Mechanistic Aspects for the Formation of Copper Dimer Bridged by Phosphonic Acid and Extending Its Dimensionality by Organic and Inorganic Linkers: Synthesis, Structural Characterization, Magnetic Properties, and Theoretical Studies

Six new copper metal complexes with formulas Cu(H2O)(2,2'-bpy) (H2L)](2) center dot H4L center dot 4 H2O (1), {Cu(H2O)(2,2'-bpy)-(H3L)}(2)(H2L)]center dot 2H(2)O (2), Cu(H2O)(1,10-phen)(H2L)](2)center dot 6H(2)O (3), Cu(2,2'-bpy)(H2L)](n)center dot nH(2)O (4), Cu(1,10-phen)(H2L)](n)center dot 3nH(2)O (5), and {Cu(2,2'-bpy)(MoO3)}(2)(L)](n)center dot 2nH(2)O (6) have been synthesized starting from p-xylylenediphosphonic acid (H4L) and 2,2'-bipyridine (2,2'-bpy) or 1,10-phenanthroline (1,10-phen) as secondary linkers and characterized by single crystal X-ray diffraction analysis, IR spectroscopy, and thermogravimetric (TG) analysis. All the complexes were synthesized by hydrothermal methods. A dinuclear motif (Cu-dimer) bridged by phosphonic acid represents a new class of simple building unit (SBU) in the construction of coordination architectures in metal phosphonate chemistry. The initial pH of the reaction mixture induced by the secondary linker plays an important role in the formation of the molecular phosphonates 1, 2, and 3. Temperature dependent hydrothermal synthesis of the compounds 1, 2, and 3 reveals the mechanism of the self assembly of the compounds based on the solubility of the phosphonic acid H4L. Two-dimensional coordination polymers 4, 5, and 6, which are formed by increasing the pH of the reaction mixture, comprise Cu-dimers as nodes, organic (H2L) and inorganic (Mo4O12) ligands as linkers. The void space-areas, created by the (4,4) connected nets in compounds 4 and 5, are occupied by lattice water molecules. Thus compounds 4 and 5 have the potential to accommodate guest species/molecules. Variable temperature magnetic studies of the compounds 3, 4, 5, and 6 reveal the antiferromagnetic interactions between the two Cu(II) ions in the eight membered ring, observed in their crystal structures. A density functional theory (DFT) calculation correlates the conformation of the Cu-dimer ring with the magnitude of the exchange parameter based on the torsion angle of the conformation.

Influence of Side-Chain on Structural Order and Photophysical Properties in Thiophene Based Diketopyrrolopyrroles: A Systematic Study

In this work, we have synthesized a series of TDPP derivatives with different alkyl groups such as n-hexyl (-C6H13) 3a, 2-ethylhexyl (-(2-C2H5)C6H12) 3b, triethylene glycol mono methyl ether (-(CH2CH2O)(3c)H-3, TEG) 3c, and octadodecyl (-(8-C8H17)C12H22) 3d. N,N dialkylation of Othiophene-diketopyrrolopyrrole (TDPP, 1) strongly influences its solubility, solid state packing, and structural order. These materials allow us to explicitly study the influence of alkyl chain on solid state packing and photophysical properties. TDPP moiety containing two different alkyl groups 3e (TEG and 2-ethylhexyl) and 3f (TEG and n-hexyl) were synthesized for the first time. The absorption spectra of all derivatives exhibited a red shift in solid state when compared to their solution spectra. The type of alkyl chains leads to change in the optical band gaps in solid state. The fluorescence study reveals that TDPP derivatives have strong pi-pi interaction in the solid state and the extent of bathochromic shift is due to combination of intramolecular interaction and formation of aggregates in solid state. This behavior strongly depends on the nature of alkyl chain. The presence of strong C-H center dot center dot center dot O inter chain interactions and CH-pi interactions in solid state exhibits strong influence on the photophysical properties of TDPP chromophore.

