An assessment of the reduction potential of hydrogen plasma

Hydrogen plasma can be used for deoxidation of functional materials containing reactive metals in both bulk and thin film forms. Since the different species in the plasma are not in thermodynamic equilibrium, application of classical thermodynamics to the analysis of such a system is associated with some difficulties. While global equilibrium approaches have been tried, with and without additional approximations or constraints, there is some ambiguity in the results obtained. Presented in this article is the application of a local equilibrium concept to assess the thermodynamic limit of the reaction of each species present in the gas with oxides or oxygen dissolved in metals. Each reaction results in a different pal tial pressure of H2O. Because of the higher reactivity of the dissociated and ionized species and the larger thermodynamic driving force for reactions involving these species, they act as powerful reducing agents. It is necessary to remove the products of reaction from the plasma to prevent back reaction and gradual approach to global equilibrium. A quantitative description using the framework of the Ellingham-Richardson-Jeffes diagrams is presented.

Estimation Of Charge Transport Parameters And Equivalent Circuit For Poly Alkyl Thiophene Field-Effect Transistors

The small signal ac response is measured across the source-drain terminals of organic field-effect transistors (OFET) under dc bias to obtain the equivalent circuit parameters of poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) and poly(3-hexyl thiophene) (P3HT) based devices. The numerically simulated response based on these parameters is in good agreement with the experimental data for PBTTT-FET except at low frequencies, while the P3HT-FET data show significant deviations. This indicates that the interface with the metal electrode is rather complex for the latter, involving additional circuit elements arising from contact impedance or charge injection processes. Such an investigation can help in identifying the operational bottlenecks and to improve the performance of OFETs.

Hollow hemisphere and microcapsules of nonionic copolymer

Hemispherical colloidal nanowells or microwells with hollow interiors are becoming increasingly important for the encapsulation of functional materials. There has been rapid progress to develop new methods to obtain such structures. In this work, we present emulsification approach to generate hemisphere and microcapsules of biocompatible organic polymer. The precise control over the size is exhibited by applying variable vortex effect. The hemispheres and microcapsules of a copolymer (BPVA-PVA) were characterized by scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). These structures were used for loading of hydrophilic molecules and submicron colloidal particles to demonstrate their potential application. The introduction of hydrophobic groups on poly(vinyl alcohol) was crucial to obtain these structures.

Role of organic fluorine in crystal engineering

The design of compounds with novel and improved physico-chemical properties as advanced functional materials with a specific application spectrum requires the knowledge about possible supramolecular packing motifs and their experimental control in crystalline lattice. Besides the structure of the individual molecule, non-covalent interactions play a significant role in the determination of molecular conformation, along with the formation of three-dimensional supramolecular architecture in a crystal as a requirement for molecular recognition processes, and the related bioactivity. Involvement of functional groups will contribute to the formation of a predefined packing motif due to their well-defined interactions. The strength and directionality of these interactions create characteristic packing motifs, which can be used for the design of supramolecular arrangements by the development of appropriate strategies for the precise control of their topology. Most relevant of these non-covalent interactions are stacking interactions and hydrogen bonds, which have been subjects of extensive study in the last two decades. In recent literature, substantial efforts have been put in by various researchers towards the understanding of interactions involving organic fluorine and the role they play in generating different packing motifs which guides assembling of molecules in the crystal lattice.

A Comparative Study of Electrical Switching Behavior of Certain Tellurium based Chalcogenide Thin Films for Phase Change Memory (PCM) Applications

This work describes the electrical switching behavior of three telluride based amorphous chalcogenide thin film samples, Al-Te, Ge-Se-Te and Ge-Te-Si. These amorphous thin films are made using bulk glassy ingots, prepared by conventional melt quenching technique, using flash evaporation technique; while Al-Te sample has been coated in coplanar electrode geometry, Ge-Se-Te and Ge-Te-Si samples have been deposited with sandwich electrodes. It is observed that all the three samples studied, exhibit memory switching behavior in thin film form, with Ge-Te-Si sample exhibiting a faster switching characteristic. The difference seen in the switching voltages of the three samples studied has been understood on the basis of difference in device geometry and thickness. Scanning electron microscopic image of switched region of a representative Ge15Te81Si4 sample shows a structural change and formation of crystallites in the electrode region, which is responsible for making a conducting channel between the two electrodes during switching.

