Reduced electron recombination of dye-sensitized solar cells based on TiO 2 spheres consisting of ultrathin nanosheets with [001] facet exposed

An anatase TiO 2 material with hierarchically structured spheres consisting of ultrathin nanosheets with 100% of the [001] facet exposed was employed to fabricate dye-sensitized solar cells (DSC s). Investigation of the electron transport and back reaction of the DSCs by electrochemical impedance spectroscopy showed that the spheres had a threefold lower electron recombination rate compared to the conventional TiO 2 nanoparticles. In contrast, the effective electron diffusion coefficient, D n, was not sensitive to the variation of the TiO 2 morphology. The TiO 2 spheres showed the same Dn as that of the nanoparticles. The influence of TiCl 4 post-treatment on the conduction band of the TiO 2 spheres and on the kinetics of electron transport and back reactions was also investigated. It was found that the TiCl 4 post-treatment caused a downward shift of the TiO 2 conduction band edge by 30 meV. Meanwhile, a fourfold increase of the effective electron lifetime of the DSC was also observed after TiCl4 treatment. The synergistic effect of the variation of the TiO 2 conduction band and the electron recombination determined the open-circuit voltage of the DSC. © 2012 Wang et al.

Hybrid graphene and graphitic carbon nitride nanocomposite : gap opening, electron–hole puddle, interfacial charge transfer, and enhanced visible light response

Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C3N4) and electronically active graphene. We find an inhomogeneous planar substrate (g-C3N4) promotes electronrich and hole-rich regions, i.e., forming a well-defined electron−hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C3N4 substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C3N4 interface opens a 70 meV gap in g-C3N4-supported graphene, a feature that can potentially allow overcoming the graphene’s band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C3N4 is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C3N4 monolayer, the hybrid graphene/g-C3N4 complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.

Hybrid graphene/titania nanocomposite : interface charge transfer, hole doping, and sensitization for visible light response

We demonstrated for the first time by large-scale ab initio calculations that a graphene/titania interface in the ground electronic state forms a charge-transfer complex due to the large difference of work functions between graphene and titania, leading to substantial hole doping in graphene. Interestingly, electrons in the upper valence band can be directly excited from graphene to the conduction band, that is, the 3d orbitals of titania, under visible light irradiation. This should yield well-separated electron−hole pairs, with potentially high photocatalytic or photovoltaic performance in hybrid graphene and titania nanocomposites. Experimental wavelength-dependent photocurrent generation of the graphene/titania photoanode demonstrated noticeable visible light response and evidently verified our ab initio prediction.

The relationship between hip-abductor strength and the magnitude of pelvic drop in patients with low back pain

Context: It has been theorized that a positive Trendelenburg test (TT) indicates weakness of the stance hip-abductor (HABD) musculature, results in contralateral pelvic drop, and represents impaired load transfer, which may contribute to low back pain. Few studies have tested whether weakness of the HABDs is directly related to the magnitude of pelvic drop (MPD). Objective: To examine the relationship between HABD strength and MPD during the static TT and during walking for patients with nonspecific low back pain (NSLBP) and healthy controls (CON). A secondary purpose was to examine this relationship in NSLBP after a 3-wk HABD-strengthening program. Design: Quasi-experimental. Setting: Clinical research laboratory. Participants: 20 (10 NSLBP and 10 CON). Intervention: HABD strengthening. Main Outcome Measures: Normalized HABD strength, MPD during TT, and maximal pelvic frontal-plane excursion during walking. Results: At baseline, the NSLBP subjects were significantly weaker (31%; P = .03) than CON. No differences in maximal pelvic frontal-plane excursion (P = .72), right MPD (P = 1.00), or left MPD (P = .40) were measured between groups. During the static TT, nonsignificant correlations were found between left HABD strength and right MPD for NSLBP (r = -.32, P = .36) and CON (r = -.24, P = .48) and between right HABD strength and left MPD for NSLBP (r = -.24, P = .50) and CON (r = -.41, P = .22). Nonsignificant correlations were found between HABD strength and maximal pelvic frontal-plane excursion for NSLBP (r = -.04, P = .90) and CON (r = -.14, P = .68). After strengthening, NSLBP demonstrated significant increases in HABD strength (12%; P = .02), 48% reduction in pain, and no differences in MPD during static TT and maximal pelvic frontal-plane excursion compared with baseline. Conclusions: HABD strength was poorly correlated to MPD during the static TT and during walking in CON and NSLBP. The results suggest that HABD strength may not be the only contributing factor in controlling pelvic stability, and the static TT has limited use as a measure of HABD function.

