One-step colloidal synthesis of biocompatible water-soluble ZnS quantum dot/chitosan nanoconjugates

Quantum dots (QDs) are luminescent semiconductor nanocrystals with great prospective for use in biomedical and environmental applications. Nonetheless, eliminating the potential cytotoxicity of the QDs made with heavy metals is still a challenge facing the research community. Thus, the aim of this work was to develop a novel facile route for synthesising biocompatible QDs employing carbohydrate ligands in aqueous colloidal chemistry with optical properties tuned by pH. The synthesis of ZnS QDs capped by chitosan was performed using a single-step aqueous colloidal process at room temperature. The nanobioconjugates were extensively characterised by several techniques, and the results demonstrated that the average size of ZnS nanocrystals and their fluorescent properties were influenced by the pH during the synthesis. Hence, novel ''cadmium-free’ biofunctionalised systems based on ZnS QDs capped by chitosan were successfully developed exhibiting luminescent activity that may be used in a large number of possible applications, such as probes in biology, medicine and pharmacy.     

Investigations of the pore formation in the lead selenide films using glacial acetic acid- and nitric acid-based electrolyte

ABSTRACT: We report a novel synthesis of porous PbSe layers on Si substrates using anodic electrochemical treatment of PbSe/CaF2/Si(111) epitaxial structures in an electrolyte solution based on glacial acetic acid and nitric acid. Electron microscopy, x-ray diffractometry, and local chemical microanalysis investigations results for the porous layers are presented. Average size of the synthesized mesopores with ~1010 cm-2 surface density was determined to be 22 nm. The observed phenomenon of the active selenium redeposition on the mesopore walls during anodic treatment is discussed.     

Structural variations of Si1-xCx and their light absorption controllability

ABSTRACT: The emergence of third-generation photovoltaics based on Si relies on tunable bandgap materials with embedded nanocrystalline Si. One of the most promising approaches is based on the mixed-phase Si1 - xCx. We have investigated the light absorption controllability of nanocrystalline Si-embedded Si1 - xCx produced by thermal annealing of the Si-rich Si1 - xCx and composition-modulated superlattice structure. In addition, stoichiometric SiC was also investigated to comparatively analyze the characteristic differences. As a result, it was found that stoichiometric changes of the matrix material and incorporation of oxygen play key roles in light absorption controllability. Based on the results of this work and literature, a design strategy of nanocrystalline Si-embedded absorber materials for third-generation photovoltaics is discussed.     

Electronic and transport properties in circular graphene structures with a pentagonal disclination

We investigate the electronic and transport properties of circular graphene structures (quantum dots) that include a pentagonal defect. In our calculations, we employ a tight-binding model determining total and local density of states, transmission function and participation number. For the closed structure, we observe that the effect of the defect is concentrated mainly on energies near to zero, which is characteristic of edge states in graphene. The density of states and transmission functions for small energies show several peaks associated with the presence of quasi-bound states generated by the defect and localized edge states produced by both the circular boundaries of the finite lattice and induced by the presence of the pentagonal defect. These results have been checked by calculating the participation number, which is obtained from the eigenstates. We observe changes in the available quasi-bound states due to the defect and the creation of new peaks in the transmission function.     

Optimization studies of HgSe thin film deposition by electrochemical atomic layer epitaxy (EC-ALE)

Studies of the optimization of HgSe thin film deposition using electrochemical atomic layer epitaxy (EC-ALE) are reported. Cyclic voltammetry was used to obtain approximate deposition potentials for each element. These potentials were then coupled with their respective solutions to deposit atomic layers of the elements, in a cycle. The cycle, used with an automated flow deposition system, was then repeated to form thin films, the number of cycles performed determining the thickness of the deposit. In the formation of HgSe, the effect of Hg and Se deposition potentials, and a Se stripping potential, were adjusted to optimize the deposition program. Electron probe microanalysis (EPMA) of 100 cycle deposits, grown using the optimized program, showed a Se/Hg ratio of 1.08. Ellipsometric measurements of the deposit indicated a thickness of 19 nm, where 35 nm was expected. X-ray diffraction displayed a pattern consistent with the formation of a zinc blende structure, with a strong (1 1 1) preferred orientation. Glancing angle fourier transform infrared spectroscopy (FTIR) absorption measurements of the deposit suggested a negative gap of 0.60 eV.     

Moving gapless indirect excitons in monolayer graphene

The existence of moving indirect excitons in monolayer graphene is theoretically evidenced in the envelope-function approximation. The excitons are formed from electrons and holes near the opposite conic points. The electron-hole binding is conditioned by the trigonal warping of the electron spectrum. It is stated that the exciton exists in some sectors of the exciton momentum space and has the strong trigonal warping of the spectrum.     

