Advances in Light-Emitting Doped Semiconductor Nanocrystals

Insertion of just a few impurity atoms in a host semiconductor nanocrystal can drastically alter its phase, shape, and physical properties. Such doped nanomaterials now constitute an important class of optical materials that can provide efficient, stable, and tunable dopant emission in visible and NIR spectral windows. Selecting proper dopants and inserting them in appropriate hosts can generate many new series of such doped nanocrystals with several unique and attractive properties in order to meet current challenges in the versatile field of luminescent materials. However, the synthesis of such doped nanomaterials with a specific dopant in a predetermined host at a desired site leading to targeted optical properties requires fundamental understanding of both the doping process as well as the resulting photophysical properties. Summarizing up to date literature reports, in this Perspective we discuss important advances in synthesis methods and in-depth understanding of the optical properties, with an emphasis on the most widely investigated Mn-doped semiconductor nanocrystals.

An eight-connected metal organic framework based on Cu(5) clusters: Synthesis, structure, magnetic and catalytic properties

A reaction of copper acetate, 5-nitroisophthalic acid in a water-methanol mixture under solvothermal condition results in a new metal-organic framework compound, [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, (1). The compound contains Cu5 pentameric cluster units connected by 5-nitro isophthalate (NIPA) moieties forming a CdCl(2)-like layer, which are further connected by another NIPA moiety forming the three-dimensional structure. The water molecules in (1) can be reversibly adsorbed. The removal of water accompanies a change in the colour as well as a structural re-organization. Magnetic studies suggest strong antiferromagnetie correlations between the Cu5 cluster units. The compound (1) exhibits heterogeneous Lewis acid catalysis for the cyanosilylation of imines with more than 95 % selectivity. Compound (1) has been characterized by IR, UV-vis, TGA, powder XRD studies.

Investigations on multimagnetron sputtered Zn1-xMgxO thin films through metal-ferroelectric-semiconductor configuration

The effect of Mg doping in ZnO is investigated through structural, electrical, and optical properties. Zn1−xMgxO (0<×<0.3) thin films were deposited on Si (100) and corning glass substrates using multimagnetron sputtering. Investigations on the structural properties of the films revealed that the increase in Mg concentration resulted in phase evolution from hexagonal to cubic phase. The temperature dependent study of dielectric constant at different frequencies exhibited a dielectric anomaly at 110 °C. The Zn0.7Mg0.3O thin films exhibited a well-defined polarization hysteresis loop with a remnant polarization of 0.2 μC/cm2 and coercive field of 8 kV/cm at room temperature. An increase in the band gap with an increase in Mg content was observed in the range of 3.3–3.8 eV for x = 0–0.3. The average transmittance of the films was higher than 90% in the wavelength region λ = 400–900 nm.

Usefulness of in Situ Single Crystal to Single Crystal Transformation (SCSC) Studies in Understanding the Temperature-Dependent Dimensionality Cross-over and Structural Reorganization in Copper-Containing Metal-Organic Frameworks (MOFs)

Two copper-containing compounds [Cu(3)(mu(3)-OH)(2)-(H(2)O)(2){(SO(3))-C(6)H(3)-(COO)(2)}(CH(3)COO)] , I, and [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, II, were prepared using sulphoisophthalic and nitroisophthalic acids. The removal of the coordinated water molecules in the compounds was investigated using in situ single crystal to single crystal (SCSC) transformation studies, temperature-dependent powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). The efficacy of SCSC transformation studies were established by the observation of dimensionality cross-over from a two-dimensional (I) to a three-dimensional structure, Cu(6)(mu(3)-OH)(4){(SO(3))-C(6)H(3)-(COO)(2)}(2)(CH(3)COO)(2), Ia, during the removal of the coordinated water molecules. Compound H exhibited a structural reorganization forming Cu(5)(mu(2)-OH)(2){(NO(2))C(6)H(3)-(COO)(2))(4)], Ha, possessing trimeric (Cu(3)O(12)) and dimeric (Cu(2)O(8)) copper clusters. The PXRD studies indicate that the three-dimensional structure (Ia) is transient and unstable, reverting back to the more stable two-dimensional structure (I) on cooling to room temperature. Compound Ha appears to be more stable at room temperature. The rehydration/dehydration studies using a modified TGA setup suggest complete rehydration of the water molecules, indicating that the water molecules in both compounds are labile. A possible model for the observed changes in the structures has been proposed. Magnetic studies indicate changes in the exchanges between the copper centers in Ha, whereas no such behavior was observed in Ia.

