Cl-35 NQR study of cation polarizability in metal salts of monochloro acetic acid

Various metal salts (Na, K, Rb, and NH4) of monochloro acetic acid were prepared and the Cl-35 nuclear quadrupole resonance frequencies were measured at room temperature. A comparative study of nuclear quadrupole resonance frequencies of monochloro acetic acid and its metal salts is carried out. The frequency shifts obtained in the respective metal chloroacetates are used to estimate the changes in the ionicity of C-Cl bond. Further, the changes in the ionicity of C-Cl bond were used to estimate the percentage of intra-molecular charge transfer between respective cation-anion of the metal salts of chloro acetic acid. The nuclear quadrupole resonance frequency is found to decrease with increasing ionicity of the alkali metal ion.

Crystal structure of 3-acetylcoumarin-o-aminobenzoylhydrazone and synthesis, spectral and thermal studies of its transition metal complexes

Transition metal [Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)] complexes of a new Schiff base, 3-acetylcoumarin-o-aminobenzoylhydrazone were synthesized and characterized by elemental analyses, magnetic moments, conductivity measurements, spectral [Electronic, IR, H-1 and C-13 NMR, EPR] and thermal studies. The ligand crystallizes in the monoclinic system, space group P2(1)/n with a = 9.201(5), b = 16.596( 9), c = 11.517(6) angstrom, beta= 101.388(9)degrees, V = 1724.2 (17) angstrom(3) and Z = 4. Conductivity measurements indicated Mn(II) and Co(II) complexes to be 1 : 1 electrolytes whereas Ni(II), Cu(II), Zn(II) and Cd(II) complexes are non-electrolytes. Electronic spectra reveal that all the complexes possess four-coordinate geometry around the metal.

Coordination polymers and hybrid networks of different dimensionalities formed by metal sulfites

In our effort to explore the use of the sulfite ion to design hybrid and open-framework materials, we have been able to prepare, under hydrothermal conditions, zero-dimensional [Zn(C12H8N2)(SO3)]center dot 2H(2)O, I (a = 7.5737(5) angstrom, b = 10.3969(6) angstrom, c = 10.3986(6) angstrom, alpha = 64.172(1)degrees, beta = 69.395(1)degrees, gamma = 79.333(1)degrees, Z = 2, and space group P (1) over bar), one-dimensional [Zn-2(C12H8N2)(SO3)(2)(H2O)], II (a = 8.0247(3) angstrom, b = 9.4962(3) angstrom, c = 10.2740(2) A, alpha = 81.070(1)degrees, beta = 80.438(1)degrees, gamma = 75.66(5)degrees, Z = 2, and space group P (1) over bar), two-dimensional [Zn-2(C10H8N2)(SO3)(2)]center dot H2O, III (a = 16.6062(1) angstrom, b = 4.7935(1) angstrom, c = 19.2721(5) angstrom, beta = 100.674(2)degrees, Z = 4, and space group C2/c), and three-dimensional [Zn-4(C6H12N2)(SO3)(4)(H2O)(4)], IV (a = 11.0793(3) angstrom, c = 8.8246(3) angstrom, Z = 2, and space group P42nm), of which the last three are coordination polymers. A hybrid open-framework sulfite-sulfate of the composition [C2H10N2][Nd(SO3)(SO4)(H2O)](2), V (a = 9.0880(3) angstrom, b = 6.9429(2) angstrom, c = 13.0805(5) A, beta = 91.551(2)degrees, Z = 2, and space group P2(1)/c), with a layered structure containing metal-oxygen-metal bonds has also been described.

Dielectric anomaly in Li-doped zinc oxide thin films grown by sol-gel route

Sol-gel route was employed to grow polycrystalline thin films of Li-doped ZnO thin films (Zn1-xLixO, x=0.15). Polycrystalline films were obtained at a growth temperature of 400-500 degrees C. Ferroelectricity in Zn0.85Li0.15O was verified by examining the temperature variation of the real and imaginary parts of dielectric constant, and from the C-V measurements. The phase transition temperature was found to be 330 K. The room-temperature dielectric constant and dissipation factor were 15.5 and 0.09 respectively, at a frequency of 100 kHz. The films exhibited well-defined hysteresis loop, and the values of spontaneous polarization (P-s) and coercive field were 0.15 mu C/cm(2) and 20 kV/cm, respectively, confirming the presence of ferroelectricity.

