Electrodeposited α- and β-phase MoO3 films and investigation of their gasochromic properties

α- and β-Phase MoO3 are synthesized using an electrodeposition method on fluorine-doped tin oxide (FTO) glass substrates from sodium-molybdate (Na2MoO4) solutions. We show that it is possible to obtain both α- and β-MoO3 by manipulating the cyclic voltammetry (CV) parameters during electrodeposition. Raman spectroscopy, X-ray diffraction, and scanning electron microscopy indicate that the applied potential range and sweep rate are strongly influential on the phase obtained and the surface morphology of the electrodeposited thin films. Gasochromic measurements were carried out on the annealed samples by exposing them to H2 gas. It was revealed that α-MoO3 thin films provided better response to H2 interaction than β-MoO3 films did. Additionally, porous films provided significantly larger responses than smooth films.

From single crystal surfaces to single atoms : investigating active sites in electrocatalysis

Electrocatalytic processes will undoubtedly be at the heart of energising future transportation and technology with the added importance of being able to create the necessary fuels required to do so in an environmentally friendly and cost effective manner. For this to be successful two almost mutually exclusive surface properties need to be reconciled, namely producing highly active/reactive surface sites that exhibit long term stability. This article reviews the various approaches which have been undertaken to study the elusive nature of these active sites on metal surfaces which are considered as adatoms or clusters of adatoms with low coordination number. This includes the pioneering studies at extended well defined stepped single crystal surfaces using cyclic voltammetry up to the highly sophisticated in situ electrochemical imaging techniques used to study chemically synthesised nanomaterials. By combining the information attained from single crystal surfaces, individual nanoparticles of defined size and shape, density functional theory calculations and new concepts such as mesoporous multimetallic thin films and single atom electrocatalysts new insights into the design and fabrication of materials with highly active but stable active sites can be achieved. The area of electrocatalysis is therefore not only a fascinating and exciting field in terms of realistic technological and economical benefits but also from the fundamental understanding that can be acquired by studying such an array of interesting materials.

Plasma-enabled growth of single-crystalline SiC/AlSiC Core–Shell nanowires on porous alumina templates

We report the catalyst-free synthesis of the arrays of core–shell, ultrathin, size-uniform SiC/AlSiC nanowires on the top of a periodic anodic aluminum oxide template. The nanowires were grown using an environmentally friendly, silane-free process by exposing the silicon supported porous alumina template to CH4 + H2 plasmas. High-resolution scanning and transmission electron microscopy studies revealed that the nanowires have a single-crystalline core with a diameter of about 10 nm and a thin (1–2 nm) amorphous AlSiC shell. Because of their remarkable length, high aspect ratio, and very high surface area-to-volume ratio, these unique structures are promising for nanoelectronic and nanophotonic applications that require efficient electron emission, light scattering, etc. A mechanism for nanowire growth is proposed based upon the reduction of the alumina template to nanosized metallic aluminum droplets forming between nanopores. The subsequent incorporation of silicon and carbon atoms from the plasma leads to nucleation and growth from the top of the alumina template.

Structural evolution of nanocrystalline silicon thin films synthesized in high-density, low-temperature reactive plasmas

Silicon thin films with a variable content of nanocrystalline phase were deposited on single-crystal silicon and glass substrates by inductively coupled plasma-assisted chemical vapor deposition using a silane precursor without any hydrogen dilution in the low substrate temperature range from 100 to 300 °C. The structural and optical properties of the deposited films are systematically investigated by Raman spectroscopy, x-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/vis spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy. It is shown that the structure of the silicon thin films evolves from the purely amorphous phase to the nanocrystalline phase when the substrate temperature is increased from 100 to 150 °C. It is found that the variations of the crystalline fraction fc, bonded hydrogen content CH, optical bandgap ETauc, film microstructure and growth rate Rd are closely related to the substrate temperature. In particular, at a substrate temperature of 300 °C, the nanocrystalline Si thin films of our interest feature a high growth rate of 1.63nms-1, a low hydrogen content of 4.0at.%, a high crystalline fraction of 69.1%, a low optical bandgap of 1.55eV and an almost vertically aligned columnar structure with a mean grain size of approximately 10nm. It is also shown that the low-temperature synthesis of nanocrystalline Si thin films without any hydrogen dilution is attributed to the outstanding dissociation ability of the high-density inductively coupled plasmas and effective plasma-surface interactions during the growth process. Our results offer a highly effective yet simple and environmentally friendly technique to synthesize high-quality nanocrystalline Si films, vitally needed for the development of new-generation solar cells and other emerging nanotechnologies.

