Structural modifications of GaN after cerium implantation

Among the family of rare earth (RE) dopants, the doping of first member Ce into GaN is the least studied system. This article reports structure properties of Ce‐doped GaN realized by technique of ion implantation. Ce ions were implanted into metal organic chemical vapor deposition grown n‐ and p‐GaN/sapphire thin films at doses 3 × 10¹⁴ and 2 × 10¹⁵ cm⁻². X‐ray diffraction scans and Raman scattering measurements exhibited expansion of lattice in the implanted portion of the samples. First order Raman scattering spectra show appearance of several disorder‐activated Raman scattering modes in addition to typical GaN features. A dose‐dependent decrease in intensity of E₂ mode was observed in Raman the spectra of the implanted samples. Ultraviolet Raman spectra of implanted samples show complete quenching of photoluminescence emission and appearance of multiple A₁(LO) phonon scattering modes up to fifth order. Moreover, a decrease in intensity and an increase in line width of LO modes as a function of wavenumber were observed for implanted samples. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermal effects in highly dispersed iron catalysts

The Mössbauer spectra of three Fe/SiO₂ catalysts with 5 wt% iron content show the presence of several Fe species and display different magnetic behaviours when the precursors are subjected to various thermal treatments. Based on the Mössbauer parameters and CO chemisorption measurements, the average crystal sizes of the catalysts are estimated and discussed in connection with the thermal pretreatment severity and magnetic properties of the samples.     

Structural and electrical properties of nanostructured cerium phosphate

Cerium phosphate nanomaterials with different morphologies and sizes were synthesized via a hydrothermal process at 150 °C using cetyl-trimethyl-ammonium-bromide and ethylene-diamine-tetra acid as surfactants. The obtained samples were characterized by X-ray diffraction and a scanning electron microscope. A possible growth mechanism was proposed to reveal the formation process. The structural properties and the electrical conductivities of CePO₄ nanomaterials were studied. The activation energies were obtained from Arrhenius plots where E _a?=?1.06 eV. The ac conductivity at different temperatures for CePO₄ nanomaterials showed frequency independence in the lower frequency range. The dielectric measurements were carried out as a function of frequency and temperature. Variation of the dielectric properties and the ac conductivity with frequency revealed that the dispersion is due to a Maxwell-Wagner type of interfacial polarization in general.     

Preparation of highly dispersed MgO and its bactericidal properties

Samples of layered double hydroxides (LDHs) were prepared by a method involving separate nucleation and aging steps recently developed in our laboratory, using varying [ Mg²⁺] /[ Al³⁺] ratios and different aging conditions. The samples were characterized by X-ray diffraction (XRD), FT-IR spectroscopy and laser granulometry. The results showed that LDHs with different particle sizes could be obtained by controlling the reaction temperature and degree of supersaturation. Calcination of these materials affords mixtures of highly dispersed MgO and mixed metal oxides. Bactericidal experiments against Bacillus subtilis var. niger and Staphylococcus aureus were carried out using materials formed by calcination of the LDHs at 500 ^○C. The mechanism of bactericidal activity was also investigated. It is known that MgO is very readily hydrated and that reaction with dissolved oxygen affords superoxide anions O₂^-, which attack the secondary amide structure of proteins leading to destruction of the bacteria. The bactericidal activity of the MgO increases with specific surface area because this leads to an increased number of surface hydroxyl groups and higher concentrations of O₂^- in solution. The bactericidal ability of MgO therefore increases with decreasing particle size.     

Polymer adsorption on the surface of highly dispersed silica

Attempts at modification of silica surface with a polymer (natural latex) directly in the course of the precipitation process have been made. The effects of temperature, non-ionic surfactants and silane coupling agent in preparation of poly[cis-isoprene]-coated silica on the precipitation of polymer/silica composites initiated by ammonium salts (NH₄Cl, (NH₄)₂SO₄, NH₄HCO₃), have been studied. The influence of the process parameters on the quality of the silicas obtained and the character of the polymer adsorption on the silica surface has been determined along with the effect of the surface impregnation with natural latex on physicochemical parameters of the silicas (bulk density, capacities to absorb water, dibutyl phthalate and paraffin oil) and their surface structure.     

Structural characterization study of nickel ferrite particles dispersed in a corrosion product deposit layer

Using X-ray absorption fine structure spectroscopy, both EXAFS and XANES, the cation distributions in NiFe₂O₄ particles dispersed in a corrosion product deposit layer have been studied. The specimen was obtained from a selected fuel rod used in a commercial boiling water reactor plant. EXAFS data allowed the quantitative determination of specific site distributions for all transition metal cations in Ni-ferrite deposits. The results show that the analyzed NiFe₂O₄ particles do not have a totally inverted spinel structure. The relative occupancy of iron and nickel cations in the tetrahedral and octahedral sites of the spinel lattice is determined from the measured data.     