Conversion of polycyclic aromatic hydrocarbons to graphite and diamond at high pressures

The polycyclic aromatic hydrocarbons (PAH): naphthalene, anthracene, pentacene, perylene, and coronene were submitted to temperatures up to 1500 °C at 8 GPa. To avoid catalytic action of metals on thermal conversion, graphite was used as container material. Moreover, graphite is very permeable to the gaseous products of thermal decomposition of PAH. The resulting thermal transformations and their evolution were studied by X-ray diffraction, Raman spectroscopy and scanning electron microscopy as a function of temperature for 60-s treatments. The nature of the initial compounds clearly affects the products of the different stages of carbonization and the first steps of graphitization. This becomes hardly discernible in the final stages of graphitization above 1000 °C. Above 1200 °C, graphite with high crystallinity forms in all cases. The temperature of the beginning of diamond formation does not seem to be influenced by the nature of the initial PAH and is equal to ∼1280 °C for all investigated compounds. Diamonds formed from the PAH are high-quality 5-40 μm single crystals. The p,T values of diamond formation here obtained are significantly lower than those previously known for direct graphite-diamond transformation.     

Reduction of SO2 on different carbons

The reduction of SO₂ on four carbons (graphite, charcoal, activated carbon and coke) was studied under steady-state conditions and when the kinetics was chemically controlled in a reactor operated under differential conditions. The reaction showed second-order kinetics: first order with respect to carbon and first order with respect to the partial pressure of SO₂. The reactivity of the different carbons, as measured by the second-order rate constants, followed the sequence of decreasing crystallinity: graphite<coke (7.34)<coke (11.73)<charcoal. The difference in reactivity between graphite and charcoal was determined by ΔH^≠, while for cokes it increased with the ash content because of a favorable ΔS^≠. The main reaction products for all carbons were CO₂ and sulfur in the ratio 2:1, considering the sulfur as S₂, which was shown to be formed through the same path. CO, COS, and CS₂ were also detected, and the product distribution depended on the carbon and whether the reaction was diffusion controlled or chemically controlled. Analysis of product ratios strongly suggested that CO, COS and CS₂ were produced from consecutive reactions of the primary products. CO was formed from CO₂ by a slow Boudouard reaction that occurred partially and under conditions of non-equilibrium. Complexed sulfur reacted with CO to form COS and CS₂. There was an interaction between the active site of reduction and the site where sulfur is inserted.     

Preparation of carbon-encapsulated iron nanoparticles by co-carbonization of aromatic heavy oil and ferrocene

Carbon-encapsulated iron nanoparticles with uniform diameters have been synthesized on a large scale by co-carbonization of an aromatic heavy oil and ferrocene at 480 °C under autogenous pressure. The morphologies and structural features of the iron/carbon composites were investigated using TEM, HREM and XRD measurements. It was found that, by increasing the amount of ferrocene added from 2 wt.% to 45 wt.%, the size of the nanoparticles increased from 15 nm to 50 nm and the morphologies of the resulting products changed from spherical-type to iron-filled carbon nanorods when the ferrocene loading was higher than 30 wt.%. The iron particles pyrolyzed from ferrocene exist mainly in the form of α-Fe and small amounts of Fe₃C were also formed when the ferrocene content was higher than 20 wt.%. The formation mechanism of carbon-encapsulated iron nanoparticles is discussed briefly. This novel and simple approach constitutes a more practical method to prepare carbon-encapsulated metal nanoparticles than those reported to date.     

Abnormal conductivity behavior in porous lead telluride films

ABSTRACT: We report the experimental observation of the novel phenomenon of the resistivity decrease in porous PbTe layers during the pore formation process. Investigations were performed on the n-PbTe films with 2.3 micrometer thickness, which were near the point of the conductivity-type inversion at room temperature. Anodic electrochemical treatment for the porous layers with 41-52% porosity fabrication was performed using a KOH-based Norr electrolyte solution. For the porous lead telluride layers, the resistivity value at 300 K decreased 2.5-3 times. For the explanation of the observed phenomenon a physical model is proposed, which takes into account the Pb/Te ratio change during the anodic treatment.     

