Broad blue-green-red emissions of SnO2/Pr3+ co-doped phosphate glasses

The photoluminescence properties of SnO₂/Pr^3 + co-doped strontium phosphate glasses (75P₂O₅-25SrO) are studied. An ultrabroad emission band covering blue, green and red is observed in co-doped glasses. In co-doped samples, three downward peaks appear in blue emission region, these coincide with Pr^3 + excitation peaks, indicating the energy transfer through cross-relaxation between SnO₂ and Pr^3 +. The mechanism has been detailed based on the energy level diagrams of SnO₂ and Pr^3 +. The chromaticity coordinates of the co-doped samples with varying doping ratio of SnO₂ to Pr^3 + are calculated. The result demonstrates the possibility of generating white light in the SnO₂/Pr^3 + co-doped phosphate glasses.     

Structural study of undoped and (Mn, In)-doped SnO2 thin films grown by RF sputtering

Undoped and 5%(Mn, In)-doped SnO₂ thin films were deposited on Si(1 0 0) and Al₂O₃ (R-cut) by RF magnetron sputtering at different deposition power, sputtering gas mixture and substrate temperature. X-ray reflectivity was used to determine the films thickness (10–130 nm) and roughness (～1 nm). The combination of X-ray diffraction and Mössbauer techniques evidenced the presence of Sn⁴⁺ in an amorphous environment, for as-grown films obtained at low power and temperature, and the formation of crystalline SnO₂ for annealed films. As the deposition power, substrate temperature or O₂ proportion are increased, SnO₂ nanocrystals are formed. Epitaxial SnO₂ films are obtained on Al₂O₃ at 550 °C. The amorphous films are quite uniform but a more columnar growth is detected for increasing deposition power. No secondary phases or segregation of dopants were detected.     

Conductivity stabilization by metal and oxide additives in ceramics on the basis of VO2 and glass V2O5–P2O5

Conductivity behavior during the temperature cycling through the phase transition temperature of VO₂ (T_t = 68 °C) was investigated in glass-ceramics based on VO₂ and vanadium phosphate glass (VPG) for compositions without and with Cu and SnO₂ additives. Copper and SnO₂ additives stabilize the conductivity of glass-ceramics at temperature cycling. For ceramics (wt%) (80 − y)VO₂–5Cu–15VPG–ySnO₂ the best stabilizing effect takes place when SnO₂ content is in the interval 35 wt% < y < 50 wt%. Ceramics with such SnO₂ content keeps a stable value of the conductivity change (∼10²) in the vicinity of VO₂ phase transition temperature and shows the conductivity decrease no more than of 2.5 times after 3000 thermal cycles. The reasons of conductivity stabilizing in VO₂-based glass-ceramics with additives of Cu and SnO₂ are being discussed. The analysis resting on the percolation theory has shown the increase of conductivity stability in VO₂-based glass-ceramics when the VO₂ volume fraction and the average size of VO₂ crystallites decrease and the ceramics surface tension increases.     

Heat treatment of amorphous silicon p-i-n solar cells with high-pressure H2O vapor

We report improvement in characteristics of hydrogenated amorphous silicon (a-Si:H ) p-i-n structured solar cells by high-pressure H₂O vapor heat treatment. a-Si:H p-i-n solar cells were formed on glass substrates coated with textured SnO₂ layer. P-, i-, and n-type a-Si:H layers were subsequently formed by plasma enhanced chemical vapor deposition. Finally an indium-tin-oxide layer was coated on the n-type a-Si:H surface. Heat treatment at 210 °C with 2 × 10⁵ Pa H₂O vapor for 1 h was applied to the a-Si:H p-i-n solar cells. Electrical characteristics were measured when samples were kept in dark and illuminated with light of AM 1.5 at 100 mW/cm². The heat treatment with H₂O vapor increased fill factor (FF) and the conversion efficiency from 0.54 and 7.7% (initial) to 0.57 and 8.4%, respectively. Marked improvement in solar cell characteristics was also observed in the case of a poor a-Si:H p-i-n solar cell. FF and the conversion efficiency were increased from 0.29 and 3.2% (initial) to 0.56 and 7.7%, respectively.     

