Molecular beam epitaxial growth of zinc-blende FeN(1 1 1) on wurtzite GaN(0 0 0 1)

We report a study of the growth of iron nitride on gallium nitride using molecular beam epitaxy with Fe e-beam evaporation and rf N-plasma growth. Thin iron nitride layers of thickness about 16 nm were grown and monitored in situ using reflection high energy electron diffraction. The samples following growth were analyzed ex situ using a variety of techniques including X-ray diffraction, Rutherford Backscattering, and atomic force microscopy. By monitoring the structure, morphology, and lattice constant evolution of the iron nitride film, the crystal phase and orientation with respect to the GaN substrate are deduced; and from RBS data, the stoichiometry is obtained. The growth is discussed in terms of a 2-D to 3-D growth mode transition, and a critical thickness is estimated.     

Synthesis of VN nanopowders by thermal nitridation of the precursor and their characterization

Vanadium nitride (VN) nanopowders can be synthesized by thermal nitridation of the precursor of ammonium vanadate (NH₄VO₃) and nanometer carbon black. The products were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the single phase VN powders can be synthesized at 1100 °C for 1 h, and the powders show good dispersion and are mainly composed of uniformly sized spherical particles with a mean diameter of 50 nm. The surface of the specimen mainly consists of V, N, O and C four species elements, the peak core at 397.24 eV corresponds to N 1s of VN. The O 1s peaks with the binding energies of 530.40 eV and 532.15 eV are ascribed to vanadium pentoxide (V⁵⁺) and H₂O (OH⁻), and the contents are very little. The C 1s profile is a single symmetric peak, which mainly comes from the polluted carbon used for the correction of the XPS measurement.     

Synthesis of novel compounds with cation ordered fluorite and α-PbO2 related structures by oxidation of Sn2Nb2O7 pyrochlore

Sn(II)_1.2(Nb(V)_1.6Sn(IV)_0.4)O₆ pyrochlore precursor was oxidized at temperature of the range 573–973 K in 1% O₂/Ar and O₂ gases for various periods of time. Two kinds of novel metastable phases with a composition of Sn(IV)_0.6(Nb(V)_0.8Sn(IV)_0.2)O_3.6 could be synthesized. Further, the other novel metastable phase with the same composition was found as a phase contained. One of the metastable phases was the cubic κ-CeZrO₄ related-type possessing the fluorite-related structure, which was formed by the cation diffusionless insertion of the oxygen atom into original oxygen vacant site of the pyrochlore-type structure. Another was an orthorhombic α-PbO₂ related-type possessing a cation ordered arrangement unlike a well known NiWO₄ structure. The other was the rutile related-type possessing a cation ordered arrangement. Appearance of the two latter metastable phases could be attributed to the displacement of the oxygen stacking in the κ-CeZrO₄ related-type phase without cation redistributions. The appearance mechanisms were analogous to the well known transformations for AX₂ compounds among rutile-type, α-PbO₂-type, and fluorite-type phases under high pressure and its release. The dependence of the appearance of these novel metastable phases on oxygen partial pressure and temperature has been discussed in terms of the driving forces and energy barriers for reactions.     

An investigation of the thermal stability, crystal structure and catalytic properties of bulk and alumina-supported transition metal nitrides

A series of bulk and alumina-supported nitrides of metals (V, Mo, Fe and Co) were synthesized by NH₃-temperature-programmed reaction and characterized by X-ray diffraction (XRD) and temperature-programmed desorption techniques. The formation of bulk Co₄N and Co₄N/γ-Al₂O₃ was further confirmed using X-ray photoelectron spectroscopic analysis. The catalytic activities of these metal nitrides for NO decomposition were evaluated. Their activities for NO decomposition ranked in the order of Co₄N > Fe₃N > Mo₂N > VN and Co₄N/γ-Al₂O₃ > Fe₃N/γ-Al₂O₃ > Mo₂N/γ-Al₂O₃ > VN/γ-Al₂O₃. The relationship between crystal structures and catalytic activities was investigated. The results indicated that metal nitrides with higher vacancy concentration exhibited higher activities for NO decomposition. There was a stronger interaction between the metal nitride phases and γ-Al₂O₃ support. It was suggested that Co₄N/γ-Al₂O₃ exhibited thermal stability significantly higher than that of bulk counterpart, owing to the strong interaction between the Co₄N phase and γ-Al₂O₃ support. We applied the XRD technique to examine the structural changes of Co₄N/γ-Al₂O₃ catalysts during the reactions. The results indicated that the rapidly loss in catalytic activity was due to the bulk oxidation of Co₄N/γ-Al₂O₃. In the NO–H₂ reaction, the oxygen generated during NO dissociation was partly reduced by H₂ and partly incorporated into the nitride lattice. By the addition of H₂ in feed gas at 600 °C, one can retain the active Co₄N/γ-Al₂O₃ phase by minimizing the presence of surface oxygen.     