Investigations on structural and optical properties of co-doped (Ag, Co) ZnO nanoparticles

Undoped and co-doped (Ag, Co) ZnO powders were synthesized by chemical co-precipitation method without using any capping agent. The X-ray diffraction results indicate that the undoped and co-doped ZnO powders have pure hexagonal structure and are consisting of nanosized single-crystalline particles. The size of the nanoparticles increases with increasing Ag concentration from 1 to 5 mol% as compared to that of undoped ZnO. The presence of substitution dopants of Ag and Co in the ZnO host material was confirmed by the Energy dispersive analysis of X-rays (EDAX). Optical absorption measurements indicate blue shift and red-shift in the absorption band edge upon doping concentration of Ag and blue emission was observed by photoluminescence (PL) studies.

Structural and mechanical properties of room temperature sputter deposited CrN coatings

Chromium nitride (CrN) thin films were deposited at room temperature on silicon and glass substrates using DC reactive magnetron sputtering in Ar + N-2 plasma. Structure and mechanical properties of these films were examined by using XRD, FESEM and nanoindentation techniques. XRD studies revealed that films are of mixed phase at lower nitrogen partial pressure (P-N2) and single phase at higher (P-N2). Microscopy results show that the films were composed of non-equiaxed columns with nanocrystallite morphology. The hardness and elastic modulus of the films increase with increasing nitrogen partial pressure (P-N2). A maximum hardness of similar to 29 GPa and elastic modulus of 341 GPa were obtained, which make these films useful for several potential applications. (C) 2012 Elsevier Ltd. All rights reserved.

Effect of Calcination Temperature on Structural, Photoluminescence, and Thermo luminescence Properties of Y2O3:Eu3+ Nanophosphor

Red light emitting cubic Y1.95Eu0.05O3 nanophosphors have been synthesized by a low temperature solution combustion method using ethylene diamine tetra acetic acid (EDTA) as fuel. The systematic studies on the effect of calcination temperature on its structural, photoluminescence (PL), and thermoluminescence (TL) properties were reported. The crystallinity of the samples increases, and the strain is reduced with increasing calcination temperature. SEM micrographs reveal that samples lose their porous nature with an increase in calcination temperature. PL spectra show that the intensity of the red emission (611 nm) is highly dependent on the calcination temperature and is found to be 10 times higher when compared to as-formed samples. The optical band gap (E-g) was found to reduce with an increase of calcination temperature due to reduction of surface defects. The thermoluminescence (TL) intensity was found to be much enhanced in the 1000 degrees C calcined sample. The increase of PL and TL intensity with calcination temperature is attributed to the decrease of the nonradiative recombination probability, which occurs through the elimination of quenching defects. The trap parameters (E, b, s) were estimated from Chen's glow peak shape method and are discussed in detail for their possible usage in dosimetry.

Structural, EPR, optical and magnetic properties of alpha-Fe2O3 nanoparticles

alpha-Fe2O3 nanoparticles were synthesized by a low temperature solution combustion method. The structural, magnetic and luminescence properties were studied. Powder X-ray diffraction (PXRD) pattern of alpha-Fe2O3 exhibits pure rhombohedral structure. SEM micrographs reveal the dumbbell shaped particles. The EPR spectrum shows an intense resonance signal at g approximate to 5.61 corresponding to isolated Fe3+ ions situated in axially distorted sites, whereas the g approximate to 2.30 is due to Fe3+ ions coupled by exchange interaction. Raman studies show A(1g) (225 cm(-1)) and E-g (293 and 409 cm(-1)) phonon modes. The absorption at 300 nm results from the ligand to metal charge transfer transitions whereas the 540 nm peak is mainly due to the (6)A(1) + (6)A(1) —> T-4(1)(4G) + T-4(1)(4G) excitation of an Fe3+-Fe3+ pair. A prominent TL glow peak was observed at 140 C at heating rate of 5 degrees C s(-1). The trapping parameters namely activation energy (E), frequency factor (s) and order of kinetics (b) were evaluated and discussed. (C) 2012 Elsevier B.V. All rights reserved.