Polarized photoreflectance and photoluminescence spectroscopy of InGaAs/GaAs quantum rods grown with As2 and As4 sources

We report photoreflectance (PR) and photoluminescence (PL) investigations of the electronic and polarization properties of different aspect ratio (height/diameter) InGaAs quantum rods (QRs) embedded in InGaAs quantum wells (QWs). These nanostructures were grown by molecular beam epitaxy using As₂or As₄sources. The impact of the As source on the spectral and polarization features of the QR- and QW-related interband transitions was investigated and explained in terms of the carrier confinement effects caused by variation of composition contrast between the QR material and the surrounding well. Polarized PR and PL measurements reveal that the polarization has a preferential direction along the [11¯0] crystal axis with a large optical anisotropy of about 60% in the (001) plane for high aspect ratio (4.1:1) InGaAs QRs. As a result, in PL spectra, the transverse magnetic mode dominated (11¯0)-cleaved surfaces (TM_[001]>TE_[110]), whereas the transverse electric mode prevailed for (110)-cleaved surfaces (TM[001]<TE[11¯0]). This strong optical anisotropy in the (001) plane is interpreted in terms of the hole wavefunction orientation along the [11¯0] direction for high aspect ratio QRs.     

Effect of oxidation pre-treatment at 220 to 270 °C on the carbonization and activation behavior of phenolic resin fiber

The effect of oxidation pre-treatment of a phenolic resin fiber was examined from two aspects: one is to examine if the pre-treatment can be a means to increase the yield of carbon fiber and activated carbon fiber (ACF), and the other is to study the effect of the pre-treatment on the carbonization and activation behavior. A phenolic resin fiber was oxidized in air at 220 to 270 °C and it was subsequently carbonized at 900 °C and activated by steam at 900 °C. The oxidation was found to affect significantly the subsequent carbonization process in the way that the yield of the carbonized fiber increased with the severity of the oxidation. On the other hand, the oxidation was found not to affect the chemical and physical properties of the carbonized fiber. The ACF produced from the oxidized fiber had almost same pore structure as the ACF produced from the non-treated fiber when compared at a same activation level. The maximum yield of ACF produced from the oxidized fiber was 1.13 times larger than the yield of ACF produced from the non-treated fiber. Thus we could increase the production yield of ACF significantly without losing its high adsorption performance.     

Donor impurity-related linear and nonlinear intraband optical absorption coefficients in quantum ring: effects of applied electric field and hydrostatic pressure

The linear and nonlinear intraband optical absorption coefficients in GaAs three-dimensional single quantum rings are investigated. Taking into account the combined effects of hydrostatic pressure and electric field, applied along the growth direction of the heterostructure, the energies of the ground and first excited states of a donor impurity have been found using the effective mass approximation and a variational method. The energies of these states are examined as functions of the dimensions of the structure, electric field, and hydrostatic pressure. We have also investigated the dependencies of the linear, nonlinear, and total optical absorption coefficients as a function of incident photon energy for several configurations of the system. It is found that the variation of distinct sizes of the structure leads to either a redshift and/or a blueshift of the resonant peaks of the intraband optical spectrum. In addition, we have found that the application of an electric field leads to a redshift, whereas the influence of hydrostatic pressure leads to a blueshift (in the case of on-ring-center donor impurity position) of the resonant peaks of the intraband optical spectrum.     

Theoretical and experimental studies of (In,Ga)As/GaP quantum dots

(In,Ga)As/GaP(001) quantum dots (QDs) are grown by molecular beam epitaxy and studied both theoretically and experimentally. The electronic band structure is simulated using a combination of k·p and tight-binding models. These calculations predict an indirect to direct crossover with the In content and the size of the QDs. The optical properties are then studied in a low-In-content range through photoluminescence and time-resolved photoluminescence experiments. It suggests the proximity of two optical transitions of indirect and direct types.     

Hydrogen adsorption studies on single wall carbon nanotubes

Hydrogen adsorption data on as-grown and heat-treated single walled carbon nanotubes (SWNTs) obtained by a volumetric procedure using a Quantachrome Autosorb-1 equipment are presented. The amounts of hydrogen adsorbed at atmospheric pressure reach approximately 0.01 wt.% at 298 K and 1 wt.% at 77 K. The isosteric heat of adsorption has been calculated for both samples from H₂ equilibrium adsorption data at three temperatures, having initial values of 7.42 and 7.75 kJ mol⁻¹. Studies in porous structure by N₂ adsorption and density measurements in helium pycnometer are reported.     

Effects of boron doping in low- and high-surface-area carbon powders

Two distinctive carbon materials (Saran char and SP-1 graphite) were doped with B at different loading to clarify the intrinsic effect of substitutional B on carbon reactivity. The carbon precursors would be affected in different style by substitutional B due to different important properties (crystallinity and surface area). The B retentivity depended on the nature of B dopant and carbon substrate; a less ordered carbon has higher B loading than its counterpart. Graphitization was enhanced by substitutional B, as expected. Furthermore, the B incorporation was still beneficial for SP-1 although it already had high crystallinity. An interesting behavior was noticed; the increase in L_a was greater than L_c. The intrinsic effect of substitutional B in carbon oxidation was proved to be a catalytic one. Unlike highly ordered SP-1 graphite, Saran char showed both a catalytic effect at low B loading and low conversion, and an inhibiting effect at high B loading and high conversion. The inductive effect was proposed to explain this catalytic effect on different crystallite size. Different sizes of carbon clusters were calculated by Gaussian 98W; the extent of the effect of substitutional B did get smaller to the carbon in bigger size of carbon cluster.     