Crystal structure of the Ag2SiS3 compound

The crystal structure of the ternary compound Ag₂SiS₃ was determined on the basis of X-ray powder diffraction. The compound belongs to a new structure type, space group P2₁/c, a = 0.66709(1), b = 0.66567(2), c = 1.31748(3) nm, and β = 118.658(1)°. Ag₂SiS₃ contains isolated [Si₂S₆] anionic units consisting of pairs of edge-shared tetrahedra. The Ag atoms are situated in the interstices formed by these fragments.     

Synthesis, optical and dielectric studies on novel semi organic nonlinear optical crystal by solution growth technique

Bisthiourea lead acetate Pb[SC(NH₂)₂]₂(CH₃COO)₂), a novel semi organic non linear optical crystal having dimensions 17 mm × 2 mm × 2 mm were grown using slow evaporation technique. The lattice parameters for the grown crystals were determined using single crystal XRD. The presence of functional groups for the grown crystals was confirmed using Fourier transform infrared (FT-IR) spectroscopy. The optical absorption studies show that the material has wide optical transparency in the entire visible region. The dielectric constant and dielectric loss has been studied as a function of frequency for various temperatures and the results were discussed in detail. The second harmonic generation was confirmed by Kurtz powder method and it is found to be 5 times than that of potassium dihydrogen phosphate (KDP) crystal.     

Tetragonal-cubic phase boundary in nanocrystalline ZrO2-Y2O3 solid solutions synthesized by gel-combustion

By means of synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy, we have detected, in a series of nanocrystalline and compositionally homogeneous ZrO₂-Y₂O₃ solid solutions, the presence at room temperature of three different phases depending on Y₂O₃ content, namely two tetragonal forms and the cubic phase. The studied materials, with average crystallite sizes within the range 7-10 nm, were synthesized by a nitrate-citrate gel-combustion process. The crystal structure of these phases was also investigated by SXPD. The results presented here indicate that the studied nanocrystalline ZrO₂-Y₂O₃ solid solutions exhibit the same phases reported in the literature for compositionally homogeneous materials containing larger (micro)crystals. The compositional boundaries between both tetragonal forms and between tetragonal and cubic phases were also determined.     

Microstructure characterization of rapidly solidified Al-Fe-Cr-Ce alloy by positron annihilation spectroscopy

Positron annihilation spectroscopy was employed for the microstructure characterization of rapidly solidified Al-3 wt.% Cr-3 wt.% Fe-0.8 wt.% Ce alloy prepared by melt spinning. Results of the positron annihilation study are analyzed within the diffusion trapping model and compared with results of X-ray diffraction, transmission electron microscopy and microhardness measurements. A good consistency among all experimental techniques was obtained. The rapidly solidified alloy exhibits ultra fine grained structure, consisting of cells separated by dislocation walls. Annealed samples showed no significant changes in structure up to 400 °C which proves good thermal stability of ultra fine grained structure. Exposure of the sample to temperature of 500 °C caused significant changes in the material.     

Lattice parameter values and phase transitions for the Cu2Cd1−zMnzSnSe4 and Cu2Cd1−zFezSnSe4 alloys

X-ray powder diffraction measurements and differential thermal analysis (DTA) were made on polycrystalline samples of the Cu₂Cd_1−zMn_zSnSe₄ and Cu₂Cd_1−zFe_zSnSe₄ alloy systems. The diffraction patterns were used to show the equilibrium conditions and to derive lattice parameter values. For Cu₂Cd_0.8Fe_0.2SnSe₄ as well as for Cu₂Cd_0.2Fe_0.8SnSe₄ the crystal structures were refined using the Rietveld method. It was found that the internal distortion parameter σ decreases as Cd is replaced by either Mn and/or Fe. For the Cu₂Cd_1−zMn_zSnSe₄ and Cu₂Cd_1−zFe_zSnSe₄ alloy systems, only two single solid phase fields, the tetragonal stannite α and the wurtz–stannite δ (Pmn2₁) structures were found to occur in the diagram. In addition to the tetragonal stannite α phase extra X-ray diffraction lines due to MnSe and/or FeSe₂ were observed for as grown samples in the range 0.7 < z < 1.0. However, it was found that the amount of the extra phase decreased for the compressed samples.     

