Interface control of surface photochemical reactivity in ultrathin epitaxial ferroelectric films

Asymmetrical electrical boundary conditions in (001)-oriented Pb(Zr 0.2TiO0.8)O3 (PZT) epitaxial ultrathin ferroelectric films are exploited to control surface photochemical reactivity determined by the sign of the surface polarization charge. It is shown that the preferential orientation of polarization in the as-grown PZT layer can be manipulated by choosing an appropriate type of bottom electrode material. PZT films deposited on the SrRuO3 electrodes exhibit preferential upward polarization (C) whilst the same films grown on the (La,Sr)CoO 3-electrodes are polarized downward (C-). Photochemical activity of the PZT surfaces with different surface polarization charges has been tested by studying deposition of silver nanoparticles from AgNO3 solution under UV irradiation. PZT surfaces with preferential C orientation possess a more active surface for metal reduction than their C- counterparts, evidenced by large differences in the concentration of deposited silver nanoparticles. This effect is attributed to band bending at the bottom interface which varies depending on the difference in work functions of PZT and electrode materials.

Increased size selectivity of Si quantum dots on SiC at low substrate temperatures : an ion-assisted self-organization approach

A simple, effective, and innovative approach based on ion-assisted self-organization is proposed to synthesize size-selected Si quantum dots (QDs) on SiC substrates at low substrate temperatures. Using hybrid numerical simulations, the formation of Si QDs through a self-organization approach is investigated by taking into account two distinct cases of Si QD formation using the ionization energy approximation theory, which considers ionized in-fluxes containing Si3+ and Si1+ ions in the presence of a microscopic nonuniform electric field induced by a variable surface bias. The results show that the highest percentage of the surface coverage by 1 and 2 nm size-selected QDs was achieved using a bias of -20 V and ions in the lowest charge state, namely, Si1+ ions in a low substrate temperature range (227-327 °C). As low substrate temperatures (≤500 °C) are desirable from a technological point of view, because (i) low-temperature deposition techniques are compatible with current thin-film Si-based solar cell fabrication and (ii) high processing temperatures can frequently cause damage to other components in electronic devices and destroy the tandem structure of Si QD-based third-generation solar cells, our results are highly relevant to the development of the third-generation all-Si tandem photovoltaic solar cells.

On equilibrium states and dust charging in dusty plasmas

The dust-charge variation process is revisited, accounting for the background density variation associated with electron capture and release by the dust grains. It appears possible to maintain overall charge neutrality in the plasma without any external particle source or sink. It is shown that if the dust charge and density are sufficiently high, the effect of the background electron density variation on dust-charge relaxation is important. The equilibrium dust charge and its rate of variation are obtained for dusty plasmas subject to strong UV irradiation. The latter releases photoelectrons from the dust surface and can significantly affect the equilibrium dust charge, its variation rate, as well as the overall charge neutrality in the plasma.

Deterministic control of plasma-assembled self-organized Ge/Si quantum dot arrays

Self-assembly of size-uniform and spatially ordered quantum dot (QD) arrays is one of the major challenges in the development of the new generation of semiconducting nanoelectronic and photonic devices. Assembly of Ge QD (in the ∼5-20 nm size range) arrays from randomly generated position and size-nonuniform nanodot patterns on plasma-exposed Si (100) surfaces is studied using hybrid multiscale numerical simulations. It is shown, by properly manipulating the incoming ion/neutral flux from the plasma and the surface temperature, the uniformity of the nanodot size within the array can be improved by 34%-53%, with the best improvement achieved at low surface temperatures and high external incoming fluxes, which are intrinsic to plasma-aided processes. Using a plasma-based process also leads to an improvement (∼22% at 700 K surface temperature and 0.1 MLs incoming flux from the plasma) of the spatial order of a randomly sampled nanodot ensemble, which self-organizes to position the dots equidistantly to their neighbors within the array. Remarkable improvements in QD ordering and size uniformity can be achieved at high growth rates (a few nms) and a surface temperature as low as 600 K, which broadens the range of suitable substrates to temperature-sensitive ultrathin nanofilms and polymers. The results of this study are generic, can also be applied to nonplasma-based techniques, and as such contributes to the development of deterministic strategies of nanoassembly of self-ordered arrays of size-uniform QDs, in the size range where nanodot ordering cannot be achieved by presently available pattern delineation techniques.

