Síntese e estudo das propriedades luminescentes do SrGa2O4 dopado com íons de Cr3+

Amostras policristalinas de Sr(Ga1-xCrx)2O4 com x = 0,01 foram estequiometricamente preparadas pela mistura dos materiais em pó SrCO3, Ga2O3 e Cr2O3. A estrutura cristalina da amostra dopada foi analisada pelas medidas de difração de raios-X. O padrão de difração revelou uma única fase relacionada a fase monoclínica do SrGa2O4. Os dados foram ajustados usando o Método de Rietveld para refinamento de estruturas e os parâmetros da rede foram determinados. A luminescência do íon de Cr3+ na rede do SrGa2O4 foi investigada pelas espectroscopias de excitação e emissão a temperatura ambiente, através das quais verificamos que os íons de Cr3+ estão localizados em dois sítios diferentes. Os espectros de emissão apresentam bandas largas associadas à transição eletrônica 4T2(4F) → 4A2(4F) para ambos os sítios. Estes resultados são analisados pela teoria de campo cristalino e o parâmetro de campo cristalino Dq e os parâmetros de Racah B e C são determinados pelas posições das bandas de excitação. A partir destes parâmetros determinamos um campo cristalino forte para ambos os sítios. Além disto, foram realizadas medidas de espectroscopia fotoacústica que confirmaram as transições identificadas e estimadas nos espectros de excitação.

Preparação, caracterização e avaliação de nanocompósitos de PBAT/amido de milho e vermiculita organofilizada

Nos últimos 20-30 anos polímeros biodegradáveis vêm sendo estudados e desenvolvidos e atualmente já são comercializados. Contudo, o custo, a processabilidade e algumas propriedades ainda dificultam a penetração desses polímeros no mercado e a competição com as chamadas commodities. Não são poucos os autores que se dedicam a desenvolver aditivos e formulações para superar essas limitações. Desta forma, esta Tese se dedicou ao desenvolvimento de compósitos de Ecobras, fabricado pela Basf e comercializado pela Corn Products, utilizando como carga mineral resíduo da extração da bauxita, no município de Santa Luzia/PB, o qual consiste em sua totalidade de vermiculita. Esta vermiculita foi quimicamente modificada com sais de alquil fosfônio para melhorar a compatibilidade com a matriz polimérica e também espaçar as camadas de aluminossilicato. De fato, a modificação com o brometo de hexadecil tributil fosfônio resultou na esfoliação da vermiculita tornando-a potencialmente apropriada para a obtenção de nanocompósitos. A preparação dos compósitos foi realizada pelo método de intercalação no estado fundido e foram comparadas a utilização da câmara interna de mistura e da mini extrusora de dupla rosca, sendo esta última mais eficaz na dispersão da vermiculita, conforme revelado pela microscopia eletrônica de varredura, difração de raios-X e reometria de placas. O grau de dispersão também foi influenciado pela estrutura química do modificador da vermiculita e pelo teor dessa carga incorporada à matriz. Teores mais elevados levaram a formação de aglomerados, enquanto a modificação da carga implicou na formação de micro e nanocompósitos. Ainda houve alterações das propriedades térmicas com aumento dos valores da temperatura de transição vítrea, de cristalização e fusão, embora o grau de cristalinidade tenha sido mantido. Nitidamente, foram obtidos materiais mais rígidos, com maior módulo e menor capacidade de deformação. Cerca de 58% de perda de massa foi observada para os micro e nanocompósitos obtidos após 17 semanas de enterro em solo simulado para avaliação da biodegradabilidade, valor bem próximo ao Ecobras puro. De modo geral, a incorporação das diferentes vermiculitas retardou nas primeiras semanas a biodegradação, provavelmente em função de modificações na estrutura cristalina, conforme sugerido pelos maiores valores de temperatura de fusão observados durante o acompanhamento do processo de biodegradação. No entanto, após 7 semanas os perfis de biodegradação dos micro e nanocompósitos se aproximaram bastante do Ecobras puro. Desta forma, foi possível nesta Tese obter um nanocompósito de Ecobras com vermiculita modificada com brometo de hexadecil fosfônio utilizando ferramentas comuns de processamento no estado fundido com biodegradabilidade próxima ao polímero de partida, porém mais rígido e menos deformável

Blue-phase templated fabrication of three-dimensional nanostructures for photonic applications.

