestinal symptoms associated with work. Half of them reported musculoskeletal complaints associated with work with a quarter reporting un-intentional work place injuries. A tenth of them were found to have reduced pulmonary function on testing and nearly half had impaired sensory functions in peripheries. Reduced pulmonary function was found to be significantly associated with heavy metal exposure (P = 0.001). Peripheral neuropathy was significantly associated with years of occupation (P = 0.001), exposure to petroleum products (P = 0.03) and exposure to heavy metals (P = 0.018). Discussion: Half of the workers were unaware of health problems associated with their occupational exposures and thereby the use of personal protection is abysmally low. A very high proportion of workers had symptoms of cough, breathlessness, abdominal pain, abdominal discomfort and muscle aches. Almost a quarter of the workers had un-intentional occupational injuries in the last 6 months. Though they work in a high-risk environment with chances of fire hazard, falls and chemical exposures, none of the workshops had fire-extinguishers, first aid kits or any such safety devices. PMID:25006310

Structure-function properties of anticorrosive exopolyaccharides

USDA-ARS?s Scientific Manuscript database

Nanoscale biobased exopolymer films were shown that provide protection to metal substrates under corrosive environments and that the films could be self-repairing in aqueous environments. This work describes the fundamental properties of thin exopolymer films including thermodynamic properties, film...

Cryogenic Research

DTIC Science & Technology

1952-05-01

needed work lies in the ultra low- temperature range available only through use of the demagnetization cycle. SUPERCONDUCTIVITY BELOW 10 ABSOLUTE In...In Figure 1 is plotted, as a function of temperature, the magnetic field required to change hafnium from the superconducting to the normal state. For...fields of crystal physics, properties of metals, and magnetism and magnetic resonance. This article discusses the work of one group, the Cryogenics

Metal Ion Reactions with Ozone and Atomic Oxygen.

DTIC Science & Technology

1979-04-05

EEEI 3 6 ....... Ii. MICROCOP Y RESOLUTION TEST CHART] / I. ~< 4 . A ’~ N ~ ~’ ~ ~. ~ ~ 4 ~ ~ ~. A ............................. ~ i, .1.’~~ AU 5 <j~1...aluminum-containing compound is ap- plied directly to a surface with high work function. Upon heating the sur- face, Al+ ions are evolved. In the...present experiments the compound was aluminum chloride, prepared by dissolving aluminum metal in hydrochloric *1 acid. The solution was then applied to the

A Novel, Free-Space Optical Interconnect Employing Vertical-Cavity Surface Emitting Laser Diodes and InGaAs Metal-Semiconductor-Metal Photodetectors for Gbit/s RF/Microwave Systems

NASA Technical Reports Server (NTRS)

Savich, Gregory R.; Simons, Rainee N.

2006-01-01

Emerging technologies and continuing progress in vertical-cavity surface emitting laser (VCSEL) diode and metal-semiconductor-metal (MSM) photodetector research are making way for novel, high-speed forms of optical data transfer in communication systems. VCSEL diodes operating at 1550 nm have only recently become commercially available, while MSM photodetectors are pushing the limits of contact lithography with interdigitated electrode widths reaching sub micron levels. We propose a novel, free-space optical interconnect operating at about 1Gbit/s utilizing VCSEL diodes and MSM photodetectors. We report on development, progress, and current work, which are as follows: first, analysis of the divergent behavior of VCSEL diodes for coupling to MSM photodetectors with a 50 by 50 m active area and second, the normalized frequency response of the VCSEL diode as a function of the modulating frequency. Third, the calculated response of MSM photodetectors with varying electrode width and spacing on the order of 1 to 3 m as well as the fabrication and characterization of these devices. The work presented here will lead to the formation and characterization of a fully integrated 1Gbit/s free-space optical interconnect at 1550 nm and demonstrates both chip level and board level functionality for RF/microwave digital systems.

Chemistry of fast electrons

PubMed Central

Maximoff, Sergey N.; Head-Gordon, Martin P.

2009-01-01

A chemicurrent is a flux of fast (kinetic energy ≳ 0.5−1.3 eV) metal electrons caused by moderately exothermic (1−3 eV) chemical reactions over high work function (4−6 eV) metal surfaces. In this report, the relation between chemicurrent and surface chemistry is elucidated with a combination of top-down phenomenology and bottom-up atomic-scale modeling. Examination of catalytic CO oxidation, an example which exhibits a chemicurrent, reveals 3 constituents of this relation: The localization of some conduction electrons to the surface via a reduction reaction, 0.5 O2 + δe− → Oδ− (Red); the delocalization of some surface electrons into a conduction band in an oxidation reaction, Oδ− + CO → CO2δ− → CO2 + δe− (Ox); and relaxation without charge transfer (Rel). Juxtaposition of Red, Ox, and Rel produces a daunting variety of metal electronic excitations, but only those that originate from CO2 reactive desorption are long-range and fast enough to dominate the chemicurrent. The chemicurrent yield depends on the universality class of the desorption process and the distribution of the desorption thresholds. This analysis implies a power-law relation with exponent 2.66 between the chemicurrent and the heat of adsorption, which is consistent with experimental findings for a range of systems. This picture also applies to other oxidation-reduction reactions over high work function metal surfaces. PMID:19561296

Functionally gradient material of the system Ni-MgO, Ni-NiO, Ni-Si3N4 or Al-AlN, by pressureless sintering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atarashiya, Koji; Kurokawa, Kazuya; Nagai, Tadao

1992-08-01

Generally speaking, the preparation of FGM-blocks, especially in the metal-nitride systems, by the method of powder metallurgy needs an extremely high temperature and high pressure. But, in this work using a ductile nickel metal powder or an ultrafine particle, the FGM-blocks were easily prepared using a powder metallurgy at a lower temperature. A mixture of a metallic powder and a non-metallic powder whose contents were gradually changed was pressed in a steel die under pressure of 20-32 MPa. These green compacts were heated at 900-1573 K in controlled atmosphere under null pressure. The FGM-blocks prepared by this method were characterizedmore » by their properties and were used in joinings. The joinings of metal/FGM/ceramics, metal/FGM and ceramics/FGM were completely accomplished at 900-1573 K. 6 refs.« less

Reliable energy level alignment at physisorbed molecule-metal interfaces from density functional theory.

PubMed

Egger, David A; Liu, Zhen-Fei; Neaton, Jeffrey B; Kronik, Leeor

2015-04-08

A key quantity for molecule-metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal-molecule interfaces. The method builds on the "DFT+Σ" approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways: first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule-metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors.

Stochastic resonance training reduces musculoskeletal symptoms in metal manufacturing workers: a controlled preventive intervention study.

PubMed

Burger, Christian; Schade, Volker; Lindner, Christina; Radlinger, Lorenz; Elfering, Achim

2012-01-01

This study examined the effects of stochastic resonance whole-body vibration training on work-related musculoskeletal symptoms and accidents. Participants were white and blue-collar employees of a Swiss metal manufacturer (N=38), and participation was voluntary. The study was designed as a switching-replications longitudinal trial with randomized group allocation. The randomized controlled cross-over design consisted of two groups each given four weeks of exercise and no intervention during a second four-week period. Outcome was measured on a daily basis with questionnaires. Three components constituted musculoskeletal symptoms: musculoskeletal pain, related function limitations and musculoskeletal well-being. Accidents were assessed by ratings for balance and daily near-accidents. For statistical analysis, a mixed model was calculated. At the end of the training period musculoskeletal pain and related function limitation were significantly reduced, whereas musculoskeletal well-being had significantly increased. For function limitation and musculoskeletal well-being, change over time was linear. There was no effect on balance or near-accidents. Stochastic resonance whole-body vibration was found to be effective in the prevention of work-related musculoskeletal symptoms. It is well suited for the use in a work environment since it requires very little effort in terms of infrastructure, time and investment from participants.

Magnetic chitosan nanocomposites: a useful recyclable tool for heavy metal ion removal.

PubMed

Liu, Xiaowang; Hu, Qiyan; Fang, Zhen; Zhang, Xiaojun; Zhang, Beibei

2009-01-06

Magnetic chitosan nanocomposites have been synthesized on the basis of amine-functionalized magnetite nanoparticles. These nanocomposites can be removed conveniently from water with the help of an external magnet because of their exceptional properties. The nanocomposites were applied to remove heavy metal ions from water because chitosan that is inactive on the surface of the magnetic nanoparticles is coordinated with them. The interaction between chitosan and heavy metal ions is reversible, which means that those ions can be removed from chitosan in weak acidic deionized water with the assistance of ultrasound radiation. On the basis of the reasons referred to above, synthesized magnetic chitosan nanocomposites were used as a useful recyclable tool for heavy metal ion removal. This work provides a potential platform for developing a unique route for heavy metal ion removal from wastewater.

Complete Transmetalation in a Metal-Organic Framework by Metal Ion Metathesis in a Single Crystal for Selective Sensing of Phosphate Ions in Aqueous Media.

PubMed

Asha, K S; Bhattacharjee, Rameswar; Mandal, Sukhendu

2016-09-12

A complete transmetalation has been achieved on a barium metal-organic framework (MOF), leading to the isolation of a new Tb-MOF in a single-crystal (SC) to single-crystal (SC) fashion. It leads to the transformation of an anionic framework with cations in the pore to one that is neutral. The mechanistic studies proposed a core-shell metal exchange through dissociation of metal-ligand bonds. This Tb-MOF exhibits enhanced photoluminescence and acts as a selective sensor for phosphate anion in aqueous medium. Thus, this work not only provides a method to functionalize a MOF that can have potential application in sensing but also elucidates the formation mechanism of the resulting MOF. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A two dimensional analytical modeling of surface potential in triple metal gate (TMG) fully-depleted Recessed-Source/Drain (Re-S/D) SOI MOSFET

NASA Astrophysics Data System (ADS)

Priya, Anjali; Mishra, Ram Awadh

2016-04-01

In this paper, analytical modeling of surface potential is proposed for new Triple Metal Gate (TMG) fully depleted Recessed-Source/Dain Silicon On Insulator (SOI) Metal Oxide Semiconductor Field Effect Transistor (MOSFET). The metal with the highest work function is arranged near the source region and the lowest one near the drain. Since Recessed-Source/Drain SOI MOSFET has higher drain current as compared to conventional SOI MOSFET due to large source and drain region. The surface potential model developed by 2D Poisson's equation is verified by comparison to the simulation result of 2-dimensional ATLAS simulator. The model is compared with DMG and SMG devices and analysed for different device parameters. The ratio of metal gate length is varied to optimize the result.

Step tunneling enhanced asymmetry in metal-insulator-insulator-metal (MIIM) diodes for rectenna applications

NASA Astrophysics Data System (ADS)

Alimardani, N.; Conley, J. F.

2013-09-01

We combine nanolaminate bilayer insulator tunnel barriers (Al2O3/HfO2, HfO2/Al2O3, Al2O3/ZrO2) deposited via atomic layer deposition (ALD) with asymmetric work function metal electrodes to produce MIIM diodes with enhanced I-V asymmetry and non-linearity. We show that the improvements in MIIM devices are due to step tunneling rather than resonant tunneling. We also investigate conduction processes as a function of temperature in MIM devices with Nb2O5 and Ta2O5 high electron affinity insulators. For both Nb2O5 and Ta2O5 insulators, the dominant conduction process is established as Schottky emission at small biases and Frenkel-Poole emission at large biases. The energy depth of the traps that dominate Frenkel-Poole emission in each material are estimated.

Electronic Transport Properties of Carbon-Nanotube Networks: The Effect of Nitrate Doping on Intratube and Intertube Conductances

NASA Astrophysics Data System (ADS)

Ketolainen, T.; Havu, V.; Jónsson, E. Ö.; Puska, M. J.

2018-03-01

The conductivity of carbon-nanotube (CNT) networks can be improved markedly by doping with nitric acid. In the present work, CNTs and junctions of CNTs functionalized with NO3 molecules are investigated to understand the microscopic mechanism of nitric acid doping. According to our density-functional-theory band-structure calculations, there is charge transfer from the CNT to adsorbed molecules indicating p -type doping. The average doping efficiency of the NO3 molecules is higher if the NO3 molecules form complexes with water molecules. In addition to electron transport along individual CNTs, we also study electron transport between different types (metallic, semiconducting) of CNTs. Reflecting the differences in the electronic structures of semiconducting and metallic CNTs, we find that in addition to turning semiconducting CNTs metallic, doping further increases electron transport most efficiently along semiconducting CNTs as well as through the junctions between them.

Gonioreflectometric properties of metal surfaces

NASA Astrophysics Data System (ADS)

Jaanson, P.; Manoocheri, F.; Mäntynen, H.; Gergely, M.; Widlowski, J.-L.; Ikonen, E.

2014-12-01

Angularly resolved measurements of scattered light from surfaces can provide useful information in various fields of research and industry, such as computer graphics, satellite based Earth observation etc. In practice, empirical or physics-based models are needed to interpolate the measurement results, because a thorough characterization of the surfaces under all relevant conditions may not be feasible. In this work, plain and anodized metal samples were prepared and measured optically for bidirectional reflectance distribution function (BRDF) and mechanically for surface roughness. Two models for BRDF (Torrance-Sparrow model and a polarimetric BRDF model) were fitted to the measured values. A better fit was obtained for plain metal surfaces than for anodized surfaces.

Nanoscale Fluorescent Metal-Organic Framework@Microporous Organic Polymer Composites for Enhanced Intracellular Uptake and Bioimaging.

PubMed

Wang, Lei; Wang, Weiqi; Zheng, Xiaohua; Li, Zhensheng; Xie, Zhigang

2017-01-26

Polymer-modified metal-organic frameworks combine the advantages of both soft polymers and crystalline metal-organic frameworks (MOFs). It is a big challenge to develop simple methods for surface modification of MOFs. In this work, MOF@microporous organic polymer (MOP) hybrid nanoparticles (UNP) have been synthesized by epitaxial growth of luminescent boron-dipyrromethene (BODIPYs)-imine MOPs on the surface of UiO-MOF seeds, which exhibit low cytotoxicity, smaller size distribution, well-retained pore integrity, and available functional sites. After folic acid grafting, the enhanced intracellular uptake and bioimaging was validated. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Observation of spin-polarized electron transport in Alq3 by using a low work function metal

NASA Astrophysics Data System (ADS)

Jang, Hyuk-Jae; Pernstich, Kurt P.; Gundlach, David J.; Jurchescu, Oana D.; Richter, Curt. A.

2012-09-01

We present the observation of magnetoresistance in Co/Ca/Alq3/Ca/NiFe spin-valve devices. Thin Ca layers contacting 150 nm thick Alq3 enable the injection of spin-polarized electrons into Alq3 due to the engineering of the band alignment. The devices exhibit symmetric current-voltage (I-V) characteristics indicating identical metal contacts on Alq3, and up to 4% of positive magnetoresistance was observed at 4.5 K. In contrast, simultaneously fabricated Co/Alq3/NiFe devices displayed asymmetric I-V curves due to the different metal electrodes, and spin-valve effects were not observed.

Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal–Organic Framework

PubMed Central

2016-01-01

An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO2 uptake of 12.6 mmol g–1 at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffraction reveals that, surprisingly, there is no direct binding between the adsorbed CO2/CH4 molecules and the pendant amide group in the pore. This observation has been confirmed unambiguously by inelastic neutron spectroscopy. This suggests that introduction of functional groups solely may not necessarily induce specific guest–host binding in porous materials, but it is a combination of pore size, geometry, and functional group that leads to enhanced gas adsorption properties. PMID:27665845

Effect of embedded metal nanocrystals on the resistive switching characteristics in NiN-based resistive random access memory cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yun, Min Ju; Kim, Hee-Dong; Man Hong, Seok

2014-03-07

The metal nanocrystals (NCs) embedded-NiN-based resistive random access memory cells are demonstrated using several metal NCs (i.e., Pt, Ni, and Ti) with different physical parameters in order to investigate the metal NC's dependence on resistive switching (RS) characteristics. First, depending on the electronegativity of metal, the size of metal NCs is determined and this affects the operating current of memory cells. If metal NCs with high electronegativity are incorporated, the size of the NCs is reduced; hence, the operating current is reduced owing to the reduced density of the electric field around the metal NCs. Second, the potential wells aremore » formed by the difference of work function between the metal NCs and active layer, and the barrier height of the potential wells affects the level of operating voltage as well as the conduction mechanism of metal NCs embedded memory cells. Therefore, by understanding these correlations between the active layer and embedded metal NCs, we can optimize the RS properties of metal NCs embedded memory cells as well as predict their conduction mechanisms.« less

Metal site occupancy and allosteric switching in bacterial metal sensor proteins.

PubMed

Guerra, Alfredo J; Giedroc, David P

2012-03-15

All prokaryotes encode a panel of metal sensor or metalloregulatory proteins that govern the expression of genes that allows an organism to quickly adapt to toxicity or deprivation of both biologically essential transition metal ions, e.g., Zn, Cu, Fe, and heavy metal pollutants. As such, metal sensor proteins can be considered arbiters of intracellular transition metal bioavailability and thus potentially control the metallation state of the metalloproteins in the cell. Metal sensor proteins are specialized allosteric proteins that regulate transcription as a result direct binding of one or two cognate metal ions, to the exclusion of all others. In most cases, the binding of the cognate metal ion induces a structural change in a protein oligomer that either activates or inhibits operator DNA binding. A quantitative measure of the degree to which a particular metal drives metalloregulation of operator DNA-binding is the allosteric coupling free energy, ΔGc. In this review, we summarize recent work directed toward understanding metal occupancy and metal selectivity of these allosteric switches in selected families of metal sensor proteins and examine the structural origins of ΔGc in the functional context a thermodynamic "set-point" model of intracellular metal homeostasis. Copyright © 2011 Elsevier Inc. All rights reserved.

Characterization of metal binding sites onto biochar using rare earth elements as a fingerprint.

PubMed

Pourret, Olivier; Houben, David

2018-02-01

The ability of biochar to immobilize metals relies on the amount of functional groups at its surface but the contribution of each functional groups (e.g. carboxylic, phenolic) to metal bonding is poorly known. Using a new approach based on previous works on rare earth element (REE) interactions with humic substances, we aim at elucidating the relative contribution of these binding sites to metal sorption under various conditions (i.e. pH and ionic strengths, IS). Using batch experiments, REE sorption onto biochar was analyzed from pH 3 to 9 and IS 10 -1 mol/L to 10 -3 mol/L. Rare earth element patterns show a Middle REE (MREE) downward concavity at acidic pH and low ionic strength. These patterns are in good agreement with existing datasets quantifying REE binding with humic substances. Indeed, the MREE downward concavity displayed by REE-biochar complexation pattern compares well with REE patterns with various organic compounds. This similarity in the REE complexation pattern shapes suggests that carboxylic groups are the main binding sites of REE in biochar. Overall, our results indicate that the strength of the metal bonding with biochar increases when pH and IS increase, suggesting that biochar is more efficient for long-term metal immobilization at near neutral pH and high ionic strength.

Low work function, stable compound clusters and generation process

DOEpatents

Dinh, Long N.; Balooch, Mehdi; Schildbach, Marcus A.; Hamza, Alex V.; McLean, II, William

2000-01-01

Low work function, stable compound clusters are generated by co-evaporation of a solid semiconductor (i.e., Si) and alkali metal (i.e., Cs) elements in an oxygen environment. The compound clusters are easily patterned during deposition on substrate surfaces using a conventional photo-resist technique. The cluster size distribution is narrow, with a peak range of angstroms to nanometers depending on the oxygen pressure and the Si source temperature. Tests have shown that compound clusters when deposited on a carbon substrate contain the desired low work function property and are stable up to 600.degree. C. Using the patterned cluster containing plate as a cathode baseplate and a faceplate covered with phosphor as an anode, one can apply a positive bias to the faceplate to easily extract electrons and obtain illumination.

Advanced optical modeling of TiN metal hard mask for scatterometric critical dimension metrology

NASA Astrophysics Data System (ADS)

Ebersbach, Peter; Urbanowicz, Adam M.; Likhachev, Dmitriy; Hartig, Carsten

2017-03-01

The majority of scatterometric production control models assume constant optical properties of the materials and only dimensional parameters are allowed to vary. However, this assumption, especially in case of thin-metal films, negatively impacts model precision and accuracy. In this work we focus on optical modeling of the TiN metal hardmask for scatterometry applications. Since the dielectric function of TiN exhibits thickness dependence, we had to take this fact into account. Moreover, presence of the highly absorbing films influences extracted thicknesses of dielectric layers underneath the metal films. The later phenomenon is often not reflected by goodness of fit. We show that accurate optical modeling of metal is essential to achieve desired scatterometric model quality for automatic process control in microelectronic production. Presented modeling methodology can be applied to other TiN applications such as diffusion barriers and metal gates as well as for other metals used in microelectronic manufacturing for all technology nodes.

Th-Based Endohedral Metallofullerenes: Anomalous Metal Position and Significant Metal-Cage Covalent Interactions with the Involvement of Th 5f Orbitals.

PubMed

Li, Ying; Yang, Le; Liu, Chang; Hou, Qinghua; Jin, Peng; Lu, Xing

2018-05-29

Endohedral metallofullerenes (EMFs) containing actinides are rather intriguing due to potential 5f-orbital participation in the metal-metal or metal-cage bonding. In this work, density functional theory calculations first characterized the structure of recently synthesized ThC 74 as Th@ D 3 h (14246)-C 74 . We found that the thorium atom adopts an unusual off-axis position inside cage due to small metal ion size and the requirement of large coordination number, which phenomenon was further extended to other Th-based EMFs. Significantly, besides the strong metal-cage electrostatic attractions, topological and orbital analysis revealed that all the investigated Th-based EMFs exhibit obvious covalent interactions between metal and cage with substantial contribution from the Th 5f orbitals. The encapsulation by fullerenes is thus proposed as a practical pathway toward the f-orbital covalency for thorium. Interestingly, the anomalous internal position of Th led to a novel three-dimensional metal trajectory at elevated temperatures in the D 3 h -C 74 cavity, as elucidated by the static computations and molecular dynamic simulations.

Decoration of multi-walled carbon nanotubes with metal nanoparticles in supercritical carbon dioxide medium as a novel approach for the modification of screen-printed electrodes.

PubMed

Moreno, Virginia; Llorent-Martínez, Eulogio J; Zougagh, Mohammed; Ríos, Angel

2016-12-01

A supercritical carbon dioxide medium was used for the decoration of functionalized multi-walled carbon nanotubes (MWCNTs) with metallic nanoparticles. This procedure allowed the rapid and simple decoration of carbon nanotubes with the selected metallic nanoparticles. The prepared nanomaterials were used to modify screen-printed electrodes, improving their electrochemical properties and allowing to obtain a wide range of working electrodes based on carbon nanotubes. These electrodes were applied to the amperometric determination of vitamin B6 in food and pharmaceutical samples as an example of the analytical potentiality of the electrodes thus prepared. Using Ru-nanoparticles-MWCNTs as the working electrode, a linear dynamic range between 2.6×10 -6 and 2×10 -4 molL -1 and a limit of detection of 0.8×10 -6 molL -1 were obtained. These parameters represented a minimum 3-fold increase in sensitivity compared to the use of bare MWCNTs or other carbon-based working electrodes. Copyright © 2016 Elsevier B.V. All rights reserved.

Towards Rational Design of Functional Fluoride and Oxyfluoride Materials from First Principles

NASA Astrophysics Data System (ADS)

Charles, Nenian

Complex transition metal compounds (TMCs) research has produced functional materials with a range of properties, including ferroelectricity, colossal magnetoresistance, nonlinear optical activity and high-temperature superconductivity. Conventional routes to tune properties in transition metal oxides, for example, have relied primarily on cation chemical substitution and interfacial effects in thin film heterostructures. In heteroanionic TMCs, exhibiting two chemically distinct anions coordinating the same or different cations, engineering of the anion sub-lattice for property control is a promising alternative approach. The presence of multiple anions provides additional design variables, such as anion order, that are absent in homoanionic counterparts. The more complex structural and chemical phase space of heteroanionic materials provides a unique opportunity to realize enhanced or unanticipated electronic, optical, and magnetic responses. Although there is growing interest in heteroanionic materials, and synthetic and characterization advances are occurring for these materials, the crystal-chemistry principles for realizing structural and property control are only slowing emerging. This dissertation employs anion engineering to investigate phenomena in transition metal fluorides and oxyfluorides compounds using first principles density functional theory calculations. Oxyfluorides are particularly intriguing owing their tendency to stabilize highly ordered anion sublattices as well as the potential to combine the advantageous properties of transition metal oxides and fluorides. This work 1) addresses the challenges of studying fluorides and oxyfluorides using first principles calculations; 2) evaluates the feasibility of using external stimuli, such as epitaxial strain and hydrostatic pressure, to control properties of fluorides and oxyfluorides; and 3) formulates a computational workflow based on multiple levels of theory and computation to elucidate structure-property relationships and anion-order descriptors. The insights gained in this work advance the understanding of oxide-fluoride anion engineered materials and we anticipate that it will motivate novel experimental efforts and materials by design in the future.

Work function of bulk-insulating topological insulator Bi{sub 2–x}Sb{sub x}Te{sub 3–y}Se{sub y}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takane, Daichi; Souma, Seigo; Center for Spintronics Research Network, Tohoku University, Sendai 980-8577

Recent discovery of bulk insulating topological insulator (TI) Bi{sub 2–x}Sb{sub x}Te{sub 3–y}Se{sub y} paved a pathway toward practical device application of TIs. For realizing TI-based devices, it is necessary to contact TIs with a metal. Since the band-bending at the interface dominates the character of devices, knowledge of TIs' work function is of essential importance. We have determined the compositional dependence of the work function in Bi{sub 2–x}Sb{sub x}Te{sub 3–y}Se{sub y} by high-resolution photoemission spectroscopy. The obtained work-function values (4.95–5.20 eV) track the energy shift of the surface chemical potential seen by angle-resolved photoemission spectroscopy. The present result serves as amore » useful guide for developing TI-based electronic devices.« less

Recent modifications of chitosan for adsorption applications: a critical and systematic review.

PubMed

Kyzas, George Z; Bikiaris, Dimitrios N

2015-01-09

Chitosan is considered to be one of the most promising and applicable materials in adsorption applications. The existence of amino and hydroxyl groups in its molecules contributes to many possible adsorption interactions between chitosan and pollutants (dyes, metals, ions, phenols, pharmaceuticals/drugs, pesticides, herbicides, etc.). These functional groups can help in establishing positions for modification. Based on the learning from previously published works in literature, researchers have achieved a modification of chitosan with a number of different functional groups. This work summarizes the published works of the last three years (2012-2014) regarding the modification reactions of chitosans (grafting, cross-linking, etc.) and their application to adsorption of different environmental pollutants (in liquid-phase).

Impact of intracellular metallothionein on metal biouptake and partitioning dynamics at bacterial interfaces.

PubMed

Présent, Romain M; Rotureau, Elise; Billard, Patrick; Pagnout, Christophe; Sohm, Bénédicte; Flayac, Justine; Gley, Renaud; Pinheiro, José P; Duval, Jérôme F L

2017-11-08

Genetically engineered microorganisms are alternatives to physicochemical methods for remediation of metal-contaminated aquifers due to their remarkable bioaccumulation capacities. The design of such biosystems would benefit from the elaboration of a sound quantitative connection between performance in terms of metal removal from aqueous solution and dynamics of the multiscale processes leading to metal biouptake. In this work, this elaboration is reported for Escherichia coli cells modified to overexpress intracellular metallothionein (MTc), a strong proteinaceous metal chelator. Depletion kinetics of Cd(ii) from bulk solution following biouptake and intracellular accumulation is addressed as a function of cell volume fraction using electroanalytical probes and ligand exchange-based analyses. It is shown that metal biouptake in the absence and presence of MTc is successfully interpreted on the basis of a formalism recently developed for metal partitioning dynamics at biointerfaces with integration of intracellular metal speciation. The analysis demonstrates how fast sequestration of metals by intracellular MTc bypasses metal excretion (efflux) and enhances the rate of metal depletion to an extent such that complete removal is achieved at sufficiently large cell volume fractions. The magnitude of the stability constant of nanoparticulate metal-MTc complexes, as derived from refined analysis of macroscopic bulk metal depletion data, is further confirmed by independent electrochemical measurement of metal binding by purified MTc extracts.

Stoichiometric and Oxygen-Deficient VO2 as Versatile Hole Injection Electrode for Organic Semiconductors.

PubMed

Fu, Keke; Wang, Rongbin; Katase, Takayoshi; Ohta, Hiromichi; Koch, Norbert; Duhm, Steffen

2018-03-28

Using photoemission spectroscopy, we show that the surface electronic structure of VO 2 is determined by the temperature-dependent metal-insulator phase transition and the density of oxygen vacancies, which depends on the temperature and ultrahigh vacuum (UHV) conditions. The atomically clean and stoichiometric VO 2 surface is insulating at room temperature and features an ultrahigh work function of up to 6.7 eV. Heating in UHV just above the phase transition temperature induces the expected metallic phase, which goes in hand with the formation of oxygen defects (up to 6% in this study), but a high work function >6 eV is maintained. To demonstrate the suitability of VO 2 as hole injection contact for organic semiconductors, we investigated the energy-level alignment with the prototypical organic hole transport material N, N'-di(1-naphthyl)- N, N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB). Evidence for strong Fermi-level pinning and the associated energy-level bending in NPB is found, rendering an Ohmic contact for holes.

Low contact resistance of the MWCNTs ohmic contact to p-GaN and its application for high power LED

NASA Astrophysics Data System (ADS)

Yokogawa, Toshiya; Miyake, Syota

2017-08-01

A low contact resistance electrode for p-GaN was obtained using the metallic multi-wall carbon nanotubes (MWCNTs) as the electrode material. The work function of the metallic MWCNTs was confirmed to be 4.84 eV as large as that of Au, Pd and Ni which are generally used for the p-GaN electrode material. Consequently the specific contact resistance was obtained to be as low as 2×10-3 Ωcm2 by optimizing the GaN surface treatment using hydrochloric acid because of the large work function of the MWCNTs. We also characterized the properties of LEDs using the MWCNTs ohmic contact for p-GaN. Low operation voltage and high optical output power was successfully obtained. Threshold voltage was about 2.7 V, and optical output power was about 0.8 W for the 1×1 mm2 size LED chip.

Collaborative research in tunneling and field emission pumped surface wave local oscillators and amplifiers for infrared and submillimeter wavelengths under director's discretionary fund

NASA Technical Reports Server (NTRS)

Gustafson, T. K.

1982-01-01

Progress is reported in work towards the development of surface wave sources for the infrared and sub-millimeter portion of the spectrum to be based upon electron pumping by tunneling electrons in metal-barrier-metal or metal-barrier-semiconductor devices. Tunneling phenomena and the coupling of radiation to tunnel junctions were studied. The propagation characteristics of surface electro-magnetic modes in metal-insulator-p(++) semiconductor structures as a function of frequency were calculated. A model for the gain process based upon Tucker's formalism was developed and used to estimate what low frequency gain might be expected from such structures. The question of gain was addressed from a more fundamental viewpoint using the method of Lasher and Stern.

Enhancing metal-insulator-insulator-metal tunnel diodes via defect enhanced direct tunneling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alimardani, Nasir; Conley, John F., E-mail: jconley@eecs.oregonstate.edu

Metal-insulator-insulator-metal tunnel diodes with dissimilar work function electrodes and nanolaminate Al{sub 2}O{sub 3}-Ta{sub 2}O{sub 5} bilayer tunnel barriers deposited by atomic layer deposition are investigated. This combination of high and low electron affinity insulators, each with different dominant conduction mechanisms (tunneling and Frenkel-Poole emission), results in improved low voltage asymmetry and non-linearity of current versus voltage behavior. These improvements are due to defect enhanced direct tunneling in which electrons transport across the Ta{sub 2}O{sub 5} via defect based conduction before tunneling directly through the Al{sub 2}O{sub 3}, effectively narrowing the tunnel barrier. Conduction through the device is dominated by tunneling,more » and operation is relatively insensitive to temperature.« less

The surface structure of silver-coated gold nanocrystals and its influence on shape control

DOE PAGES

Padmos, J. Daniel; Personick, Michelle L.; Tang, Qing; ...

2015-07-08

Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A uniquemore » approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals.« less

Respiratory morbidity of pattern and model makers exposed to wood, plastic, and metal products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robins, T.G.; Haboubi, G.; Demers, R.Y.

Pattern and model makers are skilled tradespersons who may be exposed to hardwoods, softwoods, phenol-formaldehyde resin-impregnated woods, epoxy and polyester/styrene resin systems, and welding and metal-casting fumes. The relationship of respiratory symptoms (wheezing, chronic bronchitis, dyspnea) and pulmonary function (FVC% predicted, FEV1% predicted, FEV1/FVC% predicted) with interview-derived cumulative exposure estimates to specific workplace agents and to all work with wood, plastic, or metal products was investigated in 751 pattern and model makers in southeast Michigan. In stratified analyses and age- and smoking-adjusted linear and logistic regression models, measures of cumulative wood exposures were associated with decrements in pulmonary function andmore » dyspnea, but not with other symptoms. In similar analyses, measures of cumulative plastic exposures were associated with wheezing, chronic bronchitis, and dyspnea, but not with decrements in pulmonary function. Prior studies of exposure levels among pattern and model makers and of respiratory health effects of specific agents among other occupational groups support the plausibility of wood-related effects more strongly than that of plastic-related effects.« less

Design of antibody-functionalized carbon nanotubes filled with radioactivable metals towards a targeted anticancer therapy

NASA Astrophysics Data System (ADS)

Spinato, Cinzia; Perez Ruiz de Garibay, Aritz; Kierkowicz, Magdalena; Pach, Elzbieta; Martincic, Markus; Klippstein, Rebecca; Bourgognon, Maxime; Wang, Julie Tzu-Wen; Ménard-Moyon, Cécilia; Al-Jamal, Khuloud T.; Ballesteros, Belén; Tobias, Gerard; Bianco, Alberto

2016-06-01

In the present work we have devised the synthesis of a novel promising carbon nanotube carrier for the targeted delivery of radioactivity, through a combination of endohedral and exohedral functionalization. Steam-purified single-walled carbon nanotubes (SWCNTs) have been initially filled with radioactive analogues (i.e. metal halides) and sealed by high temperature treatment, affording closed-ended CNTs with the filling material confined in the inner cavity. The external functionalization of these filled CNTs was then achieved by nitrene cycloaddition and followed by the derivatization with a monoclonal antibody (Cetuximab) targeting the epidermal growth factor receptor (EGFR), overexpressed by several cancer cells. The targeting efficiency of the so-obtained conjugate was evaluated by immunostaining with a secondary antibody and by incubation of the CNTs with EGFR positive cells (U87-EGFR+), followed by flow cytometry, confocal microscopy or elemental analyses. We demonstrated that our filled and functionalized CNTs can internalize more efficiently in EGFR positive cancer cells.In the present work we have devised the synthesis of a novel promising carbon nanotube carrier for the targeted delivery of radioactivity, through a combination of endohedral and exohedral functionalization. Steam-purified single-walled carbon nanotubes (SWCNTs) have been initially filled with radioactive analogues (i.e. metal halides) and sealed by high temperature treatment, affording closed-ended CNTs with the filling material confined in the inner cavity. The external functionalization of these filled CNTs was then achieved by nitrene cycloaddition and followed by the derivatization with a monoclonal antibody (Cetuximab) targeting the epidermal growth factor receptor (EGFR), overexpressed by several cancer cells. The targeting efficiency of the so-obtained conjugate was evaluated by immunostaining with a secondary antibody and by incubation of the CNTs with EGFR positive cells (U87-EGFR+), followed by flow cytometry, confocal microscopy or elemental analyses. We demonstrated that our filled and functionalized CNTs can internalize more efficiently in EGFR positive cancer cells. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07923c

A DFT and ab initio benchmarking study of metal-alkane interactions and the activation of carbon-hydrogen bonds.

PubMed

Flener-Lovitt, Charity; Woon, David E; Dunning, Thom H; Girolami, Gregory S

2010-02-04

Density functional theory and ab initio methods have been used to calculate the structures and energies of minima and transition states for the reactions of methane coordinated to a transition metal. The reactions studied are reversible C-H bond activation of the coordinated methane ligand to form a transition metal methyl hydride complex and dissociation of the coordinated methane ligand. The reaction sequence can be summarized as L(x)M(CH(3))H <==> L(x)M(CH(4)) <==> L(x)M + CH(4), where L(x)M is the osmium-containing fragment (C(5)H(5))Os(R(2)PCH(2)PR(2))(+) and R is H or CH(3). Three-center metal-carbon-hydrogen interactions play an important role in this system. Both basis sets and functionals have been benchmarked in this work, including new correlation consistent basis sets for a third transition series element, osmium. Double zeta quality correlation consistent basis sets yield energies close to those from calculations with quadruple-zeta basis sets, with variations that are smaller than the differences between functionals. The energies of important species on the potential energy surface, calculated by using 10 DFT functionals, are compared both to experimental values and to CCSD(T) single point calculations. Kohn-Sham natural bond orbital descriptions are used to understand the differences between functionals. Older functionals favor electrostatic interactions over weak donor-acceptor interactions and, therefore, are not particularly well suited for describing systems--such as sigma-complexes--in which the latter are dominant. Newer kinetic and dispersion-corrected functionals such as MPW1K and M05-2X provide significantly better descriptions of the bonding interactions, as judged by their ability to predict energies closer to CCSD(T) values. Kohn-Sham and natural bond orbitals are used to differentiate between bonding descriptions. Our evaluations of these basis sets and DFT functionals lead us to recommend the use of dispersion corrected functionals in conjunction with double-zeta or larger basis sets with polarization functions for calculations involving weak interactions, such as those found in sigma-complexes with transition metals.

Screened hybrid density functionals for solid-state chemistry and physics.

PubMed

Janesko, Benjamin G; Henderson, Thomas M; Scuseria, Gustavo E

2009-01-21

Density functional theory incorporating hybrid exchange-correlation functionals has been extraordinarily successful in providing accurate, computationally tractable treatments of molecular properties. However, conventional hybrid functionals can be problematic for solids. Their nonlocal, Hartree-Fock-like exchange term decays slowly and incorporates unphysical features in metals and narrow-bandgap semiconductors. This article provides an overview of our group's work on designing hybrid functionals for solids. We focus on the Heyd-Scuseria-Ernzerhof screened hybrid functional [J. Chem. Phys. 2003, 118, 8207], its applications to the chemistry and physics of solids and surfaces, and our efforts to build upon its successes.

A novel approach for the improvement of electrostatic behaviour of physically doped TFET using plasma formation and shortening of gate electrode with hetero-gate dielectric

NASA Astrophysics Data System (ADS)

Soni, Deepak; Sharma, Dheeraj; Aslam, Mohd.; Yadav, Shivendra

2018-04-01

This article presents a new device configuration to enhance current drivability and suppress negative conduction (ambipolar conduction) with improved RF characteristics of physically doped TFET. Here, we used a new approach to get excellent electrical characteristics of hetero-dielectric short gate source electrode TFET (HD-SG SE-TFET) by depositing a metal electrode of 5.93 eV work function over the heavily doped source (P+) region. Deposition of metal electrode induces the plasma (thin layer) of holes under the Si/HfO2 interface due to work function difference of metal and semiconductor. Plasma layer of holes is advantageous to increase abruptness as well as decrease the tunneling barrier at source/channel junction for attaining higher tunneling rate of charge carriers (i.e., electrons), which turns into 86.66 times higher ON-state current compared with the conventional physically doped TFET (C-TFET). Along with metal electrode deposition, gate electrode is under-lapped for inducing asymmetrical concentration of charge carriers in the channel region, which is helpful for widening the tunneling barrier width at the drain/channel interface. Consequently, HD-SG SE-TFET shows suppression of ambipolar behavior with reduction in gate-to-drain capacitance which is beneficial for improvement in RF performance. Furthermore, the effectiveness of hetero-gate dielectric concept has been used for improving the RF performance. Furthermore, reliability of C-TFET and proposed structures has been confirmed in term of linearity.

A generalized ligand-exchange strategy enabling sequential surface functionalization of colloidal nanocrystals.

PubMed

Dong, Angang; Ye, Xingchen; Chen, Jun; Kang, Yijin; Gordon, Thomas; Kikkawa, James M; Murray, Christopher B

2011-02-02

The ability to engineer surface properties of nanocrystals (NCs) is important for various applications, as many of the physical and chemical properties of nanoscale materials are strongly affected by the surface chemistry. Here, we report a facile ligand-exchange approach, which enables sequential surface functionalization and phase transfer of colloidal NCs while preserving the NC size and shape. Nitrosonium tetrafluoroborate (NOBF4) is used to replace the original organic ligands attached to the NC surface, stabilizing the NCs in various polar, hydrophilic media such as N,N-dimethylformamide for years, with no observed aggregation or precipitation. This approach is applicable to various NCs (metal oxides, metals, semiconductors, and dielectrics) of different sizes and shapes. The hydrophilic NCs obtained can subsequently be further functionalized using a variety of capping molecules, imparting different surface functionalization to NCs depending on the molecules employed. Our work provides a versatile ligand-exchange strategy for NC surface functionalization and represents an important step toward controllably engineering the surface properties of NCs.

Demonstration of near infrared gas sensing using gold nanodisks on functionalized silicon.

PubMed

Rodríguez-Cantó, P J; Martínez-Marco, M; Rodríguez-Fortuño, F J; Tomás-Navarro, B; Ortuño, R; Peransí-Llopis, S; Martínez, A

2011-04-11

In this work, we demonstrate experimentally the use of an array of gold nanodisks on functionalized silicon for chemosensing purposes. The metallic nanostructures are designed to display a very strong plasmonic resonance in the infrared regime, which results in highly sensitive sensing. Unlike usual experiments which are based on the functionalization of the metal surface, we functionalized here the silicon substrate. This silicon surface was modified chemically by buildup of an organosilane self-assembled monolayer (SAM) containing isocyanate as functional group. These groups allow for an easy surface regeneration by simple heating, thanks to the thermally reversible interaction isocyanate-analyte, which allows the cyclic use of the sensor. The technique showed a high sensitivity to surface binding events in gas and allowed the surface regeneration by heating of the sensor at 150 °C. A relative wavelength shift ∆λ(max)λ(0)=0.027 was obtained when the saturation level was reached. © 2011 Optical Society of America

Large-Scale, Three–Dimensional, Free–Standing, and Mesoporous Metal Oxide Networks for High–Performance Photocatalysis

PubMed Central

Bai, Hua; Li, Xinshi; Hu, Chao; Zhang, Xuan; Li, Junfang; Yan, Yan; Xi, Guangcheng

2013-01-01

Mesoporous nanostructures represent a unique class of photocatalysts with many applications, including splitting of water, degradation of organic contaminants, and reduction of carbon dioxide. In this work, we report a general Lewis acid catalytic template route for the high–yield producing single– and multi–component large–scale three–dimensional (3D) mesoporous metal oxide networks. The large-scale 3D mesoporous metal oxide networks possess large macroscopic scale (millimeter–sized) and mesoporous nanostructure with huge pore volume and large surface exposure area. This method also can be used for the synthesis of large–scale 3D macro/mesoporous hierarchical porous materials and noble metal nanoparticles loaded 3D mesoporous networks. Photocatalytic degradation of Azo dyes demonstrated that the large–scale 3D mesoporous metal oxide networks enable high photocatalytic activity. The present synthetic method can serve as the new design concept for functional 3D mesoporous nanomaterials. PMID:23857595

Heavy metals in the finest size fractions of road-deposited sediments.

PubMed

Lanzerstorfer, Christof

2018-08-01

The concentration of heavy metals in urban road-deposited sediments (RDS) can be used as an indicator for environmental pollution. Thus, their occurrence has been studied in whole road dust samples as well as in size fractions obtained by sieving. Because of the limitations of size separation by sieving little information is available about heavy metal concentrations in the road dust size fractions <20 μm. In this study air classification was applied for separation of dust size fractions smaller than 20 μm from RDS collected at different times during the year. The results showed only small seasonal variations in the heavy metals concentrations and size distribution. According to the Geoaccumulation Index the pollution of the road dust samples deceased in the following order: Sb » As > Cu ≈ Zn > Cr > Cd ≈ Pb ≈ Mn > Ni > Co ≈ V. For all heavy metals the concentration was higher in the fine size fractions compared to the coarse size fractions, while the concentration of Sr was size-independent. The enrichment of the heavy metals in the finest size fraction compared to the whole RDS <200 μm was up to 4.5-fold. The size dependence of the concentration decreased in the following order: Co ≈ Cd > Sb > (Cu) ≈ Zn ≈ Pb > As ≈ V » Mn. The approximation of the size dependence of the concentration as a function of the particle size by power functions worked very well. The correlation between particle size and concentration was high for all heavy metals. The increased heavy metals concentrations in the finest size fractions should be considered in the evaluation of the contribution of road dust re-suspension to the heavy metal contamination of atmospheric dust. Thereby, power functions can be used to describe the size dependence of the concentration. Copyright © 2018 Elsevier Ltd. All rights reserved.