Simulation of ion flux distribution in conductive and nonconductive nanotip patterns

The distribution of flux of carbon-bearing cations over nanopatterned surfaces with conductive nanotips and nonconductive nanoislands is simulated using the Monte-Carlo technique. It is shown that the ion current is focused to nanotip surfaces when the negative substrate bias is low and only slightly perturbed at higher substrate biases. In the low-bias case, the mean horizontal ion displacement caused by the nanotip electric field exceeds 10 nm. However, at higher substrate biases, this value reduces down to 2 nm. In the nonconductive nanopattern case, the ion current distribution is highly nonuniform, with distinctive zones of depleted current density around the nanoislands. The simulation results suggest the efficient means to control ion fluxes in plasma-aided nanofabrication of ordered nanopatterns, such as nanotip microemitter structures and quantum dot or nanoparticle arrays. © World Scientific Publishing Company.

Visible-light-induced selective photocatalytic oxidation of benzylamine into imine over supported Ag/AgI photocatalysts

Titanate nanotubes (TNT) supported AgI nanoparticles were prepared by a two-step method: the deposition of Ag2O on titanate nanotubes from AgNO3 solution and the subsequent I-adsorption process from NaI solution. It is found that the supported AgI samples exhibited excellent photoactivity for the selective oxidation of benzylamine to the corresponding imine under visible light illumination and the photocatalyst can be used for many times without apparent activity loss. X-ray diffraction studies, transmission electron microscopy, diffuse reflectance UV-Vis spectroscopy and nitrogen adsorption measurements were used for the characterization of the as-prepared and recycled AgI samples. It is found that under visible light irradiation, AgI partially decomposed to produce Ag/AgI nanostructure and thus stabilized. The photoactivity of supported Ag/AgI for the selective oxidation of benzylamine was studied in terms of the light intensity, wavelength, temperature and substituent. It is proposed that the formation of plasmonic Ag nanoparticles should be responsible for the high activity and selectivity.

A statistical approach to quantify the impact on voltage quality caused by PV generators

A probabilistic method is proposed to evaluate voltage quality of grid-connected photovoltaic (PV) power systems. The random behavior of solar irradiation is described in statistical terms and the resulting voltage fluctuation probability distribution is then derived. Reactive power capabilities of the PV generators are then analyzed and their operation under constant power factor mode is examined. By utilizing the reactive power capability of the PV-generators to the full, it is shown that network voltage quality can be greatly enhanced.

Water heating and dehumidification with heat pump utilizing solar, ambient and waste heat

The low temperature operation of a heat pump makes it an excellent match for the use of solar energy. At the National University of Singapore, a solar assisted heat pump system has been designed, fabricated and installed to provide water heating and drying. The system also utilizes the air con waste heat, which would normally be released to atmosphere adding to global warming. Experimental results show that the twophase unglazed solar evaporator-collector, instead of losing energy to the ambient, gained a significant amount due to low operating temperature of the collector. As a result, the collector efficiency attains a value greater than 1, when conventional collector equations are used. With this evaporator-collector, the system can be operated even in the absence of solar irradiation. The waste heat was collected from an air-con system, which maintained a room at 20-22 oC. In the condenser side, water at 60 oC was produced at a rate of 3 liter/minute and the drying capacity was 2.2kg/hour. Maximum COP of the system was found to be about 5.5.

A furan-containing conjugated polymer for high mobility ambipolar organic thin film transistors

Furan substituted diketopyrrolopyrrole (DBF) combined with benzothiadiazole based polymer semiconductor PDPP-FBF has been synthesized and evaluated as an ambipolar semiconductor in organic thin-film transistors. Hole and electron mobilities as high as 0.20 cm 2 V -1 s -1 and 0.56 cm 2 V -1 s -1, respectively, are achieved for PDPP-FBF.

