First-principles study on the transport properties of phenyl dithiol oligomers

We present first-principles studies on the transport properties of oligomers, polyphenyl dithiol, PP(n)DTs, sandwiched between two Al(1 0 0) electrodes. The variation of the current-voltage curve for PP(2)DT in different tilt angles is investigated systematically. The results indicate that PP(2)DT can be functioned as a molecular switch controlled by molecular conformation. We also study the variation of the equilibrium conductance and current-voltage properties of PP(n)DT as a function of n.     

Single-molecule linewidths of terrylene in incommensurate biphenyl: Thermocycling and time-resolved experiments

The purely electronic linewidth δ of terrylene impurity molecules in monocrystalline biphenyl is studied at temperatures T between 1.7 and 3.5 K using the technique of single-molecule spectroscopy (SMS). Based on the data obtained, individual molecules appear to have their own law of δ(T) dependence; further, hysteresis effects have been observed in thermocycling experiments. The single-molecule (SM) lines investigated quickly broaden and vanish at temperatures between 3 and 3.5 K and reappear after the sample is cooled down again. At T≈2 K, a slow process of spectral diffusion (SD) was observed on timescales longer than 10 s. To learn about the role of faster SD processes, the technique of intensity-time-frequency correlation (ITFC) SMS was applied to a stable SM line after it had been broadened by 75% as a result of a thermocycling experiment. At 2 and 2.3 K, no significant line broadening could be revealed on timescales between 0.16 ms and 10 s.     

Effect of substrate temperature on the structural and optical properties of ZnO and Al-doped ZnO thin films prepared by dc magnetron sputtering

ZnO and Al-doped ZnO(ZAO) thin films have been prepared on glass substrates by direct current (dc) magnetron sputtering from 99.99% pure Zn metallic and ZnO:3 wt%Al₂O₃ ceramic targets, the effects of substrate temperature on the crystallization behavior and optical properties of the films have been studied. It shows that the surface morphologies of ZAO films exhibit difference from that of ZnO films, while their preferential crystalline growth orientation revealed by X-ray diffraction remains always the (0 0 2). The optical transmittance and photoluminescence (PL) spectra of both ZnO and ZAO films are obviously influenced by the substrate temperature. All films exhibit a transmittance higher than 86% in the visible region, while the optical transmittance of ZAO films is slightly smaller than that of ZnO films. More significantly, Al-doping leads to a larger optical band gap (E_g) of the films. It is found from the PL measurement that near-band-edge (NBE) emission and deep-level (DL) emission are observed in pure ZnO thin films. However, when Al was doped into thin films, the DL emission of the thin films is depressed. As the substrate temperature increases, the peak of NBE emission has a blueshift to region of higher photon energy, which shows a trend similar to the E_g in optical transmittance measurement.     

Deformation of single crystal sample using D-DIA apparatus coupled with synchrotron X-rays: In situ stress and strain measurements at high pressure and temperature

We present a technique for high pressure and high temperature deformation experiment on single crystals, using the Deformation-DIA apparatus at the X17B2 beamline of the NSLS. While deformation experiments on polycrystalline samples using D-DIA in conjunction with synchrotrons have been previously reported, this technical paper focuses on single crystal application of the technique. Our single crystals are specifically oriented such that only [1 0 0] slip or [0 0 1] slip in (0 1 0) plane is allowed. Constant applied stress (sigma <300 MPa) and specimen strain rates were monitored using in situ time-resolved X-ray diffraction and radiography imaging, respectively. Rheological properties of each activated slip system in the crystals can be revealed using this technique. In this paper, we describe the principle of sample preparation (e.g. [1 1 0]_c and [0 1 1]_c orientations) to activate specific slip systems (i.e. [1 0 0](0 1 0) and [0 0 1](0 1 0), respectively), stress measurement and procedures of the deformation experiments.     