Nanostructured GdxZn1-xO thin films by nebulizer spray pyrolysis technique: Role of doping concentration on the structural and optical properties

Nanostructured GdxZn1-xO thin films with different Gd concentration from 0% to 10% deposited at 400 degrees C using the NSF technique. The films were characterized by structural, surface and optical properties, respectively. X-ray diffraction analysis shows that the Gd doped ZnO films have lattice parameters a = 3.2497 angstrom and c = 5.2018 angstrom with hexagonal structure and preferential orientation along (002) plane. The estimated values compare well with the standard values. When film thickness increases from 222 to 240 nm a high visible region transmittance (>70%) is observed. The optical band gap energy, optical constants (n and k), complex dielectric constants (epsilon(r), and epsilon(i)) and optical conductivities (sigma(r), and sigma(i)) were calculated from optical transmittance data. The optical band gap energy is 3.2 eV for pure ZnO film and 3.6 eV for Gd0.1Zn0.9-O film. The PL studies confirm the presence of a strong UV emission peak at 399 nm. Besides, the UV emission of ZnO films decreases with the increase of Gd doping concentration correspondingly the ultra-violet emission is replaced by blue and green emissions.

Structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films

We investigated the structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films grown by magnetron sputtering from Sm and Co multitargets successively. The growth of the films was carried out at elevated substrate temperature followed by in situ annealing. On Si (100) substrate, X-ray diffraction confirms the formation of textured (110) SmCo5 hard phase, whereas on MgO (110) substrate, the diffraction pattern shows the epitaxial growth of SmCo5 phase with crystalline orientation along 100] direction. Secondary Ion Mass Spectroscopy reveals the structural transformation from multilayered (Sm/Co) to SmCo5/Co nano-composite films due to high reactivity of Sm at elevated temperature. Transmission electron microscopy indicates the existence of nanocrystalline phase of SmCo5 along with unreacted Co. Observed single phase behavior in magnetic hysteresis measurements indicates well exchange coupling between the soft and the hard phases in these nano-composite films. For samples with samarium layer thickness, t(sm)=3.2 nm and cobalt layer thickness, t(Co)= 11.4 nm, the values of (BH)(max) were obtained as 20.1 MGOe and 12.38 MGOe with H-c value similar to 3.0 kOe grown on MgO and Si substrates, respectively.

Influence of annealing on structural, morphological, compositional and surface properties of magnetron sputtered nickel-titanium thin films

Thin films of NiTi were deposited by DC magnetron sputtering from an equiatomic alloy target (Ni/Ti: 50/50 at.%). The films were deposited without intentional heating of the substrates. The thickness of the deposited films was approximately 2 mu m. The structure and morphology of NiTi films annealed at different temperatures were analyzed in order to understand the effect of annealing on physical properties of the films. The compositional investigations of fresh and annealed films were also evaluated by energy dispersive X-ray spectroscopy (EDS) and X-ray photo-electron spectroscopy (XPS) techniques. X-ray diffraction (XRD) studies showed that as-deposited films were amorphous in nature whereas annealed films were found to poly-crystalline with the presence of Austenite phase as the dominant phase. AFM investigations showed higher grain size and surface roughness values in the annealed films. In annealed films, the grain size and film roughness values were increased from 10 to 85 nm and 2-18 nm. Film composition measured by EDS were found to 52.5 atomic percent of Ni and 47.5 atomic percent of Ti. XPS investigations, demonstrated the presence of Ni content on the surface of the films, in fresh films, whereas annealed films did not show any nickel. From HR-XPS investigations, it can be concluded that annealed NiTi films have higher tendency to form metal oxide (titanium dioxide) layer on the surface of the films than fresh NiTi films. (C) 2013 Elsevier B. V. All rights reserved.