Electrooptical Kerr phenomenon and Raman spectroscopy of one lithium–niobium–silicate glass-forming system

Raman spectra and electrooptical Kerr coefficients of glasses belonging to one lithium–niobate–silicate glass-forming system xNb₂O₅ · (66 ? x)SiO₂ · 19Li₂O · 11K₂O · 2B₂O₃ · 2CdO are studied. It has been found that these glasses demonstrate a record value of electrooptical Kerr coefficient; the glass with x = 35 showed electrooptical Kerr coefficient equal to 266 × 10^?16 m/V². Using Raman spectroscopy combined with the concept of Constant Stoichiometric Groupings, a correlation of electrooptical Kerr coefficients of these glasses with the content of Li₂O · Nb₂O₅ (or 2LiNbO₃) groupings has been demonstrated. The hypothesis that electrooptical Kerr sensitivity of glasses is related to the ordered regions with composition and symmetry corresponding to some of known electrooptical crystals has been verified. These regions, which the authors called ‘Crystal Motifs’, are identified with the groupings found in studying Raman spectra of the glasses.     

Effect of the surfactant nature on the thermo-stability of surface modified SnO2 nanoparticles

The modification of particle surface properties by the addition of small surfactant molecules in the initial sol is one strategy to minimize the strong tendency to aggregation and coarsening of nanoparticles prepared from the sol–gel process. In this work, the effect of the nature of the surfactant, Tiron^® ((OH)₂C₆H₂(SO₃Na)₂ · H₂O, anionic) or Catechol^® (C₆H₄-1,2-(OH)₂, non-ionic) or Maptac^® ([N(CH₃)₃(CH₂)₃NHCOC(CH₂CH₃)]⁺Cl^?, cationic), grafted on the SnO₂ nanoparticles on the mesoporosity of powders fired at 600 °C is presented. SnO₂ powders were prepared from an one-pot sol–gel route in which the hydrolysis of SnCl₄ · 5H₂O in aqueous solution was carried out in presence of the surfactant. The Fourier transform infrared (FTIR) spectroscopy and gravimetric and differential thermo-analysis (TG/DTA) results show that the thermo-stability of surface grafted SnO₂ nanoparticles obeys the following series: Tiron^® > Catechol^® > Maptac^®. The N₂ adsorption isotherms results evidence that the mesopores texture (specific surface area, pore volume and average pore size) can be tuned in a controlled way by increasing the amounts of Tiron^® or Catechol^® molecules grafted on the surface of SnO₂ nanoparticles.     

Structural evolution of SnO2 nanostructure from core–shell faceted pyramids to nanorods and its gas-sensing properties

Tin oxide (SnO₂) nanorods were synthesized through an aqueous hexamethylenetetramine (HMTA) assisted synthesis route and their structural evolution from core–shell type faceted pyramidal assembly was investigated. Structural analysis revealed that the as-synthesized faceted SnO₂ structures were made of randomly arranged nanocrystals with diameter of 2–5 nm. The shell thickness (0–80 nm) was dependent on the molar concentration of HMTA (1–10 mM) in aqueous solution. It was revealed that the self-assembly was possible only with tin (II) chloride solution as precursor and not with tin (IV) chloride solution. At longer synthesis hours, the pyramidal nanostructures were gradually disintegrated into single crystalline nanorods with diameter of about 5–10 nm and length of about 100–200 nm. The SnO₂ nanorods showed high sensitivity towards acetone, but they were relatively less sensitive to methane, butane, sulfur dioxide, carbon monoxide and carbon dioxide. Possible mechanisms for the growth and sensing properties of the nanostructures were discussed.     

