Substrate nitridation induced modulations in transport properties of wurtzite GaN/p-Si (100) heterojunctions grown by molecular beam epitaxy

Phase pure wurtzite GaN films were grown on Si (100) substrates by introducing a silicon nitride layer followed by low temperature GaN growth as buffer layers. GaN films grown directly on Si (100) were found to be phase mixtured, containing both cubic (beta) and hexagonal (alpha) modifications. The x-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy studies reveal that the significant enhancement in the structural as well as in the optical properties of GaN films grown with silicon nitride buffer layer grown at 800 degrees C when compared to the samples grown in the absence of silicon nitride buffer layer and with silicon nitride buffer layer grown at 600 degrees C. Core-level photoelectron spectroscopy of Si(x)N(y) layers reveals the sources for superior qualities of GaN epilayers grown with the high temperature substrate nitridation process. The discussion has been carried out on the typical inverted rectification behavior exhibited by n-GaN/p-Si heterojunctions. Considerable modulation in the transport mechanism was observed with the nitridation conditions. The heterojunction fabricated with the sample of substrate nitridation at high temperature exhibited superior rectifying nature with reduced trap concentrations. Lowest ideality factors (similar to 1.5) were observed in the heterojunctions grown with high temperature substrate nitridation which is attributed to the recombination tunneling at the space charge region transport mechanism at lower voltages and at higher voltages space charge limited current conduction is the dominating transport mechanism. Whereas, thermally generated carrier tunneling and recombination tunneling are the dominating transport mechanisms in the heterojunctions grown without substrate nitridation and low temperature substrate nitridation, respectively. (C) 2011 American Institute of Physics. [doi:10.1063/1.3658867]

Self-Assembling Peptides: From Molecules to Nanobiomaterials

Abstract | Molecular self-assembly plays a vital role in the construction of various nanostructures using the ‘bottom-up’ approach. Peptides have been considered important bio-molecular building blocks for different nanoscale structures as they are biocompatible, biodegradable, generally non-toxic and can be attuned to environmental responses like pH, temperature, salt concentration and others. Peptide based nanostructures can offer various wonderful biological applications in tissue engineering, cell culture, regenerative medicine and drug delivery. In this review, the construction of short peptide-based different nanostructures including nanotubes, nanovesicles and nanofibers, short peptide-based nanoporous materials, short peptide-based nanofibrous hydrogels and nanovesicles for various biological applications has been discussed. Moreover, morphological transformations from one nanoscopic structure to an other type of nanostructure (e.g., nanotubes to nanovesicles) are also clearly discussed in this review.

Mercury Segregation and Diselenide Self-Assembly on Gold

We have investigated the self-assembly of didecyldiselenide on gold containing mercury using X-ray photoelectron spectroscopy, cyclic voltammetry and infrared spectroscopy. The analysis of intensity and chemical shift of selected Se, Hg, and Au photoelectron lines on samples with increasing Hg content, show that didecyldiselenide adsorption strongly contributed to segregation of bulk Hg to the surface. The voltammetry results support this conclusion and suggest the formation of Hg-Au surface amalgam. The Hg surface segregation effect must be related to the restructuring of the surface following initial adsorption, and to the strong selenophilicity of Hg. The reflectance absorbance infrared spectroscopy studies show that the molecular layer on Hg-Au substrates lacks good order.

Atomic layer deposition of ZrO2 thin films: Study of growth kinetics and dielectric behaviour

Thin films of ZrO2 have been deposited by ALD on Si(100) and SIMOX using two different metalorganic complexes of Zr as precursors. These films are characterized by X-ray diffraction, transmission and scanning electron microscopies, infrared spectroscopy, and electrical measurements. These show that amorphous ZrO2 films of high dielectric quality may be grown on Si(100) starting about 400degreesC. As the growth temperature is raised, the films become crystalline, the phase formed and the microstructure depending on precursor molecular structure. The phase of ZrO2 formed depends also on the relative duration of the precursor and oxygen pulses. XPS and IR spectroscopy show that films grown at low temperatures contain chemically unbound carbon, its extent depending on the precursor. C-V measurements show that films grown on Si(100) have low interface state density, low leakage current, a hysteresis width of only 10-250 mV and a dielectric constant of similar to16-25.

