Effect of Stress and Interface defects on Photo Luminescence of Si nano-crystals embedded in SiO2

Effect of stress and interface defects on photo luminescence property of a silicon nano-crystal (Si-nc) embedded in amorphous silicon dioxide (a-SiO2) are studied in this paper using a self-consistent quantum-continuum based modeling framework. Si-ncs or quantum dots show photoluminescence at room temperature. Whether its origin is due to Si-nc/a-SiO2 interface defects or quantum confinement of carriers in Si-nc is still an outstanding question. Earlier reports have shown that stresses greater than 12 GPa change the indirect energy band gap structure of bulk Si to a direct energy band gap structure. Such stresses are observed very often in nanostructures and these stresses influence the carrier confinement energy significantly. Hence, it is important to determine the effect of stress in addition to the structure of interface defects on photoluminescence property of Si-nc. In the present work, first a Si-nc embedded in a-SiO2 is constructed using molecular dynamics simulation framework considering the actual conditions they are grown so that the interface and residual stress in the structure evolves naturally during formation. We observe that the structure thus created has an interface of about 1 nm thick consisting of 41.95% of defective states mostly Sin+ (n = 0 to 3) coordination states. Further, both the Si-nc core and the embedding matrix are observed to be under a compressive strain. This residual strain field is applied in an effective mass k.p Hamiltonian formulation to determine the energy states of the carriers. The photo luminescence property computed based on the carrier confinement energy and interface energy states associated with defects will be analysed in details in the paper.

Bolaamphiphiles as carriers for siRNA delivery: From chemical syntheses to practical applications

In this study we have investigated a new class of cationic lipids - ``bolaamphiphiles'' or ``bolas'' - for their ability to efficiently deliver small interfering RNAs (siRNAs) to cancer cells. The bolas of this study consist of a hydrophobic chain with one or more positively charged head groups at each end. Recently, we reported that micelles of the bolas GLH-19 and GLH-20 (derived from vernonia oil) efficiently deliver siRNAs, while having relatively low toxicities in vitro and in vivo. Our previous studies validated that; bolaamphiphiles can be designed to vary the magnitude of siRNA shielding, its delivery, and its subsequent release. To further understand the structural features of bolas critical for siRNAs delivery, new structurally related bolas (GLH-58 and GLH-60) were designed and synthesized from jojoba oil. Both bolas have similar hydrophobic domains and contain either one, in GLH-58, or two, in GLH-60 positively charged head groups at each end of the hydrophobic core. We have computationally predicted and experimentally validated that GLH-58 formed more stable nano sized micelles than GLH-60 and performed significantly better in comparison to GLH-60 for siRNA delivery. GLH-58/siRNA complexes demonstrated better efficiency in silencing the expression of the GFP gene in human breast cancer cells at concentrations of 5 mu g/mL, well below the toxic dose. Moreover, delivery of multiple different siRNAs targeting the HIV genome demonstrated further inhibition of virus production. Published by Elsevier B.V.

Probing Photoexcited Carriers in a Few-Layer MoS2 Laminate by Time-Resolved Optical Pump-Terahertz Probe Spectroscopy

We report the dynamics of photoinduced carriers in a free-standing MoS2 laminate consisting of a few layers (1-6 layers) using time-resolved optical pump-terahertz probe spectroscopy. Upon photoexcitation with the 800 nm pump pulse, the terahertz conductivity increases due to absorption by the photoinduced charge carriers. The relaxation of the non-equilibrium carriers shows fast as well as slow decay channels, analyzed using a rate equation model incorporating defect-assisted Auger scattering of photoexcited electrons, holes, and excitons. The fast relaxation time occurs due to the capture of electrons and holes by defects via Auger processes, resulting in nonradiative recombination. The slower relaxation arises since the excitons are bound to the defects, preventing the defect-assisted Auger recombination of the electrons and the holes. Our results provide a comprehensive understanding of the non-equilibrium carrier kinetics in a system of unscreened Coulomb interactions, where defect-assisted Auger processes dominate and should be applicable to other 2D systems.

Nano-indentation studies on polymer matrix composites reinforced by few-layer graphene

The mechanical properties of polyvinyl alcohol (PVA) and poly(methyl methacrylate) (PMMA)-matrix composites reinforced by functionalized few-layer graphene (FG) have been evaluated using the nano-indentation technique. A significant increase in both the elastic modulus and hardness is observed with the addition of 0.6 wt% of graphene. The crystallinity of PVA also increases with the addition of FG. This and the good mechanical interaction between the polymer and the FG, which provides better load transfer between the matrix and the fiber, are suggested to be responsible for the observed improvement in mechanical properties of the polymers.

Reduction of Permittivity in Epoxy Nanocomposites at Low Nano-filler Loadings

Experimental studies reveal a reduction in the values of permittivity for epoxy nanocomposites; at low filler loadings as compared to neat epoxy over a wide frequency range. This permittivity reduction is attributed to the interaction dynamics between nanoparticles: and epoxy chains at the interface region and interestingly, this interaction has also been found to influence the glass transition temperatures (T-g) of the examined nanocomposite systems. Accordingly, a dual nanolayer interface model for an epoxy based nanocomposite system is analyzed to explain the obtained permittivity characteristics.

Study of Structural Stability and Electronic Structure of Nonstoichiometric CdS Nano Clusters from First Principles

Structural stability of small sized nonstoichiometric CdS nano clusters between zincblende and wurtzite structures has been investigated using first-principles density functional calculations. Our study shows that the relative stability of these two structures depends sensitively on whether the surface is S-terminated or Cd-terminated. The associated band gap also exhibits non-monotonic behavior as a function of cluster size. Our findings may shed light on contradictory reports of experimentally observed structures of CdS nano clusters found in the literature.