Solution processable low bandgap diketopyrrolopyrrole (DPP) based derivatives : novel acceptors for organic solar cells

Novel low bandgap solution processable diketopyrrolopyrrole (DPP) based derivatives functionalized with electron withdrawing end capping groups (trifluoromethylphenyl and trifluorophenyl) were synthesized, and their photophysical, electrochemical and photovoltaic properties were investigated. These compounds showed optical bandgaps ranging from 1.81 to 1.94 eV and intense absorption bands that cover a wide range from 300 to 700 nm, attributed to charge transfer transition between electron rich phenylene-thienylene moieties and the electron withdrawing diketopyrrolopyrrole core. All of the compounds were found to be fluorescent in solution with an emission wavelength ranging from 600 to 800 nm. Cyclic voltammetry indicated reversible oxidation and reduction processes with tuning of HOMO-LUMO energy levels. Bulk heterojunction (BHJ) solar cells using poly(3-hexylthiophene) (P3HT) as the electron donor with these new acceptors were used for fabrication. The best power conversion efficiencies (PCE) using 1:2 donor-acceptor by weight mixture were 1% under simulated AM 1.5 solar irradiation of 100 mW cm-2. These findings suggested that a DPP core functionalized with electron accepting end-capping groups were a promising new class of solution processable low bandgap n-type organic semiconductors for organic solar cell applications.

Synthesis and study of conductivity behaviour of blended conducting polymer films irradiated with swift heavy ions of silicon

In recent times, blended polymers have shown a lot of promise in terms of easy processability in different shapes and forms. In the present work, polyaniline emeraldine base (PANi-EB) was doped with camphor sulfonic acid (CSA) and combined with the conducting polymer polyfluorene (PF) as well as the insulating polymer polyvinyl chloride (PVC) to synthesize CSA doped PANi-PF and PANi-PVC blended polymers. It is well known that PANi when doped with CSA becomes highly conducting. However, its poor mechanical properties, such as low tensile, compressive, and flexural strength render PANi a non-ideal material to be processed for its various practical applications, such as electromagnetic shielding, anti-corrosion shielding, photolithography and microelectronic devices etc. Thus the search for polymers which are easily processable and are capable of showing high conductivity still continues. PANi-PVC blend was prepared, which showed low conductivity which is limiting factor for certain applications. Therefore, another processable polymer PF was chosen as conducting matrix. Conducting PF can be easily processed into various shapes and forms. Therefore, a blend mixture was prepared by using PANi and PF through the use of CSA as a counter ion which forms a "bridge" between the two polymeric components of the inter-polymer complex. Two blended polymers have been synthesized and investigated for their conductivity behaviour. It was observed that the blended film of CSA doped PANi-PVC showed a room temperature electrical conductivity of 2.8 × 10-7 S/cm where as the blended film made by CSA doped PANi with conducting polymer PF showed a room temperature conductivity of 1.3 × 10-5 S/cm. Blended films were irradiated with 100 MeV silicon ions with a view to increase their conductivity with a fluence ranging from 1011 ions to 1013 per cm2 from 15 UD Pelletron accelerator at NSC, New Delhi.

Synthesis, characterization and activity of an immobilized photocatalyst : natural porous diatomite supported titania nanoparticles

Diatomite, a porous non-metal mineral, was used as support to prepare TiO2/diatomite composites by a modified sol–gel method. The as-prepared composites were calcined at temperatures ranging from 450 to 950 _C. The characterization tests included X-ray powder diffraction (XRD), scanning electron microscopy (SEM) with an energy-dispersive X-ray spectrometer (EDS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption/desorption measurements. The XRD analysis indicated that the binary mixtures of anatase and rutile exist in the composites. The morphology analysis confirmed the TiO2 particles were uniformly immobilized on the surface of diatom with a strong interfacial anchoring strength, which leads to few drain of photocatalytic components during practical applications. In further XPS studies of hybrid catalyst, we found the evidence of the presence of Ti–O–Si bond and increased percentage of surface hydroxyl. In addition, the adsorption capacity and photocatalytic activity of synthesized TiO2/diatomite composites were evaluated by studying the degradation kinetics of aqueous Rhodamine B under UV-light irradiation. The photocatalytic degradation was found to follow pseudo-first order kinetics according to the Langmuir–Hinshelwood model. The preferable removal efficiency was observed in composites by 750 _C calcination, which is attributed to a relatively appropriate anatase/rutile mixing ratio of 90/10.