Self-assembly of Ru-4 and Ru-8 assemblies by coordination using organometallic Ru(II)(2) precursors: Synthesis, characterization and properties

Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II) complexes [Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) or [Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)(MeOH)(2)(eta(6)-p-cymene)(2)]( O3SCF3)(2) (1b) separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4-benzoquinonato (dhbq) bridged binuclear complex [Ru-2(mu-eta(C6H2O4)-C-4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1c) in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the self-assembled macrocycles 2a-2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear (H-1, C-13 and F-19) NMR, infrared (IR) and electrospray ionization mass spectrometry (ESIMS). In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 angstrom x 12.39 angstrom. Furthermore, the photo-and electrochemical properties of these newly synthesized assemblies have been studied by using UV-vis absorption and cyclic voltammetry analysis.

Influence of the Methane-Zeolite A Interaction Potential on the Concentration Dependence of Self-diffusivity

Studies on the diffusion of methane in a zeolite structure type LTA (as per IZA nomenclature) have indicated that different types of methane zeolite potentials exist in the literature in which methane is treated within the united-atom model. One set of potentials, referred to as model A, has a methane oxygen diameter of 3.14 angstrom, while another set of potential parameters, model B, employs a larger value of 3.46 angstrom. Fritzsche and co-workers (1993) have shown that these two potentials lead to two distinctly different energetic barriers for the passage of methane through the eight-ring window in the cation-free form of zeolite A. Here, we compute the variation of the self-diffusivity (D) with loading (c) for these two types of potentials and show that this slight variation in the diameter changes the concentration dependence qualitatively: thus, D decreases monotonically with c for model A, while D increases and goes through a maximum before finally decreasing for model B. This effect and the surprising congruence of the diffusion coefficients for both models at high loadings is examined in detail at the molecular level. Simulations for different temperatures reveal the Arrhenius behaviour of the self-diffusion coefficient. The apparent activation energy is found to vary with the loading. We conclude that beside the cage-to-cage jumps, which are essential for the migration of the guest molecules, at high concentrations migration within the cage and guest guest interactions with other molecules become increasingly dominant influences on the diffusion coefficient and make the guest zeolite interaction less important for both model A and model B.

Spontaneous self-assembly of designed cyclic dipeptide (Phg-Phg) into two-dimensional nano- and mesosheets

In this study, we present the spontaneous self-assembly of designed simplest aromatic cyclic dipeptides of (L-Phg-L-Phg) and (D-Phg-L-Phg) to form highly stable two-dimensional (2D) nano- and mesosheets with large lateral surface area. Various microscopy data revealed that the morphology of 2D mesosheets resembles the hierarchical natural materials with layered structure. Solution and solid-state NMR studies on cyclo(L-Phg-L-Phg) revealed the presence of strong (N-H-O) hydrogen-bonded molecular chains supported by aromatic pi-pi interactions to form 2D mesosheets. Interestingly, cyclo(D-Phg-L-Phg) self-assembles to form single-crystalline as well as non-crystalline 2D rhomboid sheets with large lateral dimension. X-ray diffraction analysis revealed the stacking of (N-H-O) hydrogen-bonded molecular layers along c-axis supported by aromatic pi-pi interactions. The thermogravimetric analysis shows two transitions with overall high thermal stability attributed to layered hierarchy found in 2D mesosheets.

Three-Component Self-Assembly of a Series of Triply Interlocked Pd12 Coordination Prisms and Their Non-Interlocked Pd6 Analogues

Template-assisted formation of multicomponent Pd6 coordination prisms and formation of their self-templated triply interlocked Pd12 analogues in the absence of an external template have been established in a single step through Pd?N/Pd?O coordination. Treatment of cis-[Pd(en)(NO3)2] with K3tma and linear pillar 4,4'-bpy (en=ethylenediamine, H3tma=benzene-1,3,5-tricarboxylic acid, 4,4'-bpy=4,4'-bipyridine) gave intercalated coordination cage [{Pd(en)}6(bpy)3(tma)2]2[NO3]12 (1) exclusively, whereas the same reaction in the presence of H3tma as an aromatic guest gave a H3tma-encapsulating non-interlocked discrete Pd6 molecular prism [{Pd(en)}6(bpy)3(tma)2(H3tma)2][NO3]6 (2). Though the same reaction using cis-[Pd(NO3)2(pn)] (pn=propane-1,2-diamine) instead of cis-[Pd(en)(NO3)2] gave triply interlocked coordination cage [{Pd(pn)}6(bpy)3(tma)2]2[NO3]12 (3) along with non-interlocked Pd6 analogue [{Pd(pn)}6(bpy)3(tma)2](NO3)6 (3'), and the presence of H3tma as a guest gave H3tma-encapsulating molecular prism [{Pd(pn)}6(bpy)3(tma)2(H3tma)2][NO3]6 (4) exclusively. In solution, the amount of 3' decreases as the temperature is decreased, and in the solid state 3 is the sole product. Notably, an analogous reaction using the relatively short pillar pz (pz=pyrazine) instead of 4,4'-bpy gave triply interlocked coordination cage [{Pd(pn)}6(pz)3(tma)2]2[NO3]12 (5) as the single product. Interestingly, the same reaction using slightly more bulky cis-[Pd(NO3)2(tmen)] (tmen=N,N,N',N'-tetramethylethylene diamine) instead of cis-[Pd(NO3)2(pn)] gave non-interlocked [{Pd(tmen)}6(pz)3(tma)2][NO3]6 (6) exclusively. Complexes 1, 3, and 5 represent the first examples of template-free triply interlocked molecular prisms obtained through multicomponent self-assembly. Formation of the complexes was supported by IR and multinuclear NMR (1H and 13C) spectroscopy. Formation of guest-encapsulating complexes (2 and 4) was confirmed by 2D DOSY and ROESY NMR spectroscopic analyses, whereas for complexes 1, 3, 5, and 6 single-crystal X-ray diffraction techniques unambiguously confirmed their formation. The gross geometries of H3tma-encapsulating complexes 2 and 4 were obtained by universal force field (UFF) simulations.