A promising approach to the fabrication of materials with nanoscale features is the transfer of liquid-crystalline structure to polymers. However, this has not been achieved in systems with full three-dimensional periodicity. Here we demonstrate the fabrication of self-assembled three-dimensional nanostructures by polymer templating blue phase I, a chiral liquid crystal with cubic symmetry. Blue phase I was photopolymerized and the remaining liquid crystal removed to create a porous free-standing cast, which retains the chiral three-dimensional structure of the blue phase, yet contains no chiral additive molecules. The cast may in turn be used as a hard template for the fabrication of new materials. By refilling the cast with an achiral nematic liquid crystal, we created templated blue phases that have unprecedented thermal stability in the range -125 to 125 °C, and that act as both mirrorless lasers and switchable electro-optic devices. Blue-phase templated materials will facilitate advances in device architectures for photonics applications in particular.

Blue-phase templated fabrication of three-dimensional nanostructures for photonic applications

A promising approach to the fabrication of materials with nanoscale features is the transfer of liquid-crystalline structure to polymers. However, this has not been achieved in systems with full three-dimensional periodicity. Here we demonstrate the fabrication of self-assembled three-dimensional nanostructures by polymer templating blue phase I, a chiral liquid crystal with cubic symmetry. Blue phase I was photopolymerized and the remaining liquid crystal removed to create a porous free-standing cast, which retains the chiral three-dimensional structure of the blue phase, yet contains no chiral additive molecules. The cast may in turn be used as a hard template for the fabrication of new materials. By refilling the cast with an achiral nematic liquid crystal, we created templated blue phases that have unprecedented thermal stability in the range-125 to 125°C, and that act as both mirrorless lasers and switchable electro-optic devices. Blue-phase templated materials will facilitate advances in device architectures for photonics applications in particular. © 2012 Macmillan Publishers Limited. All rights reserved.

Noncontact measurement of charge carrier lifetime and mobility in GaN nanowires

The first noncontact photoconductivity measurements of gallium nitride nanowires (NWs) are presented, revealing a high crystallographic and optoelectronic quality achieved by use of catalyst-free molecular beam epitaxy. In comparison with bulk material, the NWs exhibit a long conductivity lifetime (>2 ns) and a high mobility (820 ± 120 cm 2/(V s)). This is due to the weak influence of surface traps with respect to other III-V semiconducting NWs and to the favorable crystalline structure of the NWs achieved via strain-relieved growth. © 2012 American Chemical Society.

High performance transistors based on the controlled growth of triisopropylsilylethynyl-pentacene crystals via non-isotropic solvent evaporation

Triisopropylsilylethynyl-pentacene (TIPS-PEN) has proven to be one of the most promising small molecules in the field of molecular electronics, due to its unique features in terms of stability, performance and ease of processing. Among a wide variety of well-established techniques for the deposition of TIPS-PEN, blade-metered methods have recently gained great interest towards the formation of uniform crystalline films over a large area. Following this rationale, we herein designed a versatile approach based on blade-coating, which overcomes the problem of anisotropic crystal formation by manipulating the solvent evaporation behaviour, in a way that brings about a preferential degree of crystal orientation. The applicability of this method was evaluated by fabricating field-effect transistors on glass as well as on silicon dioxide/silicon (SiO2/Si) substrates. Interestingly, in an attempt to improve the rheological and wetting behaviour of the liquid films on the SiO2/Si substrates, we introduced a polymeric interlayer of polystyrene (PS) or polymethylmethacrylate (PMMA) which concurrently acts as passivation and crystallization assisting layer. In this case, the synergistic effects of the highly-ordered crystalline structure and the oxide surface modification were thoroughly investigated. The overall performance of the fabricated devices revealed excellent electrical characteristics, with high saturation mobilities up to 0.72 cm2 V-1 s-1 (on glass with polymeric dielectric), on/off current ratio >104 and low threshold voltage values (<-5 V). This journal is © the Partner Organisations 2014.

