Studies on ß-arylhydrazone-imine nickel(II) complexes—Examples of metal template syntheses

ß-arylhydrazone-imine ligand complexes of nickel(II), namely, 4,10-dimethyl-5,9-diazatrideca-4,9-diene-2,12-dione-3,11-diphenylhydrazonato nickel(II), Ni(acacpn)(N2Ph-R)2 and 1,11-diphenyl-3,9-dimethyl-4,8-diazaun-deca-3,8-diene,1,11-dione-2,10-diphenyl hydrazonato nickel(II), Ni (beacpn) (N2Ph-R)2, [R = H, o-CH3p-CH3] have been prepared by metal template reactions and characterized. Both the azomethine nitrogens and α-nitrogens of bis-hydrazone form the coordination sites of the square-planar geometry around the nickel(II) ion. Loss of CO from the molecule and subsequently an interesting methyl group migration to the nucleus of the chelate ring have been observed in the mass spectrum. Structures are proposed based on the spectral and magnetic properties.

The impact of ultra thin silicon nitride buffer layer on GaN growth on Si (1 1 1) by RF-MBE

Ultra thin films of pure silicon nitride were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma with a high content of nitrogen atoms. The effect of annealing of silicon nitride surface was investigated with core-level photoelectron spectroscopy. The Si 2p photoelectron spectra reveals a characteristic series of components for the Si species, not only in stoichiometric Si3N4 (Si4+) but also in the intermediate nitridation states with one (Si1+) or three (Si3+) nitrogen nearest neighbors. The Si 2p core-level shifts for the Si1+, Si3+, and Si4+ components are determined to be 0.64, 2.20, and 3.05 eV, respectively. In annealed sample it has been observed that the Si4+ component in the Si 2p spectra is significantly improved, which clearly indicates the crystalline nature of silicon nitride. The high resolution X-ray diffraction (HRXRD), scanning electron microscopy (SEM) and photoluminescence (PL) studies showed a significant improvement of the crystalline qualities and enhancement of the optical properties of GaN grown on the stoichiometric Si3N4 by molecular beam epitaxy (MBE). (C) 2010 Elsevier B.V. All rights reserved.

Growth temperature induced effects in non-polar a-plane GaN on r-plane sapphire substrate by RF-MBE

Non-polar a-plane GaN films were grown on an r-plane sapphire substrate by plasma assisted molecular beam epitaxy (PAMBE). The effect of growth temperature on structural, morphological and optical properties has been studied. The growth of non-polar a-plane (1 1 - 2 0) orientation of the GaN epilayers were confirmed by high resolution X-ray diffraction (HRXRD) study. The X-ray rocking curve (XRC) full width at half maximum of the (1 1 - 2 0) reflection shows in-plane anisotropic behavior and found to decrease with increase in growth temperature. The atomic force micrograph (AFM) shows island-like growth for the film grown at a lower temperature. Surface roughness has been decreased with increase in growth temperature. Room temperature photoluminescence shows near band edge emission at 3.434-3.442 eV. The film grown at 800 degrees C shows emission at 2.2 eV, which is attributed to yellow luminescence along with near band edge emission. (C) 2010 Elsevier B.V. All rights reserved.

Negative differential capacitance in n-GaN/p-Si heterojunctions

Negative differential capacitance (NDC) has been observed in n-GaN/p-Si heterojunctions grown by plasma assisted molecular beam epitaxy (PAMBE). The NDC is observed at low frequencies 1 and 10 kilohertz (kHz) and disappeared at a higher testing frequency of 100 kHz. The NDC is also studied with temperature and found that it has disappeared above 323 degrees C. Current-Voltage (I-V) characteristics of n-GaN /p-Si heterojunction were measured at different temperatures and are attributed to the space-charge-limited current (SCLC). A simple model involving two quantum states is proposed to explain the observed NDC behavior. (C) 2010 Elsevier Ltd. All rights reserved.

Temperature dependent electrical transport behavior of InN/GaN heterostructure based Schottky diodes

InN/GaN heterostructure based Schottky diodes were fabricated by plasma-assisted molecular beam epitaxy. The temperature dependent electrical transport properties were carried out for InN/GaN heterostructure. The barrier height and the ideality factor of the Schottky diodes were found to be temperature dependent. The temperature dependence of the barrier height indicates that the Schottky barrier height is inhomogeneous in nature at the heterostructure interface. The higher value of the ideality factor and its temperature dependence suggest that the current transport is primarily dominated by thermionic field emission (TFE) other than thermionic emission (TE). The room temperature barrier height obtained by using TE and TFE models were 1.08 and 1.43 eV, respectively. (C) 2011 American Institute of Physics. doi: 10.1063/1.3549685]