Kerr studies of several tellurite glasses

Estimates of Kerr electrooptical sensitivity of several tellurite glasses are presented. The highest value of Kerr coefficient B ～ 190 × 10^?16 m V^?2 is registered for 0.6TeO₂–0.3TlO_0.5–0.1ZnO glass. This evidences the prospects of thallium–tellurite glass system for electrooptical applications. A gradual decrease of B from 41 × 10^?16 to 26 × 10^?16 m V^?2 in (1 ? x) TeO₂ – xNbO_2.5 system is revealed for x increasing from 0.1 to 0.15. No crystalline phase was found in that system, thus allowing attributing its Kerr sensitivity to the intrinsic properties of the glass matrix. The Kerr coefficient variation from 66 to 81 × 10^?16 m V^?2 was observed for 0.85TeO₂–0.15WO₃ glasses co-doped with small amounts of silver and cerium. The analysis of optical absorption spectra of several silver-containing tellurium–tungsten oxide glasses makes it possible to think that introducing cerium provokes formation of new mid-range orderings.     

Bulk-quantity SnO2 nanorods synthesized from simple calcining process based on annealing precursor powders

Tin dioxide (SnO₂) nanorods have been successfully synthesized in bulk quantity by a calcining process based on annealing precursor powders in which sodium chloride, sodium carbonate, and stannic chloride were homogeneously mixed. Transmission electron microscopy shows that the as-prepared nanorods are structurally perfect and uniform, with widths of 10–25 nm, and lengths of several hundreds nanometers to a few micrometers. X-ray diffraction and energy-dispersive X-ray spectroscopy analysis indicate that the as-prepared nanorods have the same crystal structure and chemical composition found in the tetragonal rutile form of SnO₂. Selected area electron diffraction and high-resolution transmission electron microscopy reveal that the as-prepared nanorods grow along the [1 1 0] crystal direction. We found that the calcined temperature has a strong influence on the size and morphology of SnO₂ nanorods. The growth process of SnO₂ nanorods is suggested to follow an Ostwald ripening mechanism. Our findings indicate that other nanorods or nanowires may be manipulated by using this technique, and might provide insight into the new opportunities to control materials fabrication.     

Influence of maghemite concentration on magnetic interactions in maghemite/PTT-block-PTMO nanocomposite

Temperature dependence of dc magnetization and ferromagnetic resonance (FMR) of two samples containing γ-Fe₂O₃ (maghemite) magnetic nanoparticles dispersed at low concentration (0.1 and 0.3 wt%) in a nanocomposite based on a poly(ether–ester) multiblock copolymer (PTT-block-PTMO) matrix was investigated. The polymer filler was in a powder form consisting of small-sized magnetic nanoparticles arranged in agglomerates 2–3 μm long and 100 nm thick. The studied samples were characterized by SEM spectroscopy. The SEM showed that the concentration of magnetic nanoparticles was homogenous in both samples The temperature dependence of the dc magnetization revealed that the blocking was about 100 K and the ZFC (zero-field cooling) mode at low magnetic fields uncovered the presence of magnetic interactions between magnetic nanoparticles depending on the properties of the matrix. FMR measurements were carried out in the temperature range 4.2–300 K. An intense resonance absorption line attributed to γ-Fe₂O₃ nanoparticles was recorded with a slightly asymmetric lineshape. At room temperature the resonance line was centered at H_r = 3241(2) and 3253(2) G, with linewidths of ΔH = 1069(1) and 1070(1) G for samples with concentrations of 0.1 and 0.3 wt%, respectively. All FMR parameters showed an anomalous behavior at matrix critical temperatures. It was shown that the difference in concentration of magnetic nanoparticles could be responsible for the observed differences in the thermal behavior of the FMR spectra.     