Highly efficient photoluminescence of Er2SiO5 films grown by reactive magnetron sputtering method

E2SiO5 thin films were fabricated on Si substrate by reactive magnetron sputtering method with subsequent annealing treatment. The morphology properties of as-deposited films have been studied by scanning electron microscope. The fraction of erbium is estimated to be 23.5 at% based on Rutherford backscattering measurement in as-deposited Er-Si-O film. X-ray diffraction measurement revealed that Er2SiO5 crystalline structure was formed as sample treated at 1100 degrees C for 1 h in O-2 atmosphere. Through proper thermal treatment, the 1.53 mu m Er3+-related emission intensity can be enhanced by a factor of 50 with respect to the sample annealed at 800 degrees C. Analysis of pump-power dependence of Er3+ PL intensity indicated that the upconversion phenomenon could be neglected even under a high photon flux of 10(21) (photons/cm(2)/sec). Temperature-dependent photoluminescence (PL) of Er2SiO5 was studied and showed a weak thermal quenching factor of 2. Highly efficienct photoluminescence of Er2SiO5 films has been demonstrated with Er3+ concentration of 10(22)/cm(3), and it opens a promising way towards future Si-based light source for Si photonics. (C) 2009 Elsevier B.V. All rights reserved.

Growth of (10(1)over-bar(3)over-bar) semipolar GaN on m-plane sapphire by hydride vapor phase epitaxy

The crystalline, surface, and optical properties of the (10 (1) over bar(3) over bar) semipolar GaN directly grown on m-plane sapphire substrates by hydride vapor phase epitaxy (HVPE) were investigated. It was found that the increase of V/III ratio led to high quality (10 (1) over bar(3) over bar) oriented GaN epilayers with a morphology that may have been produced by step-flow growth and with minor evidence of anisotropic crystalline structure. After etching in the mixed acids, the inclined pyramids dominated the GaN surface with a density of 2 X 10(5) cm(-2), revealing the N-polarity characteristic. In the low-temperature PL spectra, weak BSF-related emission at 3.44eV could be observed as a shoulder of donor-bound exciton lines for the epilayer at high V/III ratio, which was indicative of obvious reduction of BSFs density. In comparison with other defect related emissions, a different quenching behavior was found for the 3.29 eV emission, characterized by the temperature-dependent PL measurement. (C) 2009 Elsevier B.V. All rights reserved.

Nanoinstabilities as revealed by shrinkage of nanocavities in silicon during irradiation

While the thermodynamic nonequilibrium properties of nanoparticles are being extensively studied, the thermodynamic nonequilibrium properties of their counterpart: nanocavities, however, are less noticed. Here, we systematically review and comprehensively model the recently published results on the newly-found thermodynamic nonequilibriurn properties of nanocavities in covalently bound materials during energetic beam irradiation. We also review and model the thermodynamic nonequilibrium properties of nanoparticles. The review and modelling not only demonstrates the novel nonequilibriurn properties of such an open-volume nanostructure during external excitation but also gives a deep insight into the nonequilibrium thermodynamics of amorphous structures and the difference in the behaviours of defects in crystalline and in amorphous silicon. Especially, the review and modelling leads to two new concepts:anti-symmetry relation between a nanoparticle and a nanocavity；energetic beam induced-soft mode and lattice instability in condensed matter；which reveals that structure of a condensed matter would be unstable not only at nanosize scale but also at a nanotime scale in general. It is also reveals that such nanoinstabilities would be more pronounced in an amorphous structure than in a crystalline structure.

Hetero-epitaxial growth of ZnO films on silicon by low-pressure metal organic chemical vapor deposition

Quality ZnO films were successfully grown on Si(100) substrate by low-pressure metal organic chemical vapor deposition method in temperature range of 300-500 degrees C using DEZn and N2O as precursor and oxygen source respectively. The crystal structure, optical properties and surface morphology of ZnO films were characterized by X-ray diffraction, optical refection and atomic force microscopy technologies. It was demonstrated that the crystalline structure and surface morphology of ZnO films strongly depend on the growth temperature.