Microstructure, shape, stability and melting inembeddednanoparticles

The present article reviews some of the current work on a new class of materials which are nanoscale granular materials. We shall discuss in this paper two phase granular materials where one of the phases having nanometric dimension is embedded in a matrix of larger dimension. Known as nanoembedded materials, nanocomposites or ultrafine granular materials, this class of materials has attracted attention because of the opportunity of basic studies on the effect of size and embedding matrix on transformation behaviors as well as some novel properties, which include structural, magnetic and transport properties. These are in addition to the tremendous interests in what is known as quantum structures(embedded particles size less than 5 nm) for the case of semiconductors, which will not be discussed here. We shall primarily review the work done on metallic systems where the dispersed phases have low melting points and borrow extensively from the work done in our group. The phase transformations of the embedded particles show distinctive behavior and yield new insights. We shall first highlight briefly the strategy of synthesis of these materials by non-equilibrium processing techniques, which will be followed by examples where the effect of length scales on phase transformation behaviors like melting and solidification are discussed.

Electrical Transport Properties of Buckled Carbon Nanotube Arrays

We report on the electrical transport properties of buckled carbon nanotube arrays synthesized by pyrolysis. Analyzing the experimental data based on the general theory of semiconductors, the arrays are predicted to be semiconducting and the band gap can be evaluated. The band gap of different arrays is in 25-50 meV range.

Temperature Dependent Photoluminescence Studies in Hg0.2Cd0.8Te Nanorods Synthesized by Solvothermal Method

Hg0.2Cd0.8Te nanorods were synthesized via solvothermal route using an air-stable Na2Te-O-3. The structural and morphological studies were done by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The diameters of the nanorods were found to be 20-50 nm. The growth of the nanorods were facilitated due to the use of CTAB as surfactant. The temperature dependent photoluminescence (PL) studies between 10-300 K show three prominent PL bands in 0.5-0.7 eV and are attributed to defect centers. The features like temperature independent peak energy and quite sensitive PL intensity which shows a thermal quenching behavior indicate that the defects are related to the compositional disorder.

Light Induced Optical Properties Change in Sb20S40Se40 Thin Films

Thin films of Sb20S40Se40 of thickness 800 nm were prepared by thermal evaporation method. The as-prepared and illuminated thin films were studied by X-ray diffraction, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy and Raman spectroscopy. The optical band gap was reduced due to photo induced effects along with the increase in disorder. These optical properties changes are due to the change of homopolar bond densities. The core level peak shifting in XPS and Raman spectra supports the optical changes happening in the film due to light exposure.

Directional grain growth from anisotropic kinetic roughening of grain boundaries in sheared colloidal crystals

The fabrication of functional materials via grain growth engineering implicitly relies on altering the mobilities of grain boundaries (GBs) by applying external fields. Although computer simulations have alluded to kinetic roughening as a potential mechanism for modifying GB mobilities, its implications for grain growth have remained largely unexplored owing to difficulties in bridging the widely separated length and time scales. Here, by imaging GB particle dynamics as well as grain network evolution under shear, we present direct evidence for kinetic roughening of GBs and unravel its connection to grain growth in driven colloidal polycrystals. The capillary fluctuation method allows us to quantitatively extract shear-dependent effective mobilities. Remarkably, our experiments reveal that for sufficiently large strains, GBs with normals parallel to shear undergo preferential kinetic roughening, resulting in anisotropic enhancement of effective mobilities and hence directional grain growth. Single-particle level analysis shows that the mobility anisotropy emerges from strain-induced directional enhancement of activated particle hops normal to the GB plane. We expect our results to influence materials fabrication strategies for atomic and block copolymeric polycrystals as well.