Symmetrical metallic and magnetic edge states of nanoribbon from semiconductive monolayer PtS2

NASA Astrophysics Data System (ADS)

Liu, Shan; Zhu, Heyu; Liu, Ziran; Zhou, Guanghui

2018-03-01

Transition metal dichalcogenides (TMD) MoS2 or graphene could be designed to metallic nanoribbons, which always have only one edge show metallic properties due to symmetric protection. In present work, a nanoribbon with two parallel metallic and magnetic edges was designed from a noble TMD PtS2 by employing first-principles calculations based on density functional theory (DFT). Edge energy, bonding charge density, band structure, density of states (DOS) and simulated scanning tunneling microscopy (STM) of four possible edge states of monolayer semiconductive PtS2 were systematically studied. Detailed calculations show that only Pt-terminated edge state among four edge states was relatively stable, metallic and magnetic. Those metallic and magnetic properties mainly contributed from 5d orbits of Pt atoms located at edges. What's more, two of those central symmetric edges coexist in one zigzag nanoribbon, which providing two atomic metallic wires thus may have promising application for the realization of quantum effects, such as Aharanov-Bohm effect and atomic power transmission lines in single nanoribbon.

Development of Experimental Setup of Metal Rapid Prototyping Machine using Selective Laser Sintering Technique

NASA Astrophysics Data System (ADS)

Patil, S. N.; Mulay, A. V.; Ahuja, B. B.

2018-04-01

Unlike in the traditional manufacturing processes, additive manufacturing as rapid prototyping, allows designers to produce parts that were previously considered too complex to make economically. The shift is taking place from plastic prototype to fully functional metallic parts by direct deposition of metallic powders as produced parts can be directly used for desired purpose. This work is directed towards the development of experimental setup of metal rapid prototyping machine using selective laser sintering and studies the various parameters, which plays important role in the metal rapid prototyping using SLS technique. The machine structure in mainly divided into three main categories namely, (1) Z-movement of bed and table, (2) X-Y movement arrangement for LASER movements and (3) feeder mechanism. Z-movement of bed is controlled by using lead screw, bevel gear pair and stepper motor, which will maintain the accuracy of layer thickness. X-Y movements are controlled using timing belt and stepper motors for precise movements of LASER source. Feeder mechanism is then developed to control uniformity of layer thickness metal powder. Simultaneously, the study is carried out for selection of material. Various types of metal powders can be used for metal RP as Single metal powder, mixture of two metals powder, and combination of metal and polymer powder. Conclusion leads to use of mixture of two metals powder to minimize the problems such as, balling effect and porosity. Developed System can be validated by conducting various experiments on manufactured part to check mechanical and metallurgical properties. After studying the results of these experiments, various process parameters as LASER properties (as power, speed etc.), and material properties (as grain size and structure etc.) will be optimized. This work is mainly focused on the design and development of cost effective experimental setup of metal rapid prototyping using SLS technique which will gives the feel of metal rapid prototyping process and its important parameters.

Biomedical Implications of Heavy Metals Induced Imbalances in Redox Systems

PubMed Central

Singh, Shweta; Siddiqi, Nikhat J.

2014-01-01

Several workers have extensively worked out the metal induced toxicity and have reported the toxic and carcinogenic effects of metals in human and animals. It is well known that these metals play a crucial role in facilitating normal biological functions of cells as well. One of the major mechanisms associated with heavy metal toxicity has been attributed to generation of reactive oxygen and nitrogen species, which develops imbalance between the prooxidant elements and the antioxidants (reducing elements) in the body. In this process, a shift to the former is termed as oxidative stress. The oxidative stress mediated toxicity of heavy metals involves damage primarily to liver (hepatotoxicity), central nervous system (neurotoxicity), DNA (genotoxicity), and kidney (nephrotoxicity) in animals and humans. Heavy metals are reported to impact signaling cascade and associated factors leading to apoptosis. The present review illustrates an account of the current knowledge about the effects of heavy metals (mainly arsenic, lead, mercury, and cadmium) induced oxidative stress as well as the possible remedies of metal(s) toxicity through natural/synthetic antioxidants, which may render their effects by reducing the concentration of toxic metal(s). This paper primarily concerns the clinicopathological and biomedical implications of heavy metals induced oxidative stress and their toxicity management in mammals. PMID:25184144

Electronic structure of transition metal-cysteine complexes from X-ray absorption spectroscopy.

PubMed

Leung, Bonnie O; Jalilehvand, Farideh; Szilagyi, Robert K

2008-04-17

The electronic structures of HgII, NiII, CrIII, and MoV complexes with cysteine were investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory. The covalency in the metal-sulfur bond was determined by analyzing the intensities of the electric-dipole allowed pre-edge features appearing in the XANES spectra below the ionization threshold. Because of the well-defined structures of the selected cysteine complexes, the current work provides a reference set for further sulfur K-edge XAS studies of bioinorganic active sites with transition metal-sulfur bonds from cysteine residues as well as more complex coordination compounds with thiolate ligands.

Homogeneous dispersion of organic p-dopants in an organic semiconductor as an origin of high charge generation efficiency

NASA Astrophysics Data System (ADS)

Lee, Jae-Hyun; Kim, Hyun-Mi; Kim, Ki-Bum; Kabe, Ryota; Anzenbacher, Pavel; Kim, Jang-Joo

2011-04-01

We report that an organic p-dopant tri[1,2-bis(trifluoromethyl)ethane-1,2-dithiolene] [Mo(tfd)3] resulted in higher density of holes than inorganic metal oxide dopants of ReO3 or MoO3 in 1,4-bis[N-(1-naphthyl)-N'-phenylamino]-4,4'-diamine even though the metal oxide dopants possess deeper work functions compared to Mo(tfd)3. Higher charge generation efficiency results largely from the homogeneous dispersion of Mo(tfd)3 in the host. In contradistinction, the transmission electron microscopy analysis revealed a formation of metal oxide nanoclusters. This highlights the importance of homogeneous dispersion for an efficient doping.

Study of solid/liquid and solid/gas interfaces in Cu-isoleucine complex by surface X-ray diffraction

NASA Astrophysics Data System (ADS)

Ferrer, Pilar; Rubio-Zuazo, Juan; Castro, German R.

2013-02-01

The enzymes could be understood like structures formed by amino acids bonded with metals, which act as active sites. The research on the coordination of metal-amino acid complexes will bring light on the behavior of metal enzymes, due to the close relation existing between the atomic structure and the functionality. The Cu-isoleucine bond is considered as a good model system to attain a better insight into the characteristics of naturally occurring copper metalloproteins. The surface structure of metal-amino acid complex could be considered as a more realistic model for real systems under biologic working conditions, since the molecular packing is decreased. In the surface, the structural constrains are reduced, keeping the structural capability of surface complex to change as a function of the surrounding environment. In this work, we present a surface X-ray diffraction study on Cu-isoleucine complex under different ambient conditions. Cu(Ile)2 crystals of about 5 mm × 5 mm × 1 mm have been growth, by seeding method in a supersaturated solution, presenting a surface of high quality. The sample for the surface diffraction study was mounted on a cell specially designed for solid/liquid or solid/gas interface analysis. The Cu-isoleucine crystal was measured under a protective dry N2 gas flow and in contact with a saturated metal amino acid solution. The bulk and the surface signals were compared, showing different atomic structures. In both cases, from surface diffraction data, it is observed that the atomic structure of the top layer undergoes a clear structural deformation. A non-uniform surface relaxation is observed producing an inhomogeneous displacement of the surface atoms towards the surface normal.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, H., E-mail: li-huanglong@mail.tsinghua.edu.cn; Gillen, R.; Robertson, J., E-mail: jr214@cam.ac.uk

The screened exchange (sX) hybrid functional has been widely used in computational material science. Although it has widely been studied in bulk systems, less is known about its functional behavior in surface systems which are crucial to many technologies such as materials synthesis and nano-electronic devices. Assessing the screening dependent functional behaviors in the surface systems is therefore important for its application in such systems. In this work, we investigate the screening effects of the sX in CO adsorption on Pt(111) surface. The differences between the sX and Heyd-Scuseria-Ernzerhof (HSE06) hybrid functionals, and the effects of screening parameters are studied.more » The screening has two effects: first, the HOMO-LUMO gap is screening dependent. This affects the site preference most significantly. In this work, atop adsorption of CO/Pt(111) is predicted by the hybrid functionals with screened exchange potential. The sX(1.44) gives the largest HOMO-LUMO gap for the isolated CO molecule. The adsorption energy difference between the atop and fcc site is also the largest by the sX(1.44) which is explained by the reduced metal d states to the CO 2π* state back-donation, with stronger effect for the fcc adsorption than for the atop adsorption; second, the adsorption energy is screening dependent. This can be seen by comparing the sX(2.38) and HSE06 which have different screening strengths. They show similar surface band structures for the CO adsorption but different adsorption energies, which is explained by the stronger CO 5σ state to the metal d states donation or the effectively screened Pauli repulsion. This work underlines the screening strength as a main difference between sX and HSE06, as well as an important hybrid functional parameter for surface calculation.« less

Band Alignment and Charge Transfer in Complex Oxide Interfaces

NASA Astrophysics Data System (ADS)

Zhong, Zhicheng; Hansmann, Philipp

2017-01-01

The synthesis of transition metal heterostructures is currently one of the most vivid fields in the design of novel functional materials. In this paper, we propose a simple scheme to predict band alignment and charge transfer in complex oxide interfaces. For semiconductor heterostructures, band-alignment rules like the well-known Anderson or Schottky-Mott rule are based on comparison of the work function or electron affinity of the bulk components. This scheme breaks down for oxides because of the invalidity of a single work-function approximation as recently shown in [Phys. Rev. B 93, 235116 (2016), 10.1103/PhysRevB.93.235116; Adv. Funct. Mater. 26, 5471 (2016), 10.1002/adfm.201600243]. Here, we propose a new scheme that is built on a continuity condition of valence states originating in the compounds' shared network of oxygen. It allows for the prediction of sign and relative amplitude of the intrinsic charge transfer, taking as input only information about the bulk properties of the components. We support our claims by numerical density functional theory simulations as well as (where available) experimental evidence. Specific applications include (i) controlled doping of SrTiO3 layers with the use of 4 d and 5 d transition metal oxides and (ii) the control of magnetic ordering in manganites through tuned charge transfer.

Feasibility study of oxygen-dispensing emitters for thermionic converters, phase 1

NASA Technical Reports Server (NTRS)

Desteese, J. G.

1972-01-01

A metal/ceramic Marchuk tube was used to measure work functions of oxygen-doped tantalum, to determine applicability of the material to plasma-mode thermionic converters. Oxygen-doped tantalum was shown to increase in work function monotonically with oxygen doping in the range 0.1 to 0.3 atomic percent. Oxygenated test emitters were run at an average temperature of 2165 K and a T/T sub Cs ratio -5.8 to observe the influence of oxygen depletion. Bare work function decreased with outgassing of oxygen. Projections were made based on outgassing kinetics and area/volume ratios to calculate the longevity of oxygen doping in a practical converter. Calculations indicated that the program goal of 10,000 hr could be achieved at 1800 K with an initial oxygen doping of 1 atomic percent and a practical emitter area/volume ratio.

Work function determination of promising electrode materials for thermionic energy converters

NASA Technical Reports Server (NTRS)

Jacobson, D.; Storms, E.; Skaggs, B.; Kouts, T.; Jaskie, J.; Manda, M.

1976-01-01

The work function determinations of candidate materials for low temperature (1400 K) thermionics through vacuum emission tests are discussed. Two systems, a vacuum emission test vehicle and a thermionic emission microscope are used for emission measurements. Some nickel and cobalt based super alloys were preliminarily examined. High temperature physical properties and corrosion behavior of some super alloy candidates are presented. The corrosion behavior of sodium is of particular interest since topping cycles might use sodium heat transfer loops. A Marchuk tube was designed for plasma discharge studies with the carbide and possibly some super alloy samples. A series of metal carbides and other alloys were fabricated and tested in a special high temperature mass spectrometer. This information coupled with work function determinations was evaluated in an attempt to learn how electron bonding occurs in transition alloys.

Chemical control of orbital polarization in artificially structured transition-metal oxides: La2NiXO6 (X=B,Al,Ga,In) from first principles

NASA Astrophysics Data System (ADS)

Han, M. J.; Marianetti, C. A.; Millis, A. J.

2010-10-01

The application of modern layer-by-layer growth techniques to transition-metal oxide materials raises the possibility of creating new classes of materials with rationally designed correlated electron properties. An important step toward this goal is the demonstration that electronic structure can be controlled by atomic composition. In compounds with partially occupied transition-metal d shells, one important aspect of the electronic structure is the relative occupancy of different d orbitals. Previous work has established that strain and quantum confinement can be used to influence orbital occupancy. In this paper we demonstrate a different modality for orbital control in transition-metal oxide heterostructures, using density-functional band calculations supplemented by a tight-binding analysis to show that the choice of nontransition-metal counterion X in transition-metal oxide heterostructures composed of alternating LaNiO3 and LaXO3 units strongly affects orbital occupancy, changing the magnitude and in some cases the sign of the orbital polarization.

Studies on the biodistribution of dextrin nanoparticles

NASA Astrophysics Data System (ADS)

Gonçalves, C.; Ferreira, M. F. M.; Santos, A. C.; Prata, M. I. M.; Geraldes, C. F. G. C.; Martins, J. A.; Gama, F. M.

2010-07-01

The characterization of biodistribution is a central requirement in the development of biomedical applications based on the use of nanoparticles, in particular for controlled drug delivery. The blood circulation time, organ biodistribution and rate of excretion must be well characterized in the process of product development. In this work, the biodistribution of recently developed self-assembled dextrin nanoparticles is addressed. Functionalization of the dextrin nanoparticles with a DOTA-monoamide-type metal chelator, via click chemistry, is described. The metal chelator functionalized nanoparticles were labelled with a γ-emitting 153Sm3 + radioisotope and the blood clearance rate and organ biodistribution of the nanoparticles were obtained. The effect of PEG surface coating on the blood clearance rate and organ biodistribution of the nanoparticles was also studied.

Aeroelastic Tailoring of a Plate Wing with Functionally Graded Materials

NASA Technical Reports Server (NTRS)

Dunning, Peter D.; Stanford, Bret K.; Kim, H. Alicia; Jutte, Christine V.

2014-01-01

This work explores the use of functionally graded materials for the aeroelastic tailoring of a metallic cantilevered plate-like wing. Pareto trade-off curves between dynamic stability (flutter) and static aeroelastic stresses are obtained for a variety of grading strategies. A key comparison is between the effectiveness of material grading, geometric grading (i.e., plate thickness variations), and using both simultaneously. The introduction of material grading does, in some cases, improve the aeroelastic performance. This improvement, and the physical mechanism upon which it is based, depends on numerous factors: the two sets of metallic material parameters used for grading, the sweep of the plate, the aspect ratio of the plate, and whether the material is graded continuously or discretely.

Reliable Energy Level Alignment at Physisorbed Molecule–Metal Interfaces from Density Functional Theory

PubMed Central

2015-01-01

A key quantity for molecule–metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal–molecule interfaces. The method builds on the “DFT+Σ” approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways: first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule–metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors. PMID:25741626

The ionic versus metallic nature of 2D electrides: a density-functional description.

PubMed

Dale, Stephen G; Johnson, Erin R

2017-10-18

The two-dimensional (2D) electrides are a highly unusual class of materials, possessing interstitial electron layers sandwiched between cationic atomic layers of the solid. In this work, density-functional theory, with the exchange-hole dipole moment dispersion correction, is used to investigate exfoliation and interlayer sliding of the only two experimentally known 2D electrides: [Ca 2 N] + e - and [Y 2 C] 2+ (2e - ). Examination of the valence states during exfoliation identifies intercalated electrons in the bulk and weakly-bound surface-states in the fully-expanded case. The calculated exfoliation energies for the 2D electrides are found to be much higher than for typical 2D materials, which is attributed to the ionic nature of the electrides and the strong Coulomb forces governing the interlayer interactions. Conversely, the calculated sliding barriers are found to be quite low, comparable to those for typical 2D materials, and are effectively unchanged by exclusion of dispersion. We conjecture that the metallic nature of the interstitial electrons allows the atomic layers to move relative to each other without significantly altering the interlayer binding. Finally, comparison with previous works reveals the importance of a system-dependent dispersion correction in the density-functional treatment.

Work Function and Conductivity Change in Polyaniline.

NASA Astrophysics Data System (ADS)

Chinn, Douglas Alan

1995-01-01

The purpose of this study was to elucidate some basic material properties of the conducting polymer polyaniline. Because of the intractable nature of the polymer, methods to make thin films were developed. The polymer was dissolved in formic acid and cast onto silicon substrates that had four metal leads in a parallel configuration. It was discovered that a cast film could be used as a substrate for the subsequent growth of additional film by electrochemical techniques. The polymer will spontaneously change oxidation states both in air and in solution if oxidized or reduced electrochemically. The change in oxidation states is seen as a changing open cell potential in solution and a change in work function and resistance in air. UV-visible and infrared spectroscopy were used to characterize the polymer during relaxation. The work function decreases from both the oxidized and reduced states, but resistance increases from the reduced state and decreases from the oxidized state in air. A two-phase model which has ordered conducting regions and disordered insulating regions has been used to describe the relaxation phenomena. The relaxation is caused by rearrangement within the film of dopant acid and water, allowing the film to develop ordered regions. It has been determined that chemical polyaniline and electrochemical polyaniline are nearly identical chemically, with the main differences being morphological. The relaxation phenomena can be used to make chemical sensors. As the film relaxes, electrons become available. The electrons reduce metallic ions, which interact with a detectant gas in a gas stream above the film. In films containing Hg_2Cl_2 work function decreases and resistance decreases when in contact with hydrogen cyanide in a dry nitrogen stream.

Equilibrium properties of simple metal thin films in the self-compressed stabilized jellium model.

PubMed

Mahmoodi, T; Payami, M

2009-07-01

In this work, we have applied the self-compressed stabilized jellium model to predict the equilibrium properties of isolated thin Al, Na and Cs slabs. To make a direct correspondence to atomic slabs, we have considered only those L values that correspond to n-layered atomic slabs with 2≤n≤20, for surface indices (100), (110), and (111). The calculations are based on the density functional theory and self-consistent solution of the Kohn-Sham equations in the local density approximation. Our results show that firstly, the quantum size effects are significant for slabs with sizes smaller than or near to the Fermi wavelength of the valence electrons λ(F), and secondly, some slabs expand while others contract with respect to the bulk spacings. Based on the results, we propose a criterion for realization of significant quantum size effects that lead to expansion of some thin slabs. For more justification of the criterion, we have tested it on Li slabs for 2≤n≤6. We have compared our Al results with those obtained from using all-electron or pseudo-potential first-principles calculations. This comparison shows excellent agreements for Al(100) work functions, and qualitatively good agreements for the other work functions and surface energies. These agreements justify the way we have used the self-compressed stabilized jellium model for the correct description of the properties of simple metal slab systems. On the other hand, our results for the work functions and surface energies of large- n slabs are in good agreement with those obtained from applying the stabilized jellium model for semi-infinite systems. In addition, we have performed the slab calculations in the presence of surface corrugation for selected Al slabs and have shown that the results are worsened.

Commercial Applications of Metal Foams: Their Properties and Production

PubMed Central

García-Moreno, Francisco

2016-01-01

This work gives an overview of the production, properties and industrial applications of metal foams. First, it classifies the most relevant manufacturing routes and methods. Then, it reviews the most important properties, with special interest in the mechanical and functional aspects, but also taking into account costs and feasibility considerations. These properties are the motivation and basis of related applications. Finally, a summary of the most relevant applications showing a large number of actual examples is presented. Concluding, we can forecast a slow, but continuous growth of this industrial sector. PMID:28787887

Surface-Functionalized Electrospun Titania Nanofibers for the Scavenging and Recycling of Precious Metal Ions.

PubMed

Dai, Yunqian; Formo, Eric; Li, Haoxuan; Xue, Jiajia; Xia, Younan

2016-10-20

Precious metals are widely used as catalysts in industry. It is of critical importance to keep the precious metal ions leached from catalysts at a level below one part per million (ppm) in the final products and to recycle the expensive precious metals. Here we demonstrate a simple and effective method for scavenging precious metal ions from an aqueous solution and thereby reduce their concentrations down to the parts per billion (ppb) level. The key component is a filtration membrane comprised of titania (TiO 2 ) nanofibers whose surface has been functionalized with a silane bearing amino or thiol group. When operated under continuous flow at a rate of 1 mL min -1 and at room temperature, up to 99.95 % of the Pd 2+ ions could be removed from a stock solution with an initial concentration of 100 ppm. This work offers a viable strategy not only for the removal of precious metal ions but also for recovering and further recycling them for use as catalysts. For example, the captured Pd 2+ ions could be converted to nanoparticles and used as catalysts for organic reactions such as Suzuki coupling in a continuous flow reactor. This system can be potentially applied to pharmaceutical industry and waste stream treatment. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size- and temperature-dependent Hamaker constants for heterogeneous systems of interacting nanoparticles

NASA Astrophysics Data System (ADS)

Pinchuk, P.; Pinchuk, A. O.

2016-09-01

Hamaker-Lifshitz constants are used to calculate van der Waals interaction forces between small particles in solution. Typically, these constants are size-independent and material specific. According to the Lifshitz theory, the Hamaker-Lifshitz constants can be calculated by taking integrals that include the dielectric permittivity, as a function of frequency, of the interacting particles and the medium around particles. The dielectric permittivity of interacting metal nanoparticles can be calculated using the free-electron Drude model for metals. For bulk metals, the Drude model does is size independent. However, the conducting electrons in small metal nanoparticles exhibit surface scattering, which changes the complex dielectric permittivity function. Additionally, the Drude model can be modified to include temperature dependence. That is, an increase in temperature leads to thermal volume expansion and increased phonon population, which affect the scattering rate of the electrons and the plasma frequency. Both of these terms contribute significantly to the Drude model for the dielectric permittivity of the particles. In this work, we show theoretically that scattering of the free conducting electrons inside noble metal nanoparticles with the size of 1 - 50 nm leads to size-dependent dielectric permittivity and Hamaker-Lifshitz constants. In addition, we calculate numerically the Hamaker-Lifshitz constants for a variety of temperatures. The results of the study might be of interest for understanding colloidal stability of metal nanoparticles.

Electronic, Magnetic and Optical Properties of 2D Metal Nanolayers: A DFT Study

NASA Astrophysics Data System (ADS)

Bhuyan, Prabal Dev; Gupta, Sanjeev K.; Singh, Deobrat; Sonvane, Yogesh; Gajjar, P. N.

2018-03-01

In the recent work, we have investigated the structural, electronic, magnetic and optical properties of graphene-like hexagonal monolayers and multilayers (up to five layers) of 3d-transition metals Fe, Co and Ni based on spin-polarized density functional theory. Here, we have taken two types of pattern namely AA-stacking and AB-stacking for the calculations. The binding energy calculations show that the AA-type configuration is energetically more stable. The calculated binding energies of Fe, Co and Ni-bilayer monolayer are - 3.24, - 2.53 and - 1.94 eV, respectively. The electronic band structures show metallic behavior for all the systems and each configurations of Fe, Co and Ni-atoms. While, the quantum ballistic conductances of these metallic systems are found to be higher for pentalayer than other layered systems. The density of states confirms the ferromagnetic behavior of monolayers and multilayers of Fe and Co having negative spin polarizations. We have also calculated frequency dependent complex dielectric function, electronic energy loss spectrum and reflectance spectrum of monolayer to pentalayer metallic systems. The ferromagnetic material shows different permittivity tensor (ɛ), which is due to high spin magnetic moment for n-layered Fe and Co two-dimensional (2D) nanolayers. The theoretical investigation suggests that the electronic, magnetic and optical properties of 3d-transition metal nanolayers offers great promise for their use in spintronics nanodevices and magneto-optical nanodevices applications.

An alternative approach for modeling strength differential effect in sheet metals with symmetric yield functions

NASA Astrophysics Data System (ADS)

Kurukuri, Srihari; Worswick, Michael J.

2013-12-01

An alternative approach is proposed to utilize symmetric yield functions for modeling the tension-compression asymmetry commonly observed in hcp materials. In this work, the strength differential (SD) effect is modeled by choosing separate symmetric plane stress yield functions (for example, Barlat Yld 2000-2d) for the tension i.e., in the first quadrant of principal stress space, and compression i.e., third quadrant of principal stress space. In the second and fourth quadrants, the yield locus is constructed by adopting interpolating functions between uniaxial tensile and compressive stress states. In this work, different interpolating functions are chosen and the predictive capability of each approach is discussed. The main advantage of this proposed approach is that the yield locus parameters are deterministic and relatively easy to identify when compared to the Cazacu family of yield functions commonly used for modeling SD effect observed in hcp materials.

Run-D.M.C.: A Mnemonic Aid for Explaining Mass Transfer in Electrochemical Systems

ERIC Educational Resources Information Center

Miles, Deon T.

2013-01-01

Electrochemistry is a significant area of analytical chemistry encompassing electrical measurements of chemical systems. The applications associated with electrochemistry appear in many aspects of everyday life: explaining how batteries work, how the human nervous system functions, and how metal corrosion occurs. The most common electrochemical…

Transition-metal prion protein attachment: Competition with copper

NASA Astrophysics Data System (ADS)

Hodak, Miroslav; Bernholc, Jerry

2012-02-01

Prion protein, PrP, is a protein capable of binding copper ions in multiple modes depending on their concentration. Misfolded PrP is implicated in a group of neurodegenerative diseases, which include ``mad cow disease'' and its human form, variant Creutzfeld-Jacob disease. An increasing amount of evidence suggests that attachment of non-copper metal ions to PrP triggers transformations to abnormal forms similar to those observed in prion diseases. In this work, we use hybrid Kohn-Sham/orbital-free density functional theory simulations to investigate copper replacement by other transition metals that bind to PrP, including zinc, iron and manganese. We consider all known copper binding modes in the N-terminal domain of PrP. Our calculations identify modes most susceptible to copper replacement and reveal metals that can successfully compete with copper for attachment to PrP.

Reduction potentials of heterometallic manganese–oxido cubane complexes modulated by redox-inactive metals

PubMed Central

Tsui, Emily Y.; Agapie, Theodor

2013-01-01

Understanding the effect of redox-inactive metals on the properties of biological and heterogeneous water oxidation catalysts is important both fundamentally and for improvement of future catalyst designs. In this work, heterometallic manganese–oxido cubane clusters [MMn3O4] (M = Sr2+, Zn2+, Sc3+, Y3+) structurally relevant to the oxygen-evolving complex (OEC) of photosystem II were prepared and characterized. The reduction potentials of these clusters and other related mixed metal manganese–tetraoxido complexes are correlated with the Lewis acidity of the apical redox-inactive metal in a manner similar to a related series of heterometallic manganese–dioxido clusters. The redox potentials of the [SrMn3O4] and [CaMn3O4] clusters are close, which is consistent with the observation that the OEC is functional only with one of these two metals. Considering our previous studies of [MMn3O2] moieties, the present results with more structurally accurate models of the OEC ([MMn3O4]) suggest a general relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidities of incorporated cations that applies to diverse structural motifs. These findings support proposals that one function of calcium in the OEC is to modulate the reduction potential of the cluster to allow electron transfer. PMID:23744039

Research on Lessening of Bonding Effects Between the Metallic and Non-Metallic Surfaces Through the Graphite Films Deposited with Pulsed Electrical Discharges Process

NASA Astrophysics Data System (ADS)

Marin, L.; Topala, P.

2017-06-01

The paper presents the results of experimental research on the physics of natural graphite film formation, the establishment of chemical composition and functional properties of the graphite films, formed on metal surfaces, as a result of the action of plasma in the air environment, at a normal pressure, under the electrical discharge in impulse conditions (EDI). The researchings were performed in the frame of doctoral thesis “Research on lessening of the bonding effects between the metallic and nonmetallic surfaces through the graphite films” and aimed to identify the phenomena that occur at the interface metal/ film of graphite, and to identify also the technological applications that it may have the surface treatment for submitting the films of graphite on metallic surfaces achieved through an innovative process of electrical pulsed discharges. After the research works from the PhD theme above mentioned, a number of interesting properties of graphite pellicle have been identified ie reducing of metal surface polarity. This led to drastic decreases for the values of adhesion when bonding of metal surfaces was performed using a structural polyurethane adhesive designed by ICECHIM. Following the thermo-gravimetric analysis, performed of the graphite film obtained by process of electrical pulsed discharges, have been also discovered other interesting properties for this, ie reversible mass additions at specific values of the working temperature Chemical and scanning electron microscopy analysis have revealed that on the metallic surface subjected to electrical pulsed discharges process, outside the graphite film, it is also obtained a series of spatial formation composed of carbon atoms fullerenes type which are responsible for the phenomenon of addition of mass.

Controlled Synthesis and Utilization of Metal and Oxide Hybrid Nanoparticles

NASA Astrophysics Data System (ADS)

Crane, Cameron

This dissertation reports the development of synthetic methods concerning rationally-designed, hybrid, and multifunctional nanomaterials. These methods are based on a wet chemical, solution phase approach that utilizes the knowledge of synthetic organic and inorganic chemistry to generate building blocks in solution for the growth of nanocrystals and hybrid nanostructures. This work builds on the prior knowledge of shape-controlled synthesis of noble metal nanocrystals and expands into the challenging realm of the more reactive first row transition metals. Specifically, a microemulsion sol-gel method was developed to synthesize Au-SiO2 dimers as precursors for the synthesis of segmented heterostructures of noble metals that can be used for catalysis. This microemulsion sol-gel method was modified to synthesize an aqueous suspension of oxidation-resistant Cu-SiO2 core-shell nanoparticles that can be used for sensing and catalysis. A thermal decomposition approach was developed, wherein zero-valence metal precursor complexes in the presence of seed nanoparticles produced metal-metal oxide core-shell structures with well-controlled shell thickness. This method was demonstrated on AuCu 3-Fe3O4, AuCu3-NiO, and AuCu3 -MnO core-shell systems. Switching the core from AuCu3 alloy to pure Cu, this method could extend to Cu-Fe3O4 and Cu-MnO systems. Further etching the Cu core in these core-shell structures led to the formation of the hollow metal oxides which provides a versatile route to hollow nanostructures of metal oxides. This work develops the synthetic library of tools for the production of hybrid nanostructures with multiple functionalities.

Using numerical simulations to study the ICM metallicity fields in clusters and groups

NASA Astrophysics Data System (ADS)

Mazzei, Renato; Vijayaraghavan, Rukmani; Sarazin, Craig L.

2018-01-01

Most baryonic matter in clusters resides in the intracluster medium (ICM) as hot and diffuse gas. The metal content of this gas is deposited from dying stars, typically synthesized in type Ia or core-collapse supernovae. The ICM gas traces the formation history of the cluster and the compositional signature of its constituent galaxies as a function of time. Studying the metallicity content thus aids in understanding the gradual evolution of the cluster as it is constructed. Within this framework, galaxy and star formation and evolution can be studied by tracing metals in the ICM. In this work we use numerical simulations to study the evolution of ICM metallicity due to the stripping of galaxies’ gas. We model metallicity fields using cloud-in-cell techniques, to determine the ratio between the mass of particles tracing galaxy outflows and the mass of ICM gas at different spatial locations in each simulation time step. Integrated abundance maps are produced. We then project photons and construct mock X-ray images to investigate the relationship between ICM metallicity and observable information.

Recent Modifications of Chitosan for Adsorption Applications: A Critical and Systematic Review

PubMed Central

Kyzas, George Z.; Bikiaris, Dimitrios N.

2015-01-01

Chitosan is considered to be one of the most promising and applicable materials in adsorption applications. The existence of amino and hydroxyl groups in its molecules contributes to many possible adsorption interactions between chitosan and pollutants (dyes, metals, ions, phenols, pharmaceuticals/drugs, pesticides, herbicides, etc.). These functional groups can help in establishing positions for modification. Based on the learning from previously published works in literature, researchers have achieved a modification of chitosan with a number of different functional groups. This work summarizes the published works of the last three years (2012–2014) regarding the modification reactions of chitosans (grafting, cross-linking, etc.) and their application to adsorption of different environmental pollutants (in liquid-phase). PMID:25584681

Maternal blood metal levels and fetal markers of metabolic function

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ashley-Martin, Jillian; Dodds, Linda, E-mail: l.dodds@dal.ca; Arbuckle, Tye E.

Exposure to metals commonly found in the environment has been hypothesized to be associated with measures of fetal growth but the epidemiological literature is limited. The Maternal–Infant Research on Environmental Chemicals (MIREC) study recruited 2001 women during the first trimester of pregnancy from 10 Canadian sites. Our objective was to assess the association between prenatal exposure to metals (lead, arsenic, cadmium, and mercury) and fetal metabolic function. Average maternal metal concentrations in 1st and 3rd trimester blood samples were used to represent prenatal metals exposure. Leptin and adiponectin were measured in 1363 cord blood samples and served as markers ofmore » fetal metabolic function. Polytomous logistic regression models were used to estimate odds ratios (OR) and 95% confidence intervals (CI) for the association between metals and both high (≥90%) and low (≤10%) fetal adiponectin and leptin levels. Leptin levels were significantly higher in female infants compared to males. A significant relationship between maternal blood cadmium and odds of high leptin was observed among males but not females in adjusted models. When adjusting for birth weight z-score, lead was associated with an increased odd of high leptin. No other significant associations were found at the top or bottom 10th percentile in either leptin or adiponectin models. This study supports the proposition that maternal levels of cadmium influence cord blood adipokine levels in a sex-dependent manner. Further investigation is required to confirm these findings and to determine how such findings at birth will translate into childhood anthropometric measures. - Highlights: • We determined relationships between maternal metal levels and cord blood adipokines. • Cord blood leptin levels were higher among female than male infants. • Maternal cadmium was associated with elevated leptin in male, not female infants. • No significant associations were observed between metals and cord blood adiponectin. • Further work will elucidate the implications of these findings on childhood obesity.« less

Adsorption of pentacene on (100) vicinal surfaces: role of coordination, surface chemistry and vdWs effects

NASA Astrophysics Data System (ADS)

Matos, Jeronimo; Kara, Abdelkader

2015-03-01

In contrast to low miller index surfaces, vicinal surfaces are characterized by steps and step edges that not only present an interesting atomic landscape for the adsorption organic molecules, but also a unique electronic structure resulting in part from the low coordinated atoms at the step edges. The adsorption of pentacene on the stepped (511), (711), (911) surfaces (respectively 3, 4 and 5-atom wide terraces) of Cu and Ag (coinage transition metals); Pt (reactive transition metal); and Ni (reactive, magnetic transition metal) are studied using density functional theory, in order to investigate the support effects arising from differing surface chemistry. We compare the adsorption energy, adsorption geometry and electronic structure predicted by the PBE functional with those obtained from one of the optimized vdW-DF methods: optB88-vdW. Work supported by the U.S. Department of Energy Basic Energy Science under Contract No. DE-FG02-11ER16243.

The structural and electronic properties of metal atoms adsorbed on graphene

NASA Astrophysics Data System (ADS)

Liu, Wenjiang; Zhang, Cheng; Deng, Mingsen; Cai, Shaohong

2017-09-01

Based on density functional theory (DFT), we studied the structural and electronic properties of seven different metal atoms adsorbed on graphene (M + graphene). The geometries, adsorption energies, density of states (DOS), band structures, electronic dipole moment, magnetic moment and work function (WF) of M + graphene were calculated. The adsorption energies ΔE indicated that Li, Na, K, Ca and Fe adsorbed on graphene were tending to form stable structures. However, diffusion would occur on Cu and Ag adsorbed on graphene. In addition, the electronic structure near the Fermi level of graphene was significantly affected by Fe (Cu and Ag), compared with Li (Na, K and Ca). The electronic dipole moment and magnetic moment of M + graphene were sensitive to the adsorbed metal atoms. Moreover, we found electropositive (electronegative) adsorption can decrease (increase) the WF of the surface. Specially, the WF of Ag + graphene and Fe + graphene would increase because surface dipole moment make a contribution to electron.

Photochromic molecules as building blocks for molecular electronics.

PubMed

Peter, Belser

2010-01-01

Energy and electron transfer processes can be easily induced by a photonic excitation of a donor metal complex ([Ru(bpy)3]2), which is connected via a wire-type molecular fragment to an acceptor metal complex ([Os(bpy)3]2+). The rate constant for the transfer process can be determined by emission measurements of the two connected metal complexes. The system can be modified by incorporation of a switching unit or an interrupter into the wire, influencing the transfer process. Such a molecular device corresponds to an interrupter, mimic the same function applied in molecular electronics. We have used organic switches, which show photochromic properties. By irradiation with light of different wavelengths, the switch changes its functionality by a photochemical reaction from an OFF- to an ON-state and vice versa. The ON- respectively OFF-state is manifested by a color change but also in different conductivity properties for energy and electron transfer processes. Therefore, the mentioned molecular device can work as a simple interrupter, controlling the rate of the transfer processes.

Selective-area growth and controlled substrate coupling of transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Bersch, Brian M.; Eichfeld, Sarah M.; Lin, Yu-Chuan; Zhang, Kehao; Bhimanapati, Ganesh R.; Piasecki, Aleksander F.; Labella, Michael, III; Robinson, Joshua A.

2017-06-01

Developing a means for true bottom-up, selective-area growth of two-dimensional (2D) materials on device-ready substrates will enable synthesis in regions only where they are needed. Here, we demonstrate seed-free, site-specific nucleation of transition metal dichalcogenides (TMDs) with precise control over lateral growth by utilizing an ultra-thin polymeric surface functionalization capable of precluding nucleation and growth. This polymer functional layer (PFL) is derived from conventional photoresists and lithographic processing, and is compatible with multiple growth techniques, precursors (metal organics, solid-source) and TMDs. Additionally, we demonstrate that the substrate can play a major role in TMD transport properties. With proper TMD/substrate decoupling, top-gated field-effect transistors (FETs) fabricated with selectively-grown monolayer MoS2 channels are competitive with current reported MoS2 FETs. The work presented here demonstrates that substrate surface engineering is key to realizing precisely located and geometrically-defined 2D layers via unseeded chemical vapor deposition techniques.

Weak coordination as a powerful means for developing broadly useful C-H functionalization reactions.

PubMed

Engle, Keary M; Mei, Tian-Sheng; Wasa, Masayuki; Yu, Jin-Quan

2012-06-19

Reactions that convert carbon-hydrogen (C-H) bonds into carbon-carbon (C-C) or carbon-heteroatom (C-Y) bonds are attractive tools for organic chemists, potentially expediting the synthesis of target molecules through new disconnections in retrosynthetic analysis. Despite extensive inorganic and organometallic study of the insertion of homogeneous metal species into unactivated C-H bonds, practical applications of this technology in organic chemistry are still rare. Only in the past decade have metal-catalyzed C-H functionalization reactions become more widely utilized in organic synthesis. Research in the area of homogeneous transition metal-catalyzed C-H functionalization can be broadly grouped into two subfields. They reflect different approaches and goals and thus have different challenges and opportunities. One approach involves reactions of completely unfunctionalized aromatic and aliphatic hydrocarbons, which we refer to as "first functionalization". Here the substrates are nonpolar and hydrophobic and thus interact very weakly with polar metal species. To overcome this weak affinity and drive metal-mediated C-H cleavage, chemists often use hydrocarbon substrates in large excess (for example, as solvent). Because highly reactive metal species are needed in first functionalization, controlling the chemoselectivity to avoid overfunctionalization is often difficult. Additionally, because both substrates and products are comparatively low-value chemicals, developing cost-effective catalysts with exceptionally high turnover numbers that are competitive with alternatives (including heterogeneous catalysts) is challenging. Although an exciting field, first functionalization is beyond the scope of this Account. The second subfield of C-H functionalization involves substrates containing one or more pre-existing functional groups, termed "further functionalization". One advantage of this approach is that the existing functional group (or groups) can be used to chelate the metal catalyst and position it for selective C-H cleavage. Precoordination can overcome the paraffin nature of C-H bonds by increasing the effective concentration of the substrate so that it need not be used as solvent. From a synthetic perspective, it is desirable to use a functional group that is an intrinsic part of the substrate so that extra steps for installation and removal of an external directing group can be avoided. In this way, dramatic increases in molecular complexity can be accomplished in a single stroke through stereo- and site-selective introduction of a new functional group. Although reactivity is a major challenge (as with first functionalization), the philosophy in further functionalization differs; the major challenge is developing reactions that work with predictable selectivity in intricately functionalized contexts on commonly occurring structural motifs. In this Account, we focus on an emergent theme within the further functionalization literature: the use of commonly occurring functional groups to direct C-H cleavage through weak coordination. We discuss our motivation for studying Pd-catalyzed C-H functionalization assisted by weakly coordinating functional groups and chronicle our endeavors to bring reactions of this type to fruition. Through this approach, we have developed reactions with a diverse range of substrates and coupling partners, with the broad scope likely stemming from the high reactivity of the cyclopalladated intermediates, which are held together through weak interactions.

Porous yolk-shell microspheres as N-doped carbon matrix for motivating the oxygen reduction activity of oxygen evolution oriented materials.

PubMed

Zhou, Jinqiu; Wang, Mengfan; Qian, Tao; Liu, Sisi; Cao, Xuecheng; Yang, Tingzhou; Yang, Ruizhi; Yan, Chenglin

2017-09-08

It is highly challenging to explore high-performance bi-functional oxygen electrode catalysts for their practical application in next-generation energy storage and conversion devices. In this work, we synthesize hierarchical N-doped carbon microspheres with porous yolk-shell structure (NCYS) as a metal-free electrocatalyst toward efficient oxygen reduction through a template-free route. The enhanced oxygen reduction performances in both alkaline and acid media profit well from the porous yolk-shell structure as well as abundant nitrogen functional groups. Furthermore, such yolk-shell microspheres can be used as precursor materials to motivate the oxygen reduction activity of oxygen evolution oriented materials to obtain a desirable bi-functional electrocatalyst. To verify its practical utility, Zn-air battery tests are conducted and exhibit satisfactory performance, indicating that this constructed concept for preparation of bi-functional catalyst will afford a promising strategy for exploring novel metal-air battery electrocatalysts.

Porous yolk-shell microspheres as N-doped carbon matrix for motivating the oxygen reduction activity of oxygen evolution oriented materials

NASA Astrophysics Data System (ADS)

Zhou, Jinqiu; Wang, Mengfan; Qian, Tao; Liu, Sisi; Cao, Xuecheng; Yang, Tingzhou; Yang, Ruizhi; Yan, Chenglin

2017-09-01

It is highly challenging to explore high-performance bi-functional oxygen electrode catalysts for their practical application in next-generation energy storage and conversion devices. In this work, we synthesize hierarchical N-doped carbon microspheres with porous yolk-shell structure (NCYS) as a metal-free electrocatalyst toward efficient oxygen reduction through a template-free route. The enhanced oxygen reduction performances in both alkaline and acid media profit well from the porous yolk-shell structure as well as abundant nitrogen functional groups. Furthermore, such yolk-shell microspheres can be used as precursor materials to motivate the oxygen reduction activity of oxygen evolution oriented materials to obtain a desirable bi-functional electrocatalyst. To verify its practical utility, Zn-air battery tests are conducted and exhibit satisfactory performance, indicating that this constructed concept for preparation of bi-functional catalyst will afford a promising strategy for exploring novel metal-air battery electrocatalysts.

Cis-dicarbonyl binding at cobalt and iron porphyrins with saddle-shape conformation.