Can Nano Silicon Be Made Optically Active?

There has been a lot of effort to make Silicon optically active. In this work we examine two methods of generating nanocrystals of Silicon from bulk fragments. This approach of ours allows us to play with the shape of the nanocrystals and therefore the degeneracy of the conduction band minimum. We go on to examine whether similar sized particles with different shapes have the same physical properties, and finally whether Silicon may be rendered optically active by this route. While we do find that similar sized particles with different shapes may have different band gaps, this route of modifying the degeneracy of the conduction band minimum makes nano Si slightly optically active.

Photocatalytic activity of Ag-substituted and impregnated nano-TiO2

Ag-substituted (Ag sub) and Ag-impregnated (Ag imp), anatase phase nano-TiO2 have been synthesized by solution combustion technique and reduction technique, respectively. The catalysts were characterized extensively by powder XRD, TEM, XPS, FT-Raman, UV absorption, FT-IR, TGA, photoluminescence, BET surface area and isoelectric pH measurements. These catalysts were used for the photodegradation of dyes and for the selective photooxidation of cyclohexane to cyclohexanone. The photoactivities of the combustion-synthesized catalysts were compared with those of commercial Degussa P 25 (DP 25) TiO2, and Ag-impregnated DP 25 (Ag DP). For the photocatalytic degradation of dyes, unsubstituted combustion-synthesized TiO2 (CS TiO2) exhibited the highest activity, followed by 1% Ag imp and 1% Ag sub. For the photoconversion of cyclohexane, the total conversion of cyclohexane and the selectivity of cyclohexanone followed the order: 1% Ag sub > DP 25 > CS TiO2 > 1% Ag imp > 1% Ag DP. The kinetics of the photodegradation of dyes and of the photooxidation of cyclohexane were modeled using Langmuir–Hinshelwood rate equation and a free radical mechanism, respectively, and the rate coefficients were determined. The difference in activity values of the catalysts observed for these two reactions and the detailed characterization of these catalysts are described in this study.

Some investigations on secondary breakdown in p-n junctions considering the effect of thermally generated carriers

The V-I characteristic of a p-n junction under breakdown is calculated taking the thermally generated carriers into account. The current density distributions computed under different conditions have been given. The light emission and other characteristics reported by Chiang and Lauritzen and others have been explained.

Light and heat induced interdiffusion in Sb/As2S3 nano-multilayered film

The light and heat induced changes in the optical band gap of Sb/As2S3 nanomultilayered chalcogenide film has been studied. Even though the changes in optical bandgap are attributed to the light and heat induced interdiffusion, the diffusional intermixing between the layers is rather different with light and heat. The observed difference in the light and heat induced interdiffusion is due to unequal diffusion coefficients of light and heat predicted by thermal spike model.

Temperature and Stress Controlled Surface Manipulation in Ni-Al Nano-Layers

In the present paper the effects of temperature and high strain rate loading on the formation of various surface patterns in Ni-Al nano-layers are discussed. Effects of boundary conditions on the B2 -> BCT phase transformation in the nano-layer are also discussed. This study is aimed at developing several interesting patterned surface structures in Ni-Al nanolayer by controlling the phase transformation temperature and mechanical loading.

Nano-meter scale plasticity in KBr studied by nanoindenter and force microscopy

The early stages of plasticity in KBr single crystals have been studied by means of nano-meter-scale indentation in complementary experiments using both a nanoindenter and an atomic force microscope. Nanoindentafion experiments precisely correlate indentation depth and forces, while force microscopy provides high-resolution force measurements and images of the surface revealing dislocation activity. The two methods provide very similar results for the onset of plasticity in KBr. Upon loading we observe yield of the surface in atomic layer units which we attribute to the nucleation of single dislocations. Unloading is accompanied by plastic recovery as evident from a non-linear force distance unloading curve and delayed discrete plasticity events.

Buckled nano rod - a two state system: quantum effects on its dynamics

We consider a suspended elastic rod under longitudinal compression. The compression can be used to adjust potential energy for transverse displacements from the harmonic to the double well regime. The two minima in potential energy curve describe two possible buckled states. Using transition state theory (TST) we have calculated the rate of conversion from one state to other. If the strain epsilon = 4 epsilon c the simple TST rate diverges. We suggest a method to correct this divergence for quantum calculations. We also find that zero point energy contributions can be quite large so that single mode calculations can lead to large errors in the rate.

Investigation of dye functional group on the photocatalytic degradation of dyes by nano-TiO2

The photocatalytic degradation of five anionic, eight cationic and three solvent dyes using combustion-synthesized nano-TiO2 (CSTiO2) and commercial Degussa P-25 TiO2 (DP-25) were evaluated to determine the effect of the functional group in the dye. The degradation of the dyes was quantified using the initial rate of decolorization and mineralization. The decolorization of the anionic dyes with CSTiO2 followed the order: indigo carmine > eosin Y > amido black 10B > alizarin cyanine green > orange G. The decolorization of the cationic dyes with DP-25 followed the order: malachite green > pyronin Y > rhodamine 6G > azure B > nile blue sulfate > auramine O approximate to acriflavine P approximate to safranin O. CSTiO2 showed higher rates of decolorization and mineralization for all the anionic dyes compared to DP-25, while DP-25 was better in terms of decolorization for most of the cationic dyes. The solvent dyes exhibited adsorption dependent decolorization. The order of decolorization and mineralization of the anionic and cationic dyes (a) with CS TiO2 and DP-25 was different and correlated with the surface properties of these catalysts (b) were rationalized with the molecular structure of the dye and the degradation pathway of the dye. (C) 2009 Elsevier B.V. All rights reserved.