Mild hydrothermal treatment to prepare highly dispersed multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) with improved dispersion property have been prepared by a mild and fast hydrothermal treatment. The hydrothermal process avoids using harsh oxidants and organic solvents, which is environmental friendly and greatly decreases the damage to intrinsic structure of MWCNTs. The modified MWCNTs were highly soluble in polar solvents such as water, ethanol and dimethylformamide. Morphological observation by TEM indicated that the diameter and inherent structure were well reserved in modified MWCNTs. X-ray photoelectron spectroscopy and Raman spectroscopy were used to quantify functional groups created on the MWCNT surface, and to determine rational parameters of hydrothermal process.     

Ultrasonic-assisted synthesis of highly dispersed MoO3 nanospheres using 3-mercaptopropyltrimethoxysilane

With ultrasonic irradiation as assistance, highly dispersed MoO(3) nanospheres were synthesized using silane coupling agent 3-mercaptopropyltrimethoxysilane HS-(CH(2))(3)Si(OCH(3))(3) (MPTS) as figuration agent. The results of X-ray powder diffractometer (XRD) showed that the precursor was hexagonal molybdenum oxide hydrate (MoO(3).0.55H(2)O). It was converted into orthorhombic MoO(3) after annealed at 400 degrees C for 2h. Transmission electron microscopy (TEM) showed that MoO(3).0.55H(2)O and MoO(3) nanoparticles were spherical with particle-size distribution of ca. 30-80 nm and 25-75 nm, respectively. Results indicated that MPTS and ultrasonic irradiation played important role in formation of highly dispersed MoO(3) nanospheres. X-ray photoelectron spectroscopy (XPS) was also adopted to confirm the growth mechanism. The possible cause of formation was based on dispersion function of ultrasonic irradiation and figuration of MPTS.     

Structural, optical and scintillation properties of cerium cyclotriphosphates and polyphosphates

The cerium cyclotriphosphate CeP₃O₉·3H₂O and polyphosphate Ce(PO₃)₃ have been optically investigated for the first time. In both materials, excitation and emission spectra under UV and X-ray excitations as well as emission decays of Ce³⁺ were measured at room temperature. The spectroscopic results of anhydrous Ce(PO₃)₃, prepared by progressively heating the corresponding CeP₃O₉. 3H₂O, are discussed and correlated with the structural data.For the Ce(PO₃)₃ polyphosphate material, the Stokes shift of the d-f emission is very small (760 cm⁻¹), inducing an efficient ultraviolet luminescence and a new application as scintillator.     

A thermodynamic study of nonstoichiometric cerium dioxide

Thermogravimetric measurements were performed on nonstoichiometric CeO_2?x in the temperature range 750–1500°C and from oxygen pressures of 10^?2 to 10^?26 atm. From this data the deviation from stoichiometry x = x(T, P_o2) was determined. The thermodynamic quantities Δ$\text{H}$_o2 and Δ$\text{S}$_o2 were calculated in the region 0.001? x ? 0.3 and found to be independent of temperature.In the composition region 0.001< x < 0.006, the variation of Δ$\text{S}$_o2 with x is consistent with a defect model involving randomly distributed doubly ionized oxygen vacancies. The experimental dependence of x and σ (electrical conductivity) is shown to be consistent with this model as Δ$\text{H}$_o2 (≈ -10 eV) exhibits a slight dependence on x. It is postulated that the variation in Δ$\text{H}$_o2 may result from lattice parameter increases with x, while the defects remain essentially randomly distributed.In the composition region 0.006 < x < 0.1, x ∝ with 1 < n < 5, and in the region 0.1 < x < 0.3, x ∝ with n increasing rapidly with x to n? 30. This behavior is believed to result from increasing defect interaction with increasing departures from stoichiometry. It is interesting to note that the ordered phase observed by Bevan and Kordis between CeO_1·72 and CeO_1·70 was not observed in this study at temperatures between 1300° and 1500°C.     

Structural phase transition and elastic properties of cerium chalcogenides at high pressure

The structural and elastic properties of cerium chalcogenides (CeZ, Z = S, Se, Te) under high pressure have been investigated by using the potential model considered up to third nearest neighbor interaction. The computed values of B1-B2 phase transition pressure, equation of state (compression curve), bulk modulus, its first order pressure derivative and elastic constants in the case of cerium chalcogenides agree well with the experimental results. The present study shows the anomalous behavior of cerium chalcogenides in comparison to the alkaline earth chalcogenides, due to the presence of Kondo effect and reentrant valence behavior of Ce in cerium chalcogenides.     

Direct chemical assembly of quaternary ammonium groups on a surface of highly dispersed silica

Direct assembly of quaternary ammonium groups onto a silica surface has been realized by use of many-stage chemical reactions. Adsorption of cholic acid in dependence on duration, equilibrium concentration, and pH solution onto a surface of silicas modified with quaternary ammonium groups has been studied. The main parameters of cholic acid adsorption have been calculated.     