PubMed

Seufert, Knud; Bocquet, Marie-Laure; Auwärter, Willi; Weber-Bargioni, Alexander; Reichert, Joachim; Lorente, Nicolás; Barth, Johannes V

2011-02-01

Diatomic molecules attached to complexed iron or cobalt centres are important in many biological processes. In natural systems, metallotetrapyrrole units carry respiratory gases or provide sensing and catalytic functions. Conceiving synthetic model systems strongly helps to determine the pertinent chemical foundations for such processes, with recent work highlighting the importance of the prosthetic groups' conformational flexibility as an intricate variable affecting their functional properties. Here, we present simple model systems to investigate, at the single molecule level, the interaction of carbon monoxide with saddle-shaped iron- and cobalt-porphyrin conformers, which have been stabilized as two-dimensional arrays on well-defined surfaces. Using scanning tunnelling microscopy we identified a novel bonding scheme expressed in tilted monocarbonyl and cis-dicarbonyl configurations at the functional metal-macrocycle unit. Modelling with density functional theory revealed that the weakly bonded diatomic carbonyl adduct can effectively bridge specific pyrrole groups with the metal atom as a result of the pronounced saddle-shape conformation of the porphyrin cage.

Structural phase transitions in monolayer molybdenum dichalcogenides

NASA Astrophysics Data System (ADS)

Choe, Duk-Hyun; Sung, Ha June; Chang, Kee Joo

2015-03-01

The recent discovery of two-dimensional materials such as graphene and transition metal dichalcogenides (TMDs) has provided opportunities to develop ultimate thin channel devices. In contrast to graphene, the existence of moderate band gap and strong spin-orbit coupling gives rise to exotic electronic properties which vary with layer thickness, lattice structure, and symmetry. TMDs commonly appear in two structures with distinct symmetries, trigonal prismatic 2H and octahedral 1T phases which are semiconducting and metallic, respectively. In this work, we investigate the structural and electronic properties of monolayer molybdenum dichalcogenides (MoX2, where X = S, Se, Te) through first-principles density functional calculations. We find a tendency that the semiconducting 2H phase is more stable than the metallic 1T phase. We show that a spontaneous symmetry breaking of 1T phase leads to various distorted octahedral (1T') phases, thus inducing a metal-to-semiconductor transition. We discuss the effects of carrier doping on the structural stability and the modification of the electronic structure. This work was supported by the National Research Foundation of Korea (NRF) under Grant No. NRF-2005-0093845 and Samsung Science and Technology Foundation under Grant No. SSTFBA1401-08.

Metal selectivity of the E. coli nickel metallochaperone, SlyD

PubMed Central

Kaluarachchi, Harini; Siebel, Judith F.; Kaluarachchi-Duffy, Supipi; Krecisz, Sandra; Sutherland, Duncan E. K.; Stillman, Martin J.; Zamble, Deborah B.

2012-01-01

SlyD is a Ni(II)-binding protein that contributes to nickel homeostasis in Escherichia coli. The C-terminal domain of SlyD contains a rich variety of metal-binding amino acids, suggesting broader metal-binding capabilities, and previous work demonstrated that the protein can coordinate several types of first row transition metals. However, the binding of SlyD to metals other than Ni(II) has not been previously characterized. To further our understanding of the in vitro metal-binding activity of SlyD and how it correlates with the in vivo function of this protein, the interactions between SlyD and the series of biologically relevant transition metals Mn(II), Fe(II), Co(II), Cu(I) and Zn(II) were examined by using a combination of optical spectroscopy and mass spectrometry. SlyD binding to Mn(II) or to Fe(II) ions was not detected but the protein coordinates multiple ions of Co(II), Zn(II) and Cu(I) with appreciable affinities (KD ≤ nM), highlighting the promiscuous nature of this protein. The order of affinities of SlyD for the metals examined is Mn(II), Fe(II) < Co(II) < Ni(II) ~ Zn(II) ≪ Cu(I). Although the purified protein is unable to overcome the large thermodynamic preference for Cu(I) and exclude Zn(II) chelation in the presence of Ni(II), in vivo studies reveal a Ni(II)-specific function for the protein. Furthermore, these latter experiments support a specific role for SlyD as a [NiFe]-hydrogenase enzyme maturation factor. The implications of the divergence between the metal selectivity of SlyD in vitro and the specific activity in vivo are discussed. PMID:22047179

Report: complexation of β-sitosterol with tris (dibenzylideneacetone) dipalladium and its anti-microbial activity.

PubMed

Mahmood, Talat; Bibi, Yasmeen; Zafar, Raana; Wahab, Aneela; Mahmood, Iffat; Arshad, Nuzhat; Sherwani, Sikandar Khan

2015-03-01

β-sitosterol is a naturally occurring plant sterol (phytosterol) present in many fruits and vegetables. Scientific research has proven that β-sitosterol is helpful in maintaining the proper functioning of our body. Previously we described the complexation of β-sitosterol with trace metals (Mahmood et al., 2013). Trace metals after the formation of complex unable to absorb in the body and hence eliminated out from the body thus reducing metal toxicity (Marsha, 1996). The present article describes the complexation of μ-sitosterol with Palladium (Pd) metal. Palladium is a toxic metal and due to polluted and hazardous environment traces of this metal can be transferred into the body, which is harmful for human health. Our aim is to make Pd-sterol complex so that this toxic metal (Pd) does not absorb in the body and hence excreted out from the body in the complex form. In order to form this complex μ-sitosterol (Ib) is reacted with Tris (dibenzylideneacetone) dipalladium or [Pd(2) (DBA)(3)] (Ia) in 2:1 ratio in an inert atmosphere and dimethylformamid (DMF) added as a solvent. The resulting complex [Pd(2) (DBA)(3).(β-sitosterol) (Ic) was identified by various spectroscopic techniques such as IR, Mass and (1)H-NMR. This new organo metallic complex (Ic) also showed significant antibacterial and antifungal activity. The present work revealed that Pd-sterol complex does not only reduce metal toxicity but also helpful in minimizing bacterial and fungal infections present in the body. Our research also concluded that we must take plenty of fruits and vegetables in our diet so that natural plant sterol such as β-sitosterol can enhance our defense mechanism and maintain other functions of our body.

Metalworking. A Bilingual Text = Trabajo en Metal. Un Texto Bilingue.

ERIC Educational Resources Information Center

Los Angeles Unified School District, CA. Div. of Career and Continuing Education.

This booklet is a course of instruction in metal working in a two-column, English-Spanish format. Following an introduction to metal working and a lesson on safety, the booklet contains 17 units organized in 2 parts. Part 1, bench metal work, covers metals, processes, and tools; cutting; filling; drilling; grinding; bending and shaping; threading;…

Luminescent microporous metal–organic framework with functional Lewis basic sites on the pore surface: Quantifiable evaluation of luminescent sensing mechanisms towards Fe{sup 3+}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Jun-Cheng; Technology Promotion Center of Nano Composite Material of Biomimetic Sensor and Detecting Technology, Preparation and Application, Anhui Provincial Laboratory West Anhui University, Anhui 237012; Guo, Rui-Li

2016-11-15

A systematic study has been conducted on a novel luminescent metal-organic framework, ([Zn(bpyp)(L-OH)]·DMF·2H{sub 2}O){sub n} (1), to explore its sensing mechanisms to Fe{sup 3+}. Structure analyses show that compound 1 exist pyridine N atoms and -OH groups on the pore surface for specific sensing of metal ions via Lewis acid-base interactions. On this consideration, the quenching mechanisms are studied and the processes are controlled by multiple mechanisms in which dynamic and static mechanisms are calculated, achieving the quantification evaluation of the quenching process. This work not only achieves the quantitative evaluation of the luminescence quenching but also provides certain insightsmore » into the quenching process, and the possible mechanisms explored in this work may inspire future research and design of target luminescent metal-organic frameworks (LMOFs) with specific functions. - Graphical abstract: A systematic study has been conducted on a novel luminescent metal-organic framework to explore its sensing mechanisms to Fe{sup 3+}. The quenching mechanisms are studied and the processes are controlled by multiple mechanisms in which dynamic and static mechanisms are calculated, achieving the quantification evaluation of the quenching process. - Highlights: • A novel porous luminescent MOF containing uncoordinated groups in interlayer channels was successfully synthesized. • The compound 1 can exhibit significant luminescent sensitivity to Fe{sup 3+}, which make its good candidate as luminescent sensor. • The corresponding dynamic and static quenching constants are calculated, achieving the quantification evaluation of the quenching process.« less

Impact of bimetal electrodes on dielectric properties of TiO2 and Al-doped TiO2 films.

PubMed

Kim, Seong Keun; Han, Sora; Jeon, Woojin; Yoon, Jung Ho; Han, Jeong Hwan; Lee, Woongkyu; Hwang, Cheol Seong

2012-09-26

Rutile structured Al-doped TiO(2) (ATO) and TiO(2) films were grown on bimetal electrodes (thin Ru/thick TiN, Pt, and Ir) for high-performance capacitors. The work function of the top Ru layer decreased on TiN and increased on Pt and Ir when it was thinner than ~2 nm, suggesting that the lower metal within the electrodes influences the work function of the very thin Ru layer. The use of the lower electrode with a high work function for bottom electrode eventually improves the leakage current properties of the capacitor at a very thin Ru top layer (≤2 nm) because of the increased Schottky barrier height at the interface between the dielectric and the bottom electrode. The thin Ru layer was necessary to achieve the rutile structured ATO and TiO(2) dielectric films.

Removing function model and experiments on ultrasonic polishing molding die

NASA Astrophysics Data System (ADS)

Huang, Qitai; Ni, Ying; Yu, Jingchi

2010-10-01

Low temperature glass molding technology is the main method on volume-producing high precision middle and small diameter optical cells in the future. While the accuracy of the molding die will effect the cell precision, so the high precision molding die development is one of the most important part of the low temperature glass molding technology. The molding die is manufactured from high rigid and crisp metal alloy, with the ultrasonic vibration character of high vibration frequency and concentrative energy distribution; abrasive particles will impact the rigid metal alloy surface with very high speed that will remove the material from the work piece. Ultrasonic can make the rigid metal alloy molding die controllable polishing and reduce the roughness and surface error. Different from other ultrasonic fabrication method, untouched ultrasonic polishing is applied on polish the molding die, that means the tool does not touch the work piece in the process of polishing. The abrasive particles vibrate around the balance position with high speed and frequency under the drive of ultrasonic vibration in the liquid medium and impact the workspace surface, the energy of abrasive particles come from ultrasonic vibration, while not from the direct hammer blow of the tool. So a nummular vibrator simple harmonic vibrates on an infinity plane surface is considered as a model of ultrasonic polishing working condition. According to Huygens theory the sound field distribution on a plane surface is analyzed and calculated, the tool removing function is also deduced from this distribution. Then the simple point ultrasonic polishing experiment is proceeded to certificate the theory validity.

Effect of Zinc Phosphate on the Corrosion Behavior of Waterborne Acrylic Coating/Metal Interface

PubMed Central

Wan, Hongxia; Song, Dongdong; Li, Xiaogang; Zhang, Dawei; Gao, Jin; Du, Cuiwei

2017-01-01

Waterborne coating has recently been paid much attention. However, it cannot be used widely due to its performance limitations. Under the specified conditions of the selected resin, selecting the function pigment is key to improving the anticorrosive properties of the coating. Zinc phosphate is an environmentally protective and efficient anticorrosion pigment. In this work, zinc phosphate was used in modifying waterborne acrylic coatings. Moreover, the disbonding resistance of the coating was studied. Results showed that adding zinc phosphate can effectively inhibit the anode process of metal corrosion and enhance the wet adhesion of the coating, and consequently prevent the horizontal diffusion of the corrosive medium into the coating/metal interface and slow down the disbonding of the coating. PMID:28773013

Towards the blackbox computation of magnetic exchange coupling parameters in polynuclear transition-metal complexes: theory, implementation, and application.

PubMed

Phillips, Jordan J; Peralta, Juan E

2013-05-07

We present a method for calculating magnetic coupling parameters from a single spin-configuration via analytic derivatives of the electronic energy with respect to the local spin direction. This method does not introduce new approximations beyond those found in the Heisenberg-Dirac Hamiltonian and a standard Kohn-Sham Density Functional Theory calculation, and in the limit of an ideal Heisenberg system it reproduces the coupling as determined from spin-projected energy-differences. Our method employs a generalized perturbative approach to constrained density functional theory, where exact expressions for the energy to second order in the constraints are obtained by analytic derivatives from coupled-perturbed theory. When the relative angle between magnetization vectors of metal atoms enters as a constraint, this allows us to calculate all the magnetic exchange couplings of a system from derivatives with respect to local spin directions from the high-spin configuration. Because of the favorable computational scaling of our method with respect to the number of spin-centers, as compared to the broken-symmetry energy-differences approach, this opens the possibility for the blackbox exploration of magnetic properties in large polynuclear transition-metal complexes. In this work we outline the motivation, theory, and implementation of this method, and present results for several model systems and transition-metal complexes with a variety of density functional approximations and Hartree-Fock.

The growth of high density network of MOF nano-crystals across macroporous metal substrates - Solvothermal synthesis versus rapid thermal deposition

NASA Astrophysics Data System (ADS)

Maina, James W.; Gonzalo, Cristina Pozo; Merenda, Andrea; Kong, Lingxue; Schütz, Jürg A.; Dumée, Ludovic F.

2018-01-01

Fabrication of metal organic framework (MOF) films and membranes across macro-porous metal substrates is extremely challenging, due to the large pore sizes across the substrates, poor wettability, and the lack of sufficient reactive functional groups on the surface, which prevent high density nucleation of MOF crystals. Herein, macroporous stainless steel substrates (pore size 44 × 40 μm) are functionalized with amine functional groups, and the growth of ZIF-8 crystals investigated through both solvothermal synthesis and rapid thermal deposition (RTD), to assess the role of synthesis routes in the resultant membranes microstructure, and subsequently their performance. Although a high density of well interconnected MOF crystals was observed across the modified substrates following both techniques, RTD was found to be a much more efficient route, yielding high quality membranes under 1 h, as opposed to the 24 h required for solvothermal synthesis. The RTD membranes also exhibited high gas permeance, with He permeance of up to 2.954 ± 0.119 × 10-6 mol m-2 s-1 Pa-1, and Knudsen selectivities for He/N2, Ar/N2 and CO2/N2, suggesting the membranes were almost defect free. This work opens up route for efficient fabrication of MOF films and membranes across macro-porous metal supports, with potential application in electrically mediated separation applications.

Technologies for deposition of transition metal oxide thin films: application as functional layers in “Smart windows” and photocatalytic systems

NASA Astrophysics Data System (ADS)

Gesheva, K.; Ivanova, T.; Bodurov, G.; Szilágyi, I. M.; Justh, N.; Kéri, O.; Boyadjiev, S.; Nagy, D.; Aleksandrova, M.

2016-02-01

“Smart windows” are envisaged for future low-energy, high-efficient architectural buildings, as well as for the car industry. By switching from coloured to fully bleached state, these windows regulate the energy of solar flux entering the interior. Functional layers in these devices are the transition metals oxides. The materials (transitional metal oxides) used in smart windows can be also applied as photoelectrodes in water splitting photocells for hydrogen production or as photocatalytic materials for self-cleaning surfaces, waste water treatment and pollution removal. Solar energy utilization is recently in the main scope of numerous world research laboratories and energy organizations, working on protection against conventional fuel exhaustion. The paper presents results from research on transition metal oxide thin films, fabricated by different methods - atomic layer deposition, atmospheric pressure chemical vapour deposition, physical vapour deposition, and wet chemical methods, suitable for flowthrough production process. The lower price of the chemical deposition processes is especially important when the method is related to large-scale glazing applications. Conclusions are derived about which processes are recently considered as most prospective, related to electrochromic materials and devices manufacturing.

Surface shift of the occupied and unoccupied 4f levels of the rare-earth metals

NASA Astrophysics Data System (ADS)

Aldén, M.; Johansson, B.; Skriver, H. L.

1995-02-01

The surface energy shifts of the occupied and unoccupied 4f levels for the lanthanide metals have been calculated from first principles by means of a Green's-function technique within the tight-binding linear muffin-tin orbitals method. We use the concept of complete screening to identify the occupied and unoccupied 4f energy level shifts as the surface segregation energy of a 4fn-1 and 4fn+1 impurity atom, respectively, in a 4fn host metal. The calculations include both initial- and final-state effects and give values that are considerably lower than those measured on polycrystalline samples as well as those found in previous initial-state model calculations. The present theory agrees well with very recent high-resolution, single-crystal film measurements for Gd, Tb, Dy, Ho, Er, Tm, and Lu. We furthermore utilize the unique possibility offered by the lanthanide metals to clarify the roles played by the initial and the different final states of the core-excitation process, permitted by the fact that the so-called initial-state effect is identical upon 4f removal and 4f addition. Surface energy and work function calculations are also reported.

In Situ Transformation of MOFs into Layered Double Hydroxide Embedded Metal Sulfides for Improved Electrocatalytic and Supercapacitive Performance.

PubMed

Yilmaz, Gamze; Yam, Kah Meng; Zhang, Chun; Fan, Hong Jin; Ho, Ghim Wei

2017-07-01

Direct adoption of metal-organic frameworks (MOFs) as electrode materials shows impoverished electrochemical performance owing to low electrical conductivity and poor chemical stability. In this study, we demonstrate self-templated pseudomorphic transformation of MOF into surface chemistry rich hollow framework that delivers highly reactive, durable, and universal electrochemically active energy conversion and storage functionalities. In situ pseudomorphic transformation of MOF-derived hollow rhombic dodecahedron template and sulfurization of nickel cobalt layered double hydroxides (NiCo-LDHs) lead to the construction of interlayered metal sulfides (NiCo-LDH/Co 9 S 8 ) system. The embedment of metal sulfide species (Co 9 S 8 ) at the LDH intergalleries offers optimal interfacing of the hybrid constituent elements and materials stability. The hybrid NiCo-LDH/Co 9 S 8 system collectively presents an ideal porous structure, rich redox chemistry, and high electrical conductivity matrix. This leads to a significant enhancement in its complementary electrocatalytic hydrogen evolution and supercapacitive energy storage properties. This work establishes the potential of MOF derived scaffold for designing of novel class hybrid inorganic-organic functional materials for electrochemical applications and beyond. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Terahertz Modulator based on Metamaterials integrated with Metal-Semiconductor-Metal Varactors

PubMed Central

Nouman, Muhammad Tayyab; Kim, Hyun-Woong; Woo, Jeong Min; Hwang, Ji Hyun; Kim, Dongju; Jang, Jae-Hyung

2016-01-01

The terahertz (THz) band of the electromagnetic spectrum, with frequencies ranging from 300 GHz to 3 THz, has attracted wide interest in recent years owing to its potential applications in numerous areas. Significant progress has been made toward the development of devices capable of actively controlling terahertz waves; nonetheless, further advances in device functionality are necessary for employment of these devices in practical terahertz systems. Here, we demonstrate a low voltage, sharp switching terahertz modulator device based on metamaterials integrated with metal semiconductor metal (MSM) varactors, fabricated on an AlGaAs/InGaAs based heterostructure. By varying the applied voltage to the MSM-varactor located at the center of split ring resonator (SRR), the resonance frequency of the SRR-based metamaterial is altered. Upon varying the bias voltage from 0 V to 3 V, the resonance frequency exhibits a transition from 0.52 THz to 0.56 THz, resulting in a modulation depth of 45 percent with an insertion loss of 4.3 dB at 0.58 THz. This work demonstrates a new approach for realizing active terahertz devices with improved functionalities. PMID:27194128

Electromechanical and Chemical Sensing at the Nanoscale: DFT and Transport Modeling

NASA Astrophysics Data System (ADS)

Maiti, Amitesh

Of the many nanoelectronic applications proposed for near to medium-term commercial deployment, sensors based on carbon nanotubes (CNT) and metal-oxide nanowires are receiving significant attention from researchers. Such devices typically operate on the basis of the changes of electrical response characteristics of the active component (CNT or nanowire) when subjected to an externally applied mechanical stress or the adsorption of a chemical or bio-molecule. Practical development of such technologies can greatly benefit from quantum chemical modeling based on density functional theory (DFT), and from electronic transport modeling based on non-equilibrium Green's function (NEGF). DFT can compute useful quantities like possible bond-rearrangements, binding energy, charge transfer, and changes to the electronic structure, while NEGF can predict changes in electronic transport behavior and contact resistance. Effects of surrounding medium and intrinsic structural defects can also be taken into account. In this work we review some recent DFT and transport investigations on (1) CNT-based nano-electromechanical sensors (NEMS) and (2) gas-sensing properties of CNTs and metal-oxide nanowires. We also briefly discuss our current understanding of CNT-metal contacts which, depending upon the metal, the deposition technique, and the masking method can have a significant effect on device performance.

Size-dependent Hamaker constants for silver and gold nanoparticles

NASA Astrophysics Data System (ADS)

Pinchuk, Pavlo; Jiang, Ke

2015-08-01

Hamaker-Lifshitz constants are material specific constants that are used to calculate van der Waals interaction forces between small particles in solution. Typically, these constants are size-independent and material specific. According to the Lifshitz theory, the Hamaker-Lifshitz constants can be calculated by taking integrals that include the dielectric permittivity, as a function of frequency, of the interacting particles and the medium around particles. The dielectric permittivity of interacting metal nanoparticles can be calculated using the Drude model, which is based on the assumption of motion of free conducting electrons. For bulk metals, the Drude model does not predict any sizedependence of the dielectric permittivity. However, the conducting electrons in small noble metal nanoparticles (R ~ 10nm) exhibit surface scattering, which changes the complex permittivity function. In this work, we show theoretically that scattering of the free conducting electrons inside silver and gold nanoparticles with the size of 1 - 50 nm leads to size-dependent dielectric permittivity and Hamaker-Lifshitz constants. We calculate numerically the Hamaker-Lifshitz constants for silver and gold nanoparticles with different diameters. The results of the study might be of interests for understanding colloidal stability of metal nanoparticles.

Dendrite-Free Sodium-Metal Anodes for High-Energy Sodium-Metal Batteries.

PubMed

Sun, Bing; Li, Peng; Zhang, Jinqiang; Wang, Dan; Munroe, Paul; Wang, Chengyin; Notten, Peter H L; Wang, Guoxiu

2018-05-31

Sodium (Na) metal is one of the most promising electrode materials for next-generation low-cost rechargeable batteries. However, the challenges caused by dendrite growth on Na metal anodes restrict practical applications of rechargeable Na metal batteries. Herein, a nitrogen and sulfur co-doped carbon nanotube (NSCNT) paper is used as the interlayer to control Na nucleation behavior and suppress the Na dendrite growth. The N- and S-containing functional groups on the carbon nanotubes induce the NSCNTs to be highly "sodiophilic," which can guide the initial Na nucleation and direct Na to distribute uniformly on the NSCNT paper. As a result, the Na-metal-based anode (Na/NSCNT anode) exhibits a dendrite-free morphology during repeated Na plating and striping and excellent cycling stability. As a proof of concept, it is also demonstrated that the electrochemical performance of sodium-oxygen (Na-O 2 ) batteries using the Na/NSCNT anodes show significantly improved cycling performances compared with Na-O 2 batteries with bare Na metal anodes. This work opens a new avenue for the development of next-generation high-energy-density sodium-metal batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adverse health effects of child labor: high exposure to chromium and oxidative DNA damage in children manufacturing surgical instruments.

PubMed

Sughis, Muhammad; Nawrot, Tim S; Haufroid, Vincent; Nemery, Benoit

2012-10-01

A considerable part of the worldwide production of surgical instruments takes place in Sialkot, Pakistan. Many children work in hazardous conditions in this industry. We investigated exposure to metals and possible health effects among children working in surgical instruments manufacturing units compared with schoolchildren from the same city. In a cross-sectional study we studied a convenience sample of 104 male children (10-14 years of age) working in surgical instruments manufacturing units and 75 male children of similar age from a school in Sialkot, Pakistan. A respiratory questionnaire was administered, spirometry was performed, and blood pressure was measured. In a spot urine sample, concentrations of metals were measured by inductively coupled plasma mass spectrometry and 8-hydroxydeoxyguanosine (8OHdG, reflecting oxidative DNA damage) by ELISA. The working children reported more asthma (10% vs. 0%; p = 0.005) and dry cough at night (36% vs. 20%; p = 0.02) than did the schoolchildren, but there were no significant differences in pulmonary function or blood pressure. The urinary concentration of chromium was 35 times higher in working children [geometric mean, 23.0 µg/L; 25th-75th percentile, 8.38-58.6] than in schoolchildren [0.66 µg/L; 0.38-1.09)], and largely in excess of the occupational Biological Exposure Index for adult workers (25 µg/L). Urinary 8-OHdG concentrations were not significantly higher in working children than in schoolchildren (19.3 vs. 17.6 µg/g creatinine, p = 0.4), but were significantly correlated with urinary nickel (r = 0.41; p < 0.0001) and with a composite index of metal exposure (r = 0.46; p < 0.0001). Children working in the surgical instruments manufacturing industry had substantial exposure to several metals, especially chromium and nickel, which are established carcinogens. Exposure to nickel was associated with evidence of increased oxidative DNA damage.

Adverse Health Effects of Child Labor: High Exposure to Chromium and Oxidative DNA Damage in Children Manufacturing Surgical Instruments

PubMed Central

Sughis, Muhammad; Nawrot, Tim S.; Haufroid, Vincent

2012-01-01

Background: A considerable part of the worldwide production of surgical instruments takes place in Sialkot, Pakistan. Many children work in hazardous conditions in this industry. Objective: We investigated exposure to metals and possible health effects among children working in surgical instruments manufacturing units compared with schoolchildren from the same city. Methods: In a cross-sectional study we studied a convenience sample of 104 male children (10–14 years of age) working in surgical instruments manufacturing units and 75 male children of similar age from a school in Sialkot, Pakistan. A respiratory questionnaire was administered, spirometry was performed, and blood pressure was measured. In a spot urine sample, concentrations of metals were measured by inductively coupled plasma mass spectrometry and 8-hydroxydeoxyguanosine (8OHdG, reflecting oxidative DNA damage) by ELISA. Results: The working children reported more asthma (10% vs. 0%; p = 0.005) and dry cough at night (36% vs. 20%; p = 0.02) than did the schoolchildren, but there were no significant differences in pulmonary function or blood pressure. The urinary concentration of chromium was 35 times higher in working children [geometric mean, 23.0 µg/L; 25th–75th percentile, 8.38–58.6] than in schoolchildren [0.66 µg/L; 0.38–1.09)], and largely in excess of the occupational Biological Exposure Index for adult workers (25 µg/L). Urinary 8-OHdG concentrations were not significantly higher in working children than in schoolchildren (19.3 vs. 17.6 µg/g creatinine, p = 0.4), but were significantly correlated with urinary nickel (r = 0.41; p < 0.0001) and with a composite index of metal exposure (r = 0.46; p < 0.0001). Conclusions: Children working in the surgical instruments manufacturing industry had substantial exposure to several metals, especially chromium and nickel, which are established carcinogens. Exposure to nickel was associated with evidence of increased oxidative DNA damage. PMID:22739056

In situ reduction of antibacterial silver ions to metallic silver nanoparticles on bioactive glasses functionalized with polyphenols

NASA Astrophysics Data System (ADS)

Ferraris, S.; Miola, M.; Cochis, A.; Azzimonti, B.; Rimondini, L.; Prenesti, E.; Vernè, E.

2017-02-01

The realization of surfaces with antibacterial properties due to silver nanoparticles loaded through a green approach is a promising research challenge of the biomaterial field. In this research work, two bioactive glasses have been doubly surface functionalized with polyphenols (gallic acid or natural polyphenols extracted from red grape skins and green tea leaves) and silver nanoparticles deposited by in situ reduction from a silver nitrate aqueous solution. The presence of biomolecules - showing reducing ability to directly obtain in situ metallic silver - and silver nanoparticles was investigated by means of UV-vis spectroscopy, X-Ray Photoelectron Spectroscopy (XPS) and Field Emission Scanning Electron Microscopy (FESEM). The antibacterial activity of the modified surfaces was tested against a multidrug resistant Staphylococcus aureus bacterial strain.

Evaluation of Thermoelectric Performance and Durability of Functionalized Skutterudite Legs

NASA Astrophysics Data System (ADS)

Skomedal, Gunstein; Kristiansen, Nils R.; Sottong, Reinhard; Middleton, Hugh

2017-04-01

Thermoelectric generators are a promising technology for waste heat recovery. As new materials and devices enter a market penetration stage, it is of interest to employ fast and efficient measurement methods to evaluate the long-term stability of thermoelectric materials in combination with metallization and coating (functionalized thermoelectric legs). We have investigated a method for measuring several thermoelectric legs simultaneously. The legs are put under a common temperature gradient, and the electrical characteristics of each leg are measured individually during thermal cycling. Using this method, one can test different types of metallization and coating applied to skutterudite thermoelectric legs and look at the relative changes over time. Postcharacterization of these initial tests with skutterudite legs using a potential Seebeck microprobe and an electron microscope showed that oxidation and interlayer diffusion are the main reasons for the gradual increase in internal resistance and the decrease in open-circuit voltage. Although we only tested skutterudite material in this work, the method is fully capable of testing all kinds of material, metallization, and coating. It is thus a promising method for studying the relationship between failure modes and mechanisms of functionalized thermoelectric legs.

Surface Charge Transfer Doping via Transition Metal Oxides for Efficient p-Type Doping of II-VI Nanostructures.

PubMed

Xia, Feifei; Shao, Zhibin; He, Yuanyuan; Wang, Rongbin; Wu, Xiaofeng; Jiang, Tianhao; Duhm, Steffen; Zhao, Jianwei; Lee, Shuit-Tong; Jie, Jiansheng

2016-11-22

Wide band gap II-VI nanostructures are important building blocks for new-generation electronic and optoelectronic devices. However, the difficulty of realizing p-type conductivity in these materials via conventional doping methods has severely handicapped the fabrication of p-n homojunctions and complementary circuits, which are the fundamental components for high-performance devices. Herein, by using first-principles density functional theory calculations, we demonstrated a simple yet efficient way to achieve controlled p-type doping on II-VI nanostructures via surface charge transfer doping (SCTD) using high work function transition metal oxides such as MoO 3 , WO 3 , CrO 3 , and V 2 O 5 as dopants. Our calculations revealed that these oxides were capable of drawing electrons from II-VI nanostructures, leading to accumulation of positive charges (holes injection) in the II-VI nanostructures. As a result, Fermi levels of the II-VI nanostructures were shifted toward the valence band regions after surface modifications, along with the large enhancement of work functions. In situ ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy characterizations verified the significant interfacial charge transfer between II-VI nanostructures and surface dopants. Both theoretical calculations and electrical transfer measurements on the II-VI nanostructure-based field-effect transistors clearly showed the p-type conductivity of the nanostructures after surface modifications. Strikingly, II-VI nanowires could undergo semiconductor-to-metal transition by further increasing the SCTD level. SCTD offers the possibility to create a variety of electronic and optoelectronic devices from the II-VI nanostructures via realization of complementary doping.

The correlation between acoustic and magnetic properties in the long working metal boiler drum with the parameters of the electron microscope

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ababkov, Nikolai, E-mail: n.ababkov@rambler.ru; Smirnov, Alexander, E-mail: galvas.kem@gmail.com

The present paper presents comparative analysis of measurement results of acoustic and magnetic properties in long working metal of boiler drums and the results obtained by methods of electronic microscopy. The structure of the metal sample from the fracture zone to the base metal (metal working sample long) and the center of the base metal before welding (weld metal sample) was investigated by electron microscopy. Studies performed by spectral acoustic, magnetic noise and electron microscopic methods were conducted on the same plots and the same samples of long working and weld metal of high-pressure boiler drums. The analysis of researchmore » results showed high sensitivity of spectral-acoustic and magnetic-noise methods to definition changes of microstructure parameters. Practical application of spectral-acoustic and magnetic noise NDT method is possible for the detection of irregularities and changes in structural and phase state of the long working and weld metal of boiler drums, made of a special molybdenum steel (such as 20M). The above technique can be used to evaluate the structure and physical-mechanical properties of the long working metal of boiler drums in the energy sector.« less

Understanding the bond-energy, hardness, and adhesive force from the phase diagram via the electron work function

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Hao; Huang, Xiaochen; Li, Dongyang, E-mail: dongyang.li@ualberta.ca

2014-11-07

Properties of metallic materials are intrinsically determined by their electron behavior. However, relevant theoretical treatment involving quantum mechanics is complicated and difficult to be applied in materials design. Electron work function (EWF) has been demonstrated to be a simple but fundamental parameter which well correlates properties of materials with their electron behavior and could thus be used to predict material properties from the aspect of electron activities in a relatively easy manner. In this article, we propose a method to extract the electron work functions of binary solid solutions or alloys from their phase diagrams and use this simple approachmore » to predict their mechanical strength and surface properties, such as adhesion. Two alloys, Fe-Ni and Cu-Zn, are used as samples for the study. EWFs extracted from phase diagrams show same trends as experimentally observed ones, based on which hardness and surface adhesive force of the alloys are predicted. This new methodology provides an alternative approach to predict material properties based on the work function, which is extractable from the phase diagram. This work may also help maximize the power of phase diagram for materials design and development.« less

NOVEL BINDERS AND METHODS FOR AGGLOMERATION OF ORE

DOE Office of Scientific and Technical Information (OSTI.GOV)

S.K. Kawatra; T.C. Eisele; J.A. Gurtler

2004-04-01

Many metal extraction operations, such as leaching of copper, leaching of precious metals, and reduction of metal oxides to metal in high-temperature furnaces, require agglomeration of ore to ensure that reactive liquids or gases are evenly distributed throughout the ore being processed. Agglomeration of ore into coarse, porous masses achieves this even distribution of fluids by preventing fine particles from migrating and clogging the spaces and channels between the larger ore particles. Binders are critically necessary to produce agglomerates that will not break down during processing. However, for many important metal extraction processes there are no binders known that willmore » work satisfactorily. Primary examples of this are copper heap leaching, where there are no binders that will work in the acidic environment encountered in this process, and advanced ironmaking processes, where binders must function satisfactorily over an extraordinarily large range of temperatures (from room temperature up to over 1200 C). As a result, operators of many facilities see a large loss of process efficiency due to their inability to take advantage of agglomeration. The large quantities of ore that must be handled in metal extraction processes also means that the binder must be inexpensive and useful at low dosages to be economical. The acid-resistant binders and agglomeration procedures developed in this project will also be adapted for use in improving the energy efficiency and performance of a broad range of mineral agglomeration applications, particularly heap leaching and advanced primary ironmaking.« less

Interfaces of electrical contacts in organic semiconductor devices

NASA Astrophysics Data System (ADS)

Demirkan, Korhan

Progress in organic semiconductor devices relies on better understanding of interfaces as well as material development. The engineering of interfaces that exhibit low resistance, low operating voltage and long-term stability to minimize device degradation is one of the crucial requirements. Photoelectron spectroscopy is a powerful technique to study the metal-semiconductor interfaces, allowing: (i) elucidation of the energy levels of the semiconductor and the contacts that determine Schottky barrier height, (ii) inspection of electrical interactions (such as charge transfer, dipole formation, formation of induced density of states or formation of polaron/bi-polaron states) that effect the energy level alignment, (iii) determination of interfacial chemistry, and (iv) estimation of interface morphology. In this thesis, we have used photoelectron spectroscopy extensively for detailed analysis of the metal organic semiconductor interfaces. In this study, we demonstrate the use of photoelectron spectroscopy for construction of energy level diagrams and display some results related to chemical tailoring of materials for engineering interfaces with lowered Schottky barriers. Following our work on the energy level alignment of poly(p-phenyene vinylene) based organic semiconductors on various substrates [Au, indium tin oxide, Si (with native oxide) and Al (with native oxide)], we tested controlling the energy level alignment by using polar self assembled molecules (SAMs). Photoelectron spectroscopy showed that, by introducing SAMs on the Au surface, we successfully changed the effective work function of Au surface. We found that in this case, the change in the effective work function of the metal surface was not reflected as a shift in the energy levels of the organic semiconductor, as opposed to the results achieved with different substrate materials. To investigate the chemical interactions at the metal/organic interface, we studied the metallization of poly(2-methoxy-5,2'-ethyl-hexyloxy-phenylene vinylene) (MEH-PPV), polystyrene (PS) and ozone treated polystyrene (PS-O3) surfaces by thermal deposition of aluminum. Photoelectron spectroscopy showed the degree of chemical interaction between Al and each polymer, for MEH-PPV, the chemical interactions were mainly through the C-O present in the side chain of the polymer structure. The chemical interaction of Al with polystyrene was less significant, but it showed a dramatic increase after ozone treatment of the polystyrene surface (due to the formation of exposed oxygen sites). Formation of metal oxide and metal-organic compound is detected during the Al metallization of MEH-PPV and ozone-treated PS surfaces. Our results showed that the condensation of Al on polymer surfaces is highly dependent on surface reactivity. Enormous differences were observed for the condensation coefficient of Al on PS and PS-O3 surfaces. For the inert PS surface, results showed that Al atoms poorly wet the polymer surface and form distributed clusters at the surface. Results on reactive polymer surfaces suggest morphology reminiscent of a Stranski-Krastanov-type growth and high contact area. Many studies have shown that the insertion of a thin interlayer of the oxide or fluoride of alkali or alkaline metals between the low work function electrode and the organic semiconductor layers dramatically lowers the onset voltage and increases the efficiency compared to identical devices without the insulating layer. Various modes have been suggested for the mechanism of device performance enhancement. We have investigated the chemical and electrical interaction of (i) LiF with MEH-PPV, (ii) Al with MEH-PPV in the presence of a thin LiF layer at the interface, and finally (iii) the interaction of Al with LiF. AFM and XPS data showed that LiF forms island on the surface. Our data in agreement with various existing models suggested the (i) alteration in the electronic properties under applied bias, (ii) doping of the organic semiconductor, (iii) formation of metal alloy (Au-Li). In addition to the possible electrical modifications at the interface suggested previously, our data also suggest a change in the film growth on LiF modified surfaces.

Scalable properties of metal clusters: A comparative study of modern exchange-correlation functionals

NASA Astrophysics Data System (ADS)

Koitz, Ralph; Soini, Thomas M.; Genest, Alexander; Trickey, S. B.; Rösch, Notker

2012-07-01

The performance of eight generalized gradient approximation exchange-correlation (xc) functionals is assessed by a series of scalar relativistic all-electron calculations on octahedral palladium model clusters Pdn with n = 13, 19, 38, 55, 79, 147 and the analogous clusters Aun (for n up through 79). For these model systems, we determined the cohesive energies and average bond lengths of the optimized octahedral structures. We extrapolate these values to the bulk limits and compare with the corresponding experimental values. While the well-established functionals BP, PBE, and PW91 are the most accurate at predicting energies, the more recent forms PBEsol, VMTsol, and VT{84}sol significantly improve the accuracy of geometries. The observed trends are largely similar for both Pd and Au. In the same spirit, we also studied the scalability of the ionization potentials and electron affinities of the Pd clusters, and extrapolated those quantities to estimates of the work function. Overall, the xc functionals can be classified into four distinct groups according to the accuracy of the computed parameters. These results allow a judicious selection of xc approximations for treating transition metal clusters.

Mechanical Modulation of Tunneling Current in Transition Metal Dichalcogenides Heterostructures: A First Principles Study

NASA Astrophysics Data System (ADS)

Kuroda, Marcelo

Recent experiments in MoS2 heterostructures reported that out-of-plane tunneling piezoresistivity (TPR) - mechanical modulation of the tunneling current - achieves sensitivities of one decade per Ådisplacement. Owing to their nanometer scale, a quantitative theoretical framework providing the TPR structure-property relationship is necessary to further improve sensitivities. To this end, first principles calculations within density functional theory are used to characterize the phenomenon in MoX2 (with X = S, Se). The TPR is quantified in relation to electrode composition and film thickness showing remarkable agreement with experiments. The origin of the TPR is attributed to the heterostructure compliance rather than band alignment changes with strain, and differs from mechanisms in other nanometer-thick bulk films. Large work function metals (Pt, Au) are singled out as best candidates for enhanced TPR gauges due to weak bonding and negligible thermionic emission; compliant bilayers show larger stress-sensitivity than monolayers. By accounting for the atomistic details and material composition of 2D material-based heterostructures, this work has the potential to advance sensor and nano-electro-mechanical system technologies.

Potentiodynamic Corrosion Testing.

PubMed

Munir, Selin; Pelletier, Matthew H; Walsh, William R

2016-09-04

Different metallic materials have different polarization characteristics as dictated by the open circuit potential, breakdown potential, and passivation potential of the material. The detection of these electrochemical parameters identifies the corrosion factors of a material. A reliable and well-functioning corrosion system is required to achieve this. Corrosion of the samples was achieved via a potentiodynamic polarization technique employing a three-electrode configuration, consisting of reference, counter, and working electrodes. Prior to commencement a baseline potential is obtained. Following the stabilization of the corrosion potential (Ecorr), the applied potential is ramped at a slow rate in the positive direction relative to the reference electrode. The working electrode was a stainless steel screw. The reference electrode was a standard Ag/AgCl. The counter electrode used was a platinum mesh. Having a reliable and well-functioning in vitro corrosion system to test biomaterials provides an in-expensive technique that allows for the systematic characterization of the material by determining the breakdown potential, to further understand the material's response to corrosion. The goal of the protocol is to set up and run an in vitro potentiodynamic corrosion system to analyze pitting corrosion for small metallic medical devices.

Electrically Tunable and Negative Schottky Barriers in Multi-layered Graphene/MoS2 Heterostructured Transistors.

PubMed

Qiu, Dongri; Kim, Eun Kyu

2015-09-03

We fabricated multi-layered graphene/MoS2 heterostructured devices by positioning mechanically exfoliated bulk graphite and single-crystalline 2H-MoS2 onto Au metal pads on a SiO2/Si substrate via a contamination-free dry transfer technique. We also studied the electrical transport properties of Au/MoS2 junction devices for systematic comparison. A previous work has demonstrated the existence of a positive Schottky barrier height (SBH) in the metal/MoS2 system. However, analysis of the SBH indicates that the contacts of the multi-layered graphene/MoS2 have tunable negative barriers in the range of 300 to -46 meV as a function of gate voltage. It is hypothesized that this tunable SBH is responsible for the modulation of the work function of the thick graphene in these devices. Despite the large number of graphene layers, it is possible to form ohmic contacts, which will provide new opportunities for the engineering of highly efficient contacts in flexible electronics and photonics.

Electrically Tunable and Negative Schottky Barriers in Multi-layered Graphene/MoS2 Heterostructured Transistors

NASA Astrophysics Data System (ADS)

Qiu, Dongri; Kim, Eun Kyu

2015-09-01

We fabricated multi-layered graphene/MoS2 heterostructured devices by positioning mechanically exfoliated bulk graphite and single-crystalline 2H-MoS2 onto Au metal pads on a SiO2/Si substrate via a contamination-free dry transfer technique. We also studied the electrical transport properties of Au/MoS2 junction devices for systematic comparison. A previous work has demonstrated the existence of a positive Schottky barrier height (SBH) in the metal/MoS2 system. However, analysis of the SBH indicates that the contacts of the multi-layered graphene/MoS2 have tunable negative barriers in the range of 300 to -46 meV as a function of gate voltage. It is hypothesized that this tunable SBH is responsible for the modulation of the work function of the thick graphene in these devices. Despite the large number of graphene layers, it is possible to form ohmic contacts, which will provide new opportunities for the engineering of highly efficient contacts in flexible electronics and photonics.

Noncompetitive and Competitive Adsorption of Heavy Metals in Sulfur-Functionalized Ordered Mesoporous Carbon.

PubMed

Saha, Dipendu; Barakat, Soukaina; Van Bramer, Scott E; Nelson, Karl A; Hensley, Dale K; Chen, Jihua

2016-12-14

In this work, sulfur-functionalized ordered mesoporous carbons were synthesized by activating the soft-templated mesoporous carbons with sulfur bearing salts that simultaneously enhanced the surface area and introduced sulfur functionalities onto the parent carbon surface. XPS analysis showed that sulfur content within the mesoporous carbons were between 8.2% and 12.9%. The sulfur functionalities include C-S, C═S, -COS, and SO x . SEM images confirmed the ordered mesoporosity within the material. The BET surface areas of the sulfur-functionalized ordered mesoporous carbons range from 837 to 2865 m 2 /g with total pore volume of 0.71-2.3 cm 3 /g. The carbon with highest sulfur functionality was examined for aqueous phase adsorption of mercury (as HgCl 2 ), lead (as Pb(NO 3 ) 2 ), cadmium (as CdCl 2 ), and nickel (as NiCl 2 ) ions in both noncompetitive and competitive mode. Under noncompetitive mode and at a pH greater than 7.0 the affinity of sulfur-functionalized carbons toward heavy metals were in the order of Hg > Pb > Cd > Ni. At lower pH, the adsorbent switched its affinity between Pb and Cd. In the noncompetitive mode, Hg and Pb adsorption showed a strong pH dependency whereas Cd and Ni adsorption did not demonstrate a significant influence of pH. The distribution coefficient for noncompetitive adsorption was in the range of 2448-4000 mL/g for Hg, 290-1990 mL/g for Pb, 550-560 mL/g for Cd, and 115-147 for Ni. The kinetics of adsorption suggested a pseudo-second-order model fits better than other models for all the metals. XPS analysis of metal-adsorption carbons suggested that 7-8% of the adsorbed Hg was converted to HgSO 4 , 14% and 2% of Pb was converted to PbSO 4 and PbS/PbO, respectively, and 5% Cd was converted to CdSO 4 . Ni was below the detection limit for XPS. Overall results suggested these carbon materials might be useful for the separation of heavy metals.

