One-step fabricated Fe3O4@C core–shell composites for dye removal: Kinetics,equilibrium and thermodynamics

B-Fe₃O₄@C core–shell composites were synthesized via one-pot hydrothermal carbonization (HTC) process and used as an adsorbent for the removal of methylene blue (MB) from aqueous solution. By using sodium borate as the catalyst, the hydrothermal carbonization process of B-Fe₃O₄@C core–shell composites was optimized and a higher surface area was obtained. The adsorbent was characterized by XRD, Raman spectra, SEM, TEM and N₂ adsorption/desorption isotherms. We studied the dye adsorption process at different conditions and analyzed the data by employing the Langmuir and Freundlich models, and the equilibrium data fitted well with both models. Kinetic analyses were conducted by using the Lagergren pseudo-first-order and pseudo-second-order model and the results showed that the adsorption process was more consistent with the pseudo-second-order kinetics. To better understand the dye adsorption process from the thermodynamics perspective, we also calculated ΔH^ο, ΔS^ο, ΔG^ο and E_a, the results suggesting that the MB adsorption process was physisorption endothermic process, and spontaneous at room temperature. The as-synthesized B-Fe₃O₄@C showing high magnetic sensitivity provides a facile and efficient way to recycle from aqueous solution.     

High efficiency small molecule white organic light-emitting devices with a multilayer structure

In this paper, a new white organic light-emitting device (WOLED) with multilayer structure has been fabricated. The structure of devices is ITO/N, N-bis-(1-naphthyl)-N, N^′-diphenyl-1, 1′-biphenyl-4, 4′-diamine (NPB) (40 nm)/NPB: QAD (1%): DCJTB (1%) (10 nm) /DPVBi (10 nm) /2, 9-dimethyl, 4, 7-diphenyl, 1, 10-phenanthroline (BCP) (d nm)/tris-(8-hydroxyquinoline) aluminium (Alq₃)(50-d nm)/LiF (1 nm)/Al (200 nm). In our devices, a red dye 4-(dicyanomethylene)-2-t-butyl-6 (1, 1, 7, 7-tetramethyl julolidyl-9-enyl)-4H-pyran (DCJTB) and a green dye quinacridone (QAD) were co-doped into NPB. The device with 8 nm BCP shows maximum luminance of 12 852 cd/m² at 20 V. The current efficiency and power efficiency reach 9.37 cd/A at 9 V and 3.60 lm/W at 8 V, respectively. The thickness of the blocking layer permit the tuning of the device spectrum to achieve a balanced white emission with Commission International de’Eclairage (CIE) chromaticity coordinates of (0.33,0.33). The CIE coordinates of device change from (0.3278, 0.3043) at 5 V to (0.3251, 0.2967) at 20 V that are well in the white region, which is largely insensitive to the applied bias.     

Auger electron spectroscopy of Au/NiOx contacts on p-GaN annealed in N2 and O2 + N2 ambients

We have designed a promising contact scheme to p-GaN. Au/NiO_x layers with a low concentration of O in NiO_x are deposited on p-GaN by reactive dc magnetron sputtering and annealed in N₂ and in a mixture of O₂ + N₂ to produce low resistivity ohmic contacts. Annealing has been studied of NiO_x layers with various contents of oxygen upon the electrical properties of Au/NiO_x/p-GaN. It has been found that the Au/NiO_x/p-GaN structure with a low content of oxygen in NiO_x layer provides a low resistivity ohmic contact even after subsequent annealing in N₂ or O₂ + N₂ ambient at 500 °C for 2 min.Auger depth profiles and transmission electron microscopy (TEM) micrographs reveal that while annealing in O₂ + N₂ ambient results in reconstruction of the initial deposited Au/NiO_x/p-GaN contact structure into a Au/p-NiO/p-GaN structure, annealing in N₂ brings about reconstruction into Au/p-NiO/p-GaN and Ni/p-NiO/p-GaN structures. Hence, in both cases, after annealing in N₂ as well as in O₂ + N₂ ambient, the ohmic properties of the contacts are determined by creation of a thin oxide layer (p-NiO) on the metal/p-GaN interface. Higher contact resistivities in the samples annealed in O₂ + N₂ ambient are most likely caused by a smaller effective area of the contact due to creation of voids.     