Structural, iono and thermoluminescence properties of heavy ion (100 MeV Si7+) bombarded Zn2SiO4:Sm3+ nanophosphor

Structural, iono (IL) and thermoluminescence (TL) studies of Zn2SiO4:Sm3+ (1-5 mol%) nanophosphor bombarded with swift heavy ions in the fluence range 3.91 x 10(12)-21.48 x 10(12) cm(-2) have been carried out. The average crystallite sizes for pristine and ion irradiated for 3.91 x 10(12) ions cm(-2) and 21.48 x 10(12) ions cm(-2) were found to be 34, 26 and 20 nm. With increase of ion fluence, the intensity of XRD peaks decreases and FWHM increases. The peak broadening indicates the stress induced point/clusters defects produced due to heavy ion irradiation. IL studies were carried out for different Sm3+ concentrations in Zn2SiO4 by irradiating with ion fluence of 15.62 x 10(12) ions cm(-2). The characteristic emission peaks at similar to 562, 599, 646 and 701 nm were recorded by exciting Si7+ ions in the fluence range 3.91 x 10(12)-21.48 x 10(12) ions cm(-2). These peaks were attributed to (4)G(5/2)-> H-6(5/2) (562 nm), (4)G(5/2)-> H-6(7/2) (599 nm), (4)G(5/2)-> H-6(9/2) (646 nm), and (4)G(5/2)-> H-6(5/2) (701 nm) transitions of Sm3+. The highest emission was recorded at 3 mol% of Sm3+ doped Zn2SiO4. TL studies were carried out for 3 mol% Sm3+ concentration in the fluence range 3.91 x 10(12)-21.48 x 10(12) ions cm(-2). Two U glow peaks at 152 and 223 degrees C were recorded. The kinetic parameters (E, b, and s), were estimated using Chen's peak shape method. Simple glow curve structure (223 degrees C), highly resistive, increase in TL. intensity up to 19.53 x 10(12) ions cm(-2), simple trap distribution makes Zn2SiO4:Sm3+ (3 mol%) phosphor highly useful in radiation dosimetry.

Post-deposition annealing influenced structural and electrical properties of Al/TiO2/Si gate capacitors

Titanium dioxide (TiO2) thin films are deposited on unheated p-Si (100) and quartz substrates by employing DC reactive magnetron sputtering technique. The effect of post-deposition annealing in air at temperatures in the range 673-973 K on the structural, electrical, and dielectric properties of the films was investigated. The chemical composition of the TiO2 films was analyzed with X-ray photoelectron spectroscopy. The surface morphology of the films was studied by atomic force microscope. The optical band gap of the as-deposited film was 3.50 eV, and it increased to 3.55 eV with the increase in annealing temperature to 773 K. The films annealed at higher temperature of 973 K showed the optical band gap of 3.43 eV. Thin film capacitors were fabricated with the MOS configuration of Al/TiO2/p-Si. The leakage current density of the as-deposited films was 1.2 x 10(-6) A/cm(2), and it decreased to 5.9 x 10(-9) A/cm(2) with the increase in annealing temperature to 973 K. These films showed high dielectric constant value of 36. (C) 2013 Elsevier Ltd. All rights reserved.

Synthesis, structural and optical properties of nanocrystalline Ba2NaNb5O15

Fine powders comprising nanocrystallites of barium sodium niobate, Ba2NaNb5O15 (BNN) were obtained via a citrate assisted sol-gel route at a much lower temperature than that of the conventional solid-state reaction route. The phase evolution of BNN as a function of temperature was investigated by thermogravimetric analysis (TGA), differential thermal analysis (DTA), Fourier transform infrared spectroscopy (FTIR) and X-ray powder diffraction (XRD). DTA data followed by XRD studies confirmed the BNN formation temperature to be around 923 K. The as-synthesized powders heat-treated at 923 K/10 h attained an orthorhombic structure akin to that of the parent BNN phase. Transmission electron microscopy revealed that the nanocrystallites are associated with dislocations. The optical band gap was calculated using the Kubelka-Munk function. These nanocrystallites exhibited strong visible photoluminescence (PL) at room temperature. The PL mechanism was explained by invoking the dielectric confinement effect, defect states and generation of self-trapped excitons.