Laboratory studies on the tribology of hard bearing hip prostheses: ceramic on ceramic and metal on metal.

PubMed

Vassiliou, K; Scholes, S C; Unsworth, A

2007-01-01

Total hip replacements offer relief to a great many patients every year around the world. With an expected service life of around 25 years on most devices, and with younger and younger patients undergoing this surgery, it is of great importance to understand the mechanisms of their function. Tribological testing of both conventional and hard bearing joint combinations have been conducted in many centres throughout the world, and, after being initially abandoned owing to premature failures, hard bearing combinations have been revisited as viable options for joint replacements. Improved design, manufacturing procedures, and material compositions have led to improved performance over first-generation designs in both metal-on-metal and ceramic-on-ceramic hip prostheses. This paper offers a review of the work conducted in an attempt to highlight the most important factors affecting joint performance and tribology of hard bearing combinations. The tribological performance of these joints is superior to that of conventional metal- or ceramic-on-polymer designs.

Simulated electron affinity tuning in metal-insulator-metal (MIM) diodes

NASA Astrophysics Data System (ADS)

Mistry, Kissan; Yavuz, Mustafa; Musselman, Kevin P.

2017-05-01

Metal-insulator-metal diodes for rectification applications must exhibit high asymmetry, nonlinearity, and responsivity. Traditional methods of improving these figures of merit have consisted of increasing insulator thickness, adding multiple insulator layers, and utilizing a variety of metal contact combinations. However, these methods have come with the price of increasing the diode resistance and ultimately limiting the operating frequency to well below the terahertz regime. In this work, an Airy Function Transfer Matrix simulation method was used to observe the effect of tuning the electron affinity of the insulator as a technique to decrease the diode resistance. It was shown that a small increase in electron affinity can result in a resistance decrease in upwards of five orders of magnitude, corresponding to an increase in operating frequency on the same order. Electron affinity tuning has a minimal effect on the diode figures of merit, where asymmetry improves or remains unaffected and slight decreases in nonlinearity and responsivity are likely to be greatly outweighed by the improved operating frequency of the diode.

Photocatalytic fluoroalkylation reactions of organic compounds.

PubMed

Barata-Vallejo, Sebastián; Bonesi, Sergio M; Postigo, Al

2015-12-14

Photocatalytic methods for fluoroalkyl-radical generation provide more convenient alternatives to the classical perfluoroalkyl-radical (Rf) production through chemical initiators, such as azo or peroxide compounds or the employment of transition metals through a thermal electron transfer (ET) initiation process. The mild photocatalytic reaction conditions tolerate a variety of functional groups and, thus, are handy to the late-stage modification of bioactive molecules. Transition metal-photocatalytic reactions for Rf radical generation profit from the redox properties of coordinatively saturated Ru or Ir organocomplexes to act as both electron donor and reductive species, thus allowing for the utilization of electron accepting and donating fluoroalkylating agents for Rf radical production. On the other hand, laboratory-available and inexpensive photoorgano catalysts (POC), in the absence of transition metals, can also act as electron exchange species upon excitation, resulting in ET reactions that produce Rf radicals. In this work, a critical account of transition metal and transition metal-free Rf radical production will be described with photoorgano catalysts, studying classical examples and the most recent investigations in the field.

First-principles simulations of transition metal ions in silicon as potential quantum bits

NASA Astrophysics Data System (ADS)

Ma, He; Seo, Hosung; Galli, Giulia

Optically active spin defects in semiconductors have gained increasing attention in recent years for use as potential solid-state quantum bits (or qubits). Examples include the nitrogen-vacancy center in diamond, transition metal impurities, and rare earth ions. In this talk, we present first-principles theoretical results on group 6 transition metal ion (Chromium, Molybdenum and Tungsten) impurities in silicon, and we investigate their potential use as qubits. We used density functional theory (DFT) to calculate defect formation energies and we found that transition metal ions have lower formation energies at interstitial than substitutional sites. We also computed the electronic structure of the defects with particular attention to the position of the defect energy levels with respect to the silicon band edges. Based on our results, we will discuss the possibility of implementing qubits in silicon using group 6 transition metal ions. This work is supported by the National Science Foundation (NSF) through the University of Chicago MRSEC under Award Number DMR-1420709.

Modeling quantum yield, emittance, and surface roughness effects from metallic photocathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dimitrov, D. A.; Bell, G. I.; Smedley, J.

Here, detailed measurements of momentum distributions of emitted electrons have allowed the investigation of the thermal limit of the transverse emittance from metal photocathodes. Furthermore, recent developments in material design and growth have resulted in photocathodes that can deliver high quantum efficiency and are sufficiently robust to use in high electric field gradient photoinjectors and free electron lasers. The growth process usually produces photoemissive material layers with rough surface profiles that lead to transverse accelerating fields and possible work function variations, resulting in emittance growth. To better understand the effects of temperature, density of states, and surface roughness on themore » properties of emitted electrons, we have developed realistic three-dimensional models for photocathode materials with grated surface structures. They include general modeling of electron excitation due to photon absorption, charge transport, and emission from flat and rough metallic surfaces. The models also include image charge and field enhancement effects. We report results from simulations with flat and rough surfaces to investigate how electron scattering, controlled roughness, work function variation, and field enhancement affect emission properties. Comparison of simulation results with measurements of the quantum yield and transverse emittance from flat Sb emission surfaces shows the importance of including efficient modeling of photon absorption, temperature effects, and the material density of states to achieve agreement with the experimental data.« less

Modeling quantum yield, emittance, and surface roughness effects from metallic photocathodes

DOE PAGES

Dimitrov, D. A.; Bell, G. I.; Smedley, J.; ...

2017-10-26

Here, detailed measurements of momentum distributions of emitted electrons have allowed the investigation of the thermal limit of the transverse emittance from metal photocathodes. Furthermore, recent developments in material design and growth have resulted in photocathodes that can deliver high quantum efficiency and are sufficiently robust to use in high electric field gradient photoinjectors and free electron lasers. The growth process usually produces photoemissive material layers with rough surface profiles that lead to transverse accelerating fields and possible work function variations, resulting in emittance growth. To better understand the effects of temperature, density of states, and surface roughness on themore » properties of emitted electrons, we have developed realistic three-dimensional models for photocathode materials with grated surface structures. They include general modeling of electron excitation due to photon absorption, charge transport, and emission from flat and rough metallic surfaces. The models also include image charge and field enhancement effects. We report results from simulations with flat and rough surfaces to investigate how electron scattering, controlled roughness, work function variation, and field enhancement affect emission properties. Comparison of simulation results with measurements of the quantum yield and transverse emittance from flat Sb emission surfaces shows the importance of including efficient modeling of photon absorption, temperature effects, and the material density of states to achieve agreement with the experimental data.« less

Mathematical Modeling of Optical Radiation Emission as a Function of Welding Power during Gas Shielded Metal Arc Welding.

PubMed

Bauer, Stefan; Janßen, Marco; Schmitz, Martin; Ott, Günter

2017-11-01

Arc welding is accompanied by intense optical radiation emission that can be detrimental not only for the welder himself but also for people working nearby or for passersby. Technological progress advances continuously in the field of joining, so an up-to-date radiation database is necessary. Additionally, many literature irradiance data have been measured for a few welding currents or for parts of the optical spectral region only. Within this paper, a comprehensive study of contemporary metal active gas, metal inert gas, and cold metal transfer welding is presented covering optical radiation emission from 200 up to 2,700 nm by means of (spectro-) radiometric measurements. The investigated welding currents range from 70 to 350 A, reflecting values usually applied in industry. Based upon these new irradiance data, three mathematical models were derived in order to describe optical radiation emission as a function of welding power. The linear, exponential, and sigmoidal emission models depend on the process variant (standard or pulsed) as well as on the welding material (mild and stainless steel, aluminum). In conjunction with the corresponding exposure limit values for incoherent optical radiation maximum permissible exposure durations were calculated as a function of welding power. Typical times are shorter than 1 s for the ultraviolet spectral region and range from 1 to 10 s for visible radiation. For the infrared regime, exposure durations are of the order of minutes to hours. Finally, a validation of the metal active gas emission models was carried out with manual arc welding.

Reliable Energy Level Alignment at Physisorbed Molecule–Metal Interfaces from Density Functional Theory

DOE PAGES

Egger, David A.; Liu, Zhen-Fei; Neaton, Jeffrey B.; ...

2015-03-05

We report a key quantity for molecule–metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal–molecule interfaces. The method builds on the “DFT+Σ” approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways:more » first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule–metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors.« less

Abiotic degradation of glyphosate into aminomethylphosphonic acid in the presence of metals.

PubMed

Ascolani Yael, J; Fuhr, J D; Bocan, G A; Daza Millone, A; Tognalli, N; Dos Santos Afonso, M; Martiarena, M L

2014-10-08

Glyphosate [N-phosphono-methylglycine (PMG)] is the most used herbicide worldwide, particularly since the development of transgenic glyphosate-resistant (GR) crops. Aminomethylphosphonic acid (AMPA) is the main glyphosate metabolite, and it may be responsible for GR crop damage upon PMG application. PMG degradation into AMPA has hitherto been reckoned mainly as a biological process, produced by soil microorganisms (bacteria and fungi) and plants. In this work, we use density functional calculations to identify the vibrational bands of PMG and AMPA in surface-enhanced Raman spectroscopy (SERS) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra experiments. SERS shows the presence of AMPA after glyphosate is deposited from aqueous solution on different metallic surfaces. AMPA is also detected in ATR-FTIR experiments when PMG interacts with metallic ions in aqueous solution. These results reveal an abiotic degradation process of glyphosate into AMPA, where metals play a crucial role.

Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique

PubMed Central

Nigl, Thomas P.; Smith, Nathan D.; Lichtenstein, Timothy; Gesualdi, Jarrod; Kumar, Kuldeep; Kim, Hojong

2017-01-01

A novel electrochemical cell based on a CaF2 solid-state electrolyte has been developed to measure the electromotive force (emf) of binary alkaline earth-liquid metal alloys as functions of both composition and temperature in order to acquire thermodynamic data. The cell consists of a chemically stable solid-state CaF2-AF2 electrolyte (where A is the alkaline-earth element such as Ca, Sr, or Ba), with binary A-B alloy (where B is the liquid metal such as Bi or Sb) working electrodes, and a pure A metal reference electrode. Emf data are collected over a temperature range of 723 K to 1,123 K in 25 K increments for multiple alloy compositions per experiment and the results are analyzed to yield activity values, phase transition temperatures, and partial molar entropies/enthalpies for each composition. PMID:29155770

Novel 3D metallic boron nitride containing only sp2 bonds

NASA Astrophysics Data System (ADS)

Wang, Hao; Zhang, Wei; Huai, Ping

2017-09-01

As the closest isoelectronic analogue of carbon, boron nitride (BN) shares a similar structure with carbon from 1D nanotubes, 2D nanosheets, and 3D diamond structures. However, most BN structures are insulators, which limits their application. In this work, under the inspiration of the sp2 hybridized carbon honeycomb, we propose a hexagonal phase of BN consisting of only sp2 bonds, which exhibits intriguingly intrinsic metallicity. First-principles calculations confirm that this phase is both thermally and dynamically stable. Moreover, the calculations on the band structure, partial density states and electron localization function suggest that the metallic behavior is attributable to the delocalized B-2p electrons, leading to second-neighbor interaction between the p z states of sp2-bonded B atoms in adjacent layers. Our findings not only enrich the BN allotrope family with 3D structures but also stimulate further experimental interest in applications of metallic BN in electronic devices.

Theory and computation of hot carriers generated by surface plasmon polaritons in noble metals

PubMed Central

Bernardi, Marco; Mustafa, Jamal; Neaton, Jeffrey B.; Louie, Steven G.

2015-01-01

Hot carriers (HC) generated by surface plasmon polaritons (SPPs) in noble metals are promising for application in optoelectronics, plasmonics and renewable energy. However, existing models fail to explain key quantitative details of SPP-to-HC conversion experiments. Here we develop a quantum mechanical framework and apply first-principles calculations to study the energy distribution and scattering processes of HCs generated by SPPs in Au and Ag. We find that the relative positions of the s and d bands of noble metals regulate the energy distribution and mean free path of the HCs, and that the electron–phonon interaction controls HC energy loss and transport. Our results prescribe optimal conditions for HC generation and extraction, and invalidate previously employed free-electron-like models. Our work combines density functional theory, GW and electron–phonon calculations to provide microscopic insight into HC generation and ultrafast dynamics in noble metals. PMID:26033445

Directly writing resistor, inductor and capacitor to composite functional circuits: a super-simple way for alternative electronics.

PubMed

Gao, Yunxia; Li, Haiyan; Liu, Jing

2013-01-01

The current strategies for making electronic devices are generally time, water, material and energy consuming. Here, the direct writing of composite functional circuits through comprehensive use of GaIn10-based liquid metal inks and matching material is proposed and investigated, which is a rather easy going and cost effective electronics fabrication way compared with the conventional approaches. Owing to its excellent adhesion and electrical properties, the liquid metal ink was demonstrated as a generalist in directly making various basic electronic components such as planar resistor, inductor and capacitor or their combination and thus composing circuits with expected electrical functions. For a precise control of the geometric sizes of the writing, a mask with a designed pattern was employed and demonstrated. Mechanisms for justifying the chemical components of the inks and the magnitudes of the target electronic elements so as to compose various practical circuits were disclosed. Fundamental tests on the electrical components including capacitor and inductor directly written on paper with working time up to 48 h and elevated temperature demonstrated their good stability and potential widespread adaptability especially when used in some high frequency circuits. As the first proof-of-concept experiment, a typical functional oscillating circuit including an integrated chip of 74HC04 with a supply voltage of 5 V, a capacitor of 10 nF and two resistors of 5 kΩ and 1 kΩ respectively was directly composed on paper through integrating specific electrical elements together, which presented an oscillation frequency of 8.8 kHz. The present method significantly extends the roles of the metal ink in recent works serving as only a single electrical conductor or interconnecting wires. It opens the way for directly writing out complex functional circuits or devices on different substrates. Such circuit composition strategy has generalized purpose and can be extended to more areas, even daily pervasive electronics.

Directly Writing Resistor, Inductor and Capacitor to Composite Functional Circuits: A Super-Simple Way for Alternative Electronics

PubMed Central

Gao, Yunxia; Li, Haiyan; Liu, Jing

2013-01-01

Background The current strategies for making electronic devices are generally time, water, material and energy consuming. Here, the direct writing of composite functional circuits through comprehensive use of GaIn10-based liquid metal inks and matching material is proposed and investigated, which is a rather easy going and cost effective electronics fabrication way compared with the conventional approaches. Methods Owing to its excellent adhesion and electrical properties, the liquid metal ink was demonstrated as a generalist in directly making various basic electronic components such as planar resistor, inductor and capacitor or their combination and thus composing circuits with expected electrical functions. For a precise control of the geometric sizes of the writing, a mask with a designed pattern was employed and demonstrated. Mechanisms for justifying the chemical components of the inks and the magnitudes of the target electronic elements so as to compose various practical circuits were disclosed. Results Fundamental tests on the electrical components including capacitor and inductor directly written on paper with working time up to 48 h and elevated temperature demonstrated their good stability and potential widespread adaptability especially when used in some high frequency circuits. As the first proof-of-concept experiment, a typical functional oscillating circuit including an integrated chip of 74HC04 with a supply voltage of 5 V, a capacitor of 10 nF and two resistors of 5 kΩ and 1 kΩ respectively was directly composed on paper through integrating specific electrical elements together, which presented an oscillation frequency of 8.8 kHz. Conclusions The present method significantly extends the roles of the metal ink in recent works serving as only a single electrical conductor or interconnecting wires. It opens the way for directly writing out complex functional circuits or devices on different substrates. Such circuit composition strategy has generalized purpose and can be extended to more areas, even daily pervasive electronics. PMID:23936349

Incorporating electron-transfer functionality into synthetic metalloproteins from the bottom-up.

PubMed

Hong, Jing; Kharenko, Olesya A; Ogawa, Michael Y

2006-12-11

The alpha-helical coiled-coil motif serves as a robust scaffold for incorporating electron-transfer (ET) functionality into synthetic metalloproteins. These structures consist of a supercoiling of two or more aplha helices that are formed by the self-assembly of individual polypeptide chains whose sequences contain a repeating pattern of hydrophobic and hydrophilic residues. Early work from our group attached abiotic Ru-based redox sites to the most surface-exposed positions of two stranded coiled-coils and used electron-pulse radiolysis to study both intra- and intermolecular ET reactions in these systems. Later work used smaller metallopeptides to investigate the effects of conformational gating within electrostatic peptide-protein complexes. We have recently designed the C16C19-GGY peptide, which contains Cys residues located at both the "a" and "d" positions of its third heptad repeat in order to construct a nativelike metal-binding domain within its hydrophobic core. It was shown that the binding of both Cd(II) and Cu(I) ions induces the peptide to undergo a conformational change from a disordered random coil to a metal-bridged coiled-coil. However, whereas the Cd(II)-protein exists as a two-stranded coiled-coil, the Cu(I) derivative exists as a four-stranded coiled-coil. Upon the incorporation of other metal ions, metal-bridged peptide dimers, tetramers, and hexamers are formed. The Cu(I)-protein is of particular interest because it exhibits a long-lived (microsecond) room-temperature luminescence at 600 nm. The luminophore in this protein is thought to be a multinuclear CuI4Cys4(N/O)4 cage complex, which can be quenched by exogenous electron acceptors in solution, as shown by emission-lifetime and transient-absorption experiments. It is anticipated that further investigation into these systems will contribute to the expanding effort of bioinorganic chemists to prepare new kinds of functionally active synthetic metalloproteins.

Surrogate models for sheet metal stamping problem based on the combination of proper orthogonal decomposition and radial basis function

NASA Astrophysics Data System (ADS)

Dang, Van Tuan; Lafon, Pascal; Labergere, Carl

2017-10-01

In this work, a combination of Proper Orthogonal Decomposition (POD) and Radial Basis Function (RBF) is proposed to build a surrogate model based on the Benchmark Springback 3D bending from the Numisheet2011 congress. The influence of the two design parameters, the geometrical parameter of the die radius and the process parameter of the blank holder force, on the springback of the sheet after a stamping operation is analyzed. The classical Design of Experience (DoE) uses Full Factorial to design the parameter space with sample points as input data for finite element method (FEM) numerical simulation of the sheet metal stamping process. The basic idea is to consider the design parameters as additional dimensions for the solution of the displacement fields. The order of the resultant high-fidelity model is reduced through the use of POD method which performs model space reduction and results in the basis functions of the low order model. Specifically, the snapshot method is used in our work, in which the basis functions is derived from snapshot deviation of the matrix of the final displacements fields of the FEM numerical simulation. The obtained basis functions are then used to determine the POD coefficients and RBF is used for the interpolation of these POD coefficients over the parameter space. Finally, the presented POD-RBF approach which is used for shape optimization can be performed with high accuracy.

Plasmons in quasi-two-dimensional metals

NASA Astrophysics Data System (ADS)

da Jornada, Felipe H.; Xian, Lede; Sen, H. Sener; Rubio, Angel; Louie, Steven G.

We employ ab initio density-functional theory (DFT) and GW calculations to understand and predict the plasmon dispersion in quasi-two-dimensional (quasi-2D) metals. We show that, unlike what is found in idealized 2D electron gases, plasmons are virtually dispersionless in real quasi-2D metals for a wide range of excitation wave vectors that are experimentally accessible. We further develop a simpler model that captures this plasmon dispersion in quasi-2D metals and which depends on a single parameter: the characteristic screening length due to interband transitions. Our ab initio calculations further predict that monolayer metallic transition metal dichalcogenides are excellent candidates to explore these dispersionless (flat) plasmons: having large excitation energy that is away from the Landau damping regions makes them ideal systems to support long-lived, spatially-localized 2D plasmons which are highly tunable with substrate. This work is supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division; the National Science Foundation; the European Research Council project (ERC-2015-AdG-694097), and the AFOSR Grant No. FA2386-15-1-0006 AOARD 144088.

Copper(II) and zinc(II) dinuclear enzymes model compounds: The nature of the metal ion in the biological function

NASA Astrophysics Data System (ADS)

Ferraresso, L. G.; de Arruda, E. G. R.; de Moraes, T. P. L.; Fazzi, R. B.; Da Costa Ferreira, A. M.; Abbehausen, C.

2017-12-01

First series transition metals are used abundantly by nature to perform catalytic transformations of several substrates. Furthermore, the cooperative activity of two proximal metal ions is common and represents a highly efficient catalytic system in living organisms. In this work three dinuclear μ-phenolate bridged metal complexes were prepared with copper(II) and zinc(II), resulting in a ZnZn, CuCu and CuZn with the ligand 2-ethylaminodimethylamino phenol (saldman) as model compounds of superoxide dismutase (CuCu and CuZn) and metallo-β-lactamases (ZnZn). Metals are coordinated in a μ-phenolate bridged symmetric system. Cu(II) presents a more distorted structure, while zinc is very symmetric. For this reason, [CuCu(saldman)] shows higher water solubility and also higher lability of the bridge. The antioxidant and hydrolytic beta-lactamase-like activity of the complexes were evaluated. The lability of the bridge seems to be important for the antioxidant activity and is suggested to because of [CuCu(saldman)] presents a lower antioxidant capacity than [CuZn(saldman)], which showed to present a more stable bridge in solution. The hydrolytic activity of the bimetallic complexes was assayed using nitrocefin as substrate and showed [ZnZn(saldman)] as a better catalyst than the Cu(II) analog. The series demonstrates the importance of the nature of the metal center for the biological function and how the reactivity of the model complex can be modulated by coordination chemistry.

Towards an Understanding of the Function of the Phytochelatin Synthase of Schistosoma mansoni

PubMed Central

Rigouin, Coraline; Nylin, Elyse; Cogswell, Alexis A.; Schaumlöffel, Dirk; Dobritzsch, Dirk; Williams, David L.

2013-01-01

Phytochelatin synthase (PCS) is a protease-like enzyme that catalyzes the production of metal chelating peptides, the phytochelatins, from glutathione (GSH). In plants, algae, and fungi phytochelatin production is important for metal tolerance and detoxification. PCS proteins also function in xenobiotic metabolism by processing GSH S-conjugates. The aim of the present study is to elucidate the role of PCS in the parasitic worm Schistosoma mansoni. Recombinant S. mansoni PCS proteins expressed in bacteria could both synthesize phytochelatins and hydrolyze various GSH S-conjugates. We found that both the N-truncated protein and the N- and C-terminal truncated form of the enzyme (corresponding to only the catalytic domain) work through a thiol-dependant and, notably, metal-independent mechanism for both transpeptidase (phytochelatin synthesis) and peptidase (hydrolysis of GSH S-conjugates) activities. PCS transcript abundance was increased by metals and xenobiotics in cultured adult worms. In addition, these treatments were found to increase transcript abundance of other enzymes involved in GSH metabolism. Highest levels of PCS transcripts were identified in the esophageal gland of adult worms. Taken together, these results suggest that S. mansoni PCS participates in both metal homoeostasis and xenobiotic metabolism rather than metal detoxification as previously suggested and that the enzyme may be part of a global stress response in the worm. Because humans do not have PCS, this enzyme is of particular interest as a drug target for schistosomiasis. PMID:23383357

Polarization of IRON-REGULATED TRANSPORTER 1 (IRT1) to the plant-soil interface plays crucial role in metal homeostasis.

PubMed

Barberon, Marie; Dubeaux, Guillaume; Kolb, Cornelia; Isono, Erika; Zelazny, Enric; Vert, Grégory

2014-06-03

In plants, the controlled absorption of soil nutrients by root epidermal cells is critical for growth and development. IRON-REGULATED TRANSPORTER 1 (IRT1) is the main root transporter taking up iron from the soil and is also the main entry route in plants for potentially toxic metals such as manganese, zinc, cobalt, and cadmium. Previous work demonstrated that the IRT1 protein localizes to early endosomes/trans-Golgi network (EE/TGN) and is constitutively endocytosed through a monoubiquitin- and clathrin-dependent mechanism. Here, we show that the availability of secondary non-iron metal substrates of IRT1 (Zn, Mn, and Co) controls the localization of IRT1 between the outer polar domain of the plasma membrane and EE/TGN in root epidermal cells. We also identify FYVE1, a phosphatidylinositol-3-phosphate-binding protein recruited to late endosomes, as an important regulator of IRT1-dependent metal transport and metal homeostasis in plants. FYVE1 controls IRT1 recycling to the plasma membrane and impacts the polar delivery of this transporter to the outer plasma membrane domain. This work establishes a functional link between the dynamics and the lateral polarity of IRT1 and the transport of its substrates, and identifies a molecular mechanism driving polar localization of a cell surface protein in plants.

Gasifiable carbon-graphite fibers

NASA Technical Reports Server (NTRS)

Humphrey, Marshall F. (Inventor); Ramohalli, Kumar N. R. (Inventor); Dowler, Warren L. (Inventor)

1982-01-01

Fine, carbon-graphite fibers do not combust during the combustion of a composite and are expelled into the air as fine conductive particles. Coating of the fibers with a salt of a metal having a work function below 4.2 eV such as an alkaline earth metal salt, e.g., calcium acetate, catalytically enhances combustion of the fibers at temperatures below 1000.degree. C. such that the fibers self-support combustion and burn to produce a non-conductive ash. Fire-polishing the fibers before application of the coating is desirable to remove sizing to expose the carbon surface to the catalyst.

Achieving high efficiency laminated polymer solar cell with interfacial modified metallic electrode and pressure induced crystallization

NASA Astrophysics Data System (ADS)

Yuan, Yongbo; Bi, Yu; Huang, Jinsong

2011-02-01

We report efficient laminated organic photovoltaic device with efficiency approach the optimized device by regular method based on Poly(3-hexylthiophene-2,5-diyl) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The high efficiency is mainly attributed to the formation of a concrete polymer/metal interface mechanically and electrically by the use of electronic-glue, and using the highly conductive and flexible silver film as anode to reduce photovoltage loss and modifying its work function for efficiency hole extraction by ultraviolet/ozone treatment, and the pressure induced crystallization of PCBM.

Nonlocal screening in metal surfaces

NASA Technical Reports Server (NTRS)

Krotscheck, E.; Kohn, W.

1986-01-01

Due to the effect of the nonuniform environment on the static screening of the Coulomb potential, the local-density approximation for the particle-hole interaction is found to be inadequate to determine the surface energy of simple metals. Use of the same set of single-particle states, and thus the same one-body density and the same work function, has eliminated the single-electron states in favor of the structure of the short-ranged correlations as the basis of this effect. A posteriori simplifications of the Fermi hypernetted-chain theory may be found to allow the same calculational accuracy with simpler computational tools.

Transparent Metal-Organic Framework/Polymer Mixed Matrix Membranes as Water Vapor Barriers.

PubMed

Bae, Youn Jue; Cho, Eun Seon; Qiu, Fen; Sun, Daniel T; Williams, Teresa E; Urban, Jeffrey J; Queen, Wendy L

2016-04-27

Preventing the permeation of reactive molecules into electronic devices or photovoltaic modules is of great importance to ensure their life span and reliability. This work is focused on the formation of highly functioning barrier films based on nanocrystals (NCs) of a water-scavenging metal-organic framework (MOF) and a hydrophobic cyclic olefin copolymer (COC) to overcome the current limitations. Water vapor transmission rates (WVTR) of the films reveal a 10-fold enhancement in the WVTR compared to the substrate while maintaining outstanding transparency over most of the visible and solar spectrum, a necessary condition for integration with optoelectronic devices.

Are scarce metals in cars functionally recycled?

PubMed

Andersson, Magnus; Ljunggren Söderman, Maria; Sandén, Björn A

2017-02-01

Improved recycling of end-of-life vehicles (ELVs) may serve as an important strategy to address resource security risks related to increased global demand for scarce metals. However, in-depth knowledge of the magnitude and fate of such metals entering ELV recycling is lacking. This paper quantifies input of 25 scarce metals to Swedish ELV recycling, and estimates the extent to which they are recycled to material streams where their metal properties are utilised, i.e. are functionally recycled. Methodologically, scarce metals are mapped to main types of applications within newly produced Swedish car models and subsequently, material flow analysis of ELV waste streams is used as basis for identifying pathways of these applications and assessing whether contained metals are functionally recycled. Results indicate that, of the scarce metals, only platinum may be functionally recycled in its main application. Cobalt, gold, manganese, molybdenum, palladium, rhodium and silver may be functionally recycled depending on application and pathways taken. For remaining 17 metals, functional recycling is absent. Consequently, despite high overall ELV recycling rates of materials in general, there is considerable risk of losing ELV scarce metals to carrier metals, construction materials, backfilling materials and landfills. Given differences in the application of metals and identified pathways, prospects for increasing functional recycling are discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cysteine-grafted nonwoven geotextile: a new and efficient material for heavy metals sorption--Part B.

PubMed

Vandenbossche, M; Vezin, H; Touati, N; Jimenez, M; Casetta, M; Traisnel, M

2014-10-01

The development of a new material designed to trap heavy metals from sediments or wastewater, based on a polypropylene non-woven covalently grafted with cysteine, has been reported in a previous paper (Part A). The non-woven was first functionalized with acrylic acid (AA) which is used as spacer, and then cysteine was immobilized on the substrate through covalent coupling in order to obtain the so-called PP-g-AA-cysteine. Some preliminary heavy metals adsorption tests gave interesting results: at 20 °C for 24 h and in a 1000 mg/L heavy metals solution, PP-g-AA-cysteine adsorbs 95 mg Cu/g PP (CuSO4 solution), 104 mg Cu/g PP (Cu(NO3)2 solution), 135 mg Pb/g PP (Pb(NO3)2 solution) and 21 mg Cr/g PP (Cr(NO3)3 solution). In this second part of the work, heavy metals sorption tests were carried out with Cu (II), Pb (II), and Cr (III) separately, in order to determine the sorption capacity of this new sorbent as a function of (i) the heavy metals concentration in the solution, (ii) the contact time with the solution, (iii) the pH and (iv) the ionic strength of the solution containing heavy metals. Moreover, the sorption capacity of PP-g-AA-Cysteine was studied using a polluted solution consisting of a mixture of these different heavy metals. An Electron Paramagnetic Resonance study was finally carried out in order to determine the coordination geometry in the environment of the copper trapped by the PP-g-AA-cysteine. Copyright © 2014 Elsevier Ltd. All rights reserved.

Line length dependencies in interconnect optimization

NASA Astrophysics Data System (ADS)

Kadoch, Daniel; Duane, Michael; Lee, Yohan

1997-09-01

Metal line delay has become increasingly important for ULSI devices. Numerous expressions and software tools have been developed to describe interconnect delay as a function of the geometry and layout. Although many of these formulas have line length effects, this has not been explored in depth. Most software tools are either geared towards circuit designers, or involve more complex and CPU-intensive 3D modeling. In this work, PISCES (a 2D device simulator) was used to extract metal capacitance per unit length. We extend this approach for various lengths by creating a ladder network of the RC components and simulating in SPICE, or using simple closed-form Elmore delay equations. A new key result is that there are optimum metal line width/space for a fixed pitch and height/space ratios that are metal length dependent. For metal lines shorter than about 1500 micrometers , it is better to have narrower metal lines, and for lengths less than 500 micrometers , shrinking metal height is desirable because the penalty in resistance is more than compensated by the decrease in capacitance. For longer lines, the time delay is dominated by resistance, and wider, taller lines are better. Increasing metal spacing or reducing dielectric constant were beneficial for both long and short metal lines.

The Sapphire (0001) Surface, Clean and with d-metal Overlayers: Density Functional - LDA Results

NASA Astrophysics Data System (ADS)

Verdozzi, C.; Jennison, D. R.; Schultz, P. A.; Sears, M. P.

1998-03-01

Previous theoretical work for the a-Al2O3(0001) surface mostly used very thin slabs, and limited theoretical information is available on the binding of metal overlayers. Also, no systematic information is available about the dependence of the metal-ceramic interaction on metal coverage. We present here results using the local density approximation for the structural and electronic properties of the a-Al2O3(0001) surface, with and without d-metal overlayers Pt, Ag, Cu, and with sufficiently thick slabs to find the bottom of the unusually large and deep surface relaxation in this material. Our thick slab site-optimized calculations are performed for 1, 2/3 and 1/3 monolayer (ML) coverage. The adhesion energy and the nature of the interfacial bond vary greatly with metal coverage and can be understood in terms of the relative roles of the surface Madelung potential and the strength of the lateral metal-metal bond. Our study should in principle succeed in bracketing the phenomenology of adhesion and wetting at least for the right-most part of the d-metal periodic table. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04-94AL85000. Corresponding author: claudio@sandia.gov.

Metallization of Self-Assembled DNA Templates for Electronic Circuit Fabrication

NASA Astrophysics Data System (ADS)

Uprety, Bibek

This work examines the deposition of metallic and semiconductor elements onto self-assembled DNA templates for the fabrication of nanodevices. Biological molecules like DNA self-assemble into a variety of 2- and 3-D architectures without the need for patterning tools. The templates can also be designed to controllably place functional nanomaterials with molecular precision. These characteristics make DNA an attractive template for fabricating electronic circuits. However, electrically conductive structures are needed for electronic applications. While metallized DNA nanostructures have been demonstrated, the ability to make thin, continuous wires that are electrically conductive still represents a formidable challenge. DNA-templated wires have generally been granular in appearance with a resistivity approximately two to three orders of magnitude higher than that of the bulk material. An improved method for the metallization of DNA origami is examined in this work that addresses these challenges of size, morphology and conductivity of the metallized structure. Specifically, we demonstrated a metallization process that uses gold nanorod seeds followed by anisotropic electroless (autocatalytic) plating to provide improved morphology and greater control of the final metallized width of conducting metal lines. Growth during electroless deposition occurs preferentially in the length direction at a rate that is approximately four times the growth rate in the width direction, which enables fabrication of narrow, continuous wires. The electrical properties of 49 nanowires with widths ranging from 13 nm to 29 nm were characterized, and resistivity values as low as 8.9 x 10-7 -m were measured, which represent some of the smallest nanowires and the lowest resistivity values reported in the literature. The metallization procedure developed on smaller templates was also successfully applied to metallize bigger DNA templates of tens of micrometers in length. In addition, a polymer-assisted annealing process was discovered to possibly improve the resistivity of DNA metal nanowires. Following metallization of bigger DNA origami structures, controlled placement of nanorods on a DNA breadboard to make rectangular, square and T-shaped metallic structures was also demonstrated. For site-specific placement, we modified the surface of the gold nanorods with single-stranded DNA. The rods were then attached to DNA templates via complementary base-pairing between the DNA on the nanorods and the attachment strands engineered into the DNA "breadboard" template. Gaps between the nanorods were then filled controllably via anisotropic plating to make 10 nm diameter continuous metallic structures. Finally, controlled placement of metal (gold) - semiconductor (tellurium) materials on a single DNA origami template was demonstrated. The combination of molecularly directed deposition of different nanomaterials and anisotropic metallization presented in this work represents important progress towards the creation of nanoelectronic devices from self-assembled biological templates.

Sandwich-like TiO2@ZnO-based noble metal (Ag, Au, Pt, or Pd) for better photo-oxidation performance: Synergistic effect between noble metal and metal oxide phases

NASA Astrophysics Data System (ADS)

Li, Shunxing; Cai, Jiabai; Wu, Xueqing; Zheng, Fengying

2018-06-01

The performance of different noble metals (NMs) with controllable size (5 nm) as co-catalyst on the photocatalytic oxidation of TiO2@ZnO hollow spheres was tested with benzyl alcohol in the presence of water under ambient conditions. A new type of solar-light-driven TiO2@NMs@ZnO nanocomposite was fabricated by using a template (surface functionalized polystyrene balls), hydrothermal reaction, and calcination. Under simulated sunlight irradiation, the photo-oxidation rate of benzyl alcohol was in the following of TiO2@Ag@ZnO > TiO2@Au@ZnO > TiO2@Pt@ZnO > TiO2@Pd@ZnO > TiO2@ZnO. This result was due to the combination of TiO2 and ZnO, as well as the sandwiched Ag NPs as electron trap site, which can store and shuttle photo-generated electrons, and then enhance photo-generation of active radicals. Electron paramagnetic resonance (EPR) spectroscopy, as well as photo-luminescence (PL), photo-reduction of Cr(VI) and electrochemical measurements were taken to verify this conclusion. Taking into account the multi-functional combination of precious metals and semiconductor materials, this work could provide new insights for the design of high-performance photocatalysts.

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE PAGES

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira; ...

2017-12-18

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Cold work study on a 316LN modified alloy for the ITER TF coil conduit

DOE PAGES

Walsh, Robert; Toplosky, V. J.; McRae, D. M.; ...

2012-06-01

The primary structural component of the cable-in-conduit conductor (CICC) magnets, such as the ITER TF coils is the conduit. This function creates requirements for 4 K strength, toughness, fatigue crack resistance, and ductility after exposure to the superconductor's reaction heat treatment. The tensile ductility of a steel is a quality factor related to fatigue and fracture resistance that can be evaluated more economically with tensile tests rather than fatigue and fracture tests. We subject 316LN modified base metal and welds to a range of cold work from 0% to 20% and a subsequent Nb 3Sn reaction heat treatment to evaluatemore » the effects on the tensile properties. With the addition of cold work, the 4 K yield strength increases while tensile elongation decreases in both the base metal and weld. Our results are compared to previously published data on the same alloy to evaluate the use of tensile ductility parameters as a materials qualification specification in magnet design.« less

Interaction between adsorbed hydrogen and potassium on a carbon nanocone containing material as studied by photoemission

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Xiaofeng; Raaen, Steinar, E-mail: sraaen@ntnu.no

2015-09-14

Hydrogen adsorption on a potassium doped carbon nanocone containing material was studied by photoelectron spectroscopy and work function measurement. The valence band spectra indicate that there is charge transfer from potassium to carbon. Upon deposition on carbon potassium is in its ionic state for lower doping and shows both ionic and metallic behavior at higher doping. Adsorption of hydrogen facilitates diffusion of potassium on the carbon material as seen by changes in the K{sub 2p} core level spectrum. Variations in the measured sample work function indicate that hydrogen initially adsorb on the K dopants and subsequently adsorb on the carbonmore » cone containing material.« less

Paradigm Change: Alternate Approaches to Constitutive and Necking Models for Sheet Metal Forming

NASA Astrophysics Data System (ADS)

Stoughton, Thomas B.; Yoon, Jeong Whan

2011-08-01

This paper reviews recent work proposing paradigm changes for the currently popular approach to constitutive and failure modeling, focusing on the use of non-associated flow rules to enable greater flexibility to capture the anisotropic yield and flow behavior of metals using less complex functions than those needed under associated flow to achieve that same level of fidelity to experiment, and on the use of stress-based metrics to more reliably predict necking limits under complex conditions of non-linear forming. The paper discusses motivating factors and benefits in favor of both associated and non-associated flow models for metal forming, including experimental, theoretical, and practical aspects. This review is followed by a discussion of the topic of the forming limits, the limitations of strain analysis, the evidence in favor of stress analysis, the effects of curvature, bending/unbending cycles, triaxial stress conditions, and the motivation for the development of a new type of forming limit diagram based on the effective plastic strain or equivalent plastic work in combination with a directional parameter that accounts for the current stress condition.

Ultrahigh Ionic Conduction in Water-Stable Close-Packed Metal-Carbonate Frameworks.

PubMed

Manna, Biplab; Desai, Aamod V; Illathvalappil, Rajith; Gupta, Kriti; Sen, Arunabha; Kurungot, Sreekumar; Ghosh, Sujit K

2017-08-21

Utilization of the robust metal-carbonate backbone in a series of water-stable, anionic frameworks has been harnessed for the function of highly efficient solid-state ion-conduction. The compact organization of hydrophilic guest ions facilitates water-assisted ion-conduction in all the compounds. The dense packing of the compounds imparts high ion-conducting ability and minimizes the possibility of fuel crossover, making this approach promising for design and development of compounds as potential components of energy devices. This work presents the first report of evaluating ion-conduction in a purely metal-carbonate framework, which exhibits high ion-conductivity on the order of 10 -2 S cm -1 along with very low activation energy, which is comparable to highly conducting well-known crystalline coordination polymers or commercialized organic polymers like Nafion.

Templated dewetting: designing entirely self-organized platforms for photocatalysis.

PubMed

Altomare, Marco; Nguyen, Nhat Truong; Schmuki, Patrik

2016-12-01

Formation and dispersion of metal nanoparticles on oxide surfaces in site-specific or even arrayed configuration are key in various technological processes such as catalysis, photonics, electrochemistry and for fabricating electrodes, sensors, memory devices, and magnetic, optical, and plasmonic platforms. A crucial aspect towards an efficient performance of many of these metal/metal oxide arrangements is a reliable fabrication approach. Since the early works on graphoepitaxy in the 70s, solid state dewetting of metal films on patterned surfaces has been much explored and regarded as a most effective tool to form defined arrays of ordered metal particles on a desired substrate. While templated dewetting has been studied in detail, particularly from a mechanistic perspective on lithographically patterned Si surfaces, the resulting outstanding potential of its applications on metal oxide semiconductors, such as titania, has received only limited attention. In this perspective we illustrate how dewetting and particularly templated dewetting can be used to fabricate highly efficient metal/TiO 2 photocatalyst assemblies e.g. for green hydrogen evolution. A remarkable advantage is that the synthesis of such photocatalysts is completely based on self-ordering principles: anodic self-organized TiO 2 nanotube arrays that self-align to a highest degree of hexagonal ordering are an ideal topographical substrate for a second self-ordering process, that is, templated-dewetting of sputter-deposited metal thin films. The controllable metal/semiconductor coupling delivers intriguing features and functionalities. We review concepts inherent to dewetting and particularly templated dewetting, and outline a series of effective tools that can be synergistically interlaced to reach fine control with nanoscopic precision over the resulting metal/TiO 2 structures (in terms of e.g. high ordering, size distribution, site specific placement, alloy formation) to maximize their photocatalytic efficiency. These processes are easy to scale up and have a high throughput and great potential to be applied to fabricate not only (photo)catalytic materials but also a large palette of other functional nanostructured elements and devices.

Templated dewetting: designing entirely self-organized platforms for photocatalysis

PubMed Central

Altomare, Marco; Nguyen, Nhat Truong

2016-01-01

Formation and dispersion of metal nanoparticles on oxide surfaces in site-specific or even arrayed configuration are key in various technological processes such as catalysis, photonics, electrochemistry and for fabricating electrodes, sensors, memory devices, and magnetic, optical, and plasmonic platforms. A crucial aspect towards an efficient performance of many of these metal/metal oxide arrangements is a reliable fabrication approach. Since the early works on graphoepitaxy in the 70s, solid state dewetting of metal films on patterned surfaces has been much explored and regarded as a most effective tool to form defined arrays of ordered metal particles on a desired substrate. While templated dewetting has been studied in detail, particularly from a mechanistic perspective on lithographically patterned Si surfaces, the resulting outstanding potential of its applications on metal oxide semiconductors, such as titania, has received only limited attention. In this perspective we illustrate how dewetting and particularly templated dewetting can be used to fabricate highly efficient metal/TiO2 photocatalyst assemblies e.g. for green hydrogen evolution. A remarkable advantage is that the synthesis of such photocatalysts is completely based on self-ordering principles: anodic self-organized TiO2 nanotube arrays that self-align to a highest degree of hexagonal ordering are an ideal topographical substrate for a second self-ordering process, that is, templated-dewetting of sputter-deposited metal thin films. The controllable metal/semiconductor coupling delivers intriguing features and functionalities. We review concepts inherent to dewetting and particularly templated dewetting, and outline a series of effective tools that can be synergistically interlaced to reach fine control with nanoscopic precision over the resulting metal/TiO2 structures (in terms of e.g. high ordering, size distribution, site specific placement, alloy formation) to maximize their photocatalytic efficiency. These processes are easy to scale up and have a high throughput and great potential to be applied to fabricate not only (photo)catalytic materials but also a large palette of other functional nanostructured elements and devices. PMID:28567258

29 CFR 570.67 - Occupations in roofing operations and on or about a roof (Order 16).

Code of Federal Regulations, 2014 CFR

2014-07-01

... proximity to a roof, including carpentry and metal work, alterations, additions, maintenance and repair... or metal), including roof trusses or joists; gutter and downspout work; the installation and... work performed in connection with the installation of roofs, including related metal work such as...