A thermodynamic study on CaO-doped nonstoichiometric cerium dioxide

Thermogravimetric measurements were performed on CaO-doped nonstoichiometric cerium dioxide (i.e. Ce_1?yCa_yO_2?y?x) in the temperature range 800–1500°C and from oxygen pressures of 10^?1–10^?21 atm. Fr data the deviation from stoichiometry x = x(T, P_O2)_y was determined for values of y = 0.01, 0.045, 0.07, 0.10 and 0.14. The thermodynamic quantities Δ H_O2; and ΔS_O2 were calculated in the region 0.001 ? x ? 0.2 and found to be independent of temperature with the exception of those for 14 mole % CaO at large deviations from stoichiometry. p]In the composition region near stoichiometry (i.e. for x between approximately 10^?3 and 10^?2), the variation of Δ S_O2 with x is consistent with a defect model involving randomly distributed doubly ionized oxygen vacancies and electrons localized on normal cerium sites. The range of nonstoichiometry with which this defect model fits the experimental results increases with increasing CaO content. In this same region ΔH?_O2 exhibits a slight dependence on x for y = 0.01 and 0.045 and is essentially independent of x for y = 0.7,0.10 and 0.14. The experimental observation that is rationalized on the basis of the above model for the case where y > x.At large deviations from stoichiometry the dependence of x = x(T, P_O2)_y is similar to the nonstoichiometric behavior of “pure” CeO_2?x when y = 0.01 or 0.045. The dependence of ΔH_O2; and ΔS_O2 on x is also similar. for y = 0.10 and 0.14 the nonstoichiometric behavior and the dependence of ΔH_O2 on x differs significantly from the behavior of “pure” CeO_2?x.     

Density functional studies of selected metal dioxides

This study investigates the optical properties of selected metal oxides due to their high dielectric constants. The local-spin-density approximation plus Hubbard U (commonly called LDA+U) is used in a study of the structural, mechanical and optical properties of UO₂. The inclusion of a Hubbard U correction to 5f electrons of uranium changes UO₂ from a metal to an insulator and, therefore, has a dramatic effect on the localisation of the electron spin and charge density of uranium. However although the band gap can be reproduced using the effective U parameter, which is equal to 3.5 eV and optical properties were calculated in our previous work, it is difficult to calculate ionic contribution to the static dielectric constant within LDA+U formalism for this compound. It is shown in the present work that the electronic structures of both ceria and thoria exhibit similarities to urania within LDA or PBE functional implementations. Within this functional and linear response theory one can easily calculate static dielectric permittivity and it is shown that in agreement with experiment the predicted values are an order of magnitude larger than the dielectric constant of SiO₂. In this work, high accuracy, first-principles calculations are also used to compare properties of urania versus ceria and thoria and how these similarities can help in understanding these compounds. It is also shown that the B3LYP functional predicts slightly overestimated band gaps for ceria and thoria as well as smaller than experimentally observed electronic contribution to the static dielectric constant, while the index of refraction is well reproduced for thoria.     

Intrachannel four-wave mixing in highly dispersed return-to-zero differential-phase-shift-keyed transmission with a nonsymmetric dispersion map

Nonlinear penalties due to intrachannel four-wave mixing (IFWM) in highly dispersed return-to-zero differential-phase-shift-keyed transmission are studied for both symmetric and nonsymmetric dispersion maps. As the dispersion map changes from symmetric to nonsymmetric, the nonlinear amplitude fluctuation overtakes the effect of the nonlinear phase fluctuation and dominates the system's nonlinear performance. The effect of IFWM on the bit error rate is assessed by using the semianalytical method.     

X-Ray photoelectron study of the reaction of water with cerium

The interaction of D₂ O with a polycrystalline cerium surface, successfully cleaned by heavy Ar⁺ bombardment and annealing, was studied at 120 were observed at BE 530.3 (Ce₂O₃) and 532.7eV (adsorbed OD). When clean Ce at 120 K was exposed to D₂ O, the O(1s) spectra were initial eV (adsorbed D₂ O). For exposures greater than 10 Langmuir (L), a multilayer of ice grows and the O(1s) spectra become dominated by a peak at 5The results of interaction with D₂ O are compared with oxidation by O₂. The significant differences are: (1) the absence of Ce(IV) when oxidati relatively small extent of oxidation that occurs when Ce is exposed to D₂ O at 120 K, and (3) the larger chemical-shift of the Ce(III)-derived specThe XPS studies of the interaction of D₂ O with Ce reported here may be summarized as follows:(1) Exposure at 300 K gives rise to O(1s) features characteristic of oxide and hydroxide, while the Ce(3d) spectra indicate Ce(III), but no CE((2) Exposure at 120 K gives O(1s) features characteristic of adsorbed OD, chemisorbed D₂ O, a multilayer of ice, and a small amount of oxide. T are characteristic of clean Ce except for slight broadening.(3) Exposure at 120 K followed by warming to 240 and 300 K gives spectra characteristic of hydroxide and oxide surface-species. Between 240 and 300 K, O(1s) intensity.(4) At 300 K, a relatively thick layer of oxide forms, and after an exposure of 50 L the features characteristic of metallic Ce are no longer observabl(5) As compared to the case for O₂, exposure to D₂ O gives rise to different satellite-splittings in the Ce(3d) spectra, suggesting that di formed in the two cases.(6) The spectra observed for Ce exposed to D₂ O are in excellent accord with those found for the heavier lanthanides [4].