New Structural Topologies in a Series of 3d Metal Complexes with Isomeric Phenylenediacetates and 1,3,5-Tris(1-imidazolyl)benzene Ligand: Syntheses, Structures, and Magnetic and Luminescence Properties

In this article we present the syntheses, characterizations, magnetic and luminescence properties of five 3d-metal complexes, Co(tib)(1,2-phda)](n)center dot(H2O)(n) (1), Co-3(tib)(2)(1,3-phda)(3)(H2O)](n)center dot(H2O)(2n) (2), Co-5(tib)(3)(1,4-phda)(5)(H2O)(3)](n)center dot(H2O)(7n) (3), Zn-3(tib)(2)(1,3-phda)(3)](n)center dot(H2O)(4n) (4), and Mn(tib)(2)(H2O)(2)](n)center dot(1,4-phdaH)(2n)center dot(H2O)(4n) (5), obtained from the use of isomeric phenylenediacetates (phda) and the neutral 1,3,5-tris(1-imidazolyl)benzene (tib) ligand. Single crystal X-ray structures showed that 1 constitutes 3,5-connected 2-nodal nets with a double-layered two-dimensional (2D) structure, while 2 forms an interpenetrated 2D network (3,4-connected 3-nodal net). Complex 3 has a complicated three-dimensional structure with 10-nodal 3,4,5-connected nets. Complex 4, although it resembles 2 in stoichiometry and basic building structures, forms a very different overall 2D assembly. In complex 5 the dicarboxylic acid, upon losing only one of the acidic protons, does not take part in coordination; instead it forms a complicated hydrogen bonding network with water molecules. Magnetic susceptibility measurements over a wide range of temperatures revealed that the metal ions exchange very poorly through the tib ligand, but for the Co(II) complexes the effects of nonquenched orbital contributions are prominent. The 3d(10) metal complex 4 showed strong luminescence with lambda(max) = 415 nm (lambda(ex) = 360 nm).

Effect of low oxygen pressure on structural and magnetic properties of quenched SrFe12O19 thin films

Strontium hexaferrite thin films have been grown on glass substrates at room temperature in oxygen environment by pulsed laser deposition method. The effect of oxygen pressure (p(o2)) on the structural and magnetic properties has been investigated. The as-deposited films were found to be amorphous in nature. The crystallization of these films was achieved by annealing at a temperature of 850 A degrees C in air. The thickness of the film increased with p(o2). The film grown at p(o2) = 0.455 Pa had a clear hexagonal structure. The values of coercivity for the films were found to increase with p(o2).

Local structural disorder and its influence on the average global structure and polar properties in Na0.5Bi0.5TiO3

Na0.5Bi0.5TiO3 (NBT) and its derivatives have prompted a great surge in interest owing to their potential as lead-free piezoelectrics. In spite of five decades since its discovery, there is still a lack of clarity on crucial issues such as the origin of significant dielectric relaxation at room temperature, structural factors influencing its depoling, and the status of the recently proposed monoclinic (Cc) structure vis-a-vis the nanosized structural heterogeneities. In this work, these issues are resolved by comparative analysis of local and global structures on poled and unpoled NBT specimens using electron, x-ray, and neutron diffraction in conjunction with first-principles calculation, dielectric, ferroelectric, and piezoelectric measurements. The reported global monoclinic (Cc) distortion is shown not to correspond to the thermodynamic equilibrium state at room temperature. The global monocliniclike appearance rather owes its origin to the presence of local structural and strain heterogeneities. Poling removes the structural inhomogeneities and establishes a long-range rhombohedral distortion. In the process the system gets irreversibly transformed from a nonergodic relaxor to a normal ferroelectric state. The thermal depoling is shown to be associated with the onset of incompatible in-phase tilted octahedral regions in the field-stabilized long range rhombohedral distortion.