Functional MRI Using Spin Lock Editing Preparation Pulses

A novel approach for detecting blood oxygenation level-dependent (BOLD) signals in the brain is investigated using spin locking (SL) pulses to selectively edit the effects of extravascular diffusion in field gradients from different sized vascular structures. We show that BOLD effects from diffusion amongst susceptibility gradients will contribute significantly not only to transverse relaxation rates (R₂* and R₂) but also to R_1ρ, the rate of longitudinal relaxation in the rotating frame. Similar to the ability of 180-degree pulses to refocus static dephasing effects in a spin echo, moderately strong SL pulses can also reduce contributions of diffusion in large-scale gradients and the choice of SL amplitude can be used to selectively emphasize smaller scale inhomogeneities (such as microvasculature) and to drastically reduce the influence of larger structures (such as veins). Moreover, measurements over a range of locking fields can be used to derive estimates of the spatial scales of intrinsic gradients. The method was used to detect BOLD activation in human visual cortex. Eight healthy young adults were imaged at 3 T using a single-slice, SL-prepped turbo spin echo (TSE) sequence with spin-lock amplitudes ω₁ = 80 Hz and 400 Hz, along with conventional T₂*-weighted and T₂-prepped sequences. The BOLD signal varied from 1.1 ± 0.4 % (ω₁ = 80 Hz) to 0.7 ± 0.2 % (at 400 Hz), whereas the T₂-weighted sequence measured 1.3 ± 0.3 % and the T₂* sequence measured 1.9 ± 0.3 %. This new R_1ρ functional contrast can be made selectively sensitive to intrinsic gradients of different spatial scales, thereby increasing the spatial specificity of the evoked response.     

Hidden symmetry of the CKM and neutrino-mapping matrices

We propose that the smallness of the light quark masses is related to the smallness of the T (i.e. CP) violation in hadronic weak interactions. Accordingly, for each of the two quark sectors (“upper” and “lower”) we construct a 3 × 3 mass matrix in a bases of unobserved quark states, such that the “upper” and “lower” basis states correspond exactly via the W^± transitions in the weak interaction. In the zeroth approximation of our formulation, we assume T conservation by making all matrix elements real. In addition, we impose a “hidden symmetry” (invariance under simultaneous translations of all three basis quark states in each sector), which ensures a zero mass eigenstate in each sector.Next, we simultaneously break the hidden symmetry and T invariance by introducing a phase factor e^iχ in the interaction for each sector. The Jarlskog invariant J_CKM, as well as the light quark masses are evaluated in terms of the parameters of the model. Comparing formulas, we find that most unknown factors drop out, resulting in a simple relation with , to leading order in χ and m_s/m_b, with A, λ the Wolfenstein parameters. (Because of the large top quark mass, the contribution from upper quark sector can be neglected.) Setting J_CKM = 3.08 × 10⁻⁵, m_b = 4.7 GeV (1s mass), m_s = 95 MeV, A = 0.818, and λ = 0.227, we find , consistent with the accepted value m_d = 3 − 7 MeV.We make a parallel proposal for the lepton sectors. With the hidden symmetry and in the approximation of T invariance, both the masses of e and ν₁ are zero. The neutrino-mapping matrix V_ν is shown to be of the same Harrison-Perkins-Scott form which is in agreement with experiments. We also examine the correction due to T violation, and evaluate the corresponding Jarlskog invariant J_ν.     

Intrinsic coercivities of molecular beam epitaxy grown single-crystal Ni films on Ag buffer layer