Spectroscopic properties of Yb in NaYbP2O7 diphosphate single crystals

Yb³⁺ absorption and fluorescent emissions were investigated for NaYbP₂O₇ diphosphate single crystals. The interpretation of electronic energy level positions has been done by using the comparison of absorption and emission spectra with those of vibronic sideband energy positions from Raman and IR absorption spectroscopies. The Yb³⁺ energy levels scheme in this host was drawn. The decay time for infrared Yb³⁺ (⁵F_5/2 excited state) fluorescence was in the range of 1–2 ms. The interest feature is leading to broad emission band at room temperature from 940 nm to 1100 nm, which seems of high interest for ultra-short laser pulse production.     

Crystal structure and magnetic properties of the new ternary actinide compounds AnPd5Al2 (An = U, Np)

We report the crystal structure and magnetic properties of new ternary actinide compounds UPd₅Al₂ and NpPd₅Al₂. Both compounds crystallize in the body-centered tetragonal ZrNi₂Al₅-type tetragonal structure (I 4/mmm). Although the magnetic susceptibility of both compounds follows the Curie–Weiss behavior at high temperature, no magnetic phase transition was observed. UPd₅Al₂ has a nonmagnetic ground state where the magnetic susceptibility saturates at low temperature, while NpPd₅Al₂ superconducts below 4.9 K as reported recently.     

Observation of hydrogen absorption/desorption reaction processes in Li–Mg–N–H system by in-situ X-ray diffractmetry

The in-situ XRD measurements on dehydrogenation/rehydrogenation of the Li–Mg–N–H system were performed in this work. The ballmilled mixture of 8LiH and 3Mg(NH₂)₂ as a hydrogenated phase gradually changed into Li₂NH as a dehydrogenated phase during heat-treatment at 200 °C in vacuum for 50 h. Neither Mg-related phases nor other intermediate phases were recognized in the dehydrogenated phase. With respect to the hydrogenation process, the dehydrogenated state gradually returned to the mixed phase of the LiH and Mg(NH₂)₂ without appearance of any intermediate phases during heat treatment at 200 °C under 5 MPa H₂ for 37 h and during slow cooling down to room temperature through 24 h. In the hydrogenation process at 200 °C under 1 MPa H₂, however, the growing up of the LiNH₂ and LiH phase was observed in the XRD profiles before the 3Mg(NH₂)₂ and 8LiH phases were formed as the final hydrogenated state. This indicates that the LiNH₂ and LiH phase essentially appears as an intermediate state in the Li–Mg–N–H system composed of 3Mg(NH₂)₂ and 8LiH.     

Study on the crystal structure of the rare earth oxyborate Yb26B12O57 from powder X-ray and neutron diffraction

Yb₂₆B₁₂O₅₇, a rare earth oxyborate previously assigned as Yb₃BO₆, has been studied by various techniques including neutron and X-ray diffraction, ¹¹B NMR spectroscopy, electron diffraction and high angle angular dark field-scanning transmission electron microscopy (HADDF-STEM). It crystallizes in the space group C2/m with cell parameters of a = 24.5780(4) Å, b = 3.58372(5) Å, c = 14.3128(3) Å and β = 115.079(1)°. The structure consists of slabs of rare earth sesquioxide and borate groups. The sesquioxide part is identified from the structural refinement, and is observed from HADDF-STEM image, while elucidation of borate groups is not straightforward. An additional oxygen atom (O31), which links two B₂O₅ groups into a B₄O₁₁ polyanion, is identified from the analysis of neutron diffraction data. The occupancy of this oxygen site is only quarter, which results in a random distribution of B₄O₁₁ and B₂O₅ groups along the b-direction. The chemical formula of ytterbium oxyborate is Yb₂₆(BO₃)₄(B₂O₅)₂(B₄O₁₁)O_24, instead of the simple stoichiometric formula Yb₃BO₆. This compound is paramagnetic but its susceptibility deviated from the Curie-Weiss law at low temperature.     

Hydrogenation of oxygen-stabilized Zr3NiOx compounds

It is shown that oxygen-stabilized compounds Zr₃NiO_x (x=0.4, 0.6, 0.8, 1.0) interact with hydrogen at ambient temperature and pressure forming saturated hydrides with a filled Re₃B-type structure. The hydrogen storage capacity decreases with increasing oxygen content from 6.65 H/f.u. for Zr₃NiO_0.4 down to 5.58 H/f.u. for Zr₃NiO_1.0. A slight decrease of the crystal lattice parameters of the parent compounds and a substantial increase of these parameters for the saturated hydrides were observed with increasing oxygen content. The partial hydrogen-induced lattice expansion, ΔV/at. H, increases from 2.333 ų for Zr₃NiO_0.4H_6.65 to 3.047 ų for Zr₃NiO_1.0H_5.58. Joint Rietveld refinement using X-ray and neutron powder diffraction data showed a distribution of deuterium atoms on similar positions as in oxygen-free Zr₃FeD_x and Zr₃CoD_x. The oxygen atoms move during deuteration from the octahedral site to one trigonal bi-pyramidal and two tetragonal interstices that are fully occupied in the saturated deuterides jointly by deuterium and oxygen. After deuterium desorption the oxygen atoms fully return to the initial octahedral site.     