Orthorhombic Pbcn SnO2 nanowires for gas sensing applications

Pure monocrystalline orthorhombic SnO₂ nanowires decorated and non-decorated with cassiterite SnO₂ nanoclusters are analyzed and compared with pure monocrystalline cassiterite SnO₂. We corroborate the coexistence of both, cassiterite and orthorhombic phases, having a higher growth speed for the cassiterite one, in the obtained nanowires by the evaporation/condensation technique. For both phases, the building blocks are the [SnO₆]^8? octahedron which are forming chains of edge-sharing octahedral along the [0 0 1] direction for the cassiterite phase, while in the orthorhombic phase, chains run in a zigzag fashion and contains four octahedra on each unit of chain instead of two previously reported for orthorhombic material obtained at high pressure conditions as Pbcn SnO₂ orthorhombic structure. Results obtained reveal singular structural characteristics of these synthesized orthorhombic nanowires.     

Magnetic properties of the micro-silica/cement matrix with carbon-coated cobalt nanoparticles and free radical DPPH

Samples of micro-silica/cement containing iron oxide, Fe₂O_3, and doped with carbon-coated cobalt nanoparticles and free radical DPPH were prepared and studied by the magnetic resonance method. The concrete’s main components (silica and cement) produced very complicated FMR/EPR (ferromagnetic and electron paramagnetic resonance) spectra. The temperature dependence of the FMR/EPR spectra was recorded in the 90–300 K temperature range. The cement/micro-silica matrix produced a very broad FMR line originating from iron oxide particles and two EPR lines originating from iron(III) ions in the crystal field of low-symmetry (centered at g_eff ～ 4.3) and from manganese(II) ions (g_eff ～ 2) of hyperfine structure. Additionally, a very narrow line and a very broad EPR/FMR line were registered and, respectively, attributed to DPPH and cobalt nanoparticles. The isolated paramagnetic iron(III) and manganese(II) centers displayed increasing intensity of the EPR spectra with decreasing temperature, while no influence of the magnetic nanoparticles was observed. The intensity of the FMR spectrum of iron oxide decreased strongly and the resonance field was effectively shifted toward low magnetic fields with decreasing temperature. The observed FMR behavior is similar to what was registered for iron oxide magnetic nanoparticles. The introduction of magnetic nanoparticles influenced the EPR spectrum of the free radical DPPH significantly: its intensity decreased above 260 K and increased slightly below this temperature, while the resonance field changed with decreasing temperature. This behavior may be associated with the porous state of cement and/or the reaction of the multi-component magnetic system. The FMR/EPR method could be very useful for the characterization of matrices containing small amounts of magnetic nanoparticles.     

Phase transformation and crystal growth behaviors of La3+/Ce3+-doped TiO2–20 wt% SnO2 gels

The transformation behaviors of La³⁺/Ce³⁺-doped TiO₂–SnO₂ gels were studied by using differential thermal analysis and X-ray diffraction methods so as to improve the phase transformation and decrease the granularity of crystals. Experimental results show that, anatase, rutile and SnO₂ nanocrystals can exist in the sintering products by varying La³⁺/Ce³⁺ contents and sintering temperatures. 0.8–1.1 wt% of La₂O₃ or CeO₂ doping greatly depresses the growth of anatase and rutile crystals, obtaining nanosized crystals when sintered up to 600 °C for 2 h. With La³⁺/Ce³⁺-doping and increasing their contents, the transformations of gel to anatase and anatase to rutile, as well as the growth of anatase and rutile crystals can be depressed, while the transformation temperature of anatase to rutile receives much less affect. Moreover, the La³⁺-doping has stronger effects on them than Ce³⁺ doping, but has a weaker inhibiting effect on precipitation and growth of SnO₂ crystals.     