Adjacency networks

We consider a finite set S={x₁,…,x_r} and associate to each element x_i a probability p_i. We then form sequences (N-strings) by drawing at random N elements from S with respect to the probabilities assigned to them. Each N-string generates a network where the elements of S are represented as vertices and edges are drawn between adjacent vertices. These structures are multigraphs having multiple edges and loops. We show that the degree distributions of these networks are invariant under permutations of the generating N-strings. We describe then a constructive method to generate scale-free networks and we show how scale-free topologies naturally emerge when the probabilities are Zipf distributed.     

The elastic behavior of dense C3N4 under high pressure: First-principles calculations

We have carried a detailed theoretical study on the geometry, density of states, elastic properties, sound velocities and Debye temperature of α-, β-, c- and p-C₃N₄ compounds under a maximum of pressure up to 100 GPa by using first principles calculations. The optimized lattice constants under zero pressure and zero temperature agreed well with the previous experimental and theoretical results. The band gaps of the four types of dense C₃N₄ were widened gradually with the increase of pressure. The calculated Poisson’s ratio γ and B/G values suggest α-, c- and p-C₃N₄ are brittle materials under 0–100 GPa, whereas β-C₃N₄ will become a ductile material as external pressure reaches 57 GPa. We found that the Debye temperature of the four dense C₃N₄ gradually reduces in the order of c-C₃N₄>p-C₃N₄>α-C₃N₄>β-C₃N₄ at 0 GPa and 0 K. However, the Debye temperature of c-C₃N₄ was lower than p-C₃N₄ when external pressure exceeds 6.3 GPa. It may hint that the results could be served as a valuable prediction for further experiments.     

Stress induced preferred orientation and phase transition for ternary WCxNy thin films

We deposit ternary WC_xN_y thin films on Si (1 0 0) substrates at 500 °C using direct current (DC) reactive magnetron sputtering in a mixture of CH₄/N₂/Ar discharge, and explore the effects of substrate bias (V_b) on the intrinsic stress, preferred orientation and phase transition for the obtained films by virtue of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and selective area electron diffraction (SAED). We find that with increasing the absolute value of V_b up to 200 V the carbon (x) and nitrogen (y) atom concentrations of WC_xN_y films keep almost constant with the values of 0.75 and 0.25, respectively. The XPS and SAED results, combined with the density-functional theory (DFT) calculations on the electronic structure of WC_0.75N_0.25, show our obtained WC_xN_y films are single-phase of carbonitrides. Furthermore, we find that the compressive stress sharply increases with increasing the absolute value of V_b, which leads to a pronounced change in the preferred orientation and phase structure for the film, in which a phase transition from cubic β-WC_xN_y to hexagonal α-WC_xN_y occurs as V_b is in the range of −40 to −120 V. In order to reveal the relationship between the stress and phase transition as well as preferred orientation, the DFT calculations are used to obtain the elastic constants for β-WC_xN_y and α-WC_xN_y. The calculated results show that the preferred orientation is dependent on the competition between strain energy and surface energy, and the phase transition can be attributed to a decrease in the strain energy.     

Experimental investigation of the CMN matrix element in the band anticrossing model for GaAsN and GaInAsN layers

The temperature dependence of bandgap energy of GaAs_0.98N_0.02 and Ga_0.95In_0.05As_0.98N_0.02 compounds has been analysed in order to determine the C_MN matrix element of the band anticrossing model. We have found that the element equals 2.48 and 2.60 eV for GaAs_0.98N_0.02 and Ga_0.95In_0.05As_0.98N_0.02 layers, respectively. When the same value has been assumed for annealed layers, an increase in the energy of the resonant nitrogen level E_N has been obtained. Two possible mechanisms leading to the increase in this energy are discussed in this work.     