Single crystal preparation and crystal structure of the Cu2Zn/Cd,Hg/SnSe4 compounds

Single crystals of Cu₂Zn/Cd/SnSe₄ were grown using a solution-fusion method. The crystal structure of the Cu₂Zn/Cd,Hg/SnSe₄ compounds were investigated using X-ray powder diffraction. These compounds crystallize in the stannite structure (space group I 2m) with the lattice parameters: a=0.56882(9), c=1.13378(9) nm, c/a=1.993 (Cu₂ZnSnSe₄), a=0.58337(2), c=1.14039(4) nm, c/a=1.955 (Cu₂CdSnSe₄) and a=0.58288(1), c=1.14179(2) nm, c/a=1.959 (Cu₂HgSnSe₄). Atomic parameters were refined in the isotropic approximation (R_I=0.0517, R_I=0.0511 and R_I=0.0695 for Cu₂ZnSnSe₄, Cu₂CdSnSe₄ and Cu₂HgSnSe₄, respectively).     

Raman study of gap mode and lattice disorder effect in InN films prepared by plasma-assisted molecular beam epitaxy

Raman scattering has been used to study lattice defects induced by non-stoichiometry in indium nitride films grown by plasma-assisted molecular beam epitaxy with different In/N ratios. A gap mode located at about 375 cm⁻¹ is observed in InN films grown at low In/N ratios. This is in good agreement with the recursion method calculation for the In vacancy-induced vibration mode. In addition, a spatial correlation model has been used to estimate the lattice disorder in InN samples. The shortest correlation length is L = 5.9 nm.     

Preparation and characterization of mullite whiskers from silica fume by using a low temperature molten salt method

Mullite whiskers were prepared from silica fume in molten Al₂(SO₄)₃-Na₂SO₄ mixture salts at low temperatures. The resulting mullite whiskers, as well as the nucleation and growth mechanism in the molten environment, have been investigated by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermogravimetric analysis (TG-DTA) techniques. XRD studies showed that the materials obtained were orthorhombic mullite. SEM, TEM and HRTEM results revealed that the mullite whiskers were single crystal fibers with diameters ranging from 30 to 150 nm and lengths of over several microns. According to thermodynamic analysis, mullite phase might be spontaneously formed in molten salts as the temperature reached the decomposition temperature of aluminum sulfate (1023 K). Moreover, the mullite crystals grew along [1 1 1] crystal plane firstly and developed into fibrous microstructure finally.     

Effects of processing parameters on the properties of tantalum nitride thin films deposited by reactive sputtering

The effects of processing parameters on the properties of tantalum nitride thin films deposited by radio frequency reactive sputtering have been investigated. The influence of the N₂ partial and (Ar + N₂) total gas pressures as well as the sputtering power on the microstructure and electrical properties is reported. Rising the N₂ partial pressure, from 2 to 10.7%, induces a change in the composition of the δ-TaN phase, from TaN to TaN_1.13. This composition change is associated with a drastic increase of the electrical resistivity over a 7.3% N₂ partial pressure. The total gas pressure is revealed to strongly affect the film microstructure since a variation in both composition and grain size is observed when the gas pressure rises from 6.8 to 24.6 Pa. When the sputtering power varied between 50 and 110 W, an increase of the grain size related to a decrease of the electrical resistivity is observed.     

Growth and characterizations of CdGeAs2 single crystal by descending crucible with rotation method

By the method of descending crucible with rotation, crack-free CdGeAs2single crystals of U15 mm 950 mm were grown in a furnace with three independen heating zones after optimizing the temperature field, and the descending and rotational speed to meet the need of CdGeAs2crystal growth. The properties of as-grown crysta were characterized by a variety of techniques. The results of X-ray diffraction(XRD) show that there are two cleavage faces, which are(110) and(101). The peaks are in high intensity and good symmetry, which demonstrates that the crystal is integral in structure and well crystallized. The energy-dispersive spectrometry results indicate that the wafer of the CdGeAs2crystal is closer to the stoichiometry The IR transmittance of the wafer is *48.6 % at 5.5 lm, and the maximum value is up to 51.6 % in the range of2.3–18.0 lm. Etch pits of(001) face are observed and the density of the etch pits is evaluated to be 1 9 105cm-2.