Suppressing the effect of cullet composition on the formation and properties of foamed glass

The process of foaming glass is very dependent on the chemical composition of the glass. In this study we used a foaming-agent/oxidizing-agent couple and a crystallization inhibitor to foam cullets of flat, container and CRT-panel glass. Foamed glass with a density of 110–120?kg?m^–3, a thermal conductivity of 50–52?mW?m^–1 K^–1 and a homogeneous pore structure was obtained from a mixture of panel glass, 0.33?wt% carbon and 4.45?wt% Fe₂O₃. We also showed that it is possible to fabricate foamed glass with the same density or pore structure as mentioned above by adding up to 50?wt% container cullet or 70?wt% flat glass to the mixture. In the foamed samples with a low content of panel glass, crystals form, resulting in an increased open porosity, density and inhomogeneous pore structure. The crystallization can, however, be inhibited by adding calcium phosphate, so enabling the preparation of high-quality foamed glass from flat glass or flat/container-glass mixture. The pore gas is predominantly CO₂ and the pressure inside the pores is 0.36–0.47?bar. The reduced effect of the composition on the foaming process suggests that there is a great potential for stabilizing the production of foamed glass and ensuring the product's quality.     

Analysis of the microporosity shrinkage upon thermal post-treatment of H3PO4 activated carbons

Starting from a commercial pelletized phosphoric acid based activated carbon, with a typical opened and developed micro and mesoporosity, a post-heat-treatment in KOH, at different KOH/activated carbon ratios, has been studied. In all the cases, a pore size shrinkage has been observed. To find an explanation for the reason of this micropore size distribution shrinkage different factors have been studied, among them: (a) effect of the presence of impurities coming from the activation process with phosphoric acid; (b) effect of the KOH post-treatment temperature; (c) heat-treatment temperature of the precursor (without chemical agent); (d) effect of the reagent nature (NaOH, NaCl and KCl vs. KOH). The variable that produces the most intense shrinkage effect, and the disappearance of the mesoporosity, is the heat-treatment in presence of hydroxide, which affects even using a low hydroxide/activated carbon ratio. Such a low hydroxide/activated carbon ratio does not produce activation, nor porosity development of the starting activated carbon during the treatment. This shrinkage phenomenon, which seems to be independent of the method of preparation used to prepare the activated carbon, can be understood considering our previous studies about the reactions involved during chemical activation by hydroxides.     

Modification of the sintering behaviour of mesophase powder from a petroleum residue

The effect of preparation conditions on the sintering behaviour of different binderless polyaromatic mesophase (BPAM) powders, obtained by extraction with different solvents of four petroleum semicokes of increasing carbonisation degree, is described. The analyses of the powders indicate that large differences in composition and structure are obtained when changing the semicoke. Increasing carbonisation degree of the semicoke produces a decrease in the amount of β-resins, increase in mesophase content, C/H ratio and aromaticity, but decreases the thermofusibility of BPAM. Increasing extraction strength of the solvent reduces the amount of light material, and thermofusibility of BPAM, being more evident with low carbonised semicokes. Selection of carbonisation conditions and solvent permits to adjust fusibility of the powders and to improve sintering. Graphitised compacts exhibited the best properties when they are produced from low carbonisation degree semicokes. In this case solvents of low extraction strength provide large thermofusibility to the material, and compacts may swell. When using semicokes of higher carbonisation degree there is a reduction of the sintering abilities of the powders, this being more evident as the strength of the solvent increases.     

Influence of embedding Cu nano-particles into a Cu/SiO2/Pt structure on its resistive switching

Cu nano-particles (Cu-NPs) were embedded into the SiO₂ layer of a Cu/SiO₂/Pt structure to examine their influence on resistive switching characteristics. The device showed a reversible resistive switching behavior, which was due to the formation and rupture of a Cu-conducting filament with an electrochemical reaction. The Cu-NPs enhanced the local electric field within the SiO₂ layer, which caused a decrease in the forming voltage. During successive switching processes, the Cu-NP was partially dissolved, which changed its shape. Therefore, the switching voltages were not reduced. Moreover, the Cu-NPs caused a non-uniform Cu concentration within the SiO₂ layer; thus, the Cu-conducting filament should be formed in a high Cu concentration region, which improves switching dispersion. The Cu-NPs within the SiO₂ layer stabilize the resistive switching, resulting in a larger switching window and better endurance characteristics.