Effect of gate-drain/source overlap on the noise in 90 nm N-channel metal oxide semiconductor field effect transistors

In this paper, we have studied the effect of gate-drain/source overlap (LOV) on the drain channel noise and induced gate current noise (SIg) in 90 nm N-channel metal oxide semiconductor field effect transistors using process and device simulations. As the change in overlap affects the gate tunneling leakage current, its effect on shot noise component of SIg has been taken into consideration. It has been shown that “control over LOV” allows us to get better noise performance from the device, i.e., it allows us to reduce noise figure, for a given leakage current constraint. LOV in the range of 0–10 nm is recommended for the 90 nm gate length transistors, in order to get the best performance in radio frequency applications.

Environmental remediation by photocatalysis

Photocatalysis refers to the oxidation and reduction reactions on semiconductor surfaces, mediated by the valence band holes and conduction band electrons, which are generated by the absorption of ultraviolet or visible light radiation. Photocatalysis is widely being practiced for the degradation and mineralization of hazardous organic compounds to CO2 and H2O, reduction of toxic metal ions to their non-toxic states, deactivation and destruction of water borne microorganisms, decomposition of air pollutants like volatile organic compounds, NOx, CO and NH3, degradation of waste plastics and green synthesis of industrially important chemicals. This review attempts to showcase the well established mechanism of photocatalysis, the use of photocatalysts for water and air pollution control,visible light responsive modified-TiO2 and non-TiO2 based materials for environmental and energy applications, and the importance of developing reaction kinetics for a comprehensive understanding and design of the processes.

Dioxomolybdenum reagents in organic synthesis: utility of redox capability to design reduction and oxidation

The usefulness of dioxomolybdenum reagents in oxo-transfer reactions have been reviewed. The redox ability of dioxomolybdenum reagent has been utilized in designing several synthetic methods, which are useful in organic synthesis. Several reactions such as oxidation of alcohols, sulfides, amines, azides olefins etc are accomplished by using dioxomolybdenum reagents. Similarly, it is also demonstrated that dioxomolybdenum complex is useful in performing reduction of aldehydes, ketones, esters, azides etc. A fine tuning of reaction conditions provides suitable conditions to perform either oxidation or reduction by using catalytic amount of reagents. The oxidation reactions are further simplified by employing the polymer supported molybdenum reagents.

Nanostructured barbed wire architecturing of organic conducting material blends by electrospinning

In this study, fibers of barbed wire structure were obtained by electrospinning blend of organic conducting crystalline material and polyethylene oxide. Thermal and structural characterization of the blend fibers has been carried out to study the fiber characteristics. An increase in crystallinity in the electrospun fibers was observed and was attributed to both electrospinning process as well as addition of organic conducting crystalline material. A mechanism for the formation of this barbed wire structure has also been proposed. (C) 2012 American Institute of Physics. [doi:10.1063/1.3673620]

Charge transfer complex states in diketopyrrolopyrrole polymers and fullerene blends: Implications for organic solar cell efficiency

The spectral photocurrent characteristics of two donor-acceptor diketopyrrolopyrrole (DPP)-based copolymers (PDPP-BBT and TDPP-BBT) blended with a fullerene derivative [6,6]-phenyl C-61-butyric acid methyl ester (PCBM) were studied using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) method. PDPP-BBT: PCBM shows the onset of the lowest charge transfer complex (CTC) state at 1.42 eV, whereas TDPP-BBT: PCBM shows no evidence of the formation of a midgap CTC state. The FTPS and PC spectra of P3HT:PCBM are also compared. The larger singlet state energy difference of TDPP-BBT and PCBM compared to PDPP-BBT/P3HT and PCBM obliterates the formation of a midgap CTC state resulting in an enhanced photovoltaic efficiency over PDPP-BBT: PCBM. (C) 2011 American Institute of Physics. [doi:10.1063/1.3670043]