Extended free radical network from condensed cyanuric chloride with p-phenylenediamine: An EPR/FMR study

A covalent layered network was obtained by condensation of cyanuric chloride with bridging paraphenylenediamine. The local chemical environment of the layered solid can be changed by a redox reaction to obtain new reconstructed derivatives. A blue product was obtained by treating an alcoholic dispersion of the layered solid with ferric nitrate or potassium persulfate, indicating the possible formation of an extended free radical. When iron nitrate was used as oxidant, the temperature-dependent magnetic resonance spectra were measured in the 290–4 K region. The magnetic resonance measurements showed the coexistence at room temperature of two spectra arising from two different magnetic centers: a narrow line centered at g = 2.0038(1) with linewidth of ΔH = 7.42(2) G (free radical) and a broad line centered at g = 2.254(1) with linewidth of ΔH = 1300(5) G (magnetic iron-oxide cluster). A new sample was prepared so that the broader line was more intense. The temperature dependence of the magnetic resonance lines was subject to intense changes in both cases. The integrated intensities decreased with decreasing temperatures in both spectra in the high temperature region. This type of behavior is similar to that of magnetic nanoparticles in non-magnetic matrices. Upon reducing the temperature with the gradient of ΔH_r/ΔT = 1.5(1) G/K, the resonance field of the broad line was shifted towards lower magnetic fields, while the narrow line was shifted towards higher magnetic fields with ΔH_r/ΔT = 0.020(1) G/K. The linewidth of the broader line increased with decreasing temperature, while the narrow line remained almost constant. The magnetic iron-oxide clusters could produce an internal magnetic field acting on free radicals. This field could compel free radicals to form a magnetic ordered state at high temperatures.     

Carbon covered magnetic nickel nanoparticles embedded in PBT-PTMO polymer: Preparation and magnetic properties

Fine particles of a face-centered-cubic phase of Ni covered with a graphite layer were prepared and embedded in a PBT-block-PTMO polymer at a concentration of 0.1 wt%. The mean crystalline size of Ni varied from 8 to 30 nm. A magnetic resonance study of the obtained nanocomposites was carried out in the 4–300 K temperature range using an electron paramagnetic resonance spectrometer. An almost symmetrical and very intense magnetic resonance line was recorded for all the investigated samples. The resonance line was centered at g = 2.253(2) (the resonance field H_r = 3003(1) Gs) and had a peak-to-peak linewidth ΔH_pp = 693(2) Gs at room temperature. The amplitude of the resonance line increased with a temperature increase in the low temperature range (T < 40 K) and in the high temperature range (T > 100 K) but was constant at intermediate temperatures. The resonance field H_r decreased and linewidth ΔH_pp increased as the temperature decreased from room temperature what was similar to the changes observed for other systems of nanoparticles. The thermal gradient of the resonance field, ΔH_r/ΔT, strongly depended on the temperature range. The temperature shift of the resonance field and the linewidth were analyzed in terms of the demagnetizing fields of nonspherical agglomerates. A strong change of linewidth and resonance field was registered below 40 K due to the freezing of the spin system’s dynamical magnetic fluctuations. A comparison was made of the results obtained on the Ni/C with the previous measurements on γ-Fe₂O₃ nanoparticles embedded in a copolymer.     

Photoelectron spectroscopy study of the effect of substrate doping on an HfO2/SiO2/n-Si gate stack

Core level photoelectron spectroscopy has been used to investigate the effect of substrate doping on the binding energies of 1 nm HfO₂/0.6 nm SiO₂/Si films. A characteristic 0.26–0.30 nm Hf_0.35Si_0.65O₂ silicate interface is formed between the gate oxide and the SiO₂ layer with an equivalent oxide thickness of 0.5 nm. High substrate doping shifts the Fermi level upwards by 0.5 eV. An interface dipole forms giving rise to a shift in the local work function. Screening from substrate electrons is confined to the SiO₂/Si interface. The principal contributions modifying the core level binding energies in the oxide are the doping dependant Fermi level position and the interface dipole strength.     