Single-crystal Ni films were made by the molecular beam epitaxy (MBE) method on Si(1 0 0) and Si(1 1 0) substrates, respectively, with an 100 Å thick Ag buffer layer. The growth temperature T_S was 270 °C, and the film thickness t was 500 Å. From reflection high-energy electron diffraction (RHEED) patterns, the crystalline symmetries of the two films are clear and as expected. Intrinsic coercivities, H_C(1 0 0) and H_C(1 1 0), are plotted as a function of the angle of rotation ? around the crystal axes [1 0 0] and [1 1 0], respectively. The results show that both H_C(1 0 0) and H_C(1 1 0) exhibit mixed features of the crystalline (K_C) and the induced uniaxial magnetic (K_u) anisotropies. K_u is the magneto-elastic energy, due to lattice mismatch at the Ni/Ag interface. Moreover, the crystalline anisotropy fields, H_K(1 0 0) and H_K(1 1 0), and the induced anisotropy filed, H_u, can be calculated as a function of ?, respectively. Then, each H_C curve is fitted by the equation: H_C = H_o + H_K + H_u, where H_o is the isotropic pinning field. Meanwhile, domain structures were examined by the Bitter method, using Ferrofluid 707. On the Ni(1 0 0) film, we observed the charged cross-tie walls, and on the Ni(1 1 0) film, the un-charged Bloch walls.     

Desorption of surfactant and sintering of surface-modified PdxNi1 − x nanoparticles

A series of Pd_xNi_1 − x nanoparticles in a diameter of 6-7 nm were prepared by wet chemical reduction. They were then modified with two surfactants, stearic acid (SA) and polyethylene glycol (PEG). Desorption of the surfactant was studied using a temperature programmed desorption technique, and the sintering behavior of surface-modified Pd_xNi_1 − x nanoparticles was examined. Since surface energy of the nanoparticles depends on the alloy composition, it can be correlated with the desorption temperature of surfactant from the nanoparticle surface. Because Ni has a higher surface energy, the surfactant desorption temperature increases as the Ni content increases. With the same stoichiometry, the desorption temperature of SA is always higher than that of PEG. The SA-modified nanoparticles have higher thermal stability and are less sintered than PEG-modified nanoparticles. The sintering and growth behavior of the nanoparticles can be correlated with variation of surface energy due to different surface modification.     

Effects of peak current density on the mechanical properties of nanocrystalline Ni-Co alloys produced by pulse electrodeposition

Cobalt content, grain size, microhardness and tensile strength of nanocrystalline Ni-Co deposits produced from a solution containing saccharin and cobalt sulfate at constant electrodeposition conditions (pulse on-time T_on at 1 ms and pulse off-time T_off at 15 ms) but varying the peak current density J_p were investigated. It is found that an increase in J_p makes the deposit Co content lower, colony-like morphology more obvious, grain size smaller, and hardness and tensile strength higher. All of the facts are believed to result from the higher overpotential and nucleation rates caused by the J_p increase. But its further increase could lead to reduction in the hardness and tensile strength. Peak current densities in the range of 100-120 A dm⁻² are recommended for the preparation of nanostructured Ni-Co alloy deposits with grain sizes in the range of 15-20 nm, containing 7-8% Co, possessing hardness of 590-600 kg mm⁻² and tensile strength of 1180-1200 MPa—significantly higher than the strength of pure nickel deposit which is produced by the similar method and gets similar grain size.     

The simulation of nanoscale sputter depth profiles using molecular dynamics

The feasibility of using molecular dynamics (MD) for simulation of a nanoscale sputter depth profile experiment is examined for the idealised case of depth profiles of individual atomic layers in a Cu(1 0 0) target. Issues relating to the extraction of depth profile information from MD simulations are discussed in detail. The simulations examine the sputter erosion of static and azimuthally-rotated Cu(1 0 0) targets produced by 3 keV Ar projectiles incident at 25° from the surface. The simulated projectile fluence extends to 5 × 10¹⁵ cm⁻², and the mean value of the sputter depth, z, amounts to 8 Cu(1 0 0) monolayers (ML) or 15 Å. The simulations directly supply progressive layer erosion profiles (curves that depict the extent of sputter erosion of each atomic layer vs. total sputter depth). A fitting method is then used to extract smooth depth profiles for each atomic layer from these predicted erosion profiles. The depth profile characteristics (height, width, shift) for the first 10 layers of the target show a pronounced dependence on layer depth.     