Weak Coordination as a Powerful Means for Developing Broadly Useful C–H Functionalization Reactions

PubMed Central

Engle, Keary M.; Mei, Tian-Sheng; Wasa, Masayuki

2011-01-01

Conspectus Reactions that convert carbon–hydrogen (C–H) bonds into carbon–carbon (C–C) or carbon–heteroatom (C–Y) bonds are attractive tools for organic chemists, potentially expediting the synthesis of target molecules through new disconnections in retrosynthetic analysis. Despite extensive inorganic and organometallic study of the insertion of homogeneous metal species into unactivated C–H bonds, practical applications of this technology in organic chemistry are still rare. Only in the past decade have metal-catalyzed C–H functionalization reactions become more widely utilized in organic synthesis. Research in the area of homogeneous transition metal–catalyzed C–H functionalization can be broadly grouped into two subfields. They reflect different approaches and goals and thus have different challenges and opportunities. One approach involves reactions of completely unfunctionalized aromatic and aliphatic hydrocarbons, which we refer to as “first functionalization.” Here the substrates are nonpolar and hydrophobic and thus interact very weakly with polar metal species. To overcome this weak affinity and drive metal-mediated C–H cleavage, chemists often use hydrocarbon substrates in large excess (for example, as solvent). Because highly reactive metal species are needed in first functionalization, controlling the chemoselectivity to avoid over-functionalization is often difficult. Additionally, because both substrates and products are comparatively low-value chemicals, developing cost-effective catalysts with exceptionally high turnover numbers that are competitive with alternatives (including heterogeneous catalysts) is challenging. Although an exciting field, first functionalization is beyond the scope of this Account. The second subfield of C–H functionalization involves substrates containing one or more pre-existing functional groups, termed “further functionalization.” One advantage of this approach is that the existing functional group (or groups) can be used to chelate the metal catalyst and position it for selective C–H cleavage. Precoordination can overcome the paraffin nature of C–H bonds by increasing the effective concentration of the substrate so that it needn't be used as solvent. From a synthetic perspective, it is desirable to use a functional group that is an intrinsic part of the substrate so that extra steps for installation and removal of an external directing group can be avoided. In this way, dramatic increases in molecular complexity can be accomplished in a single stroke through stereo- and site-selective introduction of a new functional group. Although reactivity is a major challenge (as with first functionalization), the philosophy in further functionalization differs—the major challenge is developing reactions that work with predictable selectivity in intricately functionalized contexts on commonly occurring structural motifs. In this Account, we focus on an emergent theme within the further functionalization literature: the use of commonly occurring functional groups to direct C–H cleavage through weak coordinations. We discuss our motivation for studying Pd-catalyzed C–H functionalization assisted by weakly coordinating functional groups and chronicle our endeavors to bring reactions of this type to fruition. Through this approach, we have developed reactions with a diverse range of substrates and coupling partners, with the broad scope likely stemming from higher reactivity of the less stable cyclopalladated intermediates held in place by weak coordinations. PMID:22166158

Electron-selective contacts via ultra-thin organic interface dipoles for silicon organic heterojunction solar cells

NASA Astrophysics Data System (ADS)

Reichel, Christian; Würfel, Uli; Winkler, Kristina; Schleiermacher, Hans-Frieder; Kohlstädt, Markus; Unmüssig, Moritz; Messmer, Christoph A.; Hermle, Martin; Glunz, Stefan W.

2018-01-01

In the last years, novel materials for the formation of electron-selective contacts on n-type crystalline silicon (c-Si) heterojunction solar cells were explored as an interfacial layer between the metal electrode and the c-Si wafer. Besides inorganic materials like transition metal oxides or alkali metal fluorides, also interfacial layers based on organic molecules with a permanent dipole moment are promising candidates to improve the contact properties. Here, the dipole effect plays an essential role in the modification of the interface and effective work function of the contact. The amino acids L-histidine, L-tryptophan, L-phenylalanine, glycine, and sarcosine, the nucleobase adenine, and the heterocycle 4-hydroxypyridine were investigated as dipole materials for an electron-selective contact on the back of p- and n-type c-Si with a metal electrode based on aluminum (Al). Furthermore, the effect of an added fluorosurfactant on the resulting contact properties was examined. The performance of n-type c-Si solar cells with a boron diffusion on the front was significantly increased when L-histidine and/or the fluorosurfactant was applied as a full-area back surface field. This improvement was attributed to the modification of the interface and the effective work function of the contact by the dipole material which was corroborated by numerical device simulations. For these solar cells, conversion efficiencies of 17.5% were obtained with open-circuit voltages (Voc) of 625 mV and fill factors of 76.3%, showing the potential of organic interface dipoles for silicon organic heterojunction solar cells due to their simple formation by solution processing and their low thermal budget requirements.

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, Meng; Nakayama, Miki; Liu, Ping

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Emergent Interfacial Ferromagnetism in CaMnO3-based Superlattices

NASA Astrophysics Data System (ADS)

Grutter, Alexander

2014-03-01

Interfaces of complex oxide materials provide a rich playground not only for the exploration of properties not found in the bulk constituents but also for the development of functional interfaces to be incorporated in spintronic applications. Emergent interfacial magnetic phenomena have been of great interest but surprisingly there have been few examples of emergent interfacial ferromagnetism. In this talk, I will describe our recent work on the stabilization of ferromagnetism in CaMnO3-based superlattices. We have demonstrated ferromagnetism at the interface between the antiferromagnetic insulator CaMnO3 and a paramagnetic metallic layer, including CaRuO3 and LaNiO3. Theoretically the ferromagnetism has been attributed to an interfacial double exchange interaction among the interfacial Mn ions that is mediated by itinerant electrons from the paramagnetic metallic layer. Through polarized neutron reflectivity and observation of exchange bias, we have demonstrated that the ferromagnetism comes from Mn ions in a single unit cell at the interfaces just as theory has predicted. We have also demonstrated that the metallicity of the paramagnetic layer is critical in stabilizing ferromagnetism at the interface and that the interfacial ferromagnetism can be suppressed by suppressing the metallicity of the paramagnetic layer. Despite the agreement with theory, there remain open questions as to the magnetic interactions among the interfacial ferromagnetic layers. For example, the saturated magnetic moment modulates as a function of the thickness of both the CaMnO3 and paramagnetic metal layers. The origins of this oscillation are not well understood and may stem from either structural effects or long-range oscillatory magnetic coupling interactions reminiscent of RKKY interactions. Evidence of the doubling of the unit cell and long range antiferromagnetic correlations support these speculations. This work was supported by the U.S. Department of Energy, Office of Science, Division of Materials Sciences and Engineering, under Contract # DE-AC05-76RL01830 and DE-SC0008505.

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE PAGES

Xue, Meng; Nakayama, Miki; Liu, Ping; ...

2017-09-13

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Catalyst and processing effects on metal-assisted chemical etching for the production of highly porous GaN

NASA Astrophysics Data System (ADS)

Geng, Xuewen; Duan, Barrett K.; Grismer, Dane A.; Zhao, Liancheng; Bohn, Paul W.

2013-06-01

Metal-assisted chemical etching is a facile method to produce micro-/nanostructures in the near-surface region of gallium nitride (GaN) and other semiconductors. Detailed studies of the production of porous GaN (PGaN) using different metal catalysts and GaN doping conditions have been performed in order to understand the mechanism by which metal-assisted chemical etching is accomplished in GaN. Patterned catalysts show increasing metal-assisted chemical etching activity to n-GaN in the order Ag < Au < Ir < Pt. In addition, the catalytic behavior of continuous films is compared to discontinuous island films. Continuous metal films strongly shield the surface, hindering metal-assisted chemical etching, an effect which can be overcome by using discontinuous films or increasing the irradiance of the light source. With increasing etch time or irradiance, PGaN morphologies change from uniform porous structures to ridge and valley structures. The doping type plays an important role, with metal-assisted chemical etching activity increasing in the order p-GaN < intrinsic GaN < n-GaN. Both the catalyst identity and the doping type effects are explained by the work functions and the related band offsets that affect the metal-assisted chemical etching process through a combination of different barriers to hole injection and the formation of hole accumulation/depletion layers at the metal-semiconductor interface.

Glennan Microsystems Initiative

NASA Technical Reports Server (NTRS)

Brillson, Leonard J.

2002-01-01

During the 2001-2002 award period, we performed research on Pt/Ti/bare 6H-SiC and bare 4H-SiC interfaces in order to identify their electronic properties as a function of surface preparation. The overall aim of this work is to optimize the electronic properties of metal contacts to SiC as well as the active SiC material itself as a function of surface preparation and subsequent processing. Initially, this work has involved identifying bare surface, subsurface, and metal induced gap states at the metal-SiC contact and correlating energies and densities of deep levels with Schottky barrier heights. We used low energy electron-excited nanoluminescence (LEEN) spectroscopy, X-ray photoemission spectroscopy (XPS), and Secondary Ion Mass Spectrometry (SIMS) in order to correlate electronic states and energy bands with chemical composition, bonding, and crystal structure. A major development has been the discovery of polytype transformations that occur in 4H-SiC under standard microelectronic process conditions used to fabricate SiC devices. Our results are consistent with the stacking fault generation, defect formation, and consequent degradation of SiC recently reported for state-of-the-art ABB commercial diodes under localized electrical stress. Our results highlight the importance of -optimizing process conditions and material properties - anneal times, temperatures and doping to control such structural changes within epitaxial SiC layers. Thus far, we have established threshold times and temperatures beyond which 4H-SiC exhibits 3C-SiC transformation bands for a subset of dopant concentrations and process conditions. On the basis of this temperature time behavior, we have been able to establish an activation energy of approximately 2.5 eV for polytype transformation and dislocation motion. Work continues to establish the fundamental mechanisms underlying the polytype changes and its dependence on material parameters.

Ambient-Pressure XPS Study of a Ni–Fe Electrocatalyst for the Oxygen Evolution Reaction

DOE PAGES

Ali-Löytty, Harri; Louie, Mary W.; Singh, Meenesh R.; ...

2016-01-05

Chemical analysis of solid–liquid interfaces under electrochemical conditions has recently become feasible due to the development of new synchrotron radiation techniques. In this paper, we report the use of “tender” X-ray ambient-pressure X-ray photoelectron spectroscopy (APXPS) to characterize a thin film of Ni–Fe oxyhydroxide electrodeposited on Au as the working electrode at different applied potentials in 0.1 M KOH as the electrolyte. Our results show that the as-prepared 7 nm thick Ni–Fe (50% Fe) film contains Fe and Ni in both their metallic as well as oxidized states, and undergoes further oxidation when the sample is subjected to electrochemical oxidation–reductionmore » cycles. Metallic Fe is oxidized to Fe 3+ and metallic Ni to Ni 2+/3+. This work shows that it is possible to monitor the chemical nature of the Ni–Fe catalyst as a function of potential when the corresponding current densities are small. This allows for operando measurements just above the onset of OER; however, current densities as they are desired in photoelectrochemical devices (~1–10 mA cm –2) could not be achieved in this work, due to ohmic losses in the thin electrolyte film. We use a two-dimensional model to describe the spatial distribution of the electrochemical potential, current density, and pH as a function of the position above the electrolyte meniscus, to provide guidance toward enabling the acquisition of operando APXPS at high current density. Finally, the shifts in binding energy of water with applied potential predicted by the model are in good agreement with the experimental values.« less

Role of non-local exchange in the electronic structure of correlated oxides

NASA Astrophysics Data System (ADS)

Iori, Federico; Gatti, Matteo; Rubio Secades, Angel

Transition-metal oxides (TMO) with partially filled d or f shells are a prototype of correlated materials. They exhibit very interesting properties, like metal-insulator phase transitions (MIT). In this work we consider several TMO insulators in which Kohn-Sham LDA band structures are metallic: VO2, V2O3, Ti2O3, LaTiO3 and YTiO3. In the past, this failure of LDA has been explained in terms of its inadequacy to capture the strong interactions taking place between correlated electrons. In the spirit of the Hubbard model, possible corrections to improve onsite correlation are the LDA +U and LDA +DMFT approaches. Here we make use of the HSE06 hybrid functional. We show that, without invoking strong-correlation effects, the contribution of the non-local Fock exchange is essential to correct the LDA results, by curing its delocalization error. In fact, HSE06 provides insulating band structures and correctly describes the MIT in all the considered compounds. We further discuss the advantages and the limitations of the HSE06 hybrid functional in correlated TMO

Assessment of the genetic risks of a metallic alloy used in medical implants.

PubMed

Gomes, Cristiano C; Moreira, Leonardo M; Santos, Vanessa J S V; Ramos, Alfeu S; Lyon, Juliana P; Soares, Cristina P; Santos, Fabio V

2011-01-01

The use of artificial implants provides a palliative or permanent solution for individuals who have lost some bodily function through disease, an accident or natural wear. This functional loss can be compensated for by the use of medical devices produced from special biomaterials. Titanium alloy (Ti-6Al-4V) is a well-established primary metallic biomaterial for orthopedic implants, but the toxicity of the chemical components of this alloy has become an issue of concern. In this work, we used the MTT assay and micronucleus assay to examine the cytotoxicity and genotoxicity, respectively, of an extract obtained from this alloy. The MTT assay indicated that the mitochondrial activity and cell viability of CHO-K1 cells were unaffected by exposure to the extract. However, the micronucleus assay revealed DNA damage and an increase in micronucleus frequency at all of the concentrations tested. These results show that ions released from Ti-6Al-4V alloy can cause DNA and nuclear damage and reinforce the importance of assessing the safety of metallic medical devices constructed from biomaterials.

Study of electronic structure and Compton profiles of transition metal diborides

NASA Astrophysics Data System (ADS)

Bhatt, Samir; Heda, N. L.; Kumar, Kishor; Ahuja, B. L.

2017-08-01

We report Compton profiles (CPs) of transition metal diborides (MB2; M= Ti and Zr) using a 740 GBq 137Cs Compton spectrometer measured at an intermediate resolution of 0.34 a.u. To validate the experimental momentum densities, we have employed the linear combination of atomic orbitals (LCAO) method to compute the theoretical CPs along with the energy bands, density of states (DOS) and Mulliken's population response. The LCAO computations have been performed in the frame work of density functional theory (DFT) and hybridization of Hartree-Fock and DFT (namely B3LYP and PBE0). For both the diborides, the CPs based on revised Perdew-Burke-Ernzerhof exchange and correlation functions (DFT-PBESol) lead to a better agreement with the experimental momentum densities than other reported approximations. Energy bands, DOS and real space analysis of CPs confirm a metallic-like character of both the borides. Further, a comparison of DFT-PBESol and experimental data on equal-valence-electron-density scale shows more ionicity in ZrB2 than that in TiB2, which is also supported by the Mulliken's population based charge transfer data.

Assessment of the genetic risks of a metallic alloy used in medical implants

PubMed Central

Gomes, Cristiano C.; Moreira, Leonardo M.; Santos, Vanessa J.S.V.; Ramos, Alfeu S.; Lyon, Juliana P.; Soares, Cristina P.; Santos, Fabio V.

2011-01-01

The use of artificial implants provides a palliative or permanent solution for individuals who have lost some bodily function through disease, an accident or natural wear. This functional loss can be compensated for by the use of medical devices produced from special biomaterials. Titanium alloy (Ti-6Al-4V) is a well-established primary metallic biomaterial for orthopedic implants, but the toxicity of the chemical components of this alloy has become an issue of concern. In this work, we used the MTT assay and micronucleus assay to examine the cytotoxicity and genotoxicity, respectively, of an extract obtained from this alloy. The MTT assay indicated that the mitochondrial activity and cell viability of CHO-K1 cells were unaffected by exposure to the extract. However, the micronucleus assay revealed DNA damage and an increase in micronucleus frequency at all of the concentrations tested. These results show that ions released from Ti-6Al-4V alloy can cause DNA and nuclear damage and reinforce the importance of assessing the safety of metallic medical devices constructed from biomaterials. PMID:21637553

Relating monolithic and granular leaching from contaminated soil treated with different cementitious binders.

PubMed

Kogbara, Reginald B; Al-Tabbaa, Abir; Stegemann, Julia A

2013-01-01

This work employed a clayey, silty, sandy gravel contaminated with a mixture of metals (Cd, Cu, Pb, Ni and Zn) and diesel. The contaminated soil was treated with 5 and 10% dosages of different cementitious binders. The binders include Portland cement, cement-fly ash, cement-slag and lime-slag mixtures. Monolithic leaching from the treated soils was evaluated over a 64-day period alongside granular leachability of 49- and 84-day old samples. Surface wash-off was the predominant leaching mechanism for monolithic samples. In this condition, with data from different binders and curing ages combined, granular leachability as a function of monolithic leaching generally followed degrees 4 and 6 polynomial functions. The only exception was for Cu, which followed the multistage dose-response model. The relationship between both leaching tests varied with the type of metal, curing age/residence time of monolithic samples in the leachant, and binder formulation. The results provide useful design information on the relationship between leachability of metals from monolithic forms of S/S treated soils and the ultimate leachability in the eventual breakdown of the stabilized/solidified soil.

Dual-Layered Film Protected Lithium Metal Anode to Enable Dendrite-Free Lithium Deposition.

PubMed

Yan, Chong; Cheng, Xin-Bing; Tian, Yang; Chen, Xiang; Zhang, Xue-Qiang; Li, Wen-Jun; Huang, Jia-Qi; Zhang, Qiang

2018-06-01

Lithium metal batteries (such as lithium-sulfur, lithium-air, solid state batteries with lithium metal anode) are highly considered as promising candidates for next-generation energy storage systems. However, the unstable interfaces between lithium anode and electrolyte definitely induce the undesired and uncontrollable growth of lithium dendrites, which results in the short-circuit and thermal runaway of the rechargeable batteries. Herein, a dual-layered film is built on a Li metal anode by the immersion of lithium plates into the fluoroethylene carbonate solvent. The ionic conductive film exhibits a compact dual-layered feature with organic components (ROCO 2 Li and ROLi) on the top and abundant inorganic components (Li 2 CO 3 and LiF) in the bottom. The dual-layered interface can protect the Li metal anode from the corrosion of electrolytes and regulate the uniform deposition of Li to achieve a dendrite-free Li metal anode. This work demonstrates the concept of rational construction of dual-layered structured interfaces for safe rechargeable batteries through facile surface modification of Li metal anodes. This not only is critically helpful to comprehensively understand the functional mechanism of fluoroethylene carbonate but also affords a facile and efficient method to protect Li metal anodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functionalized magnetic nanoparticles for the decontamination of water polluted with cesium

NASA Astrophysics Data System (ADS)

Helal, Ahmed S.; Decorse, Philippe; Perruchot, Christian; Novak, Sophie; Lion, Claude; Ammar, Souad; El Hage Chahine, Jean-Michel; Hémadi, Miryana

2016-05-01

Magnetic nanoparticles are attracting considerable interest because of their potential applications in practically all fields of science and technology, including the removal of heavy metals from contaminated waters. It is, therefore, of great importance to adapt the surfaces of these nanoparticles according to the application. In this work advanced nanoparticles (NPs) with well-tailored surface functionalities were synthesized using the polyol method. The efficiency of a chelating agent, succinyl-β-cyclodextrin (SBCD), was first investigated spectrophotometrically and by Isothermal Titration Calorimetry (ITC). SBCD was then grafted onto nanoparticles previously functionalized with 3-aminopropyl triethoxsilane (NP-APTES). The resulting NP-SBCD system was then incubated with a solution of cesium. After magnetic separation, the solid residue was removed from the supernatant and characterized by X-Ray Photoelectron spectrometry (XPS), X-Ray Fluorescence spectrometry (XRF) and Superconducting QUantum Interference Device (SQUID) magnetometry. These characterizations show the presence of cesium in the solid residue, which indicates Cs uptake by the NP-SBCD system. This nanohybrid system constitutes a promising model for heavy metal decontamination.

Functional Performances of CuZnAl Shape Memory Alloy Open-Cell Foams

NASA Astrophysics Data System (ADS)

Biffi, C. A.; Casati, R.; Bassani, P.; Tuissi, A.

2018-01-01

Shape memory alloys (SMAs) with cellular structure offer a unique mixture of thermo-physical-mechanical properties. These characteristics can be tuned by changing the pore size and make the shape memory metallic foams very attractive for developing new devices for structural and functional applications. In this work, CuZnAl SMA foams were produced through the liquid infiltration of space holder method. In comparison, a conventional CuZn brass alloy was foamed trough the same method. Functional performances were studied on both bulk and foamed SMA specimens. Calorimetric response shows similar martensitic transformation (MT) below 0 °C. Compressive response of CuZnAl revealed that mechanical behavior is strongly affected by sample morphology and that damping capacity of metallic foam is increased above the MT temperatures. The shape memory effect was detected in the CuZnAl foams. The conventional brass shows a compressive response similar to that of the martensitic CuZnAl, in which plastic deformation accumulation occurs up to the cellular structure densification after few thermal cycles.

Efficient Adsorption Characteristics of Pristine and Silver-Doped Graphene Oxide Towards Contaminants: A Potential Membrane Material for Water Purification?

PubMed

Panigrahi, Puspamitra; Dhinakaran, Ashok Kumar; Sekar, Yuvaraj; Ahuja, Rajeev; Hussain, Tanveer

2018-05-16

In this work, we have investigated the potential of pristine and silver (Ag)-functionalized graphene oxide monolayers GO (GO-Ag) as efficient membranes for water filtration. Our first principles calculations based on density functional theory (DFT) reveal the hydrophilic nature of GO surfaces. The phonon frequency calculations within density functional perturbation theory (DFPT) confirmed the stability of GO sheets in aqueous media. Van der Waals-corrected binding energies of GO sheet towards heavy metals suggest that even pristine GO sheets are completely impermeable to various heavy metals like arsenic (As) and lead (Pb). However, compared to GO, the GO-Ag sheets have a much higher affinity towards the three amino acids histidine, phenyl-alanine and tyrosine, which are the main component of a bacteria cell wall. The GO-Ag sheet is found to be extremely efficient for bacteria inactivation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the self-assembly process and behavior of metal-seamed pyrogallol[4]arene nanocapsules

NASA Astrophysics Data System (ADS)

Mossine, Andrew V.

C-alkylpyrogallol[4]arenes (PgCs) are bowl-shaped compounds that are commonly used as supramolecular building blocks in the construction of larger entities such as capsules, nanotubes, and layered networks. Many of these assemblies are constructed using non-covalent means and, as such, are inherently unstable in polar media. Although metal coordination with the hydroxyl-rich PgC upper rim can be exploited to synthesize assemblies with enhanced stability, few reports of this can be found in the literature. Thus, a thorough investigation of these metal-seamed assemblies and their manipulation is of importance. Prior work in the Atwood lab has produced three examples of metal-organic nanocapsules (MONCs) based on PgCs. These include two hexameric MONCs (based on Cu2+ and Ga3+) as well as a single example of a dimeric MONC (based on Zn2+). As it was unknown whether other metal cations could lead to the formation of similar entities, PgC complexation experiments were conducted with other first series transition metal cations, notably Ni2+, Co2+ and Mn2+. All of these led to nanocapsular materials, which were identified and studied using single crystal X-ray diffraction (scXRD). Once the foundational studies were complete, syntheses were also performed under varied conditions, specifically with Ni2+ and Cu2+. This led to the characterization of both dimeric and hexameric MONCs with these two metals, as well as the characterization of many other capsular materials. The information collected from these experiments also led to an intriguing question: which specific conditions lead to the formation of dimeric vs. hexameric MONCs? To answer this question, solid-state analysis using scXRD was coupled to in situ analysis utilizing small angle neutron scattering (SANS). This work showed that the formation of the dimer is typically favored at higher temperatures while the formation of the hexamer is favored at lower temperatures for both of the metals tested. Studies that varied time of measurement as well as the solvent system during synthesis were also performed. Furthermore, SANS was also used to study Fe3+-PgC complexes. These complexes are difficult if not impossible to crystallize, and therefore cannot be studied using scXRD. SANS was used in conjunction with elemental analysis to deduce a structure for these materials. In addition to understanding the synthesis of MONCs, another goal was to also use them for other (possibly practical) purposes. To this end, PgC-based MONCs were used as building blocks in metal-organic frameworks (MOFs). This involved the use of divergent ligands to "link" capsular monomers together, resulting in one and two dimensional frameworks. This work not only produced functional materials that may be useful in future research efforts, but also showed that exo-ligand exchange can be used to derivatize MONCs into potentially useful and functional materials. The introduction of radioisotopes into the nanocapsule was another method by which functionality could theoretically be imparted into MONCs. It was envisioned that MONCs could potentially be used as carrier systems for radioisotopes, and thereby function as agents for therapy or medical imaging. Copper hexamers constructed from 64Cu2+ were therefore prepared and studied in a living system. However, these studies were unsuccessful at showing that the copper-seamed MONCs differed in behavior from 64Cu in vivo, either due to poor labeling efficiency or metabolism. Nevertheless, radiolabeling of hexameric nanocapsules was helpful in broadening our understanding of these materials. Some of the studies that were conducted include those that gauge the solubility and stability of nanocapsules, as well as others that explore the conditions required for cationic uptake and exchange.

Hydrostatic Stress Effects in Metal Plasticity

NASA Technical Reports Server (NTRS)

Wilson, Christopher D.

1999-01-01

Since the 1940s, the theory of plasticity has assumed that hydrostatic stress does not affect the yield or postyield behavior of metals. This assumption is based on the early work of Bridgman. Bridgman found that hydrostatic pressure (compressive stress) does not affect yield behavior until a substantial amount of pressure (greater than 100 ksi) is present. The objective of this study was to determine the effect of hydrostatic tension on yield behavior. Two different specimen geometries were examined: an equal-arm bend specimen and a double edge notch specimen. The presence of a notch is sufficient to develop high enough hydrostatic tensile stresses to affect yield. The von Mises yield function, which does not have a hydrostatic component, and the Drucker-Prager yield function, which includes a hydrostatic component, were used in finite element analyses of the two specimen geometries. The analyses were compared to test data from IN 100 specimens. For both geometries, the analyses using the Drucker-Prager yield function more closely simulated the test data. The von Mises yield function lead to 5-10% overprediction of the force-displacement or force-strain response of the test specimens.

Electrical and optical properties of carbon films

NASA Astrophysics Data System (ADS)

Kulkarni, Pranita

Carbon and carbon-based materials, including graphite, diamond, and other thin-film structures, are being intensively researched for a wide range of electronic applications. A variety of graphitic, nano-structured carbon materials can be synthesized that have current or potential applications as thin-film transistors, photovoltaics, and supercapacitors. Diamond has been pursued for many years for electronics that can be used in extreme conditions, such as high temperature, high power, high frequency, and radiation environments. In this research study, electronic properties of diamond and graphitic films with crystallite or grain sizes in the nanometer range were investigated. The nano-structured graphitic carbon films were grown using a previously developed method based on the pyrolysis of poly(acrylonitrile) and poly(n-butyl acrylate) block copolymers (PAN-b-PBA). An important characteristic of these films is that the morphology (and therefore other properties) can be controlled by the compositions and processing of the starting block copolymers. Spherical, cylindrical, lamellar, and branched morphologies have been fabricated. The crystallite sizes, optical absorption, and morphology of PAN-b-PBA (containing 17.8% PAN) pyrolyzed between 400 and 600°C were determined and were compared to those derived by pyrolysis of PAN homopolymers at the same temperatures. Hall-effect measurements on pyrolyzed PAN-b-PBA films with spherical, cylindrical, and branched morphologies and homopolymer PAN films pyrolyzed at the same temperatures revealed that both PAN-b-PBA with different morphologies and PAN homopolymer-derived films had n-type conductivity; differences in carrier concentration and mobility values were correlated with the morphological differences of the films. Optical absorption measurements in the ultra-violet through visible wavelength range were also conducted on these films; measurements of the pseudo band-gaps and absorption coefficients were correlated with the morphology and graphitic cluster sizes that were obtained from Raman scattering. To enable the development of future devices based on nanostructured carbon films, four metals (Zr, Ti, Cu, and Pt) with substantially different work functions and catalytic activity were deposited on pyrolyzed PAN-b-PBA films. All metals formed ohmic contacts to the films in the 'as-deposited' state with contact resistances of the order of 105 O. The ohmicity of all metals and the modulation of the pseudo-gap with graphitic cluster sizes were explained using the simple single-orbital tight-binding calculations for nanometer-sized graphitic clusters. Unlike most inorganic single-crystal semiconductors but commonly observed in organic or nanocrystalline materials, our modeling of resistivity-temperature measurements showed that variable-range-hopping (VRH) was the dominant current transport mechanism in the films up to room-temperature with a crossover from Mott-VRH to Efros-Skhlovskii-VRH at temperatures below 100 K. Specific contact resistivity values for all metal-copolymer (PAN-b-PBA)-derived films pyrolyzed at 600°C increased with increasing work function of the metal, suggesting that the films are n-type; this conclusion agrees with the n-type result obtained from the Hall-effect measurements. Nanocrystalline diamond (NCD) films have a variety of potential applications, including optical windows, Schottky diodes, and electron emitting surfaces for field emission displays. In this study Zr, Ti, Cu and Pt on intrinsic and lightly sulfur-doped (n-type) NCD films were characterized electrically and photoelectrically. All metals showed linear (ohmic) current-voltage characteristics in the as-deposited state. The Schottky barrier heights (phiB) at the metal-film interface were investigated using x-ray and ultra-violet photoelectron spectroscopy. The undoped NCD films exhibited a negative electron affinity and a band gap of 5.0 +/- 0.4 eV. The phiB were calculated based on this band gap measurement and the consistent indication from Hall-effect measurements that the films are n-type. The phiB values increased with metal work function for both intrinsic and S-doped films. In general accordance with the barrier height trends, the specific contact resistivity values also increased with the metal work functions. Based on the collection of electrical and photoelectrical results, an electronic band-structure model for NCD films is proposed. The model describes the bulk of the material as n-type but with p-type, inverted surfaces corresponding with strong upward band bending.

Rhenium-phthalocyanine molecular nanojunction with high magnetic anisotropy and high spin filtering efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, J.; Institute of Nanomaterial and Nanostructure, Changsha University of Science and Technology, Changsha 410114; Hu, J.

2015-07-20

Using the density functional and non-equilibrium Green's function approaches, we studied the magnetic anisotropy and spin-filtering properties of various transition metal-Phthalocyanine molecular junctions across two Au electrodes. Our important finding is that the Au-RePc-Au junction has both large spin filtering efficiency (>80%) and large magnetic anisotropy energy, which makes it suitable for device applications. To provide insights for the further experimental work, we discussed the correlation between the transport property, magnetic anisotropy, and wave function features of the RePc molecule, and we also illustrated the possibility of controlling its magnetic state.

Composite films of oxidized multiwall carbon nanotube and poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) as a contact electrode for transistor and inverter devices.

PubMed

Yun, Dong-Jin; Rhee, Shi-Woo

2012-02-01

Composite films of multiwall carbon nanotube (MWNT)/poly(3,4-ethylenedioxythiophene) polymerized with poly(4-styrenesulfonate) (PEDOT:PSS) were prepared by spin-coating a mixture solution. The effect of the MWNT loading and the MWNT oxidation, with acid solution or ultraviolet (UV)-ozone treatment, on the film properties such as surface roughness, work function, surface energy, optical transparency and conductivity were studied. Also pentacene thin film transistors and inverters were made with these composite films as a contact metal and the device characteristics were measured. The oxidation of MWNT reduced the conductivity of MWNT/PEDOT:PSS composite film but increased the work function and transparency. UV-ozone treated MWNT/PEDOT:PSS composite film showed higher conductivity (14000 Ω/□) and work function (4.9 eV) than acid-oxidized MWNT/PEDOT:PSS composite film and showed better performance as a source/drain electrode in organic thin film transistor (OTFT) than other types of MWNT/PEDOT:PSS composite films. Hole injection barrier of the UV-ozone treated MWNT/PEDOT:PSS composite film with pentacene was significantly lower than any other films because of the higher work function.

Nanoporous Block Polymer Thin Films Functionalized with Bio-Inspired Ligands for the Efficient Capture of Heavy Metal Ions from Water.

PubMed

Weidman, Jacob L; Mulvenna, Ryan A; Boudouris, Bryan W; Phillip, William A

2017-06-07

Heavy metal contamination of water supplies poses a serious threat to public health, prompting the development of novel and sustainable treatment technologies. One promising approach is to molecularly engineer the chemical affinity of a material for the targeted removal of specific molecules from solution. In this work, nanoporous polymer thin films generated from tailor-made block polymers were functionalized with the bio-inspired moieties glutathione and cysteamine for the removal of heavy metal ions, including lead and cadmium, from aqueous solutions. In a single equilibrium stage, the films achieved removal rates of the ions in excess of 95%, which was consistent with predictions based on the engineered material properties. In a flow-through configuration, the thin films achieved an even greater removal rate of the metal ions. Furthermore, in mixed ion solutions the capacity of the thin films, and corresponding removal rates, did not demonstrate any reduction due to competitive adsorption effects. After such experiments the material was repeatedly regenerated quickly with no observed loss in capacity. Thus, these membranes provide a sustainable platform for the efficient purification of lead- and cadmium-contaminated water sources to safe levels. Moreover, their straightforward chemical modifications suggest that they could be engineered to treat sources containing other recalcitrant environmental contaminants as well.

Functionalized Graphitic Carbon Nitride for Metal-free, Flexible and Rewritable Nonvolatile Memory Device via Direct Laser-Writing

NASA Astrophysics Data System (ADS)

Zhao, Fei; Cheng, Huhu; Hu, Yue; Song, Long; Zhang, Zhipan; Jiang, Lan; Qu, Liangti

2014-07-01

Graphitic carbon nitride nanosheet (g-C3N4-NS) has layered structure similar with graphene nanosheet and presents unusual physicochemical properties due to the s-triazine fragments. But their electronic and electrochemical applications are limited by the relatively poor conductivity. The current work provides the first example that atomically thick g-C3N4-NSs are the ideal candidate as the active insulator layer with tunable conductivity for achieving the high performance memory devices with electrical bistability. Unlike in conventional memory diodes, the g-C3N4-NSs based devices combined with graphene layer electrodes are flexible, metal-free and low cost. The functionalized g-C3N4-NSs exhibit desirable dispersibility and dielectricity which support the all-solution fabrication and high performance of the memory diodes. Moreover, the flexible memory diodes are conveniently fabricated through the fast laser writing process on graphene oxide/g-C3N4-NSs/graphene oxide thin film. The obtained devices not only have the nonvolatile electrical bistability with great retention and endurance, but also show the rewritable memory effect with a reliable ON/OFF ratio of up to 105, which is the highest among all the metal-free flexible memory diodes reported so far, and even higher than those of metal-containing devices.

Understanding the Role of Metal Ions in RNA Folding and Function: Lessons from RNase P, a Ribonucleoprotein Enzyme

NASA Astrophysics Data System (ADS)

Harris, Michael E.; Christian, Eric L.

There is a large and rapidly growing literature relating RNA function to metal ion identity and concentration; however, due to the complexity and large number of interactions it remains a significant experimental challenge to tie the interactions of individual ions to specific aspects of RNA function. Investigation of the ribonculeopro-tein enzyme RNase P function has assisted in defining characteristics of RNA—metal ion interactions and provided a useful model system for understanding RNA catalysis and ribonucleoprotein assembly. The goal of this chapter is to review progress in understanding the physical basis of functional metal ion interactions with P RNA and relate this progress to the development of our understanding of RNA metal ion interactions in general. The research results reviewed here encompass: (1) Determination of the contribution of divalent metal ion binding to specific aspects of enzyme function, (2) Identification of individual metal ion binding sites in P RNA and their contribution to function, and (3) The effect of protein binding on RNA—metal ion affinity.

Enhanced Lifetime of Polymer Solar Cells by Surface Passivation of Metal Oxide Buffer Layers.

PubMed

Venkatesan, Swaminathan; Ngo, Evan; Khatiwada, Devendra; Zhang, Cheng; Qiao, Qiquan

2015-07-29

The role of electron selective interfaces on the performance and lifetime of polymer solar cells were compared and analyzed. Bilayer interfaces consisting of metal oxide films with cationic polymer modification namely poly ethylenimine ethoxylated (PEIE) were found to enhance device lifetime compared to bare metal oxide films when used as an electron selective cathode interface. Devices utilizing surface-modified metal oxide layers showed enhanced lifetimes, retaining up to 85% of their original efficiency when stored in ambient atmosphere for 180 days without any encapsulation. The work function and surface potential of zinc oxide (ZnO) and ZnO/PEIE interlayers were evaluated using Kelvin probe and Kelvin probe force microscopy (KPFM) respectively. Kelvin probe measurements showed a smaller reduction in work function of ZnO/PEIE films compared to bare ZnO films when aged in atmospheric conditions. KPFM measurements showed that the surface potential of the ZnO surface drastically reduces when stored in ambient air for 7 days because of surface oxidation. Surface oxidation of the interface led to a substantial decrease in the performance in aged devices. The enhancement in the lifetime of devices with a bilayer interface was correlated to the suppressed surface oxidation of the metal oxide layers. The PEIE passivated surface retained a lower Fermi level when aged, which led to lower trap-assisted recombination at the polymer-cathode interface. Further photocharge extraction by linearly increasing voltage (Photo-CELIV) measurements were performed on fresh and aged samples to evaluate the field required to extract maximum charges. Fresh devices with a bare ZnO cathode interlayer required a lower field than devices with ZnO/PEIE cathode interface. However, aged devices with ZnO required a much higher field to extract charges while aged devices with ZnO/PEIE showed a minor increase compared to the fresh devices. Results indicate that surface modification can act as a suitable passivation layer to suppress oxidation in metal oxide thin films for enhanced lifetime in inverted organic solar cells.

A summary of special coatings projects conducted in support of the Die Casting Program

DOE Office of Scientific and Technical Information (OSTI.GOV)

Selle, J.E.

1988-09-12

The usefulness of various kinds of coatings to the die casting program has been studied. This work includes heat transfer and fluid flow calculations, as well as experimental work, to examine the feasibility and characteristics of various types of coatings. Calculations include the effect of surface roughness on fluid flow, conductance as a function of coating thickness, conductivity as a function of coating porosity, and solidification and possible remelting of microspheres of metal. In each case, the model is described and the results are presented. Experimental work involved evaluating the relative insulating value of various coatings and an analysis ofmore » commercial flame-sprayed coatings, low-density coatings, and release coatings. In each case, description of the experimental arrangement is given and the results are described. 5 refs., 28 figs., 6 tabs.« less

Metal Composition and Polyethylenimine Doping Capacity Effects on Semiconducting Metal Oxide-Polymer Blend Charge Transport.

PubMed

Huang, Wei; Guo, Peijun; Zeng, Li; Li, Ran; Wang, Binghao; Wang, Gang; Zhang, Xinan; Chang, Robert P H; Yu, Junsheng; Bedzyk, Michael J; Marks, Tobin J; Facchetti, Antonio

2018-04-25

Charge transport and film microstructure evolution are investigated in a series of polyethylenimine (PEI)-doped (0.0-6.0 wt%) amorphous metal oxide (MO) semiconductor thin film blends. Here, PEI doping generality is broadened from binary In 2 O 3 to ternary (e.g., In+Zn in IZO, In+Ga in IGO) and quaternary (e.g., In+Zn+Ga in IGZO) systems, demonstrating the universality of this approach for polymer electron doping of MO matrices. Systematic comparison of the effects of various metal ions on the electronic transport and film microstructure of these blends are investigated by combined thin-film transistor (TFT) response, AFM, XPS, XRD, X-ray reflectivity, and cross-sectional TEM. Morphological analysis reveals that layered MO film microstructures predominate in PEI-In 2 O 3 , but become less distinct in IGO and are not detectable in IZO and IGZO. TFT charge transport measurements indicate a general coincidence of a peak in carrier mobility (μ peak ) and overall TFT performance at optimal PEI doping concentrations. Optimal PEI loadings that yield μ peak values depend not only on the MO elemental composition but also, equally important, on the metal atomic ratios. By investigating the relationship between the MO energy levels and PEI doping by UPS, it is concluded that the efficiency of PEI electron-donation is highly dependent on the metal oxide matrix work function in cases where film morphology is optimal, as in the IGO compositions. The results of this investigation demonstrate the broad generality and efficacy of PEI electron doping applied to electronically functional metal oxide systems and that the resulting film microstructure, morphology, and energy level modifications are all vital to understanding charge transport in these amorphous oxide blends.

Fine-Tuning of the Carbon Dioxide Capture Capability of Diamine-Grafted Metal-Organic Framework Adsorbents Through Amine Functionalization.

PubMed

Jo, Hyuna; Lee, Woo Ram; Kim, Nam Woo; Jung, Hyun; Lim, Kwang Soo; Kim, Jeong Eun; Kang, Dong Won; Lee, Hanyeong; Hiremath, Vishwanath; Seo, Jeong Gil; Jin, Hailian; Moon, Dohyun; Han, Sang Soo; Hong, Chang Seop

2017-02-08

A combined sonication and microwave irradiation procedure provides the most effective functionalization of ethylenediamine (en) and branched primary diamines of 1-methylethylenediamine (men) and 1,1-dimethylethylenediamine (den) onto the open metal sites of Mg 2 (dobpdc) (1). The CO 2 capacities of the advanced adsorbents 1-en and 1-men under simulated flue gas conditions are 19 wt % and 17.4 wt %, respectively, which are the highest values reported among amine-functionalized metal-organic frameworks (MOFs) to date. Moreover, 1-den exhibits both a significant working capacity (12.2 wt %) and superb CO 2 uptake (11 wt %) at 3 % CO 2 . Additionally, this framework showcases the superior recyclability; ultrahigh stability after exposure to O 2 , moisture, and SO 2 ; and exceptional CO 2 adsorption capacity under humid conditions, which are unprecedented among MOFs. We also elucidate that the performance of CO 2 adsorption can be controlled by the structure of the diamine ligands grafted such as the number of amine end groups or the presence of side groups, which provides the first systematic and comprehensive demonstration of fine-tuning of CO 2 uptake capability using different amines. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diagnostics of Carbon Nanotube Formation in a Laser Produced Plume: An Investigation of the Metal Catalyst by Laser Ablation Atomic Fluorescence Spectroscopy

NASA Technical Reports Server (NTRS)

deBoer, Gary; Scott, Carl

2003-01-01

Carbon nanotubes, elongated molecular tubes with diameters of nanometers and lengths in microns, hold great promise for material science. Hopes for super strong light-weight material to be used in spacecraft design is the driving force behind nanotube work at JSC. The molecular nature of these materials requires the appropriate tools for investigation of their structure, properties, and formation. The mechanism of nanotube formation is of particular interest because it may hold keys to controlling the formation of different types of nanotubes and allow them to be produced in much greater quantities at less cost than is currently available. This summer's work involved the interpretation of data taken last summer and analyzed over the academic year. The work involved diagnostic studies of carbon nanotube formation processes occurring in a laser-produced plume. Laser ablation of metal doped graphite to produce a plasma plume in which carbon nanotubes self assemble is one method of making carbon nanotube. The laser ablation method is amenable to applying the techniques of laser spectroscopy, a powerful tool for probing the energies and dynamics of atomic and molecular species. The experimental work performed last summer involved probing one of the metal catalysts, nickel, by laser induced fluorescence. The nickel atom was studied as a function of oven temperature, probe laser wavelength, time after ablation, and position in the laser produced plume. This data along with previously obtained data on carbon was analyzed over the academic year. Interpretations of the data were developed this summer along with discussions of future work. The temperature of the oven in which the target is ablated greatly influences the amount of material ablated and the propagation of the plume. The ablation conditions and the time scale of atomic and molecular lifetimes suggest that initial ablation of the metal doped carbon target results in atomic and small molecular species. The metal atoms survive for several milliseconds while the gaseous carbon atoms and small molecules nucleate more rapidly. Additional experiments and the development of in situ methods for carbon nanotube detection would allow these results to be interpreted from the perspective of carbon nanotube formation.