Coordination-Driven Self-Assembly of 2D-Metallamacrocycles Using a New Carbazole-Based Dipyridyl Donor: Synthesis, Characterization, and C-60 Binding Study

A new carbazole-based 90 degrees dipyridyl donor 3,6-di(4-pyridylethynyl)carbazole (L) containing carbazole-ethynyl functionality is synthesized in reasonable yield using the Sonagashira coupling reaction. Multinuclear NMR, electrospray ionization-mass spectrometry (ESI-MS), including single crystal X-ray diffraction analysis characterized this 90 degrees building unit. The stoichiometry combination of L with several Pd(II)/Pt(II)-based 90 degrees acceptors (1a-1d) yielded 2 + 2] self-assembled metallacycles (2a-2d) under mild conditions in quantitative yields 1a = cis-(dppf)Pd(OTf)(2); 1b = cis-(dppf)Pt(OTf)(2); 1c = cis-(tmen)Pd(NO3)(2); 1d = 3,6-bis{trans-Pt(C C) (PEt3)(2)(NO3))carbazole]. All these macrocycles were characterized by various spectroscopic techniques, and the molecular structure of 2a was unambiguously determined by single crystal X-ray diffraction analysis. Incorporation of ethynyl functionality to the carbazole backbone causes the resulted macrocycles (2a-2d) to be pi-electron rich and thereby exhibit strong emission characteristics. The macrocycle 2a has a large internal concave aromatic surface. The fluorescence quenching study suggests that 2a forms a similar to 1:1 complex with C-60 with a high association constant of K-sv = 1.0 X 10(5) M-1.

Dependence of diffusivity on density and solute diameter in liquid phase: A molecular dynamics study of Lennard-Jones system

Investigations into the variation of self-diffusivity with solute radius, density, and degree of disorder of the host medium is explored. The system consists of a binary mixture of a relatively smaller sized solute, whose size is varied and a larger sized solvent interacting via Lennard-Jones potential. Calculations have been performed at three different reduced densities of 0.7, 0.8, and 0.933. These simulations show that diffusivity exhibits a maximum for some intermediate size of the solute when the solute diameter is varied. The maximum is found at the same size of the solute at all densities which is at variance with the prediction of the levitation effect. In order to understand this anomaly, additional simulations were carried out in which the degree of disorder has been varied while keeping the density constant. The results show that the diffusivity maximum gradually disappears with increase in disorder. Disorder has been characterized by means of the minimal spanning tree. Simulations have also been carried out in which the degree of disorder is constant and only the density is altered. The results from these simulations show that the maximum in diffusivity now shifts to larger distances with decrease in density. This is in agreement with the changes in void and neck distribution with density of the host medium. These results are in excellent agreement with the predictions of the levitation effect. They suggest that the effect of disorder is to shift the maximum in diffusivity towards smaller solute radius while that of the decrease in density is to shift it towards larger solute radius. Thus, in real systems where the degree of disorder is lower at higher density and vice versa, the effect due to density and disorder have opposing influences. These are confirmed by the changes seen in the velocity autocorrelation function, self part of the intermediate scattering function and activation energy. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.3701619]

Valence band offset at GaN/beta-Si3N4 and beta-Si3N4/Si(111) heterojunctions formed by plasma-assisted molecular beam epitaxy