Preparation of metal-TCNQ charge-transfer complexes on conducting and insulating surfaces by photocrystallization

A generic method for the synthesis of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) charge-transfer complexes on both conducting and nonconducting substrates is achieved by photoexcitation of TCNQ in acetonitrile in the presence of a sacrificial electron donor and the relevant metal cation. The photochemical reaction leads to reduction of TCNQ to the TCNQ- monoanion. In the presence of Mx+(MeCN), reaction with TCNQ-(MeCN) leads to deposition of Mx+[TCNQ]x crystals onto a solid substrate with morphologies that are dependent on the metal cation. Thus, CuTCNQ phase I photocrystallizes as uniform microrods, KTCNQ as microrods with a random size distribution, AgTCNQ as very long nanowires up to 30 μm in length and with diameters of less than 180 nm, and Co[TCNQ]2(H2O)2 as nanorods and wires. The described charge-transfer complexes have been characterized by optical and scanning electron microscopy and IR and Raman spectroscopy. The CuTCNQ and AgTCNQ complexes are of particular interest for use in memory storage and switching devices. In principle, this simple technique can be employed to generate all classes of metal−TCNQ complexes and opens up the possibility to pattern them in a controlled manner on any type of substrate.

Physisorption-induced electron scattering on the surface of carbon-metal core-shell nanowire arrays for hydrogen sensing

Palladium is sputtered on multi-walled carbon nanotube forests to form carbon-metal core-shell nanowire arrays. These hybrid nanostructures exhibited resistive responses when exposed to hydrogen with an excellent baseline recovery at room temperature. The magnitude of the response is shown to be tuneable by an applied voltage. Unlike the charge-transfer mechanism commonly attributed to Pd nanoparticle-decorated carbon nanotubes, this demonstrates that the hydrogen response mechanism of the multi-walled carbon nanotube-Pd core-shell nanostructure is due to the increase in electron scattering induced by physisorption of hydrogen. These hybrid core-shell nanostructures are promising for gas detection in hydrogen storage applications.

Electron transport across magnetic field in low-temperature plasmas : an alternative approach for obtaining evidence of Bohm mechanism

A comparative study involving both experimental and numerical investigations was made to resolve a long-standing problem of understanding electron conductivity mechanism across magnetic field in low-temperature plasmas. We have calculated the plasma parameters from experimentally obtained electric field distribution, and then made a 'back' comparison with the distributions of electron energy and plasma density obtained in the experiment. This approach significantly reduces an influence of the assumption about particular phenomenology of the electron conductivity in plasma. The results of the experiment and calculations made by this technique have showed that the classical conductivity is not capable of providing realistic total current and electron energy, whereas the phenomenological anomalous Bohm mobility has demonstrated a very good agreement with the experiment. These results provide an evidence in favor of the Bohm conductivity, thus making it possible to clarify this pressing long-living question about the main driving mechanism responsible for the electron transport in low-temperature plasmas.