Fabrication and characterization of nanorod solar cells with an ultrathin a-Si:H absorber layer

In this paper, we present a three-dimensional nanorod solar cell design. As the backbone of the nanorod device, density-controlled zinc oxide (ZnO) nanorods were synthesized by a simple aqueous solution growth technique at 80 °C on ZnO thin film pre-coated glass substrate. The as-prepared ZnO nanorods were coated by an amorphous hydrogenated silicon (a-Si:H) light absorber layer to form a nanorod solar cell. The light management, current–voltage characteristics and corresponding external quantum efficiency of the solar cells were investigated. An energy conversion efficiency of 3.9% was achieved for the nanorod solar cells with an a-Si:H absorber layer thickness of 75 nm, which is significantly higher than the 2.6% and the 3.0% obtained for cells with the same a-Si:H absorber layer thickness on planar ZnO and on textured SnO₂:F counterparts, respectively. A short-circuit current density of 11.6 mA/cm² and correspondingly, a broad external quantum efficiency profile were achieved for the nanorod device. An absorbed light fraction higher than 80% in the wavelength range of 375–675 nm was also demonstrated for the nanorod solar cells, including a peak value of ~ 90% at 520–530 nm.     

Rare earth centers properties and electron trapping in SnO2 thin films produced by sol–gel route

Some very relevant optical, electrical, and structural properties of SnO₂ doped with rare-earth ions Er³⁺ and Eu³⁺ are presented. Films are produced by the sol–gel-dip coating process, and may be described as a combination of nanoscopic dimension crystallites (about 3–10 nm) with their respective intergrain potential barriers. The Er³⁺ and Eu³⁺ ions are expected to act as acceptors in SnO_2, which is a natural n-type conductor, inducing a high degree of charge compensation. Electron trapping and emission spectra data are presented and are rather distinct, depending on the location of the rare-earth impurity. This behavior allows the identification of two distinct centers: located either in the SnO₂ lattice or segregated at the particles surface. Based on a model for thermally activated cross-section defects, the difference between the capture energy of the photo-excited electron and the intergrain potential barrier is evaluated, leading to distinct values for high and low symmetry sites. A higher distortion in the lattice of undoped SnO₂ and SnO₂:Eu (1 at.%) was evaluated from Rietveld refinements of X-ray diffraction data. This was confirmed by Raman spectra, which are associated with the particles size and disorder. By comparing the samples with the same doping concentration, it was found that this disorder is higher in Eu-doped SnO₂ than in Er-doped SnO₂, which is in agreement with a higher energy for the lattice relaxation in the trapping process by Eu³⁺ centers.     

Optical activity of Sn-variants of oxygen deficient centers in fluorine-modified silica

Photoluminescence in fluorine-modified Sn-doped silica has been analyzed by means of synchrotron radiation in the UV and vacuum-UV, from 120 to 330 nm, looking at the optical activity of oxygen-deficient-centers ODC(II) in Sn-substituted cationic sites. The comparison between F-modified Sn-doped samples and previous data on F-free Sn-doped material evidences differences in the intensity of the 3.2 eV emission band excited at 3.7 eV, and in the thermal dependence of the intensity of this emission excited via intersystem crossing. The role of fluorine in modifying the optical activity of ODC(II) and in the SnO₂ clustering is discussed, showing that an efficient excitation transfer may be activated from SnO₂ to the Sn-variant of ODC(II).     

Magnetic properties of TiCx/C nanocomposites

The magnetic properties of nanocrystalline titanium carbide dispersed in a carbon matrix (TiC_x/C) prepared by the non-hydrolytic sol–gel process have been studied by dc magnetization measurements. The superconducting phase of titanium carbide has been observed at low temperatures with the onset of the superconducting transition temperature T_c at about 3.5 K, superimposed on a ferromagnetic component. At T > T_c the magnetic response of TiC_x/C is determined by the interplay of the ferromagnetic contribution with the paramagnetic/diamagnetic signal of the metallic system and the contribution of exchange coupled paramagnetic ions. Moreover, significant differences are observed in the magnetic response for samples of the same preparation batch, indicative of the magnetic/electronic inhomogeneity of nanocrystalline titanium carbide which is important for its practical applications.