Mixing and magnetic properties of surface alloys: The role of the substrate

In this paper, we have performed ab initio density functional theory calculations to compare the miscibility and magnetic properties of two-dimensional binary surface alloys of the form M_xN_1−x (M = Fe or Co; N = Pt, Au, Ag, Cd or Pb) on two different substrates - Rh(1 1 1) and Ru(0 0 0 1). The trends in miscibility for the two substrates are found to be strikingly similar. The magnetic moments show qualitatively similar behavior, but their magnitudes differ: surface alloys on Rh(1 1 1) have larger magnetic moments than on Ru(0 0 0 1). We infer that strain plays the determining role in stabilizing these two-dimensional alloys, whereas the differences in magnetic moments can be ultimately attributed to the different number of d-electrons in Rh and Ru.     

Thermal annealing of FePt thin films by millisecond plasma arc pulses

A series of 20 and 100 nm Fe₅₃Pt₄₇ thin films sputter-deposited onto Si substrates have been thermally annealed using a pulsed thermal plasma arc lamp. A series of one, three or five pulses were applied to the thin films with widths of either 50 or 100 ms. The microstructure and magnetic properties of these annealed Fe₅₃Pt₄₇ films are discussed according to the various annealing conditions and A1 to L1₀ phase transformation. Upon pulse annealing, the average in-plane grain size of 15 nm (nearly equivalent for both film thicknesses) was observed to increase to values near 20 nm. In general, increasing the pulse width or number of pulses increased the L1₀ order parameter, tetragonality of the c/a ratio and coercivity of the specimen. The exception to this trend was for five pulses at 100 ms for both film thicknesses, which indicated a reduction of the order parameter and coercivity. This reduction is believed to be a result of the interdiffusion of Fe and Pt into the Si substrate and the formation of iron oxide clusters in the grain boundaries characterized by atom probe tomography.     

Impurity effects on the phase transformations and equations of state of zirconium metals

The in situ high P-T X-ray diffraction experiments were conducted at pressures up to 17 GPa and temperatures up to 1273 K to study the phase transformations and equations of state for two grades of zirconium metals. At ambient temperature, our results reveal significant differences in both the transition pressure and kinetics of the α-ω phase transformation between the ultra-pure Zr (35 ppm Hf and <50 ppm O) and impure Zr (1.03 at% Hf and 4.5 at% O). These observations indicate that impurities, particularly oxygen ions, play important roles in the transformation mechanisms as well as crystal stability. On the other hand, impurities have no measurable effects on either the elastic bulk moduli of both α and ω phases or the volume change across the α-ω phase transformation. At elevated temperature, both impure and ultra-pure Zr show similar transition temperatures for the ω-β phase boundary over a pressure range of 6-16 GPa, suggesting that impure oxygen and hafnium ions can only be an α-Zr stabilizer; they do not seem to significantly increase the stability of the ω-Zr relative to the β-Zr.     

Adsorption and film growth of N-methylamino substituted triazoles on copper surfaces in hydrocarbon media

The adsorption of benzotriazole (BTA), tolyltriazole (TTA) and two different N-methylaminosubstituted triazoles on copper surfaces in hydrocarbon media has been examined by in situ ellipsometry and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). All four triazoles were found to form films and from the ellipsometric study were the film thicknesses estimated to be in the range of 0.5-2 nm after 1000 min exposure time. The layers formed from BTA and TTA were thicker (up to 2 nm) than the layers from N-aminomethyl substituted triazoles (roughly 0.5 nm). Desorption was studied qualitatively and 20% or less of the adsorbed material were found to desorb. The ToF-SIMS study showed that while BTA and TTA adsorbed intact did the N-aminomethyl substituted triazoles appear to loose their aminomethyl tails on binding since only signals corresponding to triazole moieties of the compounds were detected.     