Theoretical investigation of the conduction and valence band offsets of GaAs1−x Nx/GaAs1−yNy heterointerfaces

Theoretical investigations of the conduction band offset (CBO) and valence band offset (VBO) of the relaxed and pseudo-morphically strained GaAs_1−xN_x/GaAs_1−yN_y heterointerfaces at various nitrogen concentrations (x and y) within the range 0-0.05 and along the [0 0 1] direction are performed by means of the model-solid theory combined with the empirical pseudopotential method under the virtual crystal approximation that takes into account the effects of the compositional disorder. It has been found that for y < x, the CBO and VBO have negative and positive signs, respectively, whereas the reverse is seen when y > x. The band gap of the GaAs_1−xN_x over layer falls completely inside the band gap of the substrate GaAs_1−yN_y and thus the alignment is of type I (straddling) for y < x. When y > x, the alignment remains of type I but in this case it is the band gap of the substrate GaAs_1−yN_y which is fully inside the band gap of the GaAs_1−xN_x over layer. Besides the CBO, the VBO and the relaxed/strained band gap of two particular cases: GaAs_1−xN_x/GaAs and GaAs_1−xN_x/GaAs_0.98N_0.02 heterointerfaces have been determined.     

Characterization of HfOxNy gate dielectrics using a hafnium oxide as target

Hafnium oxynitride (HfO_xN_y) gate dielectric has been deposited on Si (1 0 0) by means of radio frequency (rf) reactive sputtering using directly a HfO₂ target in N₂/Ar ambient. The thermal stability and microstructural characteristics for the HfO_xN_y films have been investigated. XPS results confirmed that nitrogen was successfully incorporated into the HfO₂ films. XRD analyses showed that the HfO_xN_y films remain amorphous after 800 °C annealing in N₂ ambient. Meanwhile the HfO_xN_y films can also effectively suppress oxygen diffusion during high temperature annealing and prevent interface layer from forming between HfO_xN_y films and Si substrates. AFM measurements demonstrated that surface roughness of the HfO_xN_y films increase slightly as compared to those pure HfO₂ films after post deposition annealing. By virtue of building reasonable model structure, the optical properties of the HfO_xN_y films have been discussed in detail.     

Compositional analysis of ferroelectric films coated with carbon layer using laser-induced plasmas spectroscopy

An experimental investigation of the effect of different thickness of carbon layer coated on ferroelectric films on the atomic emission intensity using laser-induced plasmas spectroscopy technique with charge-coupled device (CCD) experimental system has been conducted. The experimental results show that the intensity of the spectra emitted with the carbon layer thickness of 15 μm is much higher than that of pure ferroelectric films. By using this best experimental condition, the atomic concentration ratios of ferroelectric films are evaluated by rationing the integrated intensities of selected spectral emission lines of the plasma produced from the films. And the experimental results show that N_La/N_Co and N_Sr/N_Co atomic concentration ratios are almost in agreement with the corresponding values obtained by traditional compositional analysis techniques of inductively coupled plasma (ICP).     

Entanglement dynamics in Coriolis coupled rovibrational states of formaldehyde

The entanglement dynamics of two vibrational modes of a polyatomic molecule coupled by Coriolis interaction to overall molecular rotation is studied in terms of two negativities, N(t) and N_s(t), respectively, defined by the minimum of the eigenvalues and by the sum of the negative eigenvalues of the partial transpose of a density matrix. Various initial states are the products of Dicke states and the products of coherent states of vibrations and rotations. Formaldehyde is taken as an example, and the von Neumann entropy s(t) is simulated for the comparison with both negativities. It is shown that negativity N_s(t) is positively correlated with entropy s(t), and the correlated behavior between negativity N(t) and entropy s(t) strongly depends on initial states. However, these three indicators of entanglement display a dominantly positive correlation for the coherent states with small or large parameters. In addition, for the latter state two quantities N(t) and s(t) are nearly unchanged for a long time. This time can be further increased by the increasing of vibrational quantum number so that molecular information processing and quantum computing is allowed. These results are useful in quantum information theory.     