MetalS2: a tool for the structural alignment of minimal functional sites in metal-binding proteins and nucleic acids.

PubMed

Andreini, Claudia; Cavallaro, Gabriele; Rosato, Antonio; Valasatava, Yana

2013-11-25

We developed a new software tool, MetalS(2), for the structural alignment of Minimal Functional Sites (MFSs) in metal-binding biological macromolecules. MFSs are 3D templates that describe the local environment around the metal(s) independently of the larger context of the macromolecular structure. Such local environment has a determinant role in tuning the chemical reactivity of the metal, ultimately contributing to the functional properties of the whole system. On our example data sets, MetalS(2) unveiled structural similarities that other programs for protein structure comparison do not consistently point out and overall identified a larger number of structurally similar MFSs. MetalS(2) supports the comparison of MFSs harboring different metals and/or with different nuclearity and is available both as a stand-alone program and a Web tool ( http://metalweb.cerm.unifi.it/tools/metals2/).

The effects of electron and hole transport layer with the electrode work function on perovskite solar cells

NASA Astrophysics Data System (ADS)

Deng, Quanrong; Li, Yiqi; Chen, Lian; Wang, Shenggao; Wang, Geming; Sheng, Yonglong; Shao, Guosheng

2016-09-01

The effects of electron and hole transport layer with the electrode work function on perovskite solar cells with the interface defects were simulated by using analysis of microelectronic and photonic structures-one-dimensional (AMPS-1D) software. The simulation results suggest that TiO2 electron transport layer provides best device performance with conversion efficiency of 25.9% compared with ZnO and CdS. The threshold value of back electrode work function for Spiro-OMeTAD, NiO, CuI and Cu2O hole transport layer are calculated to be 4.9, 4.8, 4.7 and 4.9 eV, respectively, to reach the highest conversion efficiency. The mechanisms of device physics with various electron and hole transport materials are discussed in details. The device performance deteriorates gradually as the increased density of interface defects located at ETM/absorber or absorber/HTM. This research results can provide helpful guidance for materials and metal electrode choice for perovskite solar cells.

Thermionic converter performance with oxide collectors

NASA Technical Reports Server (NTRS)

Lieb, D.; Goodale, D.; Briere, T.; Balestra, C.

1977-01-01

Thermionic converters using a variety of metal oxide collector surfaces have been fabricated and tested. Both work function and power output data are presented and evaluated. Oxides of barium, strontium, zinc, tungsten and titanium have been incorporated into a variable spacing converter. Tungsten oxide was found to give the highest converter performance and to furnish oxygen for the emitter at the same time. Oxygenated emitters operate at reduced cesium pressure with an increase in electrode spacing. Electron spectroscopy for chemical analysis (ESCA) performed on several tungsten oxide collectors showed cesium penetration of the oxide layer, possibly forming a cesium tungstate bronze. Titanium oxide showed high performance but did not furnish oxygen for the emitter; strontium oxide, in the form of a sprayed layer, appeared to dissociate in the presence of cesium. Sprayed coatings of barium and zinc oxides produced collector work functions of about 1.3 eV, but had excessive series resistance. Lanthanum hexaboride, in combination with oxygen introduced through a silver tube, and cesium produced a low work function collector and better than average performance.

Electron Excess Doping and Effective Schottky Barrier Reduction on the MoS2/h-BN Heterostructure.

PubMed

Joo, Min-Kyu; Moon, Byoung Hee; Ji, Hyunjin; Han, Gang Hee; Kim, Hyun; Lee, Gwanmu; Lim, Seong Chu; Suh, Dongseok; Lee, Young Hee

2016-10-12

Layered hexagonal boron nitride (h-BN) thin film is a dielectric that surpasses carrier mobility by reducing charge scattering with silicon oxide in diverse electronics formed with graphene and transition metal dichalcogenides. However, the h-BN effect on electron doping concentration and Schottky barrier is little known. Here, we report that use of h-BN thin film as a substrate for monolayer MoS 2 can induce ∼6.5 × 10 11 cm -2 electron doping at room temperature which was determined using theoretical flat band model and interface trap density. The saturated excess electron concentration of MoS 2 on h-BN was found to be ∼5 × 10 13 cm -2 at high temperature and was significantly reduced at low temperature. Further, the inserted h-BN enables us to reduce the Coulombic charge scattering in MoS 2 /h-BN and lower the effective Schottky barrier height by a factor of 3, which gives rise to four times enhanced the field-effect carrier mobility and an emergence of metal-insulator transition at a much lower charge density of ∼1.0 × 10 12 cm -2 (T = 25 K). The reduced effective Schottky barrier height in MoS 2 /h-BN is attributed to the decreased effective work function of MoS 2 arisen from h-BN induced n-doping and the reduced effective metal work function due to dipole moments originated from fixed charges in SiO 2 .

Morphological effects on the selectivity of intramolecular versus intermolecular catalytic reaction on Au nanoparticles.

PubMed

Wang, Dan; Sun, Yuanmiao; Sun, Yinghui; Huang, Jing; Liang, Zhiqiang; Li, Shuzhou; Jiang, Lin

2017-06-14

It is hard for metal nanoparticle catalysts to control the selectivity of a catalytic reaction in a simple process. In this work, we obtain active Au nanoparticle catalysts with high selectivity for the hydrogenation reaction of aromatic nitro compounds, by simply employing spine-like Au nanoparticles. The density functional theory (DFT) calculations further elucidate that the morphological effect on thermal selectivity control is an internal key parameter to modulate the nitro hydrogenation process on the surface of Au spines. These results show that controlled morphological effects may play an important role in catalysis reactions of noble metal NPs with high selectivity.

A force field for dynamic Cu-BTC metal-organic framework.

PubMed

Zhao, Lei; Yang, Qingyuan; Ma, Qintian; Zhong, Chongli; Mi, Jianguo; Liu, Dahuan

2011-02-01

A new force field that can describe the flexibility of Cu-BTC metal-organic framework (MOF) was developed in this work. Part of the parameters were obtained using density functional theory calculations, and the others were taken from other force fields. The new force field could reproduce well the experimental crystal structure, negative thermal expansion, vibrational properties as well as adsorption behavior in Cu-BTC. In addition, the bulk modulus of Cu-BTC was predicted using the new force field. We believe the new force field is useful in understanding the structure-property relationships for MOFs, and the approach can be extended to other MOFs.

Optical Properties and Plasmonic Performance of Titanium Nitride

PubMed Central

Patsalas, Panos; Kalfagiannis, Nikolaos; Kassavetis, Spyros

2015-01-01

Titanium nitride (TiN) is one of the most well-established engineering materials nowadays. TiN can overcome most of the drawbacks of palsmonic metals due to its high electron conductivity and mobility, high melting point and due to the compatibility of its growth with Complementary Metal Oxide Semiconductor (CMOS) technology. In this work, we review the dielectric function spectra of TiN and we evaluate the plasmonic performance of TiN by calculating (i) the Surface Plasmon Polariton (SPP) dispersion relations and (ii) the Localized Surface Plasmon Resonance (LSPR) band of TiN nanoparticles, and we demonstrate a significant plasmonic performance of TiN.

Comparison of junctionless and inversion-mode p-type metal-oxide-semiconductor field-effect transistors in presence of hole-phonon interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dib, E., E-mail: elias.dib@for.unipi.it; Carrillo-Nuñez, H.; Cavassilas, N.

Junctionless transistors are being considered as one of the alternatives to conventional metal-oxide field-effect transistors. In this work, it is then presented a simulation study of silicon double-gated p-type junctionless transistors compared with its inversion-mode counterpart. The quantum transport problem is solved within the non-equilibrium Green's function formalism, whereas hole-phonon interactions are tackled by means of the self-consistent Born approximation. Our findings show that junctionless transistors should perform as good as a conventional transistor only for ultra-thin channels, with the disadvantage of requiring higher supply voltages in thicker channel configurations.

Laser-induced forward transfer of single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Palla-Papavlu, A.; Dinescu, M.; Wokaun, A.; Lippert, T.

2014-10-01

The objective of this work is the application of laser-induced forward transfer (LIFT) for the fabrication of chemiresistor sensors. The receiver substrate is an array with metal electrodes and the active materials placed by LIFT are single-walled carbon nanotubes (SWCNT). The functionality of such sensors depends on the geometry of the active material onto the metallic electrodes. First the best geometry for the sensing materials and electrodes was determined, including the optimization of the process parameters for printing uniform pixels of SWCNT onto the sensor electrodes. The sensors were characterized in terms of their sensing characteristics, i.e., upon exposure to ammonia, proving the feasibility of LIFT.

Single-step generation of metal-plasma polymer multicore@shell nanoparticles from the gas phase.

PubMed

Solař, Pavel; Polonskyi, Oleksandr; Olbricht, Ansgar; Hinz, Alexander; Shelemin, Artem; Kylián, Ondřej; Choukourov, Andrei; Faupel, Franz; Biederman, Hynek

2017-08-17

Nanoparticles composed of multiple silver cores and a plasma polymer shell (multicore@shell) were prepared in a single step with a gas aggregation cluster source operating with Ar/hexamethyldisiloxane mixtures and optionally oxygen. The size distribution of the metal inclusions as well as the chemical composition and the thickness of the shells were found to be controlled by the composition of the working gas mixture. Shell matrices ranging from organosilicon plasma polymer to nearly stoichiometric SiO 2 were obtained. The method allows facile fabrication of multicore@shell nanoparticles with tailored functional properties, as demonstrated here with the optical response.

[Novel Hyphenated Techniques of Atomic Spectrometry for Metal Species Interaction with Biomolecules].

PubMed

Li, Yan; Yan, Xiu-ping

2015-09-01

Trace metals may be adopted by biological systems to assist in the syntheses and metabolic functions of genes (DNA and RNA) and proteins in the environment. These metals may be beneficial or may pose a risk to humans and other life forms. Novel hybrid techniques are required for studies on the interaction between different metal species and biomolecules, which is significant for biology, biochemistry, nutrition, agriculture, medicine, pharmacy, and environmental science. In recent years, our group dwells on new hyphenated techniques based on capillary electrophoresis (CE), electrothermal atomic absorption spectrometry (ETAAS), and inductively coupled plasma mass spectroscopy (ICP-MS), and their application for different metal species interaction with biomolecules such as DNA, HSA, and GSH. The CE-ETAAS assay and CE-ICP-MS assay allow sensitively probing the level of biomolecules such as DNA damage by different metal species and extracting the kinetic and thermodynamic information on the interactions of different metal species with biomolecules, provides direct evidences for the formation of different metal species--biomolecule adducts. In addition, the consequent structural information were extracted from circular dichroism (CD) and X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The present works represent the most complete and extensive study to date on the interactions between different metal species with biomolecules, and also provide new evidences for and insights into the interactions of different metal species with biomolecules for further understanding of the toxicological effects of metal species.

Improvement of gas-adsorption performances of Ag-functionalized monolayer MoS2 surfaces: A first-principles study

NASA Astrophysics Data System (ADS)

Song, Jian; Lou, Huan

2018-05-01

Investigations of the adsorptions of representative gases (NO2, NH3, H2S, SO2, CO, and HCHO) on different Ag-functionalized monolayer MoS2 surfaces were performed by first principles methods. The adsorption configurations, adsorption energies, electronic structure properties, and charge transfer were calculated, and the results show that the adsorption activities to gases of monolayer MoS2 are dramatically enhanced by the Ag-modification. The Ag-modified perfect MoS2 (Ag-P) and MoS2 with S-vacancy (Ag-Vs) substrates exhibit a more superior adsorption activity to NO2 than other gases, which is consistent with the experimental reports. The charge transfer processes of different molecules adsorbed on different surfaces exhibit various characteristics, with potential benefits to gas selectivity. For instance, the NO2 and SO2 obtain more electrons from both Ag-P and Ag-Vs substrates but the NH3 and H2S donate more electrons to materials than others. In addition, the CO and HCHO possess totally opposite charge transfer directs on both substrates, respectively. The BS and PDOS calculations show that semiconductor types of gas/Ag-MoS2 systems are more determined by the metal-functionalization of material, and the directs and numbers of charge transfer process between gases and adsorbents can cause the increase or decline of material resistance theoretically, which is helpful to gas detection and distinction. The further analysis indicates suitable co-operation between the gain-lost electron ability of gas and metallicity of featuring metal might adjust the resistivity of complex and contribute to new thought for metal-functionalization. Our works provide new valuable ideas and theoretical foundation for the potential improvement of MoS2-based gas sensor performances, such as sensitivity and selectivity.

Exploring simulated early star formation in the context of the ultrafaint dwarf galaxies

NASA Astrophysics Data System (ADS)

Corlies, Lauren; Johnston, Kathryn V.; Wise, John H.

2018-04-01

Ultrafaint dwarf galaxies (UFDs) are typically assumed to have simple, stellar populations with star formation ending at reionization. Yet as the observations of these galaxies continue to improve, their star formation histories (SFHs) are revealed to be more complicated than previously thought. In this paper, we study how star formation, chemical enrichment, and mixing proceed in small, dark matter haloes at early times using a high-resolution, cosmological, hydrodynamical simulation. The goals are to inform the future use of analytic models and to explore observable properties of the simulated haloes in the context of UFD data. Specifically, we look at analytic approaches that might inform metal enrichment within and beyond small galaxies in the early Universe. We find that simple assumptions for modelling the extent of supernova-driven winds agree with the simulation on average, whereas inhomogeneous mixing and gas flows have a large effect on the spread in simulated stellar metallicities. In the context of the UFDs, this work demonstrates that simulations can form haloes with a complex SFH and a large spread in the metallicity distribution function within a few hundred Myr in the early Universe. In particular, bursty and continuous star formation are seen in the simulation and both scenarios have been argued from the data. Spreads in the simulated metallicities, however, remain too narrow and too metal-rich when compared to the UFDs. Future work is needed to help reduce these discrepancies and advance our interpretation of the data.

Polyenergetic known-component CT reconstruction with unknown material compositions and unknown x-ray spectra

NASA Astrophysics Data System (ADS)

Xu, S.; Uneri, A.; Khanna, A. Jay; Siewerdsen, J. H.; Stayman, J. W.

2017-04-01

Metal artifacts can cause substantial image quality issues in computed tomography. This is particularly true in interventional imaging where surgical tools or metal implants are in the field-of-view. Moreover, the region-of-interest is often near such devices which is exactly where image quality degradations are largest. Previous work on known-component reconstruction (KCR) has shown the incorporation of a physical model (e.g. shape, material composition, etc) of the metal component into the reconstruction algorithm can significantly reduce artifacts even near the edge of a metal component. However, for such approaches to be effective, they must have an accurate model of the component that include energy-dependent properties of both the metal device and the CT scanner, placing a burden on system characterization and component material knowledge. In this work, we propose a modified KCR approach that adopts a mixed forward model with a polyenergetic model for the component and a monoenergetic model for the background anatomy. This new approach called Poly-KCR jointly estimates a spectral transfer function associated with known components in addition to the background attenuation values. Thus, this approach eliminates both the need to know component material composition a prior as well as the requirement for an energy-dependent characterization of the CT scanner. We demonstrate the efficacy of this novel approach and illustrate its improved performance over traditional and model-based iterative reconstruction methods in both simulation studies and in physical data including an implanted cadaver sample.

MetalS(3), a database-mining tool for the identification of structurally similar metal sites.

PubMed

Valasatava, Yana; Rosato, Antonio; Cavallaro, Gabriele; Andreini, Claudia

2014-08-01

We have developed a database search tool to identify metal sites having structural similarity to a query metal site structure within the MetalPDB database of minimal functional sites (MFSs) contained in metal-binding biological macromolecules. MFSs describe the local environment around the metal(s) independently of the larger context of the macromolecular structure. Such a local environment has a determinant role in tuning the chemical reactivity of the metal, ultimately contributing to the functional properties of the whole system. The database search tool, which we called MetalS(3) (Metal Sites Similarity Search), can be accessed through a Web interface at http://metalweb.cerm.unifi.it/tools/metals3/ . MetalS(3) uses a suitably adapted version of an algorithm that we previously developed to systematically compare the structure of the query metal site with each MFS in MetalPDB. For each MFS, the best superposition is kept. All these superpositions are then ranked according to the MetalS(3) scoring function and are presented to the user in tabular form. The user can interact with the output Web page to visualize the structural alignment or the sequence alignment derived from it. Options to filter the results are available. Test calculations show that the MetalS(3) output correlates well with expectations from protein homology considerations. Furthermore, we describe some usage scenarios that highlight the usefulness of MetalS(3) to obtain mechanistic and functional hints regardless of homology.

Evaluating the use of electronegativity in band alignment models through the experimental slope parameter of lanthanum aluminate heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Z. Q.; Chim, W. K.; Chiam, S. Y

2011-11-01

In this work, photoelectron spectroscopy is used to characterize the band alignment of lanthanum aluminate heterostructures which possess a wide range of potential applications. It is found that our experimental slope parameter agrees with theory using the metal-induced gap states model while the interface induced gap states (IFIGS) model yields unsatisfactory results. We show that this discrepancy can be attributed to the correlation between the dielectric work function and the electronegativity in the IFIGS model. It is found that the original trend, as established largely by metals, may not be accurate for larger band gap materials. By using a newmore » correlation, our experimental data shows good agreement of the slope parameter using the IFIGS model. This correlation, therefore, plays a crucial role in heterostructures involving wider bandgap materials for accurate band alignment prediction using the IFIGS model.« less

Postsynthetic Tuning of Metal-Organic Frameworks for Targeted Applications.

PubMed

Islamoglu, Timur; Goswami, Subhadip; Li, Zhanyong; Howarth, Ashlee J; Farha, Omar K; Hupp, Joseph T

2017-04-18

Metal-organic frameworks (MOFs) are periodic, hybrid, atomically well-defined porous materials that typically form by self-assembly and consist of inorganic nodes (metal ions or clusters) and multitopic organic linkers. MOFs as a whole offer many intriguing properties, including ultrahigh porosity, tunable chemical functionality, and low density. These properties point to numerous potential applications, including gas storage, chemical separations, catalysis, light harvesting, and chemical sensing, to name a few. Reticular chemistry, or the linking of molecular building blocks into predetermined network structures, has been employed to synthesize thousands of MOFs. Given the vast library of candidate nodes and linkers, the number of potentially synthetically accessible MOFs is enormous. Nevertheless, a powerful complementary approach to obtain specific structures with desired chemical functionality is to modify known MOFs after synthesis. This approach is particularly useful when incorporation of particular chemical functionalities via direct synthesis is challenging or impossible. The challenges may stem from limited stability or solubility of precursors, unwanted secondary reactivity of precursors, or incompatibility of functional groups with the conditions needed for direct synthesis. MOFs can be postsynthetically modified by replacing the metal nodes and/or organic linkers or via functionalization of the metal nodes and/or organic linkers. Here we describe some of our efforts toward the development and application of postsynthetic strategies for imparting desired chemical functionalities in MOFs of known topology. The techniques include methods for functionalizing MOF nodes, i.e., solvent-assisted ligand incorporation (SALI) and atomic layer deposition in MOFs (AIM) as well as a method to replace structural linkers, termed solvent-assisted linker exchange (SALE), also known as postsynthethic exchange (PSE). For each functionalization strategy, we first describe its chemical basis along with the requirements for its successful implementation. We then present a small number of examples, with an emphasis on those that (a) convey the underlying concepts and/or (b) lead to functional structures (e.g., catalysts) that would be difficult or impossible to access via direct routes. The examples, however, are only illustrative, and a significant body of work exists from both our lab and others, especially for the SALE/PSE strategy. We refer readers to the papers cited and to the references therein. More exciting, in our view, will be new examples and new applications of the functionalization strategies-especially applications made possible by creatively combining the strategies. Underexplored (again, in our view) are implementations that impart electrical conductivity, enable increasingly selective chemical sensing, or facilitate cascade catalysis. It will be interesting to see where these strategies and others take this compelling field over the next few years.

Self-templated formation of uniform NiCo2O4 hollow spheres with complex interior structures for lithium-ion batteries and supercapacitors.

PubMed

Shen, Laifa; Yu, Le; Yu, Xin-Yao; Zhang, Xiaogang; Lou, Xiong Wen David

2015-02-02

Despite the significant advancement in preparing metal oxide hollow structures, most approaches rely on template-based multistep procedures for tailoring the interior structure. In this work, we develop a new generally applicable strategy toward the synthesis of mixed-metal-oxide complex hollow spheres. Starting with metal glycerate solid spheres, we show that subsequent thermal annealing in air leads to the formation of complex hollow spheres of the resulting metal oxide. We demonstrate the concept by synthesizing highly uniform NiCo2O4 hollow spheres with a complex interior structure. With the small primary building nanoparticles, high structural integrity, complex interior architectures, and enlarged surface area, these unique NiCo2O4 hollow spheres exhibit superior electrochemical performances as advanced electrode materials for both lithium-ion batteries and supercapacitors. This approach can be an efficient self-templated strategy for the preparation of mixed-metal-oxide hollow spheres with complex interior structures and functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical model of gravitational perturbation of current collector axisymmetric flow field

NASA Astrophysics Data System (ADS)

Walker, John S.; Brown, Samuel H.; Sondergaard, Neal A.

1989-03-01

Some designs of liquid metal collectors in homopolar motors and generators are essentially rotating liquid metal fluids in cylindrical channels with free surfaces and will, at critical rotational speeds, become unstable. The role of gravity in modifying this ejection instability is investigated. Some gravitational effects can be theoretically treated by perturbation techniques on the axisymmetric base flow of the liquid metal. This leads to a modification of previously calculated critical current collector ejection values neglecting gravity effects. The derivation of the mathematical model which determines the perturbation of the liquid metal base flow due to gravitational effects is documented. Since gravity is a small force compared with the centrifugal effects, the base flow solutions can be expanded in inverse powers of the Froude number and modified liquid flow profiles can be determined as a function of the azimuthal angle. This model will be used in later work to theoretically study the effects of gravity on the ejection point of the current collector. A rederivation of the hydrodynamic instability threshold of a liquid metal current collector is presented.

Multi-level Capacitive Memory Effect in Metal/Oxide/Floating-Schottky Junction

NASA Astrophysics Data System (ADS)

Choi, Gahyun; Jung, Sungchul; Yoon, Hoon Hahn; Jeon, Youngeun; Park*, Kibog

2015-03-01

A memory computing (memcomputing) system can store and process information at the same physical location simultaneously. The essential components of memcomputing are passive devices with memory functionality, such as memristor, memcapacitor, and meminductor. We report the realization of a Schottky contact memcapacitor compatible with the current Si CMOS technology. Our memcapacitor is formed by depositing a stack of metal and oxide thin films on top of a Schottky contact. Here, the metal electrode of the Schottky contact is floating. The working principle of our memcapacitor is based on the fact that the depletion width of the Schottky contact varies according to the amount of charge stored in the floating metal electrode. The voltage pulse applied across the Metal/Oxide/Floating-Schottky junction controls charge flow in the Schottky contact and determines the amount of charge stored eventually. It is demonstrated experimentally that our memcapacitor exhibits hysteresis behaviors in capacitance-voltage curves and possesses multiple capacitance values that are switchable by the applied voltage pulse. Supported by NRF in South Korea (2013R1A1A2007070).

Metal ion reactive thin films using spray electrostatic LbL assembly.

PubMed

Krogman, Kevin C; Lyon, Katharine F; Hammond, Paula T

2008-11-20

By using the spray-layer-by-layer (Spray-LbL) technique, the number of metal counterions trapped within LbL coatings is significantly increased by kinetically freezing the film short of equilibrium, potentially limiting interchain penetration and forcing chains to remain extrinsically compensated to a much greater degree than observed in the traditional dipped LbL technique. The basis for the enhanced entrapment of metal ions such as Cu2+, Fe2+, and Ag+ is addressed, including the equilibrium driving force for extrinsic compensation by soft versus hard metal ions and the impact of Spray-LbL on the kinetics of polymer-ion complexation. These polymer-bound metal-ion coatings are also demonstrated to be effective treatments for air filtration, functionalizing existing filters with the ability to strongly bind toxic industrial compounds such as ammonia or cyanide gases, as well as chemical warfare agent simulants such as chloroethyl ethyl sulfide. On the basis of results reported here, future work could extend this method to include other toxic soft-base ligands such as carbon monoxide, benzene, or organophosphate nerve agents.

Coupled modeling of the competitive gettering of transition metals and impact on performance of lifetime sensitive devices

NASA Astrophysics Data System (ADS)

Yazdani, Armin; Chen, Renyu; Dunham, Scott T.

2017-03-01

This work models competitive gettering of metals (Cu, Ni, Fe, Mo, and W) by boron, phosphorus, and dislocation loops, and connects those results directly to device performance. Density functional theory calculations were first performed to determine the binding energies of metals to the gettering sites, and based on that, continuum models were developed to model the redistribution and trapping of the metals. Our models found that Fe is most strongly trapped by the dislocation loops while Cu and Ni are most strongly trapped by the P4V clusters formed in high phosphorus concentrations. In addition, it is found that none of the mentioned gettering sites are effective in gettering Mo and W. The calculated metal redistribution along with the associated capture cross sections and trap energy levels are passed to device simulation via the recombination models to calculate carrier lifetime and the resulting device performance. Thereby, a comprehensive and predictive TCAD framework is developed to optimize the processing conditions to maximize performance of lifetime sensitive devices.

Kinetics of Spontaneous Bimetallization between Silver and Noble Metal Nanoparticles.

PubMed

Hirakawa, Kazutaka; Kaneko, Tetsuya; Toshima, Naoki

2018-06-05

A physical mixture of polymer-protected Ag nanoparticles and Rh, Pd, or Pt nanoparticles spontaneously forms Ag-core bimetallic nanoparticles. The formed nanoparticles were smaller than the parent Ag nanoparticles. In the initial process of this reaction, the surface plasmon absorption of Ag nanoparticles diminished and then almost ceased within one hour. Within several minutes, the decrease in Ag surface plasmon absorption could be analyzed by second-order reaction. This reaction was accelerated with an increase of temperature and the energy gap in the Fermi level between Ag and the other metals. The activation energy (E a ) of this reaction could be determined. An electron transfer reaction from Ag to other metal nanoparticles was proposed as the initial interaction between these metal nanoparticles because the Fermi level of Ag is relatively high, and the electron transfer is possible in terms of energy. The Marcus plot between the rate constant and the driving force, roughly estimated from the work function of metals, and the observed E a values reasonably explained the proposed electron transfer mechanism. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hot-electron-based solar energy conversion with metal-semiconductor nanodiodes.

PubMed

Lee, Young Keun; Lee, Hyosun; Lee, Changhwan; Hwang, Euyheon; Park, Jeong Young

2016-06-29

Energy dissipation at metal surfaces or interfaces between a metal and a dielectric generally results from elementary excitations, including phonons and electronic excitation, once external energy is deposited to the surface/interface during exothermic chemical processes or an electromagnetic wave incident. In this paper, we outline recent research activities to develop energy conversion devices based on hot electrons. We found that photon energy can be directly converted to hot electrons and that hot electrons flow through the interface of metal-semiconductor nanodiodes where a Schottky barrier is formed and the energy barrier is much lower than the work function of the metal. The detection of hot electron flow can be successfully measured using the photocurrent; we measured the photoyield of photoemission with incident photons-to-current conversion efficiency (IPCE). We also show that surface plasmons (i.e. the collective oscillation of conduction band electrons induced by interaction with an electromagnetic field) are excited on a rough metal surface and subsequently decay into secondary electrons, which gives rise to enhancement of the IPCE. Furthermore, the unique optical behavior of surface plasmons can be coupled with dye molecules, suggesting the possibility for producing additional channels for hot electron generation.

The Photoelectric Effect: Experimental Confirmation Concerning a Widespread Misconception in the Theory

ERIC Educational Resources Information Center

Wong, Darren; Lee, Paul; Shenghan, Gao; Xuezhou, Wang; Qi, Huan Yan; Kit, Foong See

2011-01-01

The photoelectric effect is widely taught in schools and institutions. It is common knowledge that in order for photoelectrons to be emitted, the energy of the incoming photons must be greater than the work function of the irradiated metal (i.e. hv greater than [phi][subscript emitter]). However, what may not be as commonly known is that the…

Single-site labeling of lysine in proteins through a metal-free multicomponent approach.

PubMed

Chilamari, Maheshwerreddy; Kalra, Neetu; Shukla, Sanjeev; Rai, Vishal

2018-06-15

We report a chemoselective and site-selective approach that distinguishes one Lys from its multiple copies, N-terminus, and other competitors. The phospha-Mannich protocol works with multiple proteins and installs probes without structural and functional perturbations. It delivers an antibody-drug conjugate with selective anti-proliferative activity towards HER2 expressing SKBR3 breast cancer cells.

One-pot synthesis of multifunctional nanoscale metal-organic frameworks as an effective antibacterial agent against multidrug-resistant Staphylococcus aureus

NASA Astrophysics Data System (ADS)

Chowdhuri, Angshuman Ray; Das, Balaram; Kumar, Amit; Tripathy, Satyajit; Roy, Somenath; Sahu, Sumanta Kumar

2017-03-01

Drug-resistant bacteria are an increasingly serious threat to global public health. In particular, infections from multidrug-resistant (MDR) Gram-positive bacteria (i.e. Staphylococcus aureus) are growing global health concerns. In this work, we report the first use of nanoscale metal-organic frameworks (NMOFs) coencapsulating an antibiotic (vancomycin) and targeting ligand (folic acid) in one pot to enhance therapeutic efficacy against MDR S. aureus. Zeolitic imidazolate framework (ZIF-8) NMOFs, which have globular morphologies coencapsulating vancomycin and folic acid, are characterized by transmission electron microscopy, field-emission scanning electron microscopy, powder x-ray diffraction, ulltraviolet-visible spectroscopy, and dynamic light-scattering techniques. We determined that the presence of folic acid on the surface of the NMOFs is significant in the sense of effective uptake by MDR S. aureus through endocytosis. The functionalized NMOFs transport vancomycin across the cell wall of MDR S. aureus and enhance antibacterial activity, which has been confirmed from studies of the minimum inhibitory concentration, minimum bactericidal concentration, cytotoxicity of bacterial cells, and generation of reactive oxygen species. This work shows that functionalized NMOFs hold great promise for effective treatment of MDR S. aureus.

The Determination of Metals in Welding Fume by X-RaySpectrometry

NASA Astrophysics Data System (ADS)

Kuznetsova, O. V.; Begunova, L. A.; Romanenko, S. V.; Solodsky, S. A.

2018-01-01

Analysis of the current hygienic situation in the welding production showed that the intensification of welding processes involves the deterioration of air quality, which negatively affects the welders health. Respiratory effects seen in full-time welders have included bronchitis, airway irritation, lung function changes, and a possible increase in the incidence of lung cancer. The metal concentration in the air of the working area have been determined using the photometric method of analysis, which involves the stage of decomposition of the sample material before analysis. However, losses of the analyzed elements are possible when the sample is decomposed. The X-ray fluorescence method of analysis has the advantage of being nondestructive. The investigations shown the data of photometric determination of metals in welding aerosols is 1.5÷2 times lower than the results of X-ray fluorescence analysis.

Metal-cluster ionization energy: A profile-insensitive exact expression for the size effect

NASA Astrophysics Data System (ADS)

Seidl, Michael; Perdew, John P.; Brajczewska, Marta; Fiolhais, Carlos

1997-05-01

The ionization energy of a large spherical metal cluster of radius R is I(R)=W+(+c)/R, where W is the bulk work function and c~-0.1 is a material-dependent quantum correction to the electrostatic size effect. We present 'Koopmans' and 'displaced-profile change-in-self-consistent-field' expressions for W and c within the ordinary and stabilized-jellium models. These expressions are shown to be exact and equivalent when the exact density profile of a large neutral cluster is employed; these equivalences generalize the Budd-Vannimenus theorem. With an approximate profile obtained from a restricted variational calculation, the 'displaced-profile' expressions are the more accurate ones. This profile insensitivity is important, because it is not practical to extract c from solutions of the Kohn-Sham equations for small metal clusters.

A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal$-$Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Jacob A.; Petersen, Brenna M.; Kormos, Attila

Here, we describe a new strategy to generate non-coordinating anions using zwitterionic metal–organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO 2) 4] $-$) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of Mn III- and Fe III-porphyrins in the zwitterionic MOFs in three representative electrocyclization reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition of aziridines and alkenes, and [4 + 2] hetero-Diels–Alder cycloaddition of aldehydesmore » with dienes. Lastly, this work paves a new way to design functional MOFs for tunable chemical catalysis.« less

Imposed Environmental Stresses Facilitate Cell-Free Nanoparticle Formation by Deinococcus radiodurans

PubMed Central

2017-01-01

ABSTRACT The biological synthesis of metal nanoparticles has been examined in a wide range of organisms, due to increased interest in green synthesis and environmental remediation applications involving heavy metal ion contamination. Deinococcus radiodurans is particularly attractive for environmental remediation involving metal reduction, due to its high levels of resistance to radiation and other environmental stresses. However, few studies have thoroughly examined the relationships between environmental stresses and the resulting effects on nanoparticle biosynthesis. In this work, we demonstrate cell-free nanoparticle production and study the effects of metal stressor concentrations and identity, temperature, pH, and oxygenation on the production of extracellular silver nanoparticles by D. radiodurans R1. We also report the synthesis of bimetallic silver and gold nanoparticles following the addition of a metal stressor (silver or gold), highlighting how production of these particles is enabled through the application of environmental stresses. Additionally, we found that both the morphology and size of monometallic and bimetallic nanoparticles were dependent on the environmental stresses imposed on the cells. The nanoparticles produced by D. radiodurans exhibited antimicrobial activity comparable to that of pure silver nanoparticles and displayed catalytic activity comparable to that of pure gold nanoparticles. Overall, we demonstrate that biosynthesized nanoparticle properties can be partially controlled through the tuning of applied environmental stresses, and we provide insight into how their application may affect nanoparticle production in D. radiodurans during bioremediation. IMPORTANCE Biosynthetic production of nanoparticles has recently gained prominence as a solution to rising concerns regarding increased bacterial resistance to antibiotics and a desire for environmentally friendly methods of bioremediation and chemical synthesis. To date, a range of organisms have been utilized for nanoparticle formation. The extremophile D. radiodurans, which can withstand significant environmental stresses and therefore is more robust for metal reduction applications, has yet to be exploited for this purpose. Thus, this work improves our understanding of the impact of environmental stresses on biogenic nanoparticle morphology and composition during metal reduction processes in this organism. This work also contributes to enhancing the controlled synthesis of nanoparticles with specific attributes and functions using biological systems. PMID:28687649

Imposed Environmental Stresses Facilitate Cell-Free Nanoparticle Formation by Deinococcus radiodurans.

PubMed

Chen, Angela; Contreras, Lydia M; Keitz, Benjamin K

2017-09-15

The biological synthesis of metal nanoparticles has been examined in a wide range of organisms, due to increased interest in green synthesis and environmental remediation applications involving heavy metal ion contamination. Deinococcus radiodurans is particularly attractive for environmental remediation involving metal reduction, due to its high levels of resistance to radiation and other environmental stresses. However, few studies have thoroughly examined the relationships between environmental stresses and the resulting effects on nanoparticle biosynthesis. In this work, we demonstrate cell-free nanoparticle production and study the effects of metal stressor concentrations and identity, temperature, pH, and oxygenation on the production of extracellular silver nanoparticles by D. radiodurans R1. We also report the synthesis of bimetallic silver and gold nanoparticles following the addition of a metal stressor (silver or gold), highlighting how production of these particles is enabled through the application of environmental stresses. Additionally, we found that both the morphology and size of monometallic and bimetallic nanoparticles were dependent on the environmental stresses imposed on the cells. The nanoparticles produced by D. radiodurans exhibited antimicrobial activity comparable to that of pure silver nanoparticles and displayed catalytic activity comparable to that of pure gold nanoparticles. Overall, we demonstrate that biosynthesized nanoparticle properties can be partially controlled through the tuning of applied environmental stresses, and we provide insight into how their application may affect nanoparticle production in D. radiodurans during bioremediation. IMPORTANCE Biosynthetic production of nanoparticles has recently gained prominence as a solution to rising concerns regarding increased bacterial resistance to antibiotics and a desire for environmentally friendly methods of bioremediation and chemical synthesis. To date, a range of organisms have been utilized for nanoparticle formation. The extremophile D. radiodurans , which can withstand significant environmental stresses and therefore is more robust for metal reduction applications, has yet to be exploited for this purpose. Thus, this work improves our understanding of the impact of environmental stresses on biogenic nanoparticle morphology and composition during metal reduction processes in this organism. This work also contributes to enhancing the controlled synthesis of nanoparticles with specific attributes and functions using biological systems. Copyright © 2017 American Society for Microbiology.

Decreased Charge Transport Barrier and Recombination of Organic Solar Cells by Constructing Interfacial Nanojunction with Annealing-Free ZnO and Al Layers.

PubMed

Liu, Chunyu; Zhang, Dezhong; Li, Zhiqi; Zhang, Xinyuan; Guo, Wenbin; Zhang, Liu; Ruan, Shengping; Long, Yongbing

2017-07-05

To overcome drawbacks of the electron transport layer, such as complex surface defects and unmatched energy levels, we successfully employed a smart semiconductor-metal interfacial nanojunciton in organic solar cells by evaporating an ultrathin Al interlayer onto annealing-free ZnO electron transport layer, resulting in a high fill factor of 73.68% and power conversion efficiency of 9.81%. The construction of ZnO-Al nanojunction could effectively fill the surface defects of ZnO and reduce its work function because of the electron transfer from Al to ZnO by Fermi level equilibrium. The filling of surface defects decreased the interfacial carrier recombination in midgap trap states. The reduced surface work function of ZnO-Al remodulated the interfacial characteristics between ZnO and [6,6]-phenyl C71-butyric acid methyl ester (PC 71 BM), decreasing or even eliminating the interfacial barrier against the electron transport, which is beneficial to improve the electron extraction capacity. The filled surface defects and reduced interfacial barrier were realistically observed by photoluminescence measurements of ZnO film and the performance of electron injection devices, respectively. This work provides a simple and effective method to simultaneously solve the problems of surface defects and unmatched energy level for the annealing-free ZnO or other metal oxide semiconductors, paving a way for the future popularization in photovoltaic devices.

Ta-Pt Alloys as Gate Materials for Metal-Oxide-Semiconductor Field Effect Transistor Application

NASA Astrophysics Data System (ADS)

Huang, Chih-Feng; Tsui, Bing-Yue

2009-03-01

In this work we explore the thermal stability of sputter-deposited Ta-rich Ta-Pt alloys. The effects of group III and V impurities on their work function are also investigated. The Ta content ranges from 65 to 82 at. %. The main phase is σ Ta-Pt. The binding energies of core-level electrons of Ta and Pt are changed due to the intermixing of Ta and Pt, which is evidence that the work function of alloys is changed in metallic alloy systems. Binding energies are thermally stable up to 800 °C. Moreover, the incorporation of Pt in Ta film induces poor crystallization and a compound phase of Ta-Pt alloys. Transmission electron microscopy analysis confirmed the absence of a clear grain boundary in Ta-Pt alloys. The Ta and Pt depth profile shows uniformity in depth after 800 °C annealing for 30 min. The diffusion and distribution of impurities in the alloys were studied by secondary ion mass spectroscopy. Arsenic cannot diffuse in the alloys following annealing at 800 °C for 30 s. In contrast, boron can easily diffuse at 800 °C. The incorporation of impurities with a dosage of 5 ×1015 cm-2 in 60 nm Ta-Pt alloy by implantation did not significantly change the flat-band voltage following annealing at 800 °C.

Investigation of Lithium Metal Hydride Materials for Mitigation of Deep Space Radiation

NASA Technical Reports Server (NTRS)

Rojdev, Kristina; Atwell, William

2016-01-01

Radiation exposure to crew, electronics, and non-metallic materials is one of many concerns with long-term, deep space travel. Mitigating this exposure is approached via a multi-faceted methodology focusing on multi-functional materials, vehicle configuration, and operational or mission constraints. In this set of research, we are focusing on new multi-functional materials that may have advantages over traditional shielding materials, such as polyethylene. Metal hydride materials are of particular interest for deep space radiation shielding due to their ability to store hydrogen, a low-Z material known to be an excellent radiation mitigator and a potential fuel source. We have previously investigated 41 different metal hydrides for their radiation mitigation potential. Of these metal hydrides, we found a set of lithium hydrides to be of particular interest due to their excellent shielding of galactic cosmic radiation. Given these results, we will continue our investigation of lithium hydrides by expanding our data set to include dose equivalent and to further understand why these materials outperformed polyethylene in a heavy ion environment. For this study, we used HZETRN 2010, a one-dimensional transport code developed by NASA Langley Research Center, to simulate radiation transport through the lithium hydrides. We focused on the 1977 solar minimum Galactic Cosmic Radiation environment and thicknesses of 1, 5, 10, 20, 30, 50, and 100 g/cm2 to stay consistent with our previous studies. The details of this work and the subsequent results will be discussed in this paper.

Metal membrane with dimer slots as a universal polarizer

NASA Astrophysics Data System (ADS)

Zhukovsky, Sergej; Zalkovskij, Maksim; Malureanu, Radu; Kremers, Christian; Chigrin, Dmitry; Tang, Peter T.; Jepsen, Peter U.; Lavrinenko, Andrei V.

2014-03-01

In this work, we show theoretically and confirm experimentally that thin metal membranes patterned with an array of slot dimers (or their Babinet analogue with metal rods) can function as a versatile spectral and polarization filter. We present a detailed covariant multipole theory for the electromagnetic response of an arbitrary dimer based on the Green functions approach. The theory confirms that a great variety of polarization properties, such as birefringence, chirality and elliptical dichroism, can be achieved in a metal layer with such slot-dimer patterning (i.e. in a metasurface). Optical properties of the metasurface can be extensively tuned by varying the geometry (shape and dimensions) of the dimer, for example, by adjusting the sizes and mutual placement of the slots (e.g. inter-slot distance and alignment angle). Three basic shapes of dimers are analyzed: II-shaped (parallel slots), V-shaped, and T-shaped. These particular shapes of dimers are found to be sensitive to variations of the slots lengths and orientation of elements. Theoretical results are well supported by full-wave three-dimensional simulations. Our findings were verified experimentally on the metal membranes fabricated using UV lithography with subsequent Ni growth. Such metasurfaces were characterized using time-domain THz spectroscopy. The samples exhibit pronounced optical activity (500 degrees per wavelength) and high transmission: even though the slots cover only 4.3 % of the total membrane area the amplitude transmission reaches 0.67 at the resonance frequency 0.56 THz.

Synthesis, characterization and computational chemical study of novel pyrazole derivatives as anticorrosion and antiscalant agents

NASA Astrophysics Data System (ADS)

El-Taib Heakal, F.; Attia, S. K.; Rizk, S. A.; Abou Essa, M. A.; Elkholy, A. E.

2017-11-01

Metals corrosion and scales deposition are two serious problems of heavy burden in most industries. Both problems can be mitigated by adding special chemicals capable of being adsorbed on metallic surfaces as well as on scale growing crystal surfaces. Efficient materials should be rich in functional groups containing heteroatoms and/or π bonds for supporting their adsorbability on surfaces. In the present work, four novel pyrazole derivatives were synthesized and characterized for their structures using elemental analysis and spectroscopic tools. The tested compounds were fabricated by treating 2,3-diaryloxirane-2,3-dicarbonitriles with different nitrogen nucleophiles. The density functional theory (DFT) was then applied to explore the structural and electronic characteristics of these materials. Molecular dynamics simulation was also run to scrutinize the ability of the prepared compounds to act as corrosion inhibitors and antiscalant agents by adsorbing on Fe and CaSO4 surfaces.

Theoretical investigations of the optical spectra and g-shift in CsVX 3 ( X=Cl, Br, I)

NASA Astrophysics Data System (ADS)

Lei, Y.; He, W. S.; Zu, X. T.; Zhao, M. G.