Temperature-dependent photoluminescence of GaN grown on beta-Si3N4/Si (111) by plasma-assisted MBE

Photoluminescence (PL) of high quality GaN epitaxial layer grown on beta-Si3N4/Si (1 1 1) substrate using nitridation-annealing-nitridation method by plasma-assisted molecular beam epitaxy (PA-MBE) was investigated in the range of 5-300 K. Crystallinity of GaN epilayers was evaluated by high resolution X-ray diffraction (HRXRD) and surface morphology by Atomic Force Microscopy (AFM) and high resolution scanning electron microscopy (HRSEM). The temperature-dependent photoluminescence spectra showed an anomalous behaviour with an `S-like' shape of free exciton (FX) emission peaks. Distant shallow donor-acceptor pair (DAP) line peak at approximately 3.285 eV was also observed at 5 K, followed by LO replica sidebands separated by 91 meV. The activation energy of the free exciton for GaN epilayers was also evaluated to be similar to 27.8 +/- 0.7 meV from the temperature-dependent PL studies. Low carrier concentrations were observed similar to 4.5 +/- 2 x 10(17) Cm-3 by measurements and it indicates the silicon nitride layer, which not only acts as a growth buffer layer, but also effectively prevents Si diffusion from the substrate to GaN epilayers. The absence of yellow band emission at around 2.2 eV signifies the high quality of film. The tensile stress in GaN film calculated by the thermal stress model agrees very well with that derived from Raman spectroscopy. (C) 2010 Elsevier B.V. All rights reserved.

Template directed asymmetric synthesis of the 1,1?-binaphthol unit

An oxidative binaphthol coupling with 65% yield and 65% selectivity has been accomplished using 7-deoxycholic acid as a chiral template.

Structural and optical properties of nonpolar (11-20) a-plane GaN grown on (1-102) r-plane sapphire substrate by plasma-assisted molecular beam epitaxy

We report the structural and optical properties of a-plane GaN film grown on r-plane sapphire substrate by plasma-assisted molecular beam epitaxy. High resolution X-ray diffraction was used to determine the out-of-plane and in-plane epitaxial relation of a-plane GaN to r-plane sapphire. Low-temperature photoluminescence emission was found to be dominated by basal stacking faults along with near-band emission. Raman spectroscopy shows that the a-GaN film is of reasonably good quality and compressively strained. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A template-free, combustion-chemical route to macroporous nickel monoliths displaying a hierarchy of pore sizes

Recently, we demonstrated a very general route to monolithic macroporous materials prepared without the use of templates (Rajamathi et al. J. Mater. Chem. 2001, 11, 2489). The route involves finding a precursor containing two metals, A and B, whose oxides are largely immiscible. Firing of the precursor followed by suitable sintering results in a monolith from which one of the oxide phases can be chemically leached out to yield a macroporous mass of the other oxide phase. The metals A and B that we employed in the demonstration were Ni and Zn. From the NiO-ZnO monolith that was obtained by decomposing the precursor, ZnO could be leached out at high pH to yield macroporous NiO. In the present work, we show that combustion-chemical (also called self-propagating) decomposition of a mixture of Ni and Zn nitrates with urea as a fuel yields an intimate mixture of the oxides that can be sintered and leached with alkali to form a macroporous NiO monolith. The new process that we present here thereby avoids the need for a crystalline single-source precursor. A novel and unanticipated aspect of the present work is that the combination of high temperatures and rapid quenching associated with combustion synthesis results in an intimate mixture of wurtzite ZnO and the metastable rock-salt Ni1-xZnxO where x is about 0.3. Leaching this monolith with alkali gives a macroporous mass of rock-salt Ni1-xZnxO, which upon reduction in H-2/Ar forms macroporous Ni and ZnO. There are thus two stages in the process that lead to two modes of pore formation. The first is associated with leaching of ZnO by alkali. The second is associated with the reduction of porous Ni1-xZnxO to give porous Ni and ZnO.

Impact of Template Layers on Dielectric and Electrical Properties of Pulsed-Laser Ablated Pb(Mg1/3 Nb2/3)O3 - PbTiO3 Thin Films

A study was done on pulsed laser deposited relaxor ferroelectric thin films of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 (PMN-PT) deposited on platinized silicon substrates with template layers to observe the influence of the template layers on physical and electrical properties. Initial results, showed that perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on Pt/Ti/SiO2/Si substrates. The films were grown at 300°C and then annealed in a rapid thermal annealing furnace in the temperature range of 750-850°C to induce crystallization. Comparison of the films annealed at different temperatures revealed a change in crystallinity, perovskite phase formation and grain size. These results were further used to improve the quality of the perovskite PMN-PT phase by inserting thin layers of TiO2 on the Pt substrate. These resulted in an increase in perovskite phase in the films even at lower annealing temperatures. Dielectric studies on the PMN-PT films show very high values of dielectric constant (1300) at room temperature, which further improved with the insertion of the template seed layer. The relaxor properties of the PMN-PT were correlated with Vogel-Fulcher theory to determine the actual nature of the relaxation process.