The Relationship of Solid-State Plasticity to Mechanochromic Luminescence in Difluoroboron Avobenzone Polymorphs

In solid-state mechanochromic luminescence (ML) materials, it remains a challenge to establish the origin of fluorescence color changes upon mechanical action and to determine why only some fluorophores exhibit ML behavior. The study of mechanical properties by nanoindentation, followed by ML experiments on green- and cyan-emitting polymorphs of difluoroboron avobenzone reveals that upon smearing, the plastically deformable cyan form shows a prominent color change to yellow, while in the harder green form the redshifted emission is barely detectable. Crystal structure analysis reveals the presence of slip planes in the softer cyan form that can facilitate the formation of recoverable and low energy defects in the structure. Hence, the cyan form exhibits prominent and reversible ML behavior. This suggests a potential design strategy for efficient ML materials.

Process Development for Functionalization of Cotton with Silver Nanoparticles Synthesized by Bio-based Approaches

Cotton is a widely used raw material for textiles but drawbacks regarding their poor mechanical properties often limit their applications as functional materials. The present investigation involved process development for one step coating of cotton with silver nanoparticles (SNP) synthesized using Azadirachta indica and Citrus limon extract to develop functional textiles. Addition of starch to functional textiles led to efficient binding of nanoparticles to fabric and led to drastic decrease in release of silver from fabricated textiles after ten washing cycles enhancing their environment friendliness. Differential scanning calorimetry, scanning electron microscopy, FT-IR analysis and mechanical studies demonstrated efficient binding of nanoparticles to fabric through bio-based processes. The functionalized textiles developed by the bio-based methods showed significant antibacterial activity against E. coli and S. aureus (with 99% microbial reduction). Present work offers a simple procedure for coating SNP using bio-based approaches with promising applications in specialized functions.

Versatility of azide in serendipitous assembly of Copper(II) Magnetic Polyclusters

Engineering at the molecular level is one of the most exciting new developments for the generation of functional materials. However, the concept of designing polynuclear extended structures from bottom up is still not mature. Although progress has been made with secondary building units (SBUs) in metal organic frameworks (MOFs), the control seems to be just an illusion when it comes to bridging ligands such as the azide ion. When we say that the azido ligand is versatile in its bridging capabilities, what we mean is that it would be difficult to predict or control its bridging properties. However, this kind of serendipity is not always bad news. For example, scientists have shown that the azido ligand can mediate magnetic exchanges between paramagnetic metals in a predictable fashion (usually depending upon the bonding geometries). Therefore, it is a well-respected ligand in polynuclear assemblies. Serendipitous assemblies offer new magnetic structures that we may not otherwise even think about synthesizing. The azido ligand forms a variety of complexes with copper(II) using different blocking amines or pyridine based ligands. Its structural nature changes upon changing the substitution on amine, as well as the amount of blocking ligand. In principle, if we take any of these complexes and provide more coordination sites to the bridging azido ligands by removing a fraction of the blocking ligands, we can get new complexes with intricate structural networks and therefore different magnetic properties with the same components as used for the parent complex. In this Account, we mainly discuss the development of a number of new topological and magnetic exchange systems synthesized using this concept. Not all of these new complexes can be grouped according to their basic building structures or even by the ratio of the metal to blocking ligand. Therefore, we divided the discussion by the nuclearity of the basic building structures. Some of the complexes with the same nuclearities have very similar or even almost identical basic structures. However, the way these building units are joined together (by the azido bridges) to form the overall extended structures differ almost in every case. The complexes having the Cu-6 core are particularly interesting from a structural point of view. Although they have almost identical basic structures, some of them are extended in three dimensions, but two of them are extended in two dimensions by two different bridging networks. In the complexes having linear Cu-4 basic units, we find that using similar ligands does not always give the same bridging networks even within the basic building structures. These complexes have also enriched the field of molecular magnetism. One of the complexes with a Cu-3 building unit has provided us with the opportunity to study the competing behavior of two different kinds of magnetic exchange mechanism (ferromagnetic and antiferromagnetic) acting simultaneously between two metal ions. Through density functional theory calculations, we showed how they work independently and their additive nature to produce the overall effect. The exciting methodology for the generation of copper(II) polyclusters presented in this Account will provide the opportunity to explore analogous serendipitous assembly of diverse structures with interesting magnetic behavior using other transition metal ions having more than one unpaired electrons.