Deterministic surface growth of single-crystalline iron oxide nanostructures in nonequilibrium plasma

An innovative approach to precise tailoring of surface density, shapes, and sizes of single-crystalline α-Fe 2O 3 nanowires and nanobelts by controlling interactions of reactive oxygen plasma-generated species with the Fe surface is proposed. This strongly nonequilibrium, rapid, almost incubation-free, high-rate growth directly from the solid-solid interface can also be applied to other oxide materials and is based on deterministic control of the density of oxygen species and the surface conditions, which determine the nanostructure nucleation and growth.

Hydrothermal synthesis and characterisation of Cu2ZnSnS4 light absorbers for solar cells

This project has extended the knowledge in the hydrothermal synthesis of copper zinc tin sulphide (CZTS) semiconductor material which is regarded as one of the most promising light absorbing material for PV technologies. The investigation of various reaction parameters on the controlled synthesis of CZTS compound has provided important insight into the formation mechanism as well as the crystal growth behaviour of the material. CZTS nanocrystals with different crystal structure and particle size were synthesised throughout this project. The growth mechanism of CZTS crystals through a high temperature annealing treatment was also explored.

Using lead sulphate instead of lead oxide in flux growth of yttrium iron garnet(YIG) crystals

Crystal growth of YIG from fluxes containing lead sulphate in place of lead oxide in the usual lead oxide-lead fluoride-boron oxide flux system has been tried. Lead sulphate decomposes during crystal growth giving lead oxide and sulphur trioxide. Due to the influence of sulphur trioxide in the system the yield of crystals almost doubles. There is no change either in the morphology of the crystals or their lattice parameter. It is possible that solubility of YIG is different in the new flux and the changed solubility causes the increase in yield of crystals.

X-ray Topographic Assessment of Dislocations in Crystals Grown from Solution

Crystals growing from solution, the vapour phase and from supercooled melt exhibit, as a rule, planar faces. The geometry and distribution of dislocations present within the crystals thus grown are strongly related to the growth on planar faces and to the different growth sectors rather than the physical properties of the crystals and the growth methods employed. As a result, many features of generation and geometrical arrangement of defects are common to extremely different crystal species. In this paper these commoner aspects of dislocation generation and configuration which permits one to predict their nature and distribution are discussed. For the purpose of imaging the defects a very versatile and widely applicable technique viz. x-ray diffraction topography is used. Growth dislocations in solution grown crystals follow straight path with strongly defined directions. These preferred directions which in most cases lie within an angle of ±15° to the growth normal depend on the growth direction and on the Burger's vector involved. The potential configuration of dislocations in the growing crystals can be evaluated using the theory developed by Klapper which is based on linear anisotropic elastic theory. The preferred line direction of a particular dislocation corresponds to that in which the dislocation energy per unit growth length is a minimum. The line direction analysis based on this theory enables one to characterise dislocations propagating in a growing crystal. A combined theoretical analysis and experimental investigation based on the above theory is presented.