Structural, optical properties and band gap alignments of ZrOxNy thin films on Si (1 0 0) by radio frequency sputtering at different deposition temperatures

ZrO_xN_y thin films have been prepared by radio frequency magnetron sputtering at various substrate temperatures. The effect of substrate temperature on structural, optical properties and energy-band alignments of as-deposited ZrO_xN_y thin films are investigated. Atomic force microscopy results indicate the decreased root-mean-square (rms) values with substrate temperature. Fourier transform infrared spectroscopy spectra indicate that an interfacial layer has been formed between Si substrate and ZrO_xN_y thin films during deposition. X-ray photoelectron spectroscopy and spectroscopy ellipsometry (SE) results indicate the increased nitrogen incorporation in ZrO_xN_y thin films and therefore, the decreased optical band gap (E_g) values as a result of the increased valence-band maximum and lowered conduction-band minimum.     

Investigation of structure and magnetic properties of the as-deposited and post-annealed iron nitride films by reactive facing-target sputtering

Structure and magnetic properties of the as-deposited and post-annealed iron nitride films have been investigated systematically. A series of phases containing α-Fe, ?-Fe₃N, ξ-Fe₂N and γ″-FeN were obtained as nitrogen flow rate (FN₂) increases from 0.5 to 30 sccm. An increase of the nitrogen concentration in the as-deposited films could be concluded from the phase transition with the increasing FN₂. After being annealed, some of the iron nitride phases are decomposed and γ′-Fe₄N appears in the films. The magnetic characteristics are dependent on FN₂, which can be ascribed to the facts that the nitrogen in the films turns the valence states of Fe into Fe⁺ or Fe^dipole with high magnetic momentum or ever H-like bond Fe^+/dipole with low magnetic momentum based on the bond-band-barrier correlation mechanism.     

Phase transition of BiVO4 nanoparticles in molten salt and the enhancement of visible-light photocatalytic activity

BiVO₄ nanoparticles are prepared by molten salt method. Tetragonal BiVO₄ completely transforms to monoclinic phase after heating in molten LiNO₃ at 270 °C for 18 h. The average particle sizes of monoclinic BiVO₄ varied from 30 to 52 nm while the initial ratio of BiVO₄ to LiNO₃ changes from 1:6 to 1:24. The photocatalytic activity is evaluated by measuring decolorization of N,N,N′,N′-tetraethylated rhodamine dye solution under visible-light irradiation. Both of the de-ethylation and chromophore cleavage are responsible for the decolorization of RB. The sample with an average particle size of 52 nm and a moderate surface area of 10 m²/g exhibit the highest visible-light photocatalytic activity. The shift of Raman peak position indicates that the symmetry distortions in the local structure of the monoclinic BiVO₄. The variations of the local structure result in the modification of the electronic structure, which is responsible for the high visible-light photocatalytic activity.     

Application of point-group bases to f−fd transitions of lanthanide and actinide ions doped in crystals

The application of point-group coupling coefficients to the modeling of f^N↔f^N−1d transitions is discussed. There are several possible coupling schemes for the states of the f^N−1d configuration. Formulae for matrix elements of the Hamiltonian for the f^N−1d configuration and the relative line strengths for f^N↔f^N−1d transitions are derived. As an example, the f-d absorption spectrum of the crystal Yb²⁺: SrCl₂ is calculated using coupling coefficients based on the software developed by Butler and co-workers, which makes use of the Racah-Wigner calculus. The advantages and disadvantages of various coupling schemes are demonstrated. These coupling schemes are related to the simple model for f-d transitions.     