Electrocatalytic properties of Cu-Zr amorphous alloy towards the electrochemical hydrogenation of nitrobenzene

The Cu-Zr amorphous alloy was studied as an electrocatalyst towards the electrochemical hydrogenation of nitrobenzene. The electrocatalyst was activated by chemical etching in HF solution. Resulted changes in the morphology, chemical composition and crystalline structure of the electrocatalyst surface were characterised by scanning electron microscopy, X-ray diffraction and Auger electron spectroscopy. The electrocatalytic properties of the Cu-Zr amorphous alloy were assessed by voltammetric measurements. Due to the formation and aggregation of Zr residue modified Cu nanocrystals on the surface caused by the selective dissolution of Zr components in the chemical etching, the activated amorphous alloy is an effective electrocatalyst for the electrochemical reduction reaction of nitrobenzene with aniline as the main product. The positive shift of the peak potential and accompanying increase in the value of peak current in voltammograms with increasing Cu content and decreasing Zr content of the alloy surface in the chemical etching are indicative of improved electrocatalytic activity. (C) 2002 Elsevier Science B.V. All rights reserved.

A simple selenium source to synthesize CdSe via the two-phase thermal approach

A novel selenium source was developed to synthesize the size-controlled CdSe nanocrystals with relatively narrow size distribution successfully in a two-phase thermal approach. A highly reactive and aqueous soluble selenium source was provided by the reduction of selenite, and in this route the size of the nanocrystals can be adjusted by the reaction temperature and time. The size, crystalline structure and optical characteristics of these nanocrystals were investigated by transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, UV-vis spectroscopy, and photoluminescence spectroscopy. The influence factors for this approach were also discussed.

CuIn(WO4)(2) nanospindles and nanorods: controlled synthesis and host for lanthanide near-infrared luminescence properties

CuIn(WO4)(2) porous nanospindles and nanorods were synthesized through a low-cost hydrothermal method without introducing any template or surfactants. An interesting formation mechanism, namely "oriented attachment", was observed for the growth of nanorods based on the experimental process and the anisotropic intrinsic crystalline structure of CuIn(WO4)(2), which is uncommon in such a system. The near-infrared luminescence of lanthanide ions (Er, Nd, Yb and Ho) doped CuIn(WO4)(2) nanostructures, especially in the 1300-1600 nm region, was discussed and of particular interest for telecommunications applications. X-Ray diffraction, scanning electron microscopy, transmission electron microscopy, electron diffraction and photoluminescence spectra were used to characterize these materials.

Isothermal Crystallization Behavior of Poly(L-lactic acid)/Organo-Montmorillonite Nanocomposites

The isothermal crystallization behavior of poly(L-lactic acid)/organo-montmorillonite nanocomposites (PLLA/OMMT) with different content of OMMT, using a kind of twice-functionalized organoclay (TFC), prepared by melt intercalation process has been investigated by optical depolarizer. In isothermal crystallization from melt, the induction periods (t(i)) and half times for overall PLLA crystallization (100 degrees C <= T-c <= 120 degrees C) were affected by the temperature and the content of TFC in nanocomposites. The kinetic of isothermal crystallization of PLLA/TFC nanocomposites was studied by Avrami theory. Also, polarized optical photomicrographs supplied a direct way to know the role of TFC in PLLA isothermal crystallization process. Wide angle X-ray diffraction (WAXD) patterns showed the nanostructure of PLLA/TFC material, and the PLLA crystalline integrality was changed as the presence of TFC. Adding TFC led to the decrease of equilibrium melting point of nanocomposites, indicating that the layered structure of clay restricted the full formation of crystalline structure of polymer.

Synthesis of dodecenyl succinic anhydride (DDSA) corn starch

Dodecenly succinic anhydride (DDSA) starches were prepared commercially by the base catalyzed reaction of DDSA in pre-emulsion with starch granular in aqueous slurry. The results indicated that the degree of substitution and reaction efficiency were 0.0256% and 42.7%, respectively, at the parameters for the preparation of DDSA starches in starch slurry 30%, DDSA/starch radio 10% (wt/wt), pH 8.5-9.0, reaction temperature 313 K. After modification, product surface chemical composite had been changed which was prone to migrate into less polar solution. The chemical structural characteristics were investigated by methods of FTIR and H-1 NMR. The results of X-ray diffraction showed the native A-type crystalline pattern, indicating that reaction of corn starch with DDSA caused no change in the crystalline structure. Compared to native starch, the hydrophobic performance of esters was greatly increased. With the DS increasing, contact angles were gradually increased, however, the adhesion works were decreased. The maximum contact angle of DDSA starch could attend to 123 degrees, and the corresponding adhesion work was 33.2 mJ m(-2).