Growth of tin oxide single crystals in porcelain tunnel kilns

Single crystals of tin oxide have been grown under conditions obtained in oil fired porcelain tunnel kilns. It was noted that the reducing conditions in the kilns help in the growth of SnO2 crystals at much lower temperatures (1300°C). The growth seems to more pronounced in presence of silicon carbide. The crystals grow as long fibres of 0.1 to 0.5 mm dia. and 10 to 50 mm length. The crystals exhibit rutile structure and the direction of growth seems to be favoured in any one of the major axes a and c.

Radical Enhanced Atomic Layer Deposition of Metals and Oxides

Atomic Layer Deposition (ALD) is a chemical, gas-phase thin film deposition method. It is known for its ability for accurate and precise thickness control, and uniform and conformal film growth. One area where ALD has not yet excelled is film deposition at low temperatures. Also deposition of metals, besides the noble metals, has proven to be quite challenging. To alleviate these limitations, more aggressive reactants are required. One such group of reactants are radicals, which may be formed by dissociating gases. Dissociation is most conveniently done with a plasma source. For example, dissociating molecular oxygen or hydrogen, oxygen or hydrogen radicals are generated. The use of radicals in ALD may surmount some of the above limitations: oxide film deposition at low temperatures may become feasible if oxygen radicals are used as they are highly reactive. Also, as hydrogen radicals are very effective reducing agents, they may be used to deposit metals. In this work, a plasma source was incorporated in an existing ALD reactor for radical generation, and the reactor was used to study five different Radical Enhanced ALD processes. The modifications to the existing reactor and the different possibilities during the modification process are discussed. The studied materials include two metals, copper and silver, and three oxides, aluminium oxide, titanium dioxide and tantalum oxide. The materials were characterized and their properties were compared to other variations of the same process, utilizing the same metal precursor, to understand what kind of effect the non-metal precursor has on the film properties and growth characteristics. Both metals were deposited successfully, and silver for the first time by ALD. The films had low resistivity and grew conformally in the ALD mode, demonstrating that the REALD of metals is true ALD. The oxide films had exceptionally high growth rates, and aluminium oxide grew at room temperature with low cycle times and resulted in good quality films. Both aluminium oxide and titanium dioxide were deposited on natural fibres without damaging the fibre. Tantalum oxide was also deposited successfully, with good electrical properties, but at slightly higher temperature than the other two oxides, due to the evaporation temperature required by the metal precursor. Overall, the ability of REALD to deposit metallic and oxide films with high quality at low temperatures was demonstrated.

Effect of oxygen partial pressure on the growth of zinc micro and nanostructures

Zinc micro and nanostructures were synthesized in vacuum by condensing evaporated zinc on Si substrate at different gas pressures. The morphology of the grown Zn structures was found to be dependent on the oxygen partial pressure. Depending on oxygen partial pressure it varied from two-dimensional microdisks to one-dimensional nanowire. The morphology and structural properties of the grown micro and nanostructures were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Transmission electron microscopy (TEM) studies on the grown Zn nanowires have shown that they exhibit core/shell-like structures, where a thin ZnO layer forms the shell. A possible growth mechanism behind the formation of different micro and nanostructures has been proposed. In addition, we have synthesized ZnO nanocanal-like structures by annealing Zn nanowires in vacuum at 350 °C for 30 min.

Experimental and Theoretical Charge Density Analysis of Polymorphic Structures: The Case of Coumarin 314 Dye

Experimental charge density distributions in two known conformational polymorphs (orange and yellow) of coumarin 314 dye are analyzed based on multipole modeling of X-ray diffraction data collected at 100 K. The experimental results are compared with the charge densities derived from multipole modeling of theoretical structure factors obtained from periodic quantum calculation with density functional theory (DFT) method and B3LYP/6-31G(d,p) level of theory. The presence of disorder at the carbonyl oxygen atom of ethoxycarbonyl group in the yellow form, which was not identified earlier, is addressed here. The investigationof intermolecular interactions, based on Hirshfeld surface analysis and topological properties via quantum theory of atoms in molecule and total electrostatic interaction energies, revealed significant differences between the polymorphs. The differences of electrostatic nature in these two polymorphic forms were unveiled via construction of three-dimensional deformation electrostatic potential maps plotted over the molecular surfaces. The lattice energies evaluated from ab initio calculations on the two polymorphic forms indicate that the yellow form is likely to be the most favorable thermodynamically. The dipole moments derived from experimental and theoretical charge densities and also from Lorentz tensor approach are compared with the single-molecule dipole moments. In each case, the differences of dipole moments between the polymorphs are identified.