Optical emission spectroscopic studies on laser ablated TiO2 plasma

Optical emission spectroscopic investigations of the plasma produced during Nd:YAG laser ablation of sintered TiO₂ targets, in oxygen and argon gas environments are reported. The spatial variations of electron temperature (T_e) and electron number density (N_e) are studied. The effect of oxygen/argon pressure on electron temperature (T_e) and electron number density (N_e) is presented. The kinematics of the emitted particles and expansion of plume edge are discussed. Spatio-temporal variations of various species in TiO₂ plasma were recorded and corresponding velocities were calculated. The effect of oxygen pressure on intensity of neutral/ion species and their corresponding velocities is also reported.     

Influence of temperature on critical fields in ZnCr2Se4

The complex ac dynamic magnetic susceptibility was used to study the influence of temperature on critical fields in polycrystalline ZnCr₂Se₄ spinel. An antiferromagnetic order with a Néel temperature T_N=20.7 K and a strong ferromagnetic exchange evidenced by a positive Curie-Weiss temperature θ_CW=55.1 K were established. An increasing static magnetic field shifts T_N to lower temperatures while a susceptibility peak at T_m in the paramagnetic region—to higher temperatures. The non-zero and negative values both of the second and third harmonics of susceptibility suggest only a parallel spin coupling in ferromagnetic clusters in the range between the Néel and Curie-Weiss temperatures. Below T_N the magnetic field dependence of susceptibility, χ_ac(H), shows two peaks at critical fields H_c1 and H_c2. The values of H_c1 decrease slightly with temperature while the values of H_c2 drop rapidly with temperature. The strong changes of H_c2 temperature induced are mainly responsible for a spin frustration of the re-entrant type in the spinel under study.     

Photon distribution function in blinking fluorescence of individual molecules

A photon distribution function w_N(T) for blinking fluorescence with bright on- and dark off-intervals is derived. The function w_N(T) is expressed via few Poissonian functions each of which relates to corresponding exponential process in quantum dynamics of a given individual molecule. The distribution of photons is calculated for short, middle and long time intervals as compared to off-intervals. The distributions are much broader than Poissonian distribution and have rather complicated shape. If time resolution of an experiment does not permit us to see off-interval and, therefore, fluorescence looks like CW emission, the distribution of photons gives a signal about existence of hidden off- intervals in such CW fluorescence.     

2-Propanol photodegradation over nitrogen-doped NaNbO3 powders under visible-light irradiation

Nitrogen-doped perovskite-type materials, yellowish NaNbO_3−xN_x powders, had been developed as visible-light-sensitive photocatalysts for decomposition of gaseous 2-propanol. The NaNbO_3−xN_x samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) light diffuse reflectance spectroscopy, Brunauer-Emmett-Teller (BET) measurement, and scanning electron microscopy (SEM). The UV-vis spectra confirmed that the spectral response of the NaNbO₃ powders could be tuned to visible-light region by nitrogen doping technique. The photocatalytic activities of NaNbO_3−xN_x samples were evaluated by decomposing gaseous 2-propanol into acetone and CO₂ under visible-light irradiation (400 nm<λ<520 nm). The NaNbO_3−xN_x sample annealed at 833 K showed the highest visible-light photocatalytic activity among all the nitrogen-doped samples. The relationship between nitrogen doping amount and photocatalytic activity of NaNbO_3−xN_x samples was also investigated and discussed.     

The evolution of magnetic,electrical and structural properties of nanogranular [FeCoBN/SiN]×n thin films

Some results concerning the magnetic, electrical and microstructural properties of multilayer [FeCoBN/Si₃N₄]×n films in view of their utilization for manufacturing thin film magnetic inductors are presented. A comparison between the magnetic, electrical and structural properties of FeCoBN and [FeCoBN/Si₃N₄]×n thin films is also reported. The [FeCoBN/Si₃N₄]×n thin films with the thickness of the FeCoBN layers varied from 10 to 30 nm, exhibit good soft magnetic characteristics and high values for electrical resistivity such as Ms of 172–185 A m²/kg, Hc of 318–1433 A/m and ρ of 82–48×10⁻⁷ Ω m, respectively. These physical properties of the samples are discussed in relation with the microstructure of the multilayer system.