2007-04-01

The paper presents a molecular orbital calculation of the optical spectra and g shift in CsVX 3 ( X=Cl, Br, I), in which the contribution due to the electrostatic parameter A0, the Trees correction, the spin-orbit coupling of the central transition metal ion and the ligand are included. In the present calculations, instead of the 10 parameters in the previous works, there are three fitting parameters because the appropriate double- ζ function of V is used. The calculated optical spectra and g shift agree well with the available experimental data. This indicates again that the double- ζ wave functions are the appropriate approximation in the calculation of the electronic structure properties. The results show that the contribution due to the 3s of the ligand and the conjunct action between the center metal ion and the ligand cannot been neglected.

Mechanical Properties of a vdW molecular monolayer at a metal surface: Structural Polymorphism leading to facile compression

NASA Astrophysics Data System (ADS)

Sun, Dezheng; Kim, Daeho; Le, Duy; Borck, Øyvind; Berland, Kristian; Kim, Kwangmoo; Lu, Wenhao; Zhu, Yeming; Luo, Miaomiao; Wyrick, Jon; Cheng, Zhihai; Einstein, T. L.; Rahman, Talat; Hyldgaard, Per; Bartels, Ludwig

2011-03-01

Intermolecular force plays an important role in self-assembly and surface pattern formation. Anthracene and similar unsubstituted arenes attach to a metallic substrate predominantly through van der Waals interaction leading. In this contribution we present images how anthracene on Cu(111) forms a large number of highly ordered patterns that feature a broad array of structural motifs. Density functional theory modeling including vdW interactions allows us to model the energetic of the pattern formation at high fidelity. Moreover, it allows us to deduce the strain energy associated with films of varying coverage. From this work, we obtain the Young's modulus and Poisson Ratio of a molecular monolayer, which resemble properties conventionally found for porous materials. These patterns are in marked contrast to those found after introduction of functional groups in the molecules, such as carbonyls or thiols.

Dynamic Optical Tuning of Interlayer Interactions in the Transition Metal Dichalcogenides

DOE PAGES

Mannebach, Ehren M.; Nyby, Clara; Ernst, Friederike; ...

2017-11-09

Modulation of weak interlayer interactions between quasi-two-dimensional atomic planes in the transition metal dichalcogenides (TMDCs) provides avenues for tuning their functional properties. Here we show that above-gap optical excitation in the TMDCs leads to an unexpected large-amplitude, ultrafast compressive force between the two-dimensional layers, as probed by in situ measurements of the atomic layer spacing at femtosecond time resolution. We show that this compressive response arises from a dynamic modulation of the interlayer van der Waals interaction and that this represents the dominant light-induced stress at low excitation densities. A simple analytic model predicts the magnitude and carrier density dependencemore » of the measured strains. Furthermore, this work establishes a new method for dynamic, nonequilibrium tuning of correlation-driven dispersive interactions and of the optomechanical functionality of TMDC quasi-two-dimensional materials.« less

Structural and Electronic Properties of α2-Graphyne Nanotubes: A Density Functional Theory Study

NASA Astrophysics Data System (ADS)

Majidi, Roya

2018-02-01

Another form of carbon-based two-dimensional material in the graphene family, named the α2-graphyne sheet, was predicted very recently. The α2-graphyne sheet was created by doubling each acetylenic linker in an α-graphyne sheet. It exhibited semimetallic Dirac point features similar to graphene and α-graphyne sheets. In the present work, single -walled carbon nanotubes based on an α2-graphyne sheet was introduced. The structural and electronic properties of these nanotubes were studied using density functional theory. It was found that armchair α2-graphyne nanotubes showed metallic behavior, while zigzag α2-graphyne nanotubes were found to have semiconducting or metallic properties depending on tube size. The energy band gap of zigzag α2-graphyne nanotubes decreased with increasing tube diameter. The results indicated that the α2-graphyne sheet and its nanotubes can be proper materials for future nanoelectronics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plessow, Philipp N.; Bajdich, Michal; Greene, Joshua

The formation of thin oxide films on metal supports is an important phenomenon, especially in the context of strong metal support interaction (SMSI). Computational predictions of the stability of these films are hampered by their structural complexity and a varying lattice mismatch with different supports. In this study, we report a large combination of supports and ultrathin oxide films studied with density functional theory (DFT). Trends in stability are investigated through a descriptor-based analysis. Since the studied films are bound to the support exclusively through metal–metal interaction, the adsorption energy of the oxide-constituting metal atom can be expected to bemore » a reasonable descriptor for the stability of the overlayers. If the same supercell is used for all supports, the overlayers experience different amounts of stress. Using supercells with small lattice mismatch for each system leads to significantly improved scaling relations for the stability of the overlayers. Finally, this approach works well for the studied systems and therefore allows the descriptor-based exploration of the thermodynamic stability of supported thin oxide layers.« less

Theory for plasticity of face-centered cubic metals.

PubMed

Jo, Minho; Koo, Yang Mo; Lee, Byeong-Joo; Johansson, Börje; Vitos, Levente; Kwon, Se Kyun

2014-05-06

The activation of plastic deformation mechanisms determines the mechanical behavior of crystalline materials. However, the complexity of plastic deformation and the lack of a unified theory of plasticity have seriously limited the exploration of the full capacity of metals. Current efforts to design high-strength structural materials in terms of stacking fault energy have not significantly reduced the laborious trial and error works on basic deformation properties. To remedy this situation, here we put forward a comprehensive and transparent theory for plastic deformation of face-centered cubic metals. This is based on a microscopic analysis that, without ambiguity, reveals the various deformation phenomena and elucidates the physical fundaments of the currently used phenomenological correlations. We identify an easily accessible single parameter derived from the intrinsic energy barriers, which fully specifies the potential diversity of metals. Based entirely on this parameter, a simple deformation mode diagram is shown to delineate a series of convenient design criteria, which clarifies a wide area of material functionality by texture control.

Theory for plasticity of face-centered cubic metals

PubMed Central

Jo, Minho; Koo, Yang Mo; Lee, Byeong-Joo; Johansson, Börje; Vitos, Levente; Kwon, Se Kyun

2014-01-01

The activation of plastic deformation mechanisms determines the mechanical behavior of crystalline materials. However, the complexity of plastic deformation and the lack of a unified theory of plasticity have seriously limited the exploration of the full capacity of metals. Current efforts to design high-strength structural materials in terms of stacking fault energy have not significantly reduced the laborious trial and error works on basic deformation properties. To remedy this situation, here we put forward a comprehensive and transparent theory for plastic deformation of face-centered cubic metals. This is based on a microscopic analysis that, without ambiguity, reveals the various deformation phenomena and elucidates the physical fundaments of the currently used phenomenological correlations. We identify an easily accessible single parameter derived from the intrinsic energy barriers, which fully specifies the potential diversity of metals. Based entirely on this parameter, a simple deformation mode diagram is shown to delineate a series of convenient design criteria, which clarifies a wide area of material functionality by texture control. PMID:24753563

In situ application of a cellulose bag and an ion exchanger for differentiation of labile and inert metal species in aquatic systems.

PubMed

Goveia, Danielle; Rosa, André Henrique; Bellin, Iramaia Corrêa; Lobo, Fabiana Aparecida; Fraceto, Leonardo Fernandes; Roveda, José Arnaldo Frutuoso; Romão, Luciane Pimenta Cruz; Dias Filho, Newton Luiz

2008-02-01

This work involved the development and application of a new analytical procedure for in-situ characterization of the lability of metal species in aquatic systems by using a system equipped with a diffusion membrane and cellulose organomodified with p-aminobenzoic acid groups (DM-Cell-PAB). To this end, the DM-Cell-PAB system was prepared by adding cellulose organomodified with p-aminobenzoic acid groups (Cell-PAB) to pre-purified cellulose bags. After the DM-Cell-PAB system was sealed, it was examined in the laboratory. The in-situ application involved immersing the DM-Cell-PAB system in two different rivers, enabling us to study the relative lability of metal species (Cu, Cd, Fe, Mn, and Ni) as a function of time and quantity of exchanger. The procedure is simple and opens up a new perspective for understanding environmental phenomena relating to the complexation, transport, stability, and lability of metal species in aquatic systems rich in organic matter.

Hydrogenation-controlled phase transition on two-dimensional transition metal dichalcogenides and their unique physical and catalytic properties.

PubMed

Qu, Yuanju; Pan, Hui; Kwok, Chi Tat

2016-09-30

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have been widely used from nanodevices to energy harvesting/storage because of their tunable physical and chemical properties. In this work, we systematically investigate the effects of hydrogenation on the structural, electronic, magnetic, and catalytic properties of 33 TMDs based on first-principles calculations. We find that the stable phases of TMD monolayers can transit from 1T to 2H phase or vice versa upon the hydrogenation. We show that the hydrogenation can switch their magnetic and electronic states accompanying with the phase transition. The hydrogenation can tune the magnetic states of TMDs among non-, ferro, para-, and antiferro-magnetism and their electronic states among semiconductor, metal, and half-metal. We further show that, out of 33 TMD monolayers, 2H-TiS 2 has impressive catalytic ability comparable to Pt in hydrogen evolution reaction in a wide range of hydrogen coverages. Our findings would shed the light on the multi-functional applications of TMDs.

Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons

PubMed Central

Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin; Malgras, Victor; Ahamad, Tansir; Alshehri, Saad M.; Kobayashi, Naoya; Tominaka, Satoshi; Ide, Yusuke; Kim, Jung Ho; Yamauchi, Yusuke

2016-01-01

Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications. PMID:27471193

Phosphorene Co-catalyst Advancing Highly Efficient Visible-Light Photocatalytic Hydrogen Production.

PubMed

Ran, Jingrun; Zhu, Bicheng; Qiao, Shi-Zhang

2017-08-21

Transitional metals are widely used as co-catalysts boosting photocatalytic H 2 production. However, metal-based co-catalysts suffer from high cost, limited abundance and detrimental environment impact. To date, metal-free co-catalyst is rarely reported. Here we for the first time utilized density functional calculations to guide the application of phosphorene as a high-efficiency metal-free co-catalyst for CdS, Zn 0.8 Cd 0.2 S or ZnS. Particularly, phosphorene modified CdS shows a high apparent quantum yield of 34.7 % at 420 nm. This outstanding activity arises from the strong electronic coupling between phosphorene and CdS, as well as the favorable band structure, high charge mobility and massive active sites of phosphorene, supported by computations and advanced characterizations, for example, synchrotron-based X-ray absorption near edge spectroscopy. This work brings new opportunities to prepare highly-active, cheap and green photocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low-loss integrated electrical surface plasmon source with ultra-smooth metal film fabricated by polymethyl methacrylate 'bond and peel' method.

PubMed

Liu, Wenjie; Hu, Xiaolong; Zou, Qiushun; Wu, Shaoying; Jin, Chongjun

2018-06-15

External light sources are mostly employed to functionalize the plasmonic components, resulting in a bulky footprint. Electrically driven integrated plasmonic devices, combining ultra-compact critical feature sizes with extremely high transmission speeds and low power consumption, can link plasmonics with the present-day electronic world. In an effort to achieve this prospect, suppressing the losses in the plasmonic devices becomes a pressing issue. In this work, we developed a novel polymethyl methacrylate 'bond and peel' method to fabricate metal films with sub-nanometer smooth surfaces on semiconductor wafers. Based on this method, we further fabricated a compact plasmonic source containing a metal-insulator-metal (MIM) waveguide with an ultra-smooth metal surface on a GaAs-based light-emitting diode wafer. An increase in propagation length of the SPP mode by a factor of 2.95 was achieved as compared with the conventional device containing a relatively rough metal surface. Numerical calculations further confirmed that the propagation length is comparable to the theoretical prediction on the MIM waveguide with perfectly smooth metal surfaces. This method facilitates low-loss and high-integration of electrically driven plasmonic devices, thus provides an immediate opportunity for the practical application of on-chip integrated plasmonic circuits.

High-performance metal mesh/graphene hybrid films using prime-location and metal-doped graphene.

PubMed

Min, Jung-Hong; Jeong, Woo-Lim; Kwak, Hoe-Min; Lee, Dong-Seon

2017-08-31

We introduce high-performance metal mesh/graphene hybrid transparent conductive layers (TCLs) using prime-location and metal-doped graphene in near-ultraviolet light-emitting diodes (NUV LEDs). Despite the transparency and sheet resistance values being similar for hybrid TCLs, there were huge differences in the NUV LEDs' electrical and optical properties depending on the location of the graphene layer. We achieved better physical stability and current spreading when the graphene layer was located beneath the metal mesh, in direct contact with the p-GaN layer. We further improved the contact properties by adding a very thin Au mesh between the thick Ag mesh and the graphene layer to produce a dual-layered metal mesh. The Au mesh effectively doped the graphene layer to create a p-type electrode. Using Raman spectra, work function variations, and the transfer length method (TLM), we verified the effect of doping the graphene layer after depositing a very thin metal layer on the graphene layers. From our results, we suggest that the nature of the contact is an important criterion for improving the electrical and optical performance of hybrid TCLs, and the method of doping graphene layers provides new opportunities for solving contact issues in other semiconductor devices.

Low-loss integrated electrical surface plasmon source with ultra-smooth metal film fabricated by polymethyl methacrylate ‘bond and peel’ method

NASA Astrophysics Data System (ADS)

Liu, Wenjie; Hu, Xiaolong; Zou, Qiushun; Wu, Shaoying; Jin, Chongjun

2018-06-01

External light sources are mostly employed to functionalize the plasmonic components, resulting in a bulky footprint. Electrically driven integrated plasmonic devices, combining ultra-compact critical feature sizes with extremely high transmission speeds and low power consumption, can link plasmonics with the present-day electronic world. In an effort to achieve this prospect, suppressing the losses in the plasmonic devices becomes a pressing issue. In this work, we developed a novel polymethyl methacrylate ‘bond and peel’ method to fabricate metal films with sub-nanometer smooth surfaces on semiconductor wafers. Based on this method, we further fabricated a compact plasmonic source containing a metal-insulator-metal (MIM) waveguide with an ultra-smooth metal surface on a GaAs-based light-emitting diode wafer. An increase in propagation length of the SPP mode by a factor of 2.95 was achieved as compared with the conventional device containing a relatively rough metal surface. Numerical calculations further confirmed that the propagation length is comparable to the theoretical prediction on the MIM waveguide with perfectly smooth metal surfaces. This method facilitates low-loss and high-integration of electrically driven plasmonic devices, thus provides an immediate opportunity for the practical application of on-chip integrated plasmonic circuits.

Structural properties of lead-lithium alloys

NASA Astrophysics Data System (ADS)

Khambholja, S. G.; Satikunvar, D. D.; Abhishek, Agraj; Thakore, B. Y.

2018-05-01

Lead-Lihtium alloys have found large number of applications as liquid metal coolants in nuclear reactors. Large number of experimental work is reported for this system. However, complete theoretical description is still rare. In this scenario, we in the present work report the study of ground state properties of Lead-Lithium system. The present study is performed using plane wave pseudopotential density functional theory as implemented in Quantum ESPRESSO package. The theoretical findings are in agreement with previously reported experimental data. Some conclusions are drawn based on present study, which will be helpful for a comprehensive study.

Specifications for Supplementary Classroom Units, Stressed Skin Panel.

ERIC Educational Resources Information Center

Waring, Robert B.; And Others

Complete outline specifications are given for the construction of supplementary classroom units using stressed skin panels. Sections included are--(1) concrete and related work, (2) masonry, (3) structural and miscellaneous metal, (4) curtain walls and metal windows, (5) carpentry and related work, (6) roofing, sheet metal, and related work, (7)…

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores.

PubMed

Pardon, Gaspard; Gatty, Hithesh K; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-11

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al(2)O(3)) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al(2)O(3) layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al(2)O(3) using ALD.

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores

NASA Astrophysics Data System (ADS)

Pardon, Gaspard; Gatty, Hithesh K.; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-01

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al2O3) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al2O3 layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al2O3 using ALD.

30 CFR 57.16013 - Working with molten metal.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Working with molten metal. 57.16013 Section 57.16013 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Materials...

30 CFR 57.16013 - Working with molten metal.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Working with molten metal. 57.16013 Section 57.16013 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Materials...

Effect of Graphene with Nanopores on Metal Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hu; Chen, Xianlang; Wang, Lei

Porous graphene, which is a novel type of defective graphene, shows excellent potential as a support material for metal clusters. In this work, the stability and electronic structures of metal clusters (Pd, Ir, Rh) supported on pristine graphene and graphene with different sizes of nanopore were investigated by first-principle density functional theory (DFT) calculations. Thereafter, CO adsorption and oxidation reaction on the Pd-graphene system were chosen to evaluate its catalytic performance. Graphene with nanopore can strongly stabilize the metal clusters and cause a substantial downshift of the d-band center of the metal clusters, thus decreasing CO adsorption. All binding energies,more » d-band centers, and adsorption energies show a linear change with the size of the nanopore: a bigger size of nanopore corresponds to a stronger metal clusters bond to the graphene, lower downshift of the d-band center, and weaker CO adsorption. By using a suitable size nanopore, supported Pd clusters on the graphene will have similar CO and O2 adsorption ability, thus leading to superior CO tolerance. The DFT calculated reaction energy barriers show that graphene with nanopore is a superior catalyst for CO oxidation reaction. These properties can play an important role in instructing graphene-supported metal catalyst preparation to prevent the diffusion or agglomeration of metal clusters and enhance catalytic performance. This work was supported by National Basic Research Program of China (973Program) (2013CB733501), the National Natural Science Foundation of China (NSFC-21176221, 21136001, 21101137, 21306169, and 91334013). D. Mei acknowledges the support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC).« less

30 CFR 56.16013 - Working with molten metal.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Working with molten metal. 56.16013 Section 56.16013 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Materials Storage...

30 CFR 56.16013 - Working with molten metal.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Working with molten metal. 56.16013 Section 56.16013 Mineral Resources MINE SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR METAL AND NONMETAL MINE SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Materials Storage...

Combined distribution functions: A powerful tool to identify cation coordination geometries in liquid systems

NASA Astrophysics Data System (ADS)

Sessa, Francesco; D'Angelo, Paola; Migliorati, Valentina

2018-01-01

In this work we have developed an analytical procedure to identify metal ion coordination geometries in liquid media based on the calculation of Combined Distribution Functions (CDFs) starting from Molecular Dynamics (MD) simulations. CDFs provide a fingerprint which can be easily and unambiguously assigned to a reference polyhedron. The CDF analysis has been tested on five systems and has proven to reliably identify the correct geometries of several ion coordination complexes. This tool is simple and general and can be efficiently applied to different MD simulations of liquid systems.

Material science as basis for nuclear medicine: Holmium irradiation for radioisotopes production

NASA Astrophysics Data System (ADS)

Usman, Ahmed Rufai; Khandaker, Mayeen Uddin; Haba, Hiromitsu; Otuka, Naohiko

2018-05-01

Material Science, being an interdisciplinary field, plays important roles in nuclear science. These applications are seen in weaponry, armoured vehicles, accelerator structure and development, semiconductor detectors, nuclear medicine and many more. Present study presents the applications of some metals in nuclear medicine (radioisotope production). The charged-particle-induced nuclear reactions by using cyclotrons or accelerators have become a very vital feature of the modern nuclear medicine. Realising the importance of excitation functions for the efficient production of medical radionuclides, some very high purity holmium metals are generally prepared or purchased for bombardment in nuclear accelerators. In the present work, various methods to obtain pure holmium for radioisotope production have been discussed while also presenting details of our present studies. From the experimental work of the present studies, some very high purity holmium foils have been used in the work for a comprehensive study of residual radionuclides production cross-sections. The study was performed using a stacked-foil activation technique combined with γ-ray spectrometry. The stack was bombarded with 50.4 MeV alpha particle beam from AVF cyclotron of RI Beam Factory, Nishina Centre for Accelerator-Based Science, RIKEN, Japan. The work produced thulium radionuclides useful in nuclear medicine.

Microbial community composition and functions are resilient to metal pollution along two forest soil gradients.

PubMed

Azarbad, Hamed; Niklińska, Maria; Laskowski, Ryszard; van Straalen, Nico M; van Gestel, Cornelis A M; Zhou, Jizhong; He, Zhili; Wen, Chongqing; Röling, Wilfred F M

2015-01-01

Despite the global importance of forests, it is virtually unknown how their soil microbial communities adapt at the phylogenetic and functional level to long-term metal pollution. Studying 12 sites located along two distinct gradients of metal pollution in Southern Poland revealed that functional potential and diversity (assessed using GeoChip 4.2) were highly similar across the gradients despite drastically diverging metal contamination levels. Metal pollution level did, however, significantly impact bacterial community structure (as shown by MiSeq Illumina sequencing of 16S rRNA genes), but not bacterial taxon richness and community composition. Metal pollution caused changes in the relative abundance of specific bacterial taxa, including Acidobacteria, Actinobacteria, Bacteroidetes, Chloroflexi, Firmicutes, Planctomycetes and Proteobacteria. Also, a group of metal-resistance genes showed significant correlations with metal concentrations in soil. Our study showed that microbial communities are resilient to metal pollution; despite differences in community structure, no clear impact of metal pollution levels on overall functional diversity was observed. While screens of phylogenetic marker genes, such as 16S rRNA genes, provide only limited insight into resilience mechanisms, analysis of specific functional genes, e.g. involved in metal resistance, appears to be a more promising strategy. © FEMS 2014. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

An internal variable constitutive model for the large deformation of metals at high temperatures

NASA Technical Reports Server (NTRS)

Brown, Stuart; Anand, Lallit

1988-01-01

The advent of large deformation finite element methodologies is beginning to permit the numerical simulation of hot working processes whose design until recently has been based on prior industrial experience. Proper application of such finite element techniques requires realistic constitutive equations which more accurately model material behavior during hot working. A simple constitutive model for hot working is the single scalar internal variable model for isotropic thermal elastoplasticity proposed by Anand. The model is recalled and the specific scalar functions, for the equivalent plastic strain rate and the evolution equation for the internal variable, presented are slight modifications of those proposed by Anand. The modified functions are better able to represent high temperature material behavior. The monotonic constant true strain rate and strain rate jump compression experiments on a 2 percent silicon iron is briefly described. The model is implemented in the general purpose finite element program ABAQUS.

Biological monitoring of glazers exposed to lead in the ceramics industry in Iran.

PubMed

Shouroki, Fatemeh Kargar; Shahtaheri, Seyed Jamaleddin; Golbabaei, Farideh; Barkhordari, Abolfazle; Rahimi-Froushani, Abbas

2015-01-01

Exposure to heavy metals, particularly lead, takes place in the ceramics industry. Lead is used in glaze to produce smooth and brilliant surfaces; thus, there is a likelihood of occupational adverse effects on humans. Urine samples were collected from 49 glazers at the start and end of the work shifts (98 samples). Solid phase extraction was used for separation and pre-concentration of the analyte. Samples were analysed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Lung function tests were performed on both control and lead exposed subjects. Statistical analysis of covariance (ANCOVA) was used to evaluate the data obtained. The concentration of lead in glazers was 6.37 times higher than in the control group. Lung functions were significantly lower in the glazers compared to the control group (p < 0.001). Results showed that poor ventilation systems, overtime work and work history are effective determinants of high exposure levels.

Empirical calibration of the near-infrared Ca II triplet - III. Fitting functions

NASA Astrophysics Data System (ADS)

Cenarro, A. J.; Gorgas, J.; Cardiel, N.; Vazdekis, A.; Peletier, R. F.

2002-02-01

Using a near-infrared stellar library of 706 stars with a wide coverage of atmospheric parameters, we study the behaviour of the CaII triplet strength in terms of effective temperature, surface gravity and metallicity. Empirical fitting functions for recently defined line-strength indices, namely CaT*, CaT and PaT, are provided. These functions can be easily implemented into stellar population models to provide accurate predictions for integrated CaII strengths. We also present a thorough study of the various error sources and their relation to the residuals of the derived fitting functions. Finally, the derived functional forms and the behaviour of the predicted CaII are compared with those of previous works in the field.

Structure-activity relationships of mononuclear metal-thiosemicarbazone complexes endowed with potent antiplasmodial and antiamoebic activities.

PubMed

Bahl, Deepa; Athar, Fareeda; Soares, Milena Botelho Pereira; de Sá, Matheus Santos; Moreira, Diogo Rodrigo Magalhães; Srivastava, Rajendra Mohan; Leite, Ana Cristina Lima; Azam, Amir

2010-09-15

A useful concept for the rational design of antiparasitic drug candidates is the complexation of bioactive ligands with transition metals. In view of this, an investigation was conducted into a new set of metal complexes as potential antiplasmodium and antiamoebic agents, in order to examine the importance of metallic atoms, as well as the kind of sphere of co-ordination, in these biological properties. Four functionalized furyl-thiosemicarbazones (NT1-4) treated with divalent metals (Cu, Co, Pt, and Pd) to form the mononuclear metallic complexes of formula [M(L)2Cl2] or [M(L)Cl2] were examined. The pharmacological characterization, including assays against Plasmodium falciparum and Entamoeba histolytica, cytotoxicity to mammalian cells, and interaction with pBR 322 plasmid DNA was performed. Structure-activity relationship data revealed that the metallic complexation plays an essential role in antiprotozoal activity, rather than the simple presence of the ligand or metal alone. Important steps towards identification of novel antiplasmodium (NT1Cu, IC50 of 4.6 microM) and antiamoebic (NT2Pd, IC50 of 0.6 microM) drug prototypes were achieved. Of particular relevance to this work, these prototypes were able to reduce the proliferation of these parasites at concentrations that are not cytotoxic to mammalian cells. Copyright (c) 2010. Published by Elsevier Ltd.

First-principles design of nanostructured hybrid photovoltaics based on layered transition metal phosphates

DOE PAGES

Lentz, Levi C.; Kolpak, Alexie M.

2017-04-28

The performance of bulk organic and hybrid organic-inorganic heterojunction photovoltaics is often limited by high carrier recombination arising from strongly bound excitons and low carrier mobility. Structuring materials to minimize the length scales required for exciton separation and carrier collection is therefore a promising approach for improving efficiency. In this work, first-principles computations are employed to design and characterize a new class of photovoltaic materials composed of layered transition metal phosphates (TMPs) covalently bound to organic absorber molecules to form nanostructured superlattices. Using a combination of transition metal substitution and organic functionalization, the electronic structure of these materials is systematicallymore » tuned to design a new hybrid photovoltaic material predicted to exhibit very low recombination due to the presence of a local electric field and spatially isolated, high mobility, two-dimensional electron and hole conducting channels. Furthermore, this material is predicted to have a large open-circuit voltage of 1.7 V. Here, this work suggests that hybrid TMPs constitute an interesting class of materials for further investigation in the search for achieving high efficiency, high power, and low cost photo Zirconium phosphate was chosen, in part, due to previous experiment voltaics.« less

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Reed, J. A.

2011-03-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which results from diffusion of oxygen into the sub-surface regions. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the Cu(100) missing row reconstructed surface under conditions of high oxygen coverage. Calculations are performed for various surface and subsurface oxygen coverages ranging from 0.50 to 1.50 monolayers. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. Estimates of the positron binding energy, positron work function, and annihilation characteristics reveal their sensitivity to atomic structure of the topmost layers of the surface and charge transfer. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

First-principles design of nanostructured hybrid photovoltaics based on layered transition metal phosphates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lentz, Levi C.; Kolpak, Alexie M.

The performance of bulk organic and hybrid organic-inorganic heterojunction photovoltaics is often limited by high carrier recombination arising from strongly bound excitons and low carrier mobility. Structuring materials to minimize the length scales required for exciton separation and carrier collection is therefore a promising approach for improving efficiency. In this work, first-principles computations are employed to design and characterize a new class of photovoltaic materials composed of layered transition metal phosphates (TMPs) covalently bound to organic absorber molecules to form nanostructured superlattices. Using a combination of transition metal substitution and organic functionalization, the electronic structure of these materials is systematicallymore » tuned to design a new hybrid photovoltaic material predicted to exhibit very low recombination due to the presence of a local electric field and spatially isolated, high mobility, two-dimensional electron and hole conducting channels. Furthermore, this material is predicted to have a large open-circuit voltage of 1.7 V. Here, this work suggests that hybrid TMPs constitute an interesting class of materials for further investigation in the search for achieving high efficiency, high power, and low cost photo Zirconium phosphate was chosen, in part, due to previous experiment voltaics.« less

Thin film thermocouples for thermoelectric characterization of nanostructured materials

NASA Astrophysics Data System (ADS)

Grayson, Matthew; Zhou, Chuanle; Varrenti, Andrew; Chyung, Seung Hye; Long, Jieyi; Memik, Seda

2011-03-01

The increased use of nanostructured materials as thermoelectrics requires reliable and accurate characterization of the anisotropic thermal coefficients of small structures, such as superlattices and quantum wire networks. Thin evaporated metal films can be used to create thermocouples with a very small thermal mass and low thermal conductivity, in order to measure thermal gradients on nanostructures and thereby measure the thermal conductivity and the Seebeck coefficient of the nanostructure. In this work we confirm the known result that thin metal films have lower Seebeck coefficients than bulk metals, and we also calibrate the Seebeck coefficient of a thin-film Ni/Cr thermocouple with 50 nm thickness, showing it to have about 1/4 the bulk value. We demonstrate reproducibility of this thin-filmSeebeck coefficient on multiple substrates, and we show that this coefficient does, in fact, change as a function of film thickness. We will discuss prototype measurement designs and preliminary work as to how these thin films can be used to study both Seebeck coefficients and thermal conductivities of superlattices in various geometries. The same technology can in principle be used on integrated circuits for thermal mapping, under the name ``Integrated On-Chip Thermocouple Array'' (IOTA).

Impact of gate work-function on memory characteristics in Al2O3/HfOx/Al2O3/graphene charge-trap memory devices

NASA Astrophysics Data System (ADS)

Lee, Sejoon; Song, Emil B.; Kim, Sungmin; Seo, David H.; Seo, Sunae; Won Kang, Tae; Wang, Kang L.

2012-01-01

Graphene-based non-volatile memory devices composed of a single-layer graphene channel and an Al2O3/HfOx/Al2O3 charge-storage layer exhibit memory functionality. The impact of the gate material's work-function (Φ) on the memory characteristics is investigated using different types of metals [Ti (ΦTi = 4.3 eV) and Ni (ΦNi = 5.2 eV)]. The ambipolar carrier conduction of graphene results in an enlargement of memory window (ΔVM), which is ˜4.5 V for the Ti-gate device and ˜9.1 V for the Ni-gate device. The increase in ΔVM is attributed to the change in the flat-band condition and the suppression of electron back-injection within the gate stack.

Bioinspired surface functionalization of metallic biomaterials.

PubMed

Su, Yingchao; Luo, Cheng; Zhang, Zhihui; Hermawan, Hendra; Zhu, Donghui; Huang, Jubin; Liang, Yunhong; Li, Guangyu; Ren, Luquan

2018-01-01

Metallic biomaterials are widely used for clinical applications because of their excellent mechanical properties and good durability. In order to provide essential biofunctionalities, surface functionalization is of particular interest and requirement in the development of high-performance metallic implants. Inspired by the functional surface of natural biological systems, many new designs and conceptions have recently emerged to create multifunctional surfaces with great potential for biomedical applications. This review firstly introduces the metallic biomaterials, important surface properties, and then elaborates some strategies on achieving the bioinspired surface functionalization for metallic biomaterials. Copyright © 2017 Elsevier Ltd. All rights reserved.

Calculations of the surface tensions of liquid metals

NASA Technical Reports Server (NTRS)

Stroud, D. G.

1981-01-01

The understanding of the surface tension of liquid metals and alloys from as close to first principles as possible is discussed. The two ingredients which are combined in these calculations are: the electron theory of metals, and the classical theory of liquids, as worked out within the framework of statistical mechanics. The results are a new theory of surface tensions and surface density profiles from knowledge purely of the bulk properties of the coexisting liquid and vapor phases. It is found that the method works well for the pure liquid metals on which it was tested; work is extended to mixtures of liquid metals, interfaces between immiscible liquid metals, and to the temperature derivative of the surface tension.

The cataphoretic emitter effect exhibited in high intensity discharge lamp electrodes

NASA Astrophysics Data System (ADS)

Mentel, Juergen

2018-01-01

A mono-layer of atoms, electropositive with respect to the substrate atoms, forms a dipole layer, reducing its work function. Such a layer is generated by diffusion of emitter material from the interior of the substrate, by vapour deposition or by deposition of emitter material onto arc electrodes by cataphoresis. This cataphoretic emitter effect is investigated within metal halide lamps with transparent YAG ceramic burners, and within model lamps. Within the YAG lamps, arcs are operated with switched-dc current between rod shaped tungsten electrodes in high pressure Hg vapour seeded with metal iodides. Within the model lamps, dc arcs are operated between rod-shaped tungsten electrodes—one doped—in atmospheric pressure Ar. Electrode temperatures are determined by 1λ -pyrometry, combined with simulation of the electrode heat balance. Plasma temperatures, atom and ion densities of emitter material are determined by emission and absorption spectroscopy. Phase resolved measurements in YAG lamps seeded with CeI3, CsI, DyI3, TmI3 and LaI3 show, within the cathodic half period, a reduction of the electrode temperature and an enhanced metal ion density in front of the electrode, and an opposite behavior after phase reversal. With increasing operating frequency, the state of the cathode overlaps onto the anodic phase—except for Cs, being low in adsorption energy. Generally, the phase averaged electrode tip temperature is reduced by seeding a lamp with emitter material; its height depends on admixtures. Measurements at tungsten electrodes doped with ThO2, La2O3 and Ce2O3 within the model lamp show that evaporated emitter material is redeposited by an emitter ion current onto the electrode surface. It reduces the work function of tungsten cathodes above the evaporation temperature of the emitter material, too; and also of cold anodes, indicating a field reversal in front of them. The formation of an emitter spot at low cathode temperature and high emitter material density is traced back to a locally reduced work function generated by a locally enhanced emitter ion current density.

Many-Body Theory of Pyrochlore Iridates and Related Materials

NASA Astrophysics Data System (ADS)

Wang, Runzhi

In this thesis we focus on two problems. First we propose a numerical method for generating optimized Wannier functions with desired properties. Second we perform the state of the art density functional plus dynamical mean-field calculations in pyrochlore iridates, to investigate the physics induced by the cooperation of spin-orbit coupling and electron correlation. We begin with the introduction for maximally localized Wannier functions and other related extensions. Then we describe the current research in the field of spin-orbit coupling and its interplay with correlation effects, followed by a brief introduction of the `hot' materials of iridates. Before the end of the introduction, we discuss the numerical methods employed in our work, including the density functional theory; dynamical mean-field theory and its combination with the exact diagonalization impurity solver. Then we propose our approach for constructing an optimized set of Wannier functions, which is a generalization of the functionality of the classic maximal localization method put forward by Marzari and Vanderbilt. Our work is motivated by the requirement of the effective description of the local subspace of the Hamiltonian by the beyond density functional theory methods. In extensions of density functional theory such as dynamical mean-field theory, one may want highly accurate description of particular local orbitals, including correct centers and symmetries; while the basis for the remaining degrees of freedom is unimportant. Therefore, we develop the selectively localized Wannier function approach which allows for a greater localization in the selected subset of Wannier functions and at the same time allows us to fix the centers and ensure the point symmetries. Applications in real materials are presented to demonstrate the power of our approach. Next we move to the investigation of pyrochlore iridates, focussing on the metal-insulator transition and material dependence in these compounds. We perform combined density functional plus dynamical mean-field calculations in Lu2Ir2O7, Y2Ir2O 7, Eu2Ir2O7, with spin-orbit coupling included and both single-site and cluster approximations appiled. A broad range of Weyl metal is predicted as the intervening phase in the metal-insulator transition. By comparing to experiments, we find that the single-site approximation fails to predict the gap values and substantial difference between the Y and Eu-compound, demonstrating the inadequacy of this approximation and indicating the key role played by the intersite effects. Finally, we provide a more accurate description of the vicinity of the metal-insulator and topological transitions implied by density functional plus cluster dynamical mean-field calculations of pyrochlore iridates. We find definitive evidence of the Weyl semimetal phase, the electronic structure of which can be approximately described as ``Weyl rings" with an extremely flat dispersion of one of the Weyl bands. This Weyl semimetal phase is further investigated by the k • p analysis fitting to the numerical results. We find that this unusual structure leads to interesting behavior in the optical conductivity including a Hall effect in the interband component, and to an enhanced susceptibility.

Effect of Electric Field on the Wetting Behavior of Eutectic Gallium-Indium Alloys in Aqueous Environment

NASA Astrophysics Data System (ADS)

Yuan, Bo; He, Zhi-Zhu; Liu, Jing

2018-02-01

Room-temperature liquid metals have many intriguing properties that have not previously been fully understood. Among them, surface tension behaviors of such metals are especially critical in a group of newly emerging areas such as printed electronics, functional materials and soft machines, etc. This study is dedicated to clarifying the wettability of liquid metals on various substrate surfaces with varied roughness immersed in solutions when subject to an electric field. The contact angles of Ga75.5In24.5 in several typical liquids were comprehensively measured and interpreted, and were revealed to be affected by the components and concentration of the environmental solution. Meanwhile, the roughness of the substrates is also revealed to be an important parameter dominating the process. The dynamic wetting behaviors of liquid metal in aqueous environment under an electric field were quantified. The contact angle values of eutectic gallium-indium alloys (eGaIn) on titanium substrates with different roughness would lead to better electrowetting performances on rougher surfaces. In particular, using an electrical field to control the wetting status of liquid metal with the matching substrate have been illustrated, which would offer a practical way to flexibly control liquid metal-based functional devices working in an aqueous environment. Furthermore, Lippmann-Young's equation reveals the relationship between contact angle and applied voltage, explaining the excellent electrowetting property of eGaIn. The power law, R = αt β , was adopted to characterize the two-stage wetting process of eGaIn under different voltages. In the initial process, β ≈ 1/2 represents the complete wetting law, while the later one, β ≈ 1/10, meets with Tanner's law of a drop spontaneously spreading on a smooth surface.

Quasiclassical Eilenberger theory of the topological proximity effect in a superconducting nanowire

NASA Astrophysics Data System (ADS)

Stanev, Valentin; Galitski, Victor

2014-05-01

We use the quasiclassical Eilenberger theory to study the topological superconducting proximity effects between a segment of a nanowire with a p-wave order parameter and a metallic segment. This model faithfully represents key qualitative features of an experimental setup, where only a part of a nanowire is in immediate contact with a bulk superconductor, inducing topological superconductivity. It is shown that the Eilenberger equations represent a viable alternative to the Bogoliubov-de Gennes theory of the topological superconducting heterostructures and provide a much simpler quantitative description of some observables. For our setup, we obtain exact analytical solutions for the quasiclassical Green's functions and the density of states as a function of position and energy. The correlations induced by the boundary involve terms associated with both p-wave and odd-frequency pairing, which are intertwined and contribute to observables on an equal footing. We recover the signatures of the standard Majorana mode near the end of the superconducting segment, but find no such localized mode induced in the metallic segment. Instead, the zero-bias feature is spread out across the entire metallic part in accordance with the previous works. In shorter wires, the Majorana mode and delocalized peak split up away from zero energy. For long metallic segments, nontopological Andreev bound states appear and eventually merge together, giving rise to a gapless superconductor.

Functionalized Graphitic Carbon Nitride for Metal-free, Flexible and Rewritable Nonvolatile Memory Device via Direct Laser-Writing

PubMed Central

Zhao, Fei; Cheng, Huhu; Hu, Yue; Song, Long; Zhang, Zhipan; Jiang, Lan; Qu, Liangti

2014-01-01

Graphitic carbon nitride nanosheet (g-C3N4-NS) has layered structure similar with graphene nanosheet and presents unusual physicochemical properties due to the s-triazine fragments. But their electronic and electrochemical applications are limited by the relatively poor conductivity. The current work provides the first example that atomically thick g-C3N4-NSs are the ideal candidate as the active insulator layer with tunable conductivity for achieving the high performance memory devices with electrical bistability. Unlike in conventional memory diodes, the g-C3N4-NSs based devices combined with graphene layer electrodes are flexible, metal-free and low cost. The functionalized g-C3N4-NSs exhibit desirable dispersibility and dielectricity which support the all-solution fabrication and high performance of the memory diodes. Moreover, the flexible memory diodes are conveniently fabricated through the fast laser writing process on graphene oxide/g-C3N4-NSs/graphene oxide thin film. The obtained devices not only have the nonvolatile electrical bistability with great retention and endurance, but also show the rewritable memory effect with a reliable ON/OFF ratio of up to 105, which is the highest among all the metal-free flexible memory diodes reported so far, and even higher than those of metal-containing devices. PMID:25073687

Hydrogel, aerogel and film of cellulose nanofibrils functionalized with silver nanoparticles.

PubMed

Dong, Hong; Snyder, James F; Tran, Dat T; Leadore, Julia L

2013-06-20

In this work, we describe hydrogels, aerogels and films of nanofibrillated cellulose (NFC) functionalized with metal nanoparticles using silver as an example. The TEMPO process used to produce NFC generates negatively charged surface carboxylate groups that provide high binding capability to transition metal species such as Ag(+). The gelation of NFC triggered by transition monovalent metal ions was revealed for the first time. The interaction was utilized to bind Ag(+) on the NFC surface and simultaneously induce formation of NFC-Ag(+) hydrogels, where Ag(+) was slowly reduced to Ag nanoparticles by hydroxyl groups on NFC without additional reducing agent. The NFC-Ag(+) hydrogel was initiated by strong association of carboxylate groups on NFC with Ag(+) and sufficient NFC surface charge reduction. The stiff hydrogel has a storage modulus leveled off at a plateau value of ~6800Pa. Porous aerogels and flat thin films comprising a continuous matrix of NFC were decorated with Ag nanoparticles through freeze-drying or solution-casting of NFC-Ag(+) dispersions with low contents of Ag(+), respectively, followed by UV reduction. The presence of Ag species on NFC reduced coalescence of nanofibrils in the film formation as revealed from AFM phase images. Copyright © 2013 Elsevier Ltd. All rights reserved.

Recent progress in density functional theory

NASA Astrophysics Data System (ADS)

Truhlar, Donald

2014-03-01

Ongoing work involves several areas of density functional theory: new methods for computing electronic excitation energies, including a new way to remove spin contamination in the spin-flip Tamm-Dancoff approximation and a configuration-interaction-corrected Tamm-Dancoff Approximation for treating conical intersections; new ways to treat open-shell states, including a reinterpreted broken-symmetry method and multi-configuration Kohn-Sham theory; a new exchange-correlation functional; new tests of density functional theory against databases for electronic transition energies and molecules and solids containing metal atoms; and applications. A selection of results will be presented. I am grateful to the following collaborators for contributions to the ongoing work: Boris Averkiev, Rebecca Carlson, Laura Fernandez, Laura Gagliardi, Chad Hoyer, Francesc Illas, Miho Isegawa, Shaohong Li, Giovanni Li Manni, Sijie Luo, Dongxia Ma, Remi Maurice, Rubén Means-Pañeda, Roberto Peverati, Nora Planas, Prasenjit Seal, Pragya Verma, Bo Wang, Xuefei Xu, Ke R. Yang, Haoyu Yu, Wenjing Zhang, and Jingjing Zheng. Supported in part by the AFOSR and U.S. DOE.

Microcontact printing of self-assembled monolayers to pattern the light-emission of polymeric light-emitting diodes

NASA Astrophysics Data System (ADS)

Brondijk, J. J.; Li, X.; Akkerman, H. B.; Blom, P. W. M.; de Boer, B.

2009-04-01

By patterning a self-assembled monolayer (SAM) of thiolated molecules with opposing dipole moments on a gold anode of a polymer light-emitting diode (PLED), the charge injection and, therefore, the light-emission of the device can be controlled with a micrometer-scale resolution. Gold surfaces were modified with SAMs based on alkanethiols and perfluorinated alkanethiols, applied by microcontact printing, and their work functions have been measured. The molecules form a chemisorbed monolayer of only ˜1.5 nm on the gold surface, thereby locally changing the work function of the metal. Kelvin probe measurements show that the local work function can be tuned from 4.3 to 5.5 eV, which implies that this anode can be used as a hole blocking electrode or as a hole injecting electrode, respectively, in PLEDs based on poly( p-phenylene vinylene) (PPV) derivatives. By microcontact printing of SAMs with opposing dipole moments, the work function was locally modified and the charge injection in the PLED could be controlled down to the micrometer length scale. Consequently, the local light-emission exhibits a high contrast. Microcontact printing of SAMs is a simple and inexpensive method to pattern, with micrometer resolution, the light-emission for low-end applications like static displays.