Studies on structural and electrical properties of sprayed SnO2 : Sb films

Thin films of antimony-doped tin oxide (SnO2:Sb) were prepared by spray pyrolysis using stannous chloride (SnCl2) and antimony trichloride (SbCl3) as precursors. The antimony doping was varied from 0 to 4 wt%. Scanning electron microscopy (SEM) revealed the surface morphology to be very smooth, yet grainy in nature. X-ray diffraction (XRD) shows films to have preferred orientation, which varies with the extent of antimony doping: undoped films prefer the (2 1 1) orientation, while the (3 0 1) orientation is preferred for doping levels of 0.5 and 1.0 wt%. For higher doping levels, the (2 0 0) orientation is preferred. This difference in preferred orientations is reflected in the SEM of the films. Atomic force microscopy (AFM) reveals that film roughness is not affected by antimony doping. The minimum sheet resistance (2.17 ohm/square) achieved in the present study is lower than values reported to date in SnO2:Sb films prepared from SnCl2 precursor. The Hall mobility of undoped SnO2 films was found to be 109.52 cm(2)/V s, which reduces to 2.55 cm(2)/ Vs for the films doped with 4 wt% of Sb. On the other hand, the carrier concentration, which is 1.23 x 10(19) cm(-3) in undoped films, increases to 2.89 x 10(21) cm(-3) for the films doped with 4 wt% of Sb. (c) 2004 Elsevier B.V. All rights reserved.

Using Water as a Design Element in Crystal Engineering. Host-Guest Compounds of Hydrated 3,5-Dihydroxybenzoic Acid

Thirteen host guest compounds of 3,5-dihydroxybenzoic acid (DHBA) have been structurally characterized. Water molecules occupy the peripheries of a hexagonal void, created with DHBA molecules, and act as ``hooks'' to connect the guest molecules with the host-framework via hydrogen bonding. The ``water hook'' is an OH group acting as a donor. Consequently, the guest molecules were chosen so that they contain good hydrogen bond acceptor functionalities. A number of multicomponent hydrates were isolated with stoichiometries (DHBA)(x)(H2O). (guest),. Of these, compounds with the following as guests were obtained as crystals that were good enough for single crystal work: ethyl acetate (EtOAc), diethyl oxalate, dimethyl oxalate, di(n-propyl) oxalate, diethyl malonate, diethyl succinate, chloroacetonitrile, N,N-dimethyl formamide (DMF), acetone, dimethyl sulfoxide (DMSO), 1-propanol, and 2-butanol. From 2-butanol, a hemihydrate, (DHBA)(2)(H2O), was also obtained concomitantly. Further to guest stabilization, water acts as a good mediator of effective crystal packing and also determines the topology of the host framework. En the present series of compounds, the role of water is wide ranging, and it is not easy to classify it specifically as a host or as a guest.

Growth and defect characterization of L-arginine phosphate monohydrate

L-arginine phosphate monohydrate (LAP) is a relatively new organic nonlinear optical material. In this paper, the results of our recent investigations on the growth of this crystal are presented. The growth of the undesirable micro-organisms was prevented by protecting the solution surface by placing a thick layer of n-hexane over it. Colouration of the solution could be avoided by keeping the growth temperature low and by protecting it from light. The effect of pH value of the solution on the solubility and habit was analysed. The grown crystals were characterized by means of X-ray topography.