Reduction of oxygen impurity at GaN/beta-Si(3)N(4)/Si interface via SiO(2) to Ga(2)O conversion by exposing of Si surface under Ga flux

The removal of native oxide from Si (1 1 1) surfaces was investigated by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectra (SIMS) depth profiles. Two different oxide removal methods, performed under ultrahigh-vacuum (UHV) conditions, were carried out and compared. The first cleaning method is thermal desorption of oxide at 900 degrees C. The second method is the deposition of metallic gallium followed by redesorption. A significant decrease in oxygen was achieved by thermal desorption at 900 degrees C under UHV conditions. By applying a subsequent Ga deposition/redesorption, a further reduction in oxygen could be achieved. We examine the merits of an alternative oxide desorption method via conversion of the stable SiO(2) surface oxide into a volatile Ca(2)O oxide by a supply of Ga metals. Furthermore, ultra thin films of pure silicon nitride buffer layer were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma followed by GaN growth. The SIMS depth profile shows that the oxygen impurity can be reduced at GaN/beta-Si(3)N(4)/Si interfaces by applying a subsequent Ga deposition/redesorption. (C) 2011 Elsevier B.V. All rights reserved.

Role of La0.5Sr0.5COO3 template layers on dielectric and electrical properties of pulsed-laser ablated Pb(Nb2/3Mg1/3)O-3-PbTiO3 thin films

Relaxor ferroelectric thin films of 0.7Pb(Mg1/3Nb2/3)O-3-0.3PbTiO(3) (PMN-PT) deposited on platinized silicon substrates with and without template layers were studied. Perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on bare Pt/Ti/SiO2/Si substrates. The films were initially grown at 300 degreesC using pulsed-laser ablation and subsequently annealed in a rapid thermal annealing furnace in the temperature range of 750-850 degreesC to induce crystallization. Comparison of microstructure of the films annealed at different temperatures showed change in perovskite phase formation and grain size etc. Results from compositional analysis of the films revealed that the films initially possessed high content of lead percentage, which subsequently decreased after annealing at temperature 750-850 degreesC. Films with highest perovskite content were found to form at 820-840 degreesC on Pt substrates where the Pb content was near stoichiometric. Further improvement in the formation of perovskite PMN-PT phase was obtained by using buffer layers of La0.5Sr0.5CoO3 (LSCO) on the Pt substrate. This resulted 100% perovskite phase formation in the films deposited at 650 degreesC. Dielectric studies on the PMN-PT films with LSCO template layers showed high values of relative dielectric constant (3800) with a loss factor (tan delta) of 0.035 at a frequency of 1 kHz at room temperature. (C) 2002 Elsevier Science B.V. All rights reserved.

Electroluminescence from GaN-polymer heterojunction

Inorganic and organic semiconductor devices are generally viewed as distinct and separate technologies. Herein we report a hybrid inorganic-organic light-emitting device employing the use of an air stable polymer, Poly (9,9-dioctylfluorene-alt-benzothiadiazole) as a p-type layer to create a heterojunction, avoiding the use of p-type GaN, which is difficult to grow, being prone to the complex and expensive fabrication techniques that characterises it. I-V characteristics of the GaN-polymer heterojunction fabricated by us exhibits excellent rectification. The luminescence onset voltage is typically about 8-10 V. The device emits yellowish white electroluminescence with CIE coordinates (0.42, 0.44). (C) 2011 Elsevier B.V. All rights reserved.

Barrier height inhomogeneities in InN/GaN heterostructure based Schottky junctions

The electrical transport properties of InN/GaN heterostructure based Schottky junctions were studied over a wide temperature range of 200-500 K. The barrier height and the ideality factor were calculated from current-voltage (I-V) characteristics based on thermionic emission (TE), and found to be temperature dependent. The barrier height was found to increase and the ideality factor to decrease with increasing temperature. The observed temperature dependence of the barrier height indicates that the Schottky barrier height is inhomogeneous in nature at the heterostructure interface. Such inhomogeneous behavior was modeled by assuming the existence of a Gaussian distribution of barrier heights at the heterostructure interface. (C) 2011 Elsevier Ltd. All rights reserved.