Ultra thin films of pure beta-Si3N4 (0001) were grown on Si (111) surface by exposing the surface to radio- frequency nitrogen plasma with a high content of nitrogen atoms. Using beta-Si3N4 layer as a buffer layer, GaN epilayers were grown on Si (111) substrate by plasma-assisted molecular beam epitaxy. The valence band offset (VBO) of GaN/beta-Si3N4/ Si heterojunctions is determined by X-ray photoemission spectroscopy. The VBO at the beta-Si3N4 /Si interface was determined by valence-band photoelectron spectra to be 1.84 eV. The valence band of GaN is found to be 0.41 +/- 0.05 eV below that of beta-Si3N4 and a type-II heterojunction. The conduction band offset was deduced to be similar to 2.36 eV, and a change of the interface dipole of 1.29 eV was observed for GaN/ beta-Si3N4 interface formation. (c) 2011 Elsevier B.V. All rights reserved.

Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd-) Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Metal-ion- (Ag, Co, Ni and Pd) doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL) self-assembly technique using a poly(styrene sulfonate sodium salt) (PSS) and poly(allylamine hydrochloride) (PAH) polyelectrolyte system. Solid diffuse reflectance (SDR) studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM), the thin films had a porous morphology and the atomic force microscope (AFM) studies showed ``rough'' surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period) using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation). The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5) reusability cycles.

Gel Sculpture: Moldable, Load-Bearing and Self-Healing Non-Polymeric Supramolecular Gel Derived from a Simple Organic Salt

An easy access to a library of simple organic salts derived from tert-butoxycarbonyl (Boc)-protected L-amino acids and two secondary amines (dicyclohexyl- and dibenzyl amine) are synthesized following a supramolecular synthon rationale to generate a new series of low molecular weight gelators (LMWGs). Out of the 12 salts that we prepared, the nitrobenzene gel of dicyclohexylammonium Boc-glycinate (GLY.1) displayed remarkable load-bearing, moldable and self-healing properties. These remarkable properties displayed by GLY.1 and the inability to display such properties by its dibenzylammonium counterpart (GLY.2) were explained using microscopic and rheological data. Single crystal structures of eight salts displayed the presence of a 1D hydrogen-bonded network (HBN) that is believed to be important in gelation. Powder X-ray diffraction in combination with the single crystal X-ray structure of GLY.1 clearly established the presence of a 1D hydrogen-bonded network in the xerogel of the nitrobenzene gel of GLY.1. The fact that such remarkable properties arising from an easily accessible (salt formation) small molecule are due to supramolecular (non-covalent) interactions is quite intriguing and such easily synthesizable materials may be useful in stress-bearing and other applications.

Mechanical properties of ZnS nanowires and thin films: Microscopic origin of the dependence on size and growth direction

Mechanical properties of ZnS nanowires and thin films are studied as a function of size and growth direction using all-atom molecular dynamics simulations. Using the stress-strain relationship we extract Young's moduli of nanowires and thin films at room temperature. Our results show that Young's modulus of 0001] nanowires has strong size dependence. On the other hand, 01 (1) over bar0] nanowires do not exhibit a strong size dependence of Young's modulus in the size range we have investigated. We provide a microscopic understanding of this behavior on the basis of bond stretching and contraction due to the rearrangement of atoms in the surface layers. The ultimate tensile strengths of the nanowires do not show much size dependence. To investigate the mechanical behavior of ZnS in two dimensions, we calculate Young's modulus of thin films under tensile strain along the 0001] direction. Young's modulus of thin films converges to the bulk value more rapidly than that of the 0001] nanowire.

Influence of Sn doping on structural, optical and electrical properties of ZnO thin films prepared by cost effective sol-gel process

Tin (Sn) doped zinc oxide (ZnO) thin films were synthesized by sol-gel spin coating method using zinc acetate di-hydrate and tin chloride di-hydrate as the precursor materials. The films were deposited on glass and silicon substrates and annealed at different temperatures in air ambient. The agglomeration of grains was observed by the addition of Sn in ZnO film with an average grain size of 60 nm. The optical properties of the films were studied using UV-VIS-NIR spectrophotometer. The optical band gap energies were estimated at different concentrations of Sn. The MOS capacitors were fabricated using Sn doped ZnO films. The capacitance-voltage (C-V), dissipation vs. voltage (D-V) and current-voltage (I-V) characteristics were studied and the electrical resistivity and dielectric constant were estimated. The porosity and surface area of the films were increased with the doping of Sn which makes these films suitable for opto-electronic applications. (C) 2012 Elsevier B.V. All rights reserved.