Combined Atomic Force Microscopy and Modeling Study of The Evolution of Octadecylamine Films on a Mica Surface

The time evolution of the film thickness and domain formation of octadecylamine molecules adsorbed oil a mica surface is investigated Using atomic force microscopy. The adsorbed Film thickness is determined by measuring the height profile across the mica-amine interface of a mica surface partially immersed in a 15 mM solution of octadecylamine in chloroform. Using this novel procedure, adsorption of amine on mica is found to occur in three distinct stages, with morphologically distinct domain Formation and growth occurring during each stage. In the first stage, where adsorption is primarily in the thin-film regime, all average Film thickness of 0.2 (+/- 0.3) nm is formed for exposure times below 30 s and 0.8 (+/- 0.2) nm for 60 s of immersion time. During this stage, large sample spanning domains are observed. The second stage, which occurs between 60-300 s, is associated with it regime of rapid film growth, and the film thickness increases from about 0.8 to 25 nm during this stage. Once the thick-film regime is established, further exposure to the amine solution results in all increase in the domain area, and it regime of lateral domain growth is observed. In this stage, the domain area coverage grows from 38 to 75%, and the FTIR spectra reveal an increased level of crystallinity in the film. Using it diffusion-controlled model and it two-step Langmuir isotherm, the time evolution of the film growth is quantitatively captured. The model predicts the time at which the thin to thick film transition occurs as well its the time required for complete film growth at longer times. The Ward-Tordai equation is also solved to determine the model parameters in the monolayer (thin-film) regime, which occurs during the initial stages of film growth.

High energy oxygen ion induced modifications in lead based perovskite thin films

The lead based ferroelectric PbZr0.53Ti0.47O3 (PZT), (Pb0.90La0.10)TiO3 (PLT10) and (Pb0.80La0.20)TiO3 (PLT20) thin films, prepared by pulsed laser ablation technique, were studied for their response to the 70 MeV oxygen ion irradiation. The dielectric analysis, capacitance-voltage (C- V) and DC leakage current measurements were performed before and after the irradiation to high-energy oxygen ions. The irradiation produced considerable changes in the dielectric, C-V, leakage characteristics and induced some amount of amorphization. The PZT films showed partial recrystallization after a thermal annealing at 400 degrees C for 10 min. The phase transition temperature [T-c] of PLT20 increased from 115 degrees C to 120 degrees C. The DC conductivity measurements showed a shift in the onset of non-linear conduction region. The current density decreased by two orders of magnitude after irradiation. After annealing the irradiated films at a temperature of 400 degrees C for 10 min, the films partially regained the dielectric and electrical properties. The results are discussed in terms of the irradiation-induced amorphization, the pinning of the ferroelectric domains by trapped charges and the thermal annealing of the defects generated during the irradiation. (C) 2007 Elsevier B.V. All rights reserved.

Electrical Properties of Thermal Evaporated Cd1−xMnxS Nanocrystalline Films

Thin films of Cd1−xMnxS (0<=x<=0.5) were deposited on glass substrates by thermal evaporation. All the films were deposited at 300 K and annealed at 373, 473, and 573 K for 1 h in a high vacuum in the range 10−4 Pa. The as-deposited and the annealed films were characterized for composition, structure, and microstructure by using energy-dispersive X-ray, X-ray diffraction, scanning electron microscopy, and atomic force microscopy (AFM). The electrical properties were studied by Hall effect measurement. Electrical conductivity was studied in the temperature range 190–450 K. AFM studies showed that all the films were in nanocrystalline form with grain size varying in the range between 36 and 82 nm. Grain size studies showed a definite increase with annealing temperature. All the films exhibited wurtzite structure of the host material. The lattice parameter varied linearly with composition, following Vegard's law in the entire composition range. Grain size, electrical conductivity, Hall mobility, carrier concentration, and activation energy varied, exhibiting either maxima or minima at x=0.3.

Investigations on magnetron sputtered ZnO thin films and Au/ZnO Schottky diodes

Magnetron sputtering is a promising technique for the growth of oxide materials including ZnO, which allows deposition of films at low temperatures with good electrical properties. The current-voltage (I-P) characteristics of An Schottky contacts on magnetron sputtered ZnO, films have been measured over a temperature range of 278-358K. Both effective barrier height (phi(B,eff)) and ideality factor (n) are found to be a function of temperature, and this behavior has been interpreted on the basis of a Gaussian distribution of barrier heights due to barrier height inhomogeneities that prevail at the interface. Density of states (DOS) near the Fermi level is determined using a model based on the space charge limited current (SCLC). The dispersion in both real and imaginary parts of the dielectric constant at low frequencies, with increase in temperature is attributed to the space charge effect. Complex impedance plots exhibited two semicircles, which corresponds to bulk grains and the grain boundaries. (c) 2006 Elsevier B.V. All rights reserved.