Nonresonant power transfer in plasma-surface interactions via two-surface wave decay

The excitation of pairs of electron surface waves via nonresonant decay of plasma waves incident onto a solid surface is studied in the context of controlling the interaction of pulsed electromagnetic radiation with plasma-exposed solid surfaces. The role of the plasma-exposed surfaces in nonlinear heating of the plasma edge and related power transfer is discussed. It is shown that the maximum efficiency of the power transfer at solid surfaces with dielectric permittivity εd <3 corresponds to the resonant two-surface wave decay. On the other hand, for solids with εd >3 the maximum power transfer efficiency is achieved through nonresonant excitation of the quasistatic surface waves. In this case the plasma waves generated by external radiation dissipate their energy into the plasma periphery most effectively.

Two-surface wave decay : controlling power transfer in plasma-surface interactions

Controlled interaction of high-power pulsed electromagnetic radiation with plasma-exposed solid surfaces is a major challenge in applications spanning from electron beam accelerators in microwave electronics to pulsed laser ablation-assisted synthesis of nanomaterials. It is shown that the efficiency of such interaction can be potentially improved via an additional channel of wave power dissipation due to nonlinear excitation of two counterpropagating surface waves, resonant excitations of the plasma-solid system.Physics.

Design and experimental testing of air slab caps which convert commercial electron diodes into dual purpose, correction-free diodes for small field dosimetry

Purpose Two diodes which do not require correction factors for small field relative output measurements are designed and validated using experimental methodology. This was achieved by adding an air layer above the active volume of the diode detectors, which canceled out the increase in response of the diodes in small fields relative to standard field sizes. Methods Due to the increased density of silicon and other components within a diode, additional electrons are created. In very small fields, a very small air gap acts as an effective filter of electrons with a high angle of incidence. The aim was to design a diode that balanced these perturbations to give a response similar to a water-only geometry. Three thicknesses of air were placed at the proximal end of a PTW 60017 electron diode (PTWe) using an adjustable “air cap”. A set of output ratios (ORfclin Det ) for square field sizes of side length down to 5 mm was measured using each air thickness and compared to ORfclin Det measured using an IBA stereotactic field diode (SFD). k fclin, f msr Qclin,Qmsr was transferred from the SFD to the PTWe diode and plotted as a function of air gap thickness for each field size. This enabled the optimal air gap thickness to be obtained by observing which thickness of air was required such that k fclin, f msr Qclin,Qmsr was equal to 1.00 at all field sizes. A similar procedure was used to find the optimal air thickness required to make a modified Sun Nuclear EDGE detector (EDGEe) which s “correction-free” in small field relative dosimetry. In addition, the feasibility of experimentally transferring k fclin, f msr Qclin,Qmsr values from the SFD to unknown diodes was tested by comparing the experimentally transferred k fclin, f msr Qclin,Qmsr values for unmodified PTWe and EDGEe diodes to Monte Carlo simulated values. Results 1.0 mm of air was required to make the PTWe diode correction-free. This modified diode (PTWeair) produced output factors equivalent to those in water at all field sizes (5–50 mm). The optimal air thickness required for the EDGEe diode was found to be 0.6 mm. The modified diode (EDGEeair) produced output factors equivalent to those in water, except at field sizes of 8 and 10 mm where it measured approximately 2% greater than the relative dose to water. The experimentally calculated k fclin, f msr Qclin,Qmsr for both the PTWe and the EDGEe diodes (without air) matched Monte Carlo simulated results, thus proving that it is feasible to transfer k fclin, f msr Qclin,Qmsr from one commercially available detector to another using experimental methods and the recommended experimental setup. Conclusions It is possible to create a diode which does not require corrections for small field output factor measurements. This has been performed and verified experimentally. The ability of a detector to be “correction-free” depends strongly on its design and composition. A nonwater-equivalent detector can only be “correction-free” if competing perturbations of the beam cancel out at all field sizes. This should not be confused with true water equivalency of a detector.