Reactive metal-oxide interfaces: A microscopic view

NASA Astrophysics Data System (ADS)

Picone, A.; Riva, M.; Brambilla, A.; Calloni, A.; Bussetti, G.; Finazzi, M.; Ciccacci, F.; Duò, L.

2016-03-01

Metal-oxide interfaces play a fundamental role in determining the functional properties of artificial layered heterostructures, which are at the root of present and future technological applications. Magnetic exchange and magnetoelectric coupling, spin filtering, metal passivation, catalytic activity of oxide-supported nano-particles are just few examples of physical and chemical processes arising at metal-oxide hybrid systems, readily exploited in working devices. These phenomena are strictly correlated with the chemical and structural characteristics of the metal-oxide interfacial region, making a thorough understanding of the atomistic mechanisms responsible of its formation a prerequisite in order to tailor the device properties. The steep compositional gradient established upon formation of metal-oxide heterostructures drives strong chemical interactions at the interface, making the metal-oxide boundary region a complex system to treat, both from an experimental and a theoretical point of view. However, once properly mastered, interfacial chemical interactions offer a further degree of freedom for tuning the material properties. The goal of the present review is to provide a summary of the latest achievements in the understanding of metal/oxide and oxide/metal layered systems characterized by reactive interfaces. The influence of the interface composition on the structural, electronic and magnetic properties will be highlighted. Particular emphasis will be devoted to the discussion of ultra-thin epitaxial oxides stabilized on highly oxidizable metals, which have been rarely exploited as oxide supports as compared to the much more widespread noble and quasi noble metallic substrates. In this frame, an extensive discussion is devoted to the microscopic characterization of interfaces between epitaxial metal oxides and the Fe(001) substrate, regarded from the one hand as a prototypical ferromagnetic material and from the other hand as a highly oxidizable metal.

Doped polymer semiconductors with ultrahigh and ultralow work functions for ohmic contacts.

PubMed

Tang, Cindy G; Ang, Mervin C Y; Choo, Kim-Kian; Keerthi, Venu; Tan, Jun-Kai; Syafiqah, Mazlan Nur; Kugler, Thomas; Burroughes, Jeremy H; Png, Rui-Qi; Chua, Lay-Lay; Ho, Peter K H

2016-11-24

To make high-performance semiconductor devices, a good ohmic contact between the electrode and the semiconductor layer is required to inject the maximum current density across the contact. Achieving ohmic contacts requires electrodes with high and low work functions to inject holes and electrons respectively, where the work function is the minimum energy required to remove an electron from the Fermi level of the electrode to the vacuum level. However, it is challenging to produce electrically conducting films with sufficiently high or low work functions, especially for solution-processed semiconductor devices. Hole-doped polymer organic semiconductors are available in a limited work-function range, but hole-doped materials with ultrahigh work functions and, especially, electron-doped materials with low to ultralow work functions are not yet available. The key challenges are stabilizing the thin films against de-doping and suppressing dopant migration. Here we report a general strategy to overcome these limitations and achieve solution-processed doped films over a wide range of work functions (3.0-5.8 electronvolts), by charge-doping of conjugated polyelectrolytes and then internal ion-exchange to give self-compensated heavily doped polymers. Mobile carriers on the polymer backbone in these materials are compensated by covalently bonded counter-ions. Although our self-compensated doped polymers superficially resemble self-doped polymers, they are generated by separate charge-carrier doping and compensation steps, which enables the use of strong dopants to access extreme work functions. We demonstrate solution-processed ohmic contacts for high-performance organic light-emitting diodes, solar cells, photodiodes and transistors, including ohmic injection of both carrier types into polyfluorene-the benchmark wide-bandgap blue-light-emitting polymer organic semiconductor. We also show that metal electrodes can be transformed into highly efficient hole- and electron-injection contacts via the self-assembly of these doped polyelectrolytes. This consequently allows ambipolar field-effect transistors to be transformed into high-performance p- and n-channel transistors. Our strategy provides a method for producing ohmic contacts not only for organic semiconductors, but potentially for other advanced semiconductors as well, including perovskites, quantum dots, nanotubes and two-dimensional materials.

Methods for Fabricating Gradient Alloy Articles with Multi-Functional Properties

NASA Technical Reports Server (NTRS)

Hofmann, Douglas C. (Inventor); Suh, Eric J. (Inventor); Borgonia, John Paul C. (Inventor); Dillon, Robert P. (Inventor); Mulder, Jerry L. (Inventor); Gardner, Paul B. (Inventor)

2015-01-01

Systems and methods for fabricating multi-functional articles comprised of additively formed gradient materials are provided. The fabrication of multi-functional articles using the additive deposition of gradient alloys represents a paradigm shift from the traditional way that metal alloys and metal/metal alloy parts are fabricated. Since a gradient alloy that transitions from one metal to a different metal cannot be fabricated through any conventional metallurgy techniques, the technique presents many applications. Moreover, the embodiments described identify a broad range of properties and applications.

Released polysaccharides (RPS) from Cyanothece sp. CCY 0110 as biosorbent for heavy metals bioremediation: interactions between metals and RPS binding sites.

PubMed

Mota, Rita; Rossi, Federico; Andrenelli, Luisa; Pereira, Sara Bernardes; De Philippis, Roberto; Tamagnini, Paula

2016-09-01

Bioremediation of heavy metals using microorganisms can be advantageous compared to conventional physicochemical methods due to the use of renewable resources and efficiencies of removal particularly cations at low concentrations. In this context, cyanobacteria/cyanobacterial extracellular polymeric substances (EPS) emerge as a valid alternative due to the anionic nature and particular composition of these polymers. In this work, various culture fractions of the unicellular cyanobacterium Cyanothece sp. CCY 0110 were employed in bioremoval assays using three of the most common heavy metal pollutants in water bodies-copper, cadmium, and lead-separately or in combined systems. Our study showed that the released polysaccharides (RPS) were the most efficient fraction, removing the metal(s) by biosorption. Therefore, this polymer was subsequently used to evaluate the interactions between the metals/RPS binding sites using SEM-EDX, ICP-OES, and FTIR. Acid and basic pretreatments applied to the polymer further improve the process efficiency, and the exposure to an alkaline solution seems to alter the RPS conformation. The differences observed in the specific metal bioremoval seem to be mainly due to the RPS organic functional groups available, mainly carboxyl and hydroxyl, than to an ion exchange mechanism. Considering that Cyanothece is a highly efficient RPS-producer and that RPS can be easily separated from the culture, immobilized or confined, this polymer can be advantageous for the establishment/improvement of heavy metal removal systems.

30 CFR 57.15007 - Protective equipment or clothing for welding, cutting, or working with molten metal.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Protective equipment or clothing for welding... equipment or clothing for welding, cutting, or working with molten metal. Protective clothing or equipment and face shields or goggles shall be worn when welding, cutting, or working with molten metal. ...

30 CFR 57.15007 - Protective equipment or clothing for welding, cutting, or working with molten metal.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Protective equipment or clothing for welding... equipment or clothing for welding, cutting, or working with molten metal. Protective clothing or equipment and face shields or goggles shall be worn when welding, cutting, or working with molten metal. ...

30 CFR 57.15007 - Protective equipment or clothing for welding, cutting, or working with molten metal.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Protective equipment or clothing for welding... equipment or clothing for welding, cutting, or working with molten metal. Protective clothing or equipment and face shields or goggles shall be worn when welding, cutting, or working with molten metal. ...

30 CFR 57.15007 - Protective equipment or clothing for welding, cutting, or working with molten metal.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Protective equipment or clothing for welding... equipment or clothing for welding, cutting, or working with molten metal. Protective clothing or equipment and face shields or goggles shall be worn when welding, cutting, or working with molten metal. ...

30 CFR 57.15007 - Protective equipment or clothing for welding, cutting, or working with molten metal.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Protective equipment or clothing for welding... equipment or clothing for welding, cutting, or working with molten metal. Protective clothing or equipment and face shields or goggles shall be worn when welding, cutting, or working with molten metal. ...

Combinatorial study of Ni-Ti-Pt ternary metal gate electrodes on HfO{sub 2} for the advanced gate stack

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, K.-S.; Green, M. L.; Suehle, J.

2006-10-02

The authors have fabricated combinatorial Ni-Ti-Pt ternary metal gate thin film libraries on HfO{sub 2} using magnetron co-sputtering to investigate flatband voltage shift ({delta}V{sub fb}), work function ({phi}{sub m}), and leakage current density (J{sub L}) variations. A more negative {delta}V{sub fb} is observed close to the Ti-rich corner than at the Ni- and Pt-rich corners, implying smaller {phi}{sub m} near the Ti-rich corners and higher {phi}{sub m} near the Ni- and Pt-rich corners. In addition, measured J{sub L} values can be explained consistently with the observed {phi}{sub m} variations. Combinatorial methodologies prove to be useful in surveying the large compositionalmore » space of ternary alloy metal gate electrode systems.« less

A viscoplastic constitutive theory for metal matrix composites at high temperature

NASA Technical Reports Server (NTRS)

Robinson, D. N.; Duffy, S. F.; Ellis, J. R.

1986-01-01

A viscoplastic constitutive theory is presented for representing the high-temperature deformation behavior of metal matrix composites. The point of view taken is a continuum one where the composite is considered a material in its own right, with its own properties that can be determined for the composite as a whole. It is assumed that a single preferential (fiber) direction is identifiable at each material point (continuum element) admitting the idealization of local transverse isotropy. A key ingredient in this work is the specification of an experimental program for the complete determination of the material functions and parameters for characterizing a particular metal matrix composite. The parameters relating to the strength of anisotropy can be determined through tension/torsion tests on longitudinally and circumferentially reinforced thin-walled tubes. Fundamental aspects of the theory are explored through a geometric interpretation of some basic features analogous to those of the classical theory of plasticity.

A viscoplastic constitutive theory for metal matrix composites at high temperature

NASA Technical Reports Server (NTRS)

Robinson, D. N.; Ellis, J. R.; Duffy, S. F.

1987-01-01

A viscoplastic theory is presented for representing the high-temperature deformation behavior of metal matrix composites. The point of view taken is a continuum one where the composite is considered a material in its own right, with its own properties that can be determined for the composite as a whole. It is presumed that a single preferential (fiber) direction is identifiable at each material point (continuum element) admitting the idealization of local transverse isotropy. A key ingredient in this work is the specification of an experimental program for the complete determination of the material functions and parameters for characterizing a particular metal matrix composite. The parameters relating to the strength of anisotropy can be determined through tension/torsion tests on longitudinally and circumferentially reinforced thin-walled tubes. Fundamental aspects of the theory are explored through a geometric interpretation of some basic features analogous to those of the classical theory of plasticity.

Investigation of electronic band structure and charge transfer mechanism of oxidized three-dimensional graphene as metal-free anodes material for dye sensitized solar cell application

NASA Astrophysics Data System (ADS)

Loeblein, Manuela; Bruno, Annalisa; Loh, G. C.; Bolker, Asaf; Saguy, Cecile; Antila, Liisa; Tsang, Siu Hon; Teo, Edwin Hang Tong

2017-10-01

Dye-sensitized solar cells (DSSCs) offer an optimal trade-off between conversion-efficiency and low-cost fabrication. However, since all its electrodes need to fulfill stringent work-function requirements, its materials have remained unchanged since DSSC's first report early-90s. Here we describe a new material, oxidized-three-dimensional-graphene (o-3D-C), with a band gap of 0.2 eV and suitable electronic band-structure as alternative metal-free material for DSSCs-anodes. o-3D-C/dye-complex has a strong chemical bonding via carboxylic-group chemisorption with full saturation after 12 sec at capacity of ∼450 mg/g (600x faster and 7x higher than optimized metal surfaces). Furthermore, fluorescence quenching of life-time by 28-35% was measured demonstrating charge-transfer from dye to o-3D-C.

CMOS integration of high-k/metal gate transistors in diffusion and gate replacement (D&GR) scheme for dynamic random access memory peripheral circuits

NASA Astrophysics Data System (ADS)

Dentoni Litta, Eugenio; Ritzenthaler, Romain; Schram, Tom; Spessot, Alessio; O’Sullivan, Barry; Machkaoutsan, Vladimir; Fazan, Pierre; Ji, Yunhyuck; Mannaert, Geert; Lorant, Christophe; Sebaai, Farid; Thiam, Arame; Ercken, Monique; Demuynck, Steven; Horiguchi, Naoto

2018-04-01

Integration of high-k/metal gate stacks in peripheral transistors is a major candidate to ensure continued scaling of dynamic random access memory (DRAM) technology. In this paper, the CMOS integration of diffusion and gate replacement (D&GR) high-k/metal gate stacks is investigated, evaluating four different approaches for the critical patterning step of removing the N-type field effect transistor (NFET) effective work function (eWF) shifter stack from the P-type field effect transistor (PFET) area. The effect of plasma exposure during the patterning step is investigated in detail and found to have a strong impact on threshold voltage tunability. A CMOS integration scheme based on an experimental wet-compatible photoresist is developed and the fulfillment of the main device metrics [equivalent oxide thickness (EOT), eWF, gate leakage current density, on/off currents, short channel control] is demonstrated.

Identification of Molecular and Cellular Responses of Desulfovibrio vulgaris Biofilms under Culture Conditions Relevant to Field Conditions for Bioreduction of Toxic Metals and Radionuclides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Judy D. Wall

2011-06-09

Our findings demonstrated that D. vulgaris surface-adhered populations produce extracellular structures, and that that the cells have altered carbon and energy flux compared to planktonic cells. Biofilms did not have greatly increased carbohydrate accumulation. Interestingly genes present on the native plasmid found in D. vulgaris Hildenborough were necessary for wild type biofilm formation. In addition, extracellular appendages dependent on functions or proteins encoded by flaG or fliA also contributed to biofilm formation. Studies with SRB biofilms have indicated that the reduction and precipitation of metals can occur within the biofilm matrix; however, little work has been done to elucidate themore » physiological state of surface-adhered cells during metal reduction (Cr6+, U6+) and how this process is affected by nutrient feed levels (i.e., the stimulant).« less

Fiber optic apparatus for detecting molecular species by surface enhanced Raman spectroscopy

DOEpatents

Angel, S.M.; Sharma, S.K.

1988-11-01

Optrode apparatus for detecting constituents of a fluid medium includes an optical fiber having a metal coating on at least a portion of a light transmissive core. The metal is one, such as silver, gold or copper, which enhances emission of Raman signal frequencies by molecules adsorbed on the surface of the coating when monochromatic probe light of a different frequency is scattered by such molecules and the metal coating is sufficiently thin to transmit light between the absorbed molecules and the core of the fiber. Probe light is directed into one end of the fiber and a detector analyzes light emitted from the fiber for Raman frequencies that identify one or more particular molecular species. In one form, the optrode may function as a working electrode of an electrochemical cell while also serving to detect the products of oxidation or reduction reactions which occur at the electrode surface. 6 figs.

Fiber optic apparatus for detecting molecular species by surface enhanced Raman spectroscopy

DOEpatents

Angel, S.M.; Sharma, S.K.

1987-11-30

Optrode apparatus for detecting constituents of a fluid medium includes an optical fiber having a metal coating on at least a portion of a light transmissive core. The metal is one, such as silver, gold or copper, which enhances emission of Raman signal frequencies by molecules adsorbed on the surface of the coating when monochromatic probe light of a different frequency is scattered by such molecules and the metal coating is sufficiently thin to transmit light between the adsorbed molecules and the core of the fiber. Probe light is directed into one end of the fiber and a detector analyzes light emitted from the fiber for Raman frequencies that identify one or more particular molecular species. In one form, the optrode may function as a working electrode of an electrochemical cell while also serving to detect the products of oxidation or reduction reactions which occur at the electrode surface. 6 figs.

Effect of size on bulk and surface cohesion energy of metallic nano-particles

NASA Astrophysics Data System (ADS)

Yaghmaee, M. S.; Shokri, B.

2007-04-01

The knowledge of nano-material properties not only helps us to understand the extreme behaviour of small-scale materials better (expected to be different from what we observe from their bulk value) but also helps us to analyse and design new advanced functionalized materials through different nano technologies. Among these fundamental properties, the cohesion (binding) energy mainly describes most behaviours of materials in different environments. In this work, we discuss this fundamental property through a nano-thermodynamical approach using two algorithms, where in the first approach the size dependence of the inner (bulk) cohesion energy is studied, and in the second approach the surface cohesion energy is considered too. The results, which are presented through a computational demonstration (for four different metals: Al, Ga, W and Ag), can be compared with some experimental values for W metallic nano-particles.

Growth of Ni nanoclusters on irradiated graphene: a molecular dynamics study.

PubMed

Valencia, F J; Hernandez-Vazquez, E E; Bringa, E M; Moran-Lopez, J L; Rogan, J; Gonzalez, R I; Munoz, F

2018-04-23

We studied the soft landing of Ni atoms on a previously damaged graphene sheet by means of molecular dynamics simulations. We found a monotonic decrease of the cluster frequency as a function of its size, but few big clusters comprise an appreciable fraction of the total number of Ni atoms. The aggregation of Ni atoms is also modeled by means of a simple phenomenological model. The results are in clear contrast with the case of hard or energetic landing of metal atoms, where there is a tendency to form mono-disperse metal clusters. This behavior is attributed to the high diffusion of unattached Ni atoms, together with vacancies acting as capture centers. The findings of this work show that a simple study of the energetics of the system is not enough in the soft landing regime, where it is unavoidable to also consider the growth process of metal clusters.

Silicene Catalyzed Reduction of Nitrobenzene to Aniline: a Computational Study

NASA Astrophysics Data System (ADS)

Morrissey, Christopher; He, Haiying

The reduction of nitrobenzene to aniline has a broad range of applications in the production of rubbers, dyes, agrochemicals, and pharmaceuticals. Currently, use of metal catalysts is the most popular method of performing this reaction on a large scale. These metal catalysts usually require high-temperature and/or high-pressure reaction conditions, and produce hazardous chemicals. This has led to a call for more environmentally friendly nonmetal catalysts. Recent studies suggest that silicene, the recently discovered silicon counterpart of graphene, could potentially work as a nonmetal catalyst due to its unique electronic property and strong interactions with molecules containing nitrogen and oxygen. In this computational study, we have investigated the plausibility of using silicene as a catalyst for the reduction of nitrobenzene. Possible reaction mechanisms will be discussed with a highlight of the difference between silicene and metal catalysts. . All calculations were performed in the framework of density functional theory.

Silicon nanowire photodetectors made by metal-assisted chemical etching

NASA Astrophysics Data System (ADS)

Xu, Ying; Ni, Chuan; Sarangan, Andrew

2016-09-01

Silicon nanowires have unique optical effects, and have potential applications in photodetectors. They can exhibit simple optical effects such as anti-reflection, but can also produce quantum confined effects. In this work, we have fabricated silicon photodetectors, and then post-processed them by etching nanowires on the incident surface. These nanowires were produced by a wet-chemical etching process known as the metal-assisted-chemical etching, abbreviated as MACE. N-type silicon substrates were doped by thermal diffusion from a solid ceramic source, followed by etching, patterning and contact metallization. The detectors were first tested for functionality and optical performance. The nanowires were then made by depositing an ultra-thin film of gold below its percolation thickness to produce an interconnected porous film. This was then used as a template to etch high aspect ratio nanowires into the face of the detectors with a HF:H2O2 mixture.

Effects of Low-Energy Excitations on Spectral Properties at Higher Binding Energy: The Metal-Insulator Transition of VO2

NASA Astrophysics Data System (ADS)

Gatti, Matteo; Panaccione, Giancarlo; Reining, Lucia

2015-03-01

The effects of electron interaction on spectral properties can be understood in terms of coupling between excitations. In transition-metal oxides, the spectral function close to the Fermi level and low-energy excitations between d states have attracted particular attention. In this work we focus on photoemission spectra of vanadium dioxide over a wide (10 eV) range of binding energies. We show that there are clear signatures of the metal-insulator transition over the whole range due to a cross coupling of the delocalized s and p states with low-energy excitations between the localized d states. This coupling can be understood by advanced calculations based on many-body perturbation theory in the G W approximation. We also advocate the fact that tuning the photon energy up to the hard-x-ray range can help to distinguish fingerprints of correlation from pure band-structure effects.

All-metal superconducting planar microwave resonator

NASA Astrophysics Data System (ADS)

Horsley, Matt; Pereverzev, Sergey; Dubois, Jonathon; Friedrich, Stephan; Qu, Dongxia; Libby, Steve; Lordi, Vincenzo; Carosi, Gianpaolo; Stoeffl, Wolfgang; Chapline, George; Drury, Owen; Quantum Noise in Superconducting Devices Team

There is common agreement that noise and resonance frequency jitter in superconducting microwave planar resonators are caused by presence of two-level systems, or fluctuators, in resonator materials- in dielectric substrate, in superconducting and dielectric layers and on the boundaries and interfaces. Scaling of noise with device dimensions indicate that fluctuators are likely concentrated around boundaries; physical nature of those fluctuators remains unclear. The presence of dielectrics is not necessary for the superconducting device functionality, and one can ask question about properties of all-metal device, where dielectric substrate and oxide films on metal are absent. Resonator made from of thin conducting layer with cuts in it is usually called slot line resonator. We report on the design, fabrication and initial testing of multiple split rings slot line resonator made out of thin molybdenum plate. This work is being funded as part of a three year strategic initiative (LDRD 16-SI-004) to better understand noise in superconducting devices.

Phenanthroline-based metal–organic frameworks for Fe-catalyzed C sp3 –H amination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thacker, Nathan C.; Ji, Pengfei; Lin, Zekai

2017-01-01

We report here the synthesis of a robust and highly porous Fe-phenanthroline-based metal–organic framework (MOF) and its application in catalyzing challenging inter- and intramolecular C–H amination reactions. For the intermolecular amination reactions, a FeBr 2-metalated MOF selectively functionalized secondary benzylic and allylic C–H bonds. The intramolecular amination reactions utilizing organic azides as the nitrene source required the reduction of the FeBr 2-metalated MOF with NaBHEt 3to generate the active catalyst. For both reactions, Fe or Zr leaching was less than 0.1%, and MOFs could be recycled and reused with no loss in catalytic activity. Furthermore, MOF catalysts were significantly moremore » active than the corresponding homogeneous analogs. This work demonstrates the great potential of MOFs in generating highly active, recyclable, and reusable earth abundant metal catalysts for challenging organic transformations.« less

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Engineering functionality gradients by dip coating process in acceleration mode.

PubMed

Faustini, Marco; Ceratti, Davide R; Louis, Benjamin; Boudot, Mickael; Albouy, Pierre-Antoine; Boissière, Cédric; Grosso, David

2014-10-08

In this work, unique functional devices exhibiting controlled gradients of properties are fabricated by dip-coating process in acceleration mode. Through this new approach, thin films with "on-demand" thickness graded profiles at the submillimeter scale are prepared in an easy and versatile way, compatible for large-scale production. The technique is adapted to several relevant materials, including sol-gel dense and mesoporous metal oxides, block copolymers, metal-organic framework colloids, and commercial photoresists. In the first part of the Article, an investigation on the effect of the dip coating speed variation on the thickness profiles is reported together with the critical roles played by the evaporation rate and by the viscosity on the fluid draining-induced film formation. In the second part, dip-coating in acceleration mode is used to induce controlled variation of functionalities by playing on structural, chemical, or dimensional variations in nano- and microsystems. In order to demonstrate the full potentiality and versatility of the technique, original graded functional devices are made including optical interferometry mirrors with bidirectional gradients, one-dimensional photonic crystals with a stop-band gradient, graded microfluidic channels, and wetting gradient to induce droplet motion.

The structural, functional, and nutritional adaptation of college basketball players over a season.

PubMed

Bolonchuk, W W; Lukaski, H C; Siders, W A

1991-06-01

The purpose of this study was to determine the structural, functional and nutritional adaptation of college basketball players over a season. Structure was determined by somatotype and body composition, function was determined by peak work capacity and work efficiency, and nutrition was determined by plasma metals analysis. The tests were performed twice on each of the eight subjects, one preseason (PRS) and one postseason (PST). A small structural adaptation was indicated by a mean decrease (less than 1 kg) in fat free weight and an increase in ectomorphy (less than 0.03). Body weight and skinfolds did not change significantly. Functional adaptation was indicated by a one minute decrease in running time for the work capacity test (p less than 0.002), and an increase (p less than 0.02) in VO2 for the work efficiency test. Nutritional adaptation was indicated by a greater mobilization of plasma Zn after exercise during PST than PRS. Plasma Cu apparently was mobilized during exercise in PST but the change during the season (-10 to -6.6%) was not statistically significant because of the large interindividual variability in response. Structural and functional adaptation to basketball training over a collegiate season is small; however, the change in Zn mobility and the tendency for a concomitant change in Cu mobilization offers a unique finding to help explain the nutritional adaptation to training.

Approach to the mechanism of hydrogen evolution electrocatalyzed by a model Co clathrochelate: A theoretical study by Density Functional Theory.

PubMed

Antuch Cubillas, Manuel; Millet, Pierre

2018-06-20

The hydrogen evolution reaction (HER) is the focus of much attention by the scientific community because of the increasing energetic demands of modern society for clean and renewable energy sources. Molecular complexes of 3d-transition metals, such as cobalt, are potential alternative candidates to platinum for the HER in acidic media. Among these, cage complexes such as tris-dioximate metal clathrochelates have shown high HER catalytic properties. However, it is not clear either the catalytic activity of this molecule is due to metal-centered activation of H+, due to a low oxidation state of the metal stabilized by the surrounding organic cage, or if it is the organic cage who has a further cooperative role in bringing protons together. In this work, we report on a DFT study of two possible mechanisms for the HER catalyzed by a model Co clathrochelate. In order to assess the putative ligand involvement in the mechanism, several protonation sites located in the organic cage along with several combinations of single and double protonation were investigated. This work further addressed two possible mechanisms for the HER. The structural and energetic analysis of relevant intermediates suggested that the electrocatalytic mechanism is not based on the cooperation between the ligand and the metal, but it is mainly due to the activation of H+ by the Co metallocenter. Our calculations further suggest that the last step in the mechanism is a proton coupled electron transfer step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the Numerical Analysis of Decay Rate Enhancement in Metallic Environment

NASA Astrophysics Data System (ADS)

Mehedinteanu, S.

2007-10-01

Motivated on the very recent experiments to determine the acceleration of the alpha decay of meta-stable radionuclides in metallic environment some work has been done to strengthten the importance in the process of electrons screening in metals. Thus, by combining the Gamow decay theory with electrostatic screening in Debye-Hückel approximation (jellium model) a formula for ``the shift'' in screening energy which enters in the decay enhancement factor expression that copes well with these experiments has been derived. It was established that to simulate the poly-atoms system containing decaying isotopes in QM&MD codes calculations, and to include ``the screening energy shift'' of protons, decay alpha, beta+ particles due to all surrounding interacting effects, it is sufficiently only to substitute the code ruly pseudo-potential input for hydrogen-like atoms (including alpha) by a screened Coulomb potential as from the well-known Gamow alpha decay theory. For demonstration is used the QM&MD code package which usually performs density-functional theory (DFT) total-energy calculations for materials ranging from insulators to transition metals. This package employs first-principles pseudo-potentials and a plane-wave basis-set, and it was used to do a special calculus for some metal environments (Pd) where protons-deuterons are implanted or when it is alloyed with a radionuclide-like isotopes (174Hf72), the results compare well with the existing experiments on the decay enhancement. These works give further arguments for a cheap solution to remove the transuranic waste (involving all alpha-decay) of used-up rods of fission reactors in a time period of a few years.

Reducing Sweeping Frequencies in Microwave NDT Employing Machine Learning Feature Selection

PubMed Central

Moomen, Abdelniser; Ali, Abdulbaset; Ramahi, Omar M.

2016-01-01

Nondestructive Testing (NDT) assessment of materials’ health condition is useful for classifying healthy from unhealthy structures or detecting flaws in metallic or dielectric structures. Performing structural health testing for coated/uncoated metallic or dielectric materials with the same testing equipment requires a testing method that can work on metallics and dielectrics such as microwave testing. Reducing complexity and expenses associated with current diagnostic practices of microwave NDT of structural health requires an effective and intelligent approach based on feature selection and classification techniques of machine learning. Current microwave NDT methods in general based on measuring variation in the S-matrix over the entire operating frequency ranges of the sensors. For instance, assessing the health of metallic structures using a microwave sensor depends on the reflection or/and transmission coefficient measurements as a function of the sweeping frequencies of the operating band. The aim of this work is reducing sweeping frequencies using machine learning feature selection techniques. By treating sweeping frequencies as features, the number of top important features can be identified, then only the most influential features (frequencies) are considered when building the microwave NDT equipment. The proposed method of reducing sweeping frequencies was validated experimentally using a waveguide sensor and a metallic plate with different cracks. Among the investigated feature selection techniques are information gain, gain ratio, relief, chi-squared. The effectiveness of the selected features were validated through performance evaluations of various classification models; namely, Nearest Neighbor, Neural Networks, Random Forest, and Support Vector Machine. Results showed good crack classification accuracy rates after employing feature selection algorithms. PMID:27104533

Destabilization of the metal site as a hub for the pathogenic mechanism of five ALS-linked mutants of copper, zinc superoxide dismutase.

PubMed

Mera-Adasme, Raúl; Erdmann, Hannes; Bereźniak, Tomasz; Ochsenfeld, Christian

2016-10-01

Amyotrophic lateral sclerosis (ALS) is a lethal neurodegenerative disease, with no effective pharmacological treatment. Its pathogenesis is unknown, although a subset of the cases is linked to genetic mutations. A significant fraction of the mutations occur in one protein, copper, zinc superoxide dismutase (SOD1). The toxic function of mutant SOD1 has not been elucidated, but damage to the metal site of the protein is believed to play a major role. In this work, we study the electrostatic loop of SOD1, which we had previously proposed to work as a "solvent seal" isolating the metal site from water molecules. Out of the five contact points identified between the electrostatic loop and its dock in the rest of the protein, three points were found to be affected by ALS-linked mutations, with a total of five mutations identified. The effect of the five mutations was studied using methods of computational chemistry. We found that four of the mutations destabilize the proposed solvent seal, while the fifth mutation directly affects the metal-site stability. In the two contact points unaffected by ALS-linked mutations, the side chains of the residues were not found to play a stabilizing role. Our results show that the docking of the electrostatic loop to the rest of SOD1 plays a role in ALS pathogenesis, in support of that structure acting as a solvent barrier for the metal site. The results provide a unified pathogenic mechanism for five different ALS-linked mutations of SOD1.

Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS2 Nanosheets via Covalent Functionalization.

PubMed

Benson, Eric E; Zhang, Hanyu; Schuman, Samuel A; Nanayakkara, Sanjini U; Bronstein, Noah D; Ferrere, Suzanne; Blackburn, Jeffrey L; Miller, Elisa M

2018-01-10

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS 2 ) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS 2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS 2 functionalized with the most electron donating functional group (p-(CH 3 CH 2 ) 2 NPh-MoS 2 ) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS 2 . The p-(CH 3 CH 2 ) 2 NPh-MoS 2 is more stable than unfunctionalized metallic MoS 2 and outperforms unfunctionalized metallic MoS 2 for continuous H 2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS 2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS 2 nanosheet. The functional groups preserve the metallic nature of the MoS 2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS 2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS 2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.

Bio-functionalization of biomedical metals.

PubMed

Xiao, M; Chen, Y M; Biao, M N; Zhang, X D; Yang, B C

2017-01-01

Bio-functionalization means to endow biomaterials with bio-functions so as to make the materials or devices more suitable for biomedical applications. Traditionally, because of the excellent mechanical properties, the biomedical metals have been widely used in clinic. However, the utilized functions are basically supporting or fixation especially for the implantable devices. Nowadays, some new functions, including bioactivity, anti-tumor, anti-microbial, and so on, are introduced to biomedical metals. To realize those bio-functions on the metallic biomedical materials, surface modification is the most commonly used method. Surface modification, including physical and chemical methods, is an effective way to alter the surface morphology and composition of biomaterials. It can endow the biomedical metals with new surface properties while still retain the good mechanical properties of the bulk material. Having analyzed the ways of realizing the bio-functionalization, this article briefly summarized the bio-functionalization concepts of six hot spots in this field. They are bioactivity, bony tissue inducing, anti-microbial, anti-tumor, anticoagulation, and drug loading functions. Copyright © 2016. Published by Elsevier B.V.

Covalent functionalization of monolayered transition metal dichalcogenides by phase engineering.

PubMed

Voiry, Damien; Goswami, Anandarup; Kappera, Rajesh; e Silva, Cecilia de Carvalho Castro; Kaplan, Daniel; Fujita, Takeshi; Chen, Mingwei; Asefa, Tewodros; Chhowalla, Manish

2015-01-01

Chemical functionalization of low-dimensional materials such as nanotubes, nanowires and graphene leads to profound changes in their properties and is essential for solubilizing them in common solvents. Covalent attachment of functional groups is generally achieved at defect sites, which facilitate electron transfer. Here, we describe a simple and general method for covalent functionalization of two-dimensional transition metal dichalcogenide nanosheets (MoS₂, WS₂ and MoSe₂), which does not rely on defect engineering. The functionalization reaction is instead facilitated by electron transfer between the electron-rich metallic 1T phase and an organohalide reactant, resulting in functional groups that are covalently attached to the chalcogen atoms of the transition metal dichalcogenide. The attachment of functional groups leads to dramatic changes in the optoelectronic properties of the material. For example, we show that it renders the metallic 1T phase semiconducting, and gives it strong and tunable photoluminescence and gate modulation in field-effect transistors.

Sol-gel precursors and products thereof

DOEpatents

Warren, Scott C.; DiSalvo, Jr., Francis J.; Weisner, Ulrich B.

2017-02-14

The present invention provides a generalizable single-source sol-gel precursor capable of introducing a wide range of functionalities to metal oxides such as silica. The sol-gel precursor facilitates a one-molecule, one-step approach to the synthesis of metal-silica hybrids with combinations of biological, catalytic, magnetic, and optical functionalities. The single-source precursor also provides a flexible route for simultaneously incorporating functional species of many different types. The ligands employed for functionalizing the metal oxides are derived from a library of amino acids, hydroxy acids, or peptides and a silicon alkoxide, allowing many biological functionalities to be built into silica hybrids. The ligands can coordinate with a wide range of metals via a carboxylic acid, thereby allowing direct incorporation of inorganic functionalities from across the periodic table. Using the single-source precursor a wide range of functionalized nanostructures such as monolith structures, mesostructures, multiple metal gradient mesostructures and Stober-type nanoparticles can be synthesized. ##STR00001##

Impurities in Antiferromagnetic Transition-Metal Oxides - Symmetry and Optical Transitions

NASA Astrophysics Data System (ADS)

Petersen, John Emil, III

The study of antiferromagnetic transition-metal oxides is an extremely active area in the physical sciences, where condensed matter physics, inorganic chemistry, and materials science blend together. The sheer number of potential commercial applications is staggering, but much of the fundamental science remains unexplained. This is not due to a lack of effort, however, as theorists have been struggling to understand these materials for decades - particularly the character of the band edges and first optical transitions. The difficulty lies in the strong correlation or Coloumb attraction between the electrons in the anisotropic d orbitals, which conventional band theory cannot describe adequately. The correlation problem is approached here by the well-accepted method of adding a Hubbard potential energy term to the ground state Hamiltonian, calculated within Density Functional Theory. The frequency-dependent complex dielectric function is calculated within the Independent Particle Approximation, and optical transitions are evaluated in multiple different ways. Peaks in the imaginary part of the dielectric function are compared energetically to orbitally decomposed density of states calculations. Optical transitions are typically analyzed in terms of atomic orbitals, which, strictly speaking, gives misleading results. Here, however, from the calculated data, two alternative interpretations are analyzed for each material studied. The first employs rigorous group theoretical analysis to determine allowed electric-dipole transitions, taking into account both orbital hybridization and crystal symmetry. The second interpretation is that of metal cation site hopping. In this interpretation, carriers hop from the x2 - y2 d orbital of one metal cation lattice site to the next metal cation site which is antiferromagnetically aligned. At times, thoughout this work, one interpretation is favorable to the other. Which interpretation is most valid depends on the material considered. For example, simple rock-salt transition-metal oxides are quite different from the high temperature superconducting cuprates. A range of materials is studied here, in order to gain a greater understanding of optical transitions in highly-correlated systems. In this work, O vacancies are introduced in NiO, along with Fe impurities, to understand better the band filling in the insulating behavior observed experimentally. These results are compared with those of La2NiO4, La2CuO4, La2-xSr xNiO4, and La2-xSrxCuO4. to elucidate the mechanisms behind the symmetry breaking phenomena in the Sr doped systems. As it turns out, indeed, the x2 - y2 orbital in these materials plays a critical role in spatial charge distribution, magnetic, and spin densities which are coupled to the dopant position in the lattice. The in-depth study of electronic and optical properties of transition-metal oxides presented here provides theoretical characterization of the infamous pseudogap in the cuprates - one of the greatest mysteries of modern solid state physics. In addition, via Density Functional Perturbation Theory, the phonon coupling with charge-density wave is explored in La2-xSr xNiO4 and found to be the dominant contributing factor to the colossal dielectric constant.

MetalPDB in 2018: a database of metal sites in biological macromolecular structures.

PubMed

Putignano, Valeria; Rosato, Antonio; Banci, Lucia; Andreini, Claudia

2018-01-04

MetalPDB (http://metalweb.cerm.unifi.it/) is a database providing information on metal-binding sites detected in the three-dimensional (3D) structures of biological macromolecules. MetalPDB represents such sites as 3D templates, called Minimal Functional Sites (MFSs), which describe the local environment around the metal(s) independently of the larger context of the macromolecular structure. The 2018 update of MetalPDB includes new contents and tools. A major extension is the inclusion of proteins whose structures do not contain metal ions although their sequences potentially contain a known MFS. In addition, MetalPDB now provides extensive statistical analyses addressing several aspects of general metal usage within the PDB, across protein families and in catalysis. Users can also query MetalPDB to extract statistical information on structural aspects associated with individual metals, such as preferred coordination geometries or aminoacidic environment. A further major improvement is the functional annotation of MFSs; the annotation is manually performed via a password-protected annotator interface. At present, ∼50% of all MFSs have such a functional annotation. Other noteworthy improvements are bulk query functionality, through the upload of a list of PDB identifiers, and ftp access to MetalPDB contents, allowing users to carry out in-depth analyses on their own computational infrastructure. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Efficient Means of Detecting Neutral Atoms in Space

NASA Astrophysics Data System (ADS)

Zinicola, W. N.

2006-12-01

This summer, The Society of Physics Students granted me the opportunity to participate in an internship for The National Aeronautics and Space Administration (NASA) and The University of Maryland. Our chief interest was analyzing low energy neutral atoms that were created from random interactions of ions in space plasma. From detecting these neutrals one can project a image of what the plasma's composition is, and how this plasma changes through interactions with the solar wind. Presently, low energy neutral atom detectors have poor efficiency, typically in the range of 1%. Our goal was to increase this efficiency. To detect low energy neutrals we must first convert them from neutral molecules to negatively charged ions. Once converted, these "new" negatively charged ions can be easily detected and completely analyzed giving us information about their energy, mass, and instantaneous direction. The efficiency of the detector is drastically affected by the surface used for converting these neutrals. My job was first to create thin metal conversion surfaces. Then, using an X-ray photoelectron spectrometer, analyze atomic surface composition and gather work function values. Once the work function values were known we placed the surfaces in our neutral detector and measured their conversion efficiencies. Finally, a relation between the work function of the metal surface an its conversion efficiency was generated. With this relationship accurately measured one could use this information to help give suggestions on what surface would be the best to increase our detection efficiency. If we could increase the efficiency of these low energy neutral atom detectors by even 1% we would be able to decrease the size of the detector therefore making it cheaper and more applicable for space exploration.* * A special thanks to Dr. Michael Coplan of the University of Maryland for his support and guidance through all my research.

The influence of hydrogenation and oxygen vacancies on molybdenum oxides work function and gap states for application in organic optoelectronics.

PubMed

Vasilopoulou, Maria; Douvas, Antonios M; Georgiadou, Dimitra G; Palilis, Leonidas C; Kennou, Stella; Sygellou, Labrini; Soultati, Anastasia; Kostis, Ioannis; Papadimitropoulos, Giorgos; Davazoglou, Dimitris; Argitis, Panagiotis

2012-10-03

Molybdenum oxide is used as a low-resistance anode interfacial layer in applications such as organic light emitting diodes and organic photovoltaics. However, little is known about the correlation between its stoichiometry and electronic properties, such as work function and occupied gap states. In addition, despite the fact that the knowledge of the exact oxide stoichiometry is of paramount importance, few studies have appeared in the literature discussing how this stoichiometry can be controlled to permit the desirable modification of the oxide's electronic structure. This work aims to investigate the beneficial role of hydrogenation (the incorporation of hydrogen within the oxide lattice) versus oxygen vacancy formation in tuning the electronic structure of molybdenum oxides while maintaining their high work function. A large improvement in the operational characteristics of both polymer light emitting devices and bulk heterojunction solar cells incorporating hydrogenated Mo oxides as hole injection/extraction layers was achieved as a result of favorable energy level alignment at the metal oxide/organic interface and enhanced charge transport through the formation of a large density of gap states near the Fermi level.

Can the ceramic industry be a new and hazardous sector for work-related asthma?

PubMed

Kurt, Ozlem Kar; Ergun, Dilek; Basaran, Nursen

2018-04-01

Work-related asthma (WRA) constitutes a significant proportion of all asthma cases and continues to be reported from different industries. The aim of the study was to identify the occupations that can be related to WRA and diagnostic steps used in suspected WRA patients. We retrospectively reviewed the clinical records of WRA suspected patients who were referred to Ankara Occupational and Environmental Diseases Hospital, Turkey from January 2015 to January 2017. Detailed occupational history, the diagnostic steps such as pulmonary function testing (PFT), peak expiratory flow (PEF) monitoring and nonspecific bronchial provocation tests (NSBPT) were recorded. Among 160 patients, 148 were male and 12 were female. Only 2 of them were diagnosed as work-exacerbated asthma (WEA). Diagnosis of asthma was based on using reversible airflow limitation 28.8% (n = 46) or NSBPT 31.9% (n = 51). Toxicological analysis showed that 28 patients had heavy metal poisoning, 9 patients had solvent poisoning, 4 patients had both. According to occupations, 32 of them were ceramic workers (20.0%) and 27 of them were metal workers (16.9%). Plastic workers (4 ± 2.8 years), cleaners (6.2 ± 5.7 years), metal workers (7.4 ± 5.4 years), painters (10 ± 5.2 years), ceramic workers (10.8 ± 5.9 years) had the shortest exposure durations for development of occupational asthma (OA). An analysis of variance showed that the effect of heavy metal and solvent poisoning on mean time for onset of OA was not significant. The results demonstrate that besides the sectors known to cause WRA, ceramic and metal industries can be related to important exposures related to WRA. Medical surveillance of employees in this sector is important in early detection. Copyright © 2018 Elsevier Ltd. All rights reserved.

Chemical gating of epitaxial graphene through ultrathin oxide layers.

PubMed

Larciprete, Rosanna; Lacovig, Paolo; Orlando, Fabrizio; Dalmiglio, Matteo; Omiciuolo, Luca; Baraldi, Alessandro; Lizzit, Silvano

2015-08-07

We achieved a controllable chemical gating of epitaxial graphene grown on metal substrates by exploiting the electrostatic polarization of ultrathin SiO2 layers synthesized below it. Intercalated oxygen diffusing through the SiO2 layer modifies the metal-oxide work function and hole dopes graphene. The graphene/oxide/metal heterostructure behaves as a gated plane capacitor with the in situ grown SiO2 layer acting as a homogeneous dielectric spacer, whose high capacity allows the Fermi level of graphene to be shifted by a few hundreds of meV when the oxygen coverage at the metal substrate is of the order of 0.5 monolayers. The hole doping can be finely tuned by controlling the amount of interfacial oxygen, as well as by adjusting the thickness of the oxide layer. After complete thermal desorption of oxygen the intrinsic doping of SiO2 supported graphene is evaluated in the absence of contaminants and adventitious adsorbates. The demonstration that the charge state of graphene can be changed by chemically modifying the buried oxide/metal interface hints at the possibility of tuning the level and sign of doping by the use of other intercalants capable of diffusing through the ultrathin porous dielectric and reach the interface with the metal.