Electrical and structural properties of zirconia thin films prepared by reactive magnetron sputtering

Thin films of ZrO2 were prepared by reactive magnetron sputtering. Annealing of the films exhibited a drastic change in the properties due to improved crystallinity and packing density. The root mean square roughness of the sample observed from atomic force microscope is about 5.75 nm which is comparable to the average grain size of the thin film which is about 6 nm obtained from X-ray diffraction. The film annealed at 873 K exhibits an optical band gap of around 4.83 eV and shows +4 oxidation state of zirconium indicating fully oxidized zirconium, whereas higher annealing temperatures lead to oxygen deficiency in the films and this is reflected in their properties. A discontinuity in the imaginary part of the AC conductivity was observed in the frequency range of tens of thousands of Hz, where as, the real part does not show such behavior.

Nanoscale Heterostructures with Molecular-Scale Single-Crystal Metal Wires

Creating nanoscale heterostructures with molecular-scale (<2 nm) metal wires is critical for many applications and remains a challenge. Here, we report the first time synthesis of nanoscale heterostructures with single-crystal molecular-scale Au nanowires attached to different nanostructure substrates. Our method involves the formation of Au nanoparticle seeds by the reduction of rocksalt AuCl nanocubes heterogeneously nucleated on the Substrates and subsequent nanowire growth by oriented attachment of Au nanoparticles from the Solution phase. Nanoscale heterostructures fabricated by such site-specific nucleation and growth are attractive for many applications including nanoelectronic device wiring, catalysis, and sensing.

Reactive Pulsed Laser Deposition of titanium nitride thin film: Optimization of process parameters using Secondary Ion Mass Spectrometry

Reactive Pulsed Laser Deposition is a single step process wherein the ablated elemental metal reacts with a low pressure ambient gas to form a compound. We report here a Secondary Ion Mass Spectrometry based analytical methodology to conduct minimum number of experiments to arrive at optimal process parameters to obtain high quality TiN thin film. Quality of these films was confirmed by electron microscopic analysis. This methodology can be extended for optimization of other process parameters and materials. (C) 2009 Elsevier B.V. All rights reserved.

Influence of surfactant and annealing temperature on optical properties of sol-gel derived nano-crystalline TiO2 thin films

Titanium dioxide thin films have been synthesized by sol-gel spin coating technique on glass and silicon substrates with and without surfactant polyethylene glycol (PEG). XRD and SEM results confirm the presence of nano-crystalline (anatase) phase at an annealing temperature of 300 degrees C. The influence of surfactant and annealing temperature on optical properties of TiO2 thin films has been studied. Optical constants and film thickness were estimated by Swanepoel's (envelope) method and by ellipsometric measurements in the visible spectral range. The optical transmittance and reflectance were found to decrease with an increase in PEG percentage. Refractive index of the films decreased and film thickness increased with the increase in percentage of surfactant. The refractive index of the un-doped TiO2 films was estimated at different annealing temperatures and it has increased with the increasing annealing temperature. The optical band gap of pure TiO2 films was estimated by Tauc's method at different annealing temperature. (C) 2010 Elsevier B.V. All rights reserved.

The effect of pressure and W-doping on the properties of ZnO thin films for NO2 gas sensing

Pure and W-doped ZnO thin films were obtained using magnetron sputtering at working pressures of 0.4 Pa and 1.33 Pa. The films were deposited on glass and alumina substrates at room temperature and subsequently annealed at 400oC for 1 hour in air. The effects of pressure and W-doping on the structure, chemical, optical and electronic properties of the ZnO films for gas sensing were examined. From AFM, the doped film deposited at higher pressure (1.33 Pa) has spiky morphology with much lower grain density and porosity compared to the doped film deposited at 0.4 Pa. The average gain size and roughness of the annealed films were estimated to be 65 nm and 2.2 nm, respectively with slightly larger grain size and roughness appeared in the doped films. From XPS the films deposited at 1.33 Pa favored the formation of adsorbed oxygen on the film surface and this has been more pronounced in the doped film which created active sites for OH adsorption. As a consequence the W-doped film deposited at 1.33 Pa was found to have lower oxidation state of W (35.1 eV) than the doped film deposited at 0.4 Pa (35.9 eV). Raman spectra indicated that doping modified the properties of the ZnO film and induced free-carrier defects. The transmittance of the samples also reveals an enhanced free-carrier density in the W-doped films. The refractive index of the pure film was also found to increase from 1.7 to 2.2 after W-doping whereas the optical band gap only slightly increased. The W-doped ZnO film deposited at 0.4 Pa appeared to have favorable properties for enhanced gas sensing. This film showed significantly higher sensing performance towards 5-10 ppm NO2 at lower operating temperature of 150oC most dominantly due to increased free-carrier defects achieved by W-doping.