Studies On Friction And Formation Of Transfer Layer In Hcp Metals

Surface texture plays an important role in the frictional behavior and transfer layer formation of contacting surfaces. In the present investigation, basic experiments were conducted using an inclined pin-on-plate sliding apparatus to better understand the role of surface texture on the coefficient of friction and the formation of a transfer layer. In the experiments, soft HCP materials such as pure Mg and pure Zn were used for the pins and a hardened 080 M40 steel was used for the plate. Two surface parameters of the steel plates—roughness and texture—were varied in tests that were conducted at a sliding speed of 2 mm/s in ambient conditions under both dry and lubricated conditions. The morphologies of the worn surfaces of the pins and the formation of the transfer layer on the counter surfaces were observed using a scanning electron microscope. In the experiments, the occurrence of stick-slip motion, the formation of a transfer layer, and the value of friction were recorded. With respect to the friction, both adhesion and plowing components were analyzed. Based on the experimental results, the effect of surface texture on the friction was attributed to differences in the amount of plowing. Both the plowing component of friction and the amplitude of stick-slip motion were determined to increase surface textures that promote plane strain conditions and decrease the textures that favor plane stress conditions.

Ground and Excited State Intramolecular Proton Transfer in Salicylic Acid: an Ab Initio Electronic Structure Investigation

Energetics of the ground and excited state intramolecular proton transfer in salicylic acid have been studied by ab initio molecular orbital calculations using the 6-31G** basis set at the restricted Hartree-Fock (RHF) and configuration interaction-single excitation (CIS) levels and also using the semiempirical method AM1 at the RHF level as well as with single and pair doubles excitation configuration interaction spanning eight frontier orbitals (PECI = 8). The ab initio potential energy profile for intramolecular proton transfer in the ground state reveals a single minimum corresponding to the primary form, in the first excited singlet state, however, there are two minima corresponding to the primary and tautomeric forms, separated by a barrier of similar to 6 kcal/mol, thus accounting for dual emission in salicylic acid. Electron density changes with electronic excitation and tautomerism indicate no zwitterion formation. Changes in spectral characteristics with change in pH, due to protonation and deprotonation of salicylic acid, are also accounted for, qualitatively. Although the AM1 calculations suggest a substantial barrier for proton transfer in the ground as well as the first excited state of SA, it predicts the transition wavelength in near quantitative accord with the experimental results for salicylic acid and its protonated and deprotonated forms.

Studies on friction and formation of transfer layer when Al-4Mg alloy pins slid at various numbers of cycles on steel plates of different surface texture

In the present investigation, various kinds of textures, namely, unidirectional, 8-ground, and random were attained on the die surfaces. Roughness of the textures was varied using different grits of emery papers or polishing powders. Then pins made of Al-4Mg alloys were slid against steel plates at various numbers of cycles, namely 1, 2, 6, 10 and 20 under both dry and lubricated conditions using an inclined pin-on-plate sliding tester. The morphologies of the worn surfaces of the pins and the formation of transfer layer on the counter surfaces were observed using a scanning electron microscope. Surface roughness parameters of the plate were measured using an optical profilometer. It was observed that the coefficient of friction and formation of transfer layer during the first few cycles depend on the die surface textures under both dry and lubricated conditions. It was also observed that under lubricated condition, the coefficient of friction decreases with number of cycles for all kinds of textures. However, under dry condition, it ecreases for unidirectional and 8-ground surfaces while for random surfaces it increases with number of cycles

Studies of Solids and Surfaces by Auger Electron Spectroscopy

Although the applications of Auger electron spectroscopy in surface analysis have by far outweighed its use as a tool to investigate electron states of solids and surfaces, there are a variety of situations where Auger spectroscopy provides unique information. Apart from the chemical shifts, Auger intensities are useful in determining the number of d-electron states in transition metal systems. Auger spectroscopy is a good probe to investigate the surface oxidation of metals. In addition to the intra-atomic Auger transitions, inter-atomic transitions observed in oxides and other systems reveal the nature of electron states of surfaces. Charge-transfer and hybridization effects in alloys are also usefully studied by Auger spectroscopy. Auger electron spectroscopy has not been a popular technique to investigate adsorption of molecules on surfaces, but the technique is useful to obtain fingerprints of surface species.