Monitoring the non-radiative relaxation time of PpIX solution with Au nanoparticles using Photoacoustic Spectroscopy

In this work we have used the Photoacoustic Spectroscopy (PAS) to determine in vitro the non-radiative relaxation time (NRRT) of a protoporphyrin IX (PpIX) standard solution and samples of PpIX(1), PpIX(2) and PpIX(3) with Au nanoparticle concentrations of 0.001008, 0.00504 and 0.01008 mmol in 25 mL of water respectively. We have used PpIX disodium salt (DS) solution of 25% HCl. The results show that the NRRT average values, obtained for each one of the solution were: τ = 29 ± 0.001, 84 ± 0.001 and 62 ± 0.009 ms for PpIX(1), PpIX(2) and PpIX(3), respectively. These values were compared with some NRRT of triplet states reported in the literature for molecules with tetrapyrrolic structure, increasing the NRRT considerably. From each solution it was obtained its PAS signal phase as a function of the light modulation frequency from 17 to 80 Hz. UV-vis spectrophotometer, photoluminescence spectroscopy and Transmission Electron Microscopy (TEM) were used in order to obtain the optical absorption spectra, the photoluminescence intensities, and the gold nanoparticle sizes respectively. Our investigations are devoted to improve the thermal treatments of drugs the porphyrins as photosensitizers used in image photodynamic therapy.     

Removal of chloridazon by natural and ammonium kerolite samples

The adsorption of chloridazon (5-amino-4-chloro-2-phenylpyridazin-3(2H)-one) on natural and ammonium kerolite samples from aqueous solution at 10, 25 and 40 °C has been studied by using batch experiments. The experimental data points were fitted to the Langmuir equation in order to calculate the adsorption capacities (X_m) of the samples; two straight lines were obtained, which indicates that the adsorption process takes place in two different stages. Values for X_m1 (first stage) ranged from 1.1 × 10⁻² mol kg⁻¹ for natural kerolite at 40 °C up to 5.1 × 10⁻² mol kg⁻¹ for ammonium kerolite at 10 °C and the values for X_m2 (second stage) ranged from 9.1 × 10⁻² mol kg⁻¹ for natural kerolite at 40 °C up to 14 × 10⁻² mol kg⁻¹ for natural kerolite at 10 °C. The adsorption experiments showed on the one hand, that the ammonium kerolite is more effective than natural kerolite to adsorb chloridazon in the range of temperature studied and on the other hand, that the lower temperature, the more effective the adsorption of chloridazon on the adsorbents studied.     

Influence of B2O3 to the inhomogeneous broadening and spectroscopic properties of Er/Yb codoped fluorophosphate glasses

In a three-components fluorophosphate glass system, the introduction of H₃BO₃ brings some valuable influence to the spectroscopic and thermal properties of the glasses. With H₃BO₃ increases from 2 to 20 mol%, Ω₆, S_ed4I13/2, FWHM, T_g and fluorescence lifetime change from 3.21×10⁻²⁰ cm², 1.77×10⁻²⁰ cm², 45 nm, 480 °C and 8.8 ms to 4.66×10⁻²⁰ cm², 2.11×10⁻²⁰ cm², 50 nm, 541 °C and 7.4 ms, respectively. σ_abs, σ_emi, FWHM×τ_f×σ_emi has a maximum when H₃BO₃ is 11 mol%. T_g and T_x−T_g increases with H₃BO₃ introduction. Results showed that in fluorophosphate glasses, proper amount of B₂O₃ can be used as a modifier to suppress upconversion and improve spectroscopic properties, broadband property and crystallization stability of the glasses while keeps the fluorescence lifetime relatively high.     