Evaluation of the role of disordered organic fluorine in crystal packing: insights from halogen substituted benzanilides

The determination of the crystal and molecular structures of a large number of compounds containing the C(sp(2))-F bond has been investigated in detail in halogenated benzanilides and also in liquids, namely the fluorinated amines. It has been observed that when the fluorine atom is present in the ortho or meta position with respect to the amide functionality in benzanilides or the amino group in fluorinated amines which are liquids at room temperature, the fluorine atom exhibits positional disorder. This is associated with changes in patterns of intermolecular interactions which affect crystal packing. Furthermore, the presence of a fluorine atom on the benzanilide framework, in the presence of a heavier halogen (chloro, bromo and iodo), meta or ortho to the amide group does not eliminate the disorder associated with these molecules. In this article, we highlight the salient features present in halogenated compounds exhibiting disorder in the position of organic fluorine with concomitant changes in crystal packing. This feature is also compared with related compounds exhibiting similarity in electronic features, namely positional disorder.

Biodegradation of some organic reagents from mineral process effluents

The utility of a soil microbe, namely Bacillus polymyxa, in the removal of organic reagents such as dodecylamine, ether diamine, isopropyl xanthate and sodium oleate from aqueous solutions is demonstrated. Time-bound removal of the above organic reagents from an alkaline solution was investigated under different experimental conditions during bacterial growth and in the presence of metabolites by frequent monitoring of residual concentrations as a function of time, reagent concentration and cell density. The stages and mechanisms in the biodegradation process were monitored through UV-visible and FTIR spectroscopy. Surface chemistry of the bacterial cells as well as the biosorption tendency for various organics were also established through electrokinetic and adsorption density measurements. Both the cationic amines were found to be biosorbed followed by their degradation through bacterial metabolism. The presence of the organic reagents promoted bacterial growth through effective bacterial utilization of nitrogen and carbon from the organics. Under optimal conditions, complete degradation and bioremoval of all the organics could be achieved.

External-cavity semiconductor laser sensor

The spectral characteristics of a diode laser are significantly affected due to interference caused between the laser diode output and the optical feedback in the external-cavity. This optical feedback effect is of practical use for linewidth reduction, tuning or for sensing applications. A sensor based on this effect is attractive due to its simplicity, low cost and compactness. This optical sensor has been used so far, in different configuration such as for sensing displacement induced by different parameters. In this paper we report a compact optical sensor consisting of a semiconductor laser coupled to an external cavity. Theoretical analysis of the self- mixing interference for optical sensing applications is given for moderate optical feedback case. A comparison is made with our experimental observations. Experimental results are in good agreement with the simulated power modulation based on self-mixing interference theory. Displacements as small as 10-4 nm have been measured using this sensor. The developed sensor showed a fringe sensitivity of one fringe per 400nm displacement for reflector distance of around 10cms. The sensor has also been tested for magnetic field and temperature induced displacement measurements.

Dithienylcyclopentadienone derivative-co-benzothiadiazole: An alternating copolymer for organic photovoltaics

Alternating copolymer of 7,9-di(thiophen-2-yl)-8H-cyclopenta[a]acenaphthylen-8-one-co-benzothia diazole was synthesized by palladium(0) catalyzed Stille coupling reaction. This solution processable copolymer shows an excellent thermal stability and has a broad absorption range from 300 to 800 nm with a band gap of about 1.51 eV. High LUMO energy level and low band gap of the synthesized copolymers suggest that, this copolymer will be a suitable donor material for use in an organic photovoltaic device. Photovoltaic devices were fabricated from the blend of copolymer and phenyl-C61-butyric acid methyl ester as the active material. (C) 2011 Elsevier By. All rights reserved.