Protection by methylproamine of irradiated human keratinocytes correlates with reduction of DNA damage

Purpose: The therapeutic ratio for ionising radiation treatment of tumour is a trade-off between normal tissue side-effects and tumour control. Application of a radioprotector to normal tissue can reduce side-effects. Here we study the effects of a new radioprotector on the cellular response to radiation. Methylproamine is a DNA-binding radioprotector which, on the basis of published pulse radiolysis studies, acts by repair of transient radiation-induced oxidative species on DNA. To substantiate this hypothesis, we studied protection by methylproamine at both clonogenic survival and radiation-induced DNA damage, assessed by γH2AX (histone 2AX phosphorylation at serine 139) focus formation endpoints. Materials and methods: The human keratinocyte cell line FEP1811 was used to study clonogenic survival and yield of γH2AX foci following irradiation (137Cs γ-rays) of cells exposed to various concentrations of methylproamine. Uptake of methylproamine into cell nuclei was measured in parallel. Results: The extent of radioprotection at the clonogenic survival endpoint increased with methylproamine concentration up to a maximum dose modification factor (DMF) of 2.0 at 10 μM. At least 0.1 fmole/nucleus of methylproamine is required to achieve a substantial level of radioprotection (DMF of 1.3) with maximum protection (DMF of 2.0) achieved at 0.23 fmole/nucleus. The γH2AX focus yield per cell nucleus 45 min after irradiation decreased with drug concentration with a DMF of 2.5 at 10 μM. Conclusions: These results are consistent with the hypothesis that radioprotection by methylproamine is mediated by attenuation of the extent of initial DNA damage.

Evaluation of the spatial distribution of γH2AX following ionizing radiation

An early molecular response to DNA double-strand breaks (DSBs) is phosphorylation of the Ser-139 residue within the terminal SQEY motif of the histone H2AX1,2. This phosphorylation of H2AX is mediated by the phosphatidyl-inosito 3-kinase (PI3K) family of proteins, ataxia telangiectasia mutated (ATM), DNA-protein kinase catalytic subunit and ATM and RAD3-related (ATR)3. The phosphorylated form of H2AX, referred to as γH2AX, spreads to adjacent regions of chromatin from the site of the DSB, forming discrete foci, which are easily visualized by immunofluorecence microscopy3. Analysis and quantitation of γH2AX foci has been widely used to evaluate DSB formation and repair, particularly in response to ionizing radiation and for evaluating the efficacy of various radiation modifying compounds and cytotoxic compounds Given the exquisite specificity and sensitivity of this de novo marker of DSBs, it has provided new insights into the processes of DNA damage and repair in the context of chromatin. For example, in radiation biology the central paradigm is that the nuclear DNA is the critical target with respect to radiation sensitivity. Indeed, the general consensus in the field has largely been to view chromatin as a homogeneous template for DNA damage and repair. However, with the use of γH2AX as molecular marker of DSBs, a disparity in γ-irradiation-induced γH2AX foci formation in euchromatin and heterochromatin has been observed5-7. Recently, we used a panel of antibodies to either mono-, di- or tri- methylated histone H3 at lysine 9 (H3K9me1, H3K9me2, H3K9me3) which are epigenetic imprints of constitutive heterochromatin and transcriptional silencing and lysine 4 (H3K4me1, H3K4me2, H3K4me3), which are tightly correlated actively transcribing euchromatic regions, to investigate the spatial distribution of γH2AX following ionizing radiation8. In accordance with the prevailing ideas regarding chromatin biology, our findings indicated a close correlation between γH2AX formation and active transcription9. Here we demonstrate our immunofluorescence method for detection and quantitation of γH2AX foci in non-adherent cells, with a particular focus on co-localization with other epigenetic markers, image analysis and 3Dmodeling.

γ-radiation-induced γH2AX formation occurs preferentially in actively transcribing euchromatic loci

The central dogma in radiation biology is that nuclear DNA is the critical target with respect to radiosensitivity. In accordance with the theoretical expectations, and in the absence of a conclusive model, the general consensus in the field has been to view chromatin as a homogeneous template for DNA damage and repair. This paradigm has been called into question by recent findings indicating a disparity in γ-irradiation-induced γH2AX foci formation in euchromatin and heterochromatin. Here, we have extended those studies and provide evidence that γH2AX foci form preferentially in actively transcribing euchromatin following γ-irradiation.