In-vivo validation of fast spectral velocity estimation techniques

Spectrograms in medical ultrasound are usually estimated with Welch’s method (WM). WM is dependent on an observation window (OW) of up to 256 emissions per estimate to achieve sufficient spectral resolution and contrast. Two adaptive filterbank methods have been suggested to reduce the OW: Blood spectral Power Capon (BPC) and the Blood Amplitude and Phase EStimation method (BAPES). Ten volunteers were scanned over the carotid artery. From each data set, 28 spectrograms were produced by combining four approaches (WM with a Hanning window (W.HAN), WM with a boxcar window (W.BOX), BPC and BAPES) and seven OWs (128, 64, 32, 16, 8, 4, 2). The full-width-at-half-maximum (FWHM) and the ratio between main and side-lobe levels were calculated at end-diastole for each spectrogram. Furthermore, all 280 spectrograms were randomized and presented to nine radiologists for visual evaluation: useful/not useful. BAPES and BPC compared to WM had better resolution (lower FWHM) for all OW < 128 while only BAPES compared to WM had improved contrast (higher ratio). According to the scores given by the radiologists, BAPES, BPC and W.HAN performed equally well (p > 0.05) at OW 128 and 64, while W.BOX scored less (p < 0.05). At OW 32, BAPES and BPC performed better than WM (p < 0.0001) and BAPES was significantly superior to BPC at OW 16 (p = 0.0002) and 8 (p < 0.0001). BPC at OW 32 performed as well as BPC at OW 128 (p = 0.29) and BAPES at OW 16 as BAPES at OW 128 (p = 0.55). WM at OW 16 and 8 failed as all four methods at OW 4 and 2. The intra-observer variability tested for three radiologist showed on average good agreement (90%, κ = 0.79) and inter-observer variability showed moderate agreement (78%, κ = 0.56). The results indicated that BPC and BAPES had better resolution and BAPES better contrast than WM, and that OW can be reduced to 32 using BPC and 16 using BAPES without reducing the usefulness of the spectrogram. This could potentially increase the temporal resolution of the spectrogram or the frame-rate of the interleaved B-mode images.     

Structural and optical properties of thermal evaporated magnesium phthalocyanine (MgPc) thin films

X-ray powder diffraction (XRD) of MgPc indicated that the material in the powder form is polycrystalline with monoclinic structure. Miller indices, h k l, values for each diffraction peak in XRD spectrum were calculated. Thermal evaporation technique was used to deposit MgPc thin films. The XRD studies were carried out for MgPc thin films where the results confirm the amorphous nature for the as-deposited films. While, polycrystalline films orientated preferentially to (1 0 0) plane with an amorphous background were obtained for films annealed at 623 K for 3 h. Optical properties of MgPc thin films were characterised by using spectrophotometric measurements of transmittance and reflectance in the spectral range from 190 to 2500 nm. The refractive index, n, and the absorption index, k, were calculated. According to the analysis of dispersion curves, the parameters, namely; the optical absorption coefficient (α), molar extinction coefficient (?_molar), oscillator energy (E_os), oscillator strength (f), and electric dipole strength (q²) were also evaluated. The recorded absorption measurements in the UV-vis region show two well defined absorption bands of phthalocyanine molecule; namely the Q-band and the Soret (B-band). The Q-band showed its splitting characteristic (Davydov splitting), and ΔQ was obtained as 0.15 eV. The analysis of the spectral behaviour of the absorption coefficient (α), in the absorption region revealed indirect transitions. The transport and the near onset energy gaps were estimated as respectively 2.74 ± 0.02 and 1.34 ± 0.01 eV.     

Calculation of the surface energy of bcc transition metals by using the second nearest-neighbor modified embedded atom method

The surface energies for 24 surfaces of all bcc transition metals Fe, Cr, Mo, W, V, Nb and Ta have been calculated by using the second nearest-neighbor modified embedded atom method. The results show that, for all bcc transition metals, the order among three low-index surface energies E_(1 1 0) < E_(1 0 0) < E_(1 1 1) is in agreement with experimental results and E_(1 1 0) is also the lowest surface energy for various surfaces. So that from surface energy minimization, the (1 1 0) texture should be favorable in the bcc films. This is also consistent with experimental results. The surface energy for the other surfaces increases linearly with increasing angle between the surfaces (h k l) and (1 1 0). Therefore, a deviation of a surface orientation from (1 1 0) can be used to estimate the relative values of the surface energy.