Surface states in template synthesized tin oxide nanoparticles

Tin-oxide nanoparticles with controlled narrow size distributions are synthesized while physically encapsulated inside silica mesoporous templates. By means of ultraviolet-visible spectroscopy, a redshift of the optical absorbance edge is observed. Photoluminescence measurements corroborate the existence of an optical transition at 3.2 eV. The associated band of states in the semiconductor gap is present even on template-synthesized nanopowders calcined at 800°C, which contrasts with the evolution of the gap states measured on materials obtained by other methods. The gap states are thus considered to be surface localized, disappearing with surface faceting or being hidden by the surface-to-bulk ratio decrease.

Mineralização de compostos nitrogenados após aplicações de lodos de esgoto em quatro cultivos de milho

O teor de N disponível em solos tratados com lodo de esgoto é um dos fatores restritivos à aplicação do resíduo em grandes volumes na agricultura, e deve ser utilizado nas normas que regulamentam seu uso agrícola com o fim de evitar a contaminação ambiental do solo e corpos d'água com nitrato. Quando se aplica o resíduo pela primeira vez em um solo, a disponibilização de N mineral a partir de compostos orgânicos naturais do solo não é diretamente considerada no cálculo da taxa de aplicação máxima, e este procedimento é comum também nas recomendações de adubação mineral. Porém, a aplicação continuada desses resíduos pode causar efeitos residuais acumulativos na geração de N mineral, o que implicaria recomendações específicas para reaplicações em uma mesma área. O objetivo deste trabalho foi avaliar a disponibilidade potencial de N mineral em um Latossolo previamente tratado com lodos de esgoto e com quatro cultivos sucessivos de milho. Amostras de solo da camada de 0-20 cm foram coletadas em subparcelas de um experimento realizado em campo, entre 1999 e 2002, em Jaguariúna (SP), onde foram aplicados 0, 14.716, 29.432, 58.864 e 117.728 kg ha-1 de lodo de origem urbana (Franca, SP) e 0, 22.700, 45.400, 90.800 e 181.600 kg ha-1 de lodo produzido a partir de esgotos urbanos e industriais (Barueri, SP). As doses foram parceladas em quatro aplicações anuais consecutivas. Em laboratório, essas amostras foram incubadas durante 15 semanas. As análises iniciais dos solos evidenciaram que houve efeito residual das aplicações prévias dos lodos sobre o acúmulo de N orgânico e de nitrato. No final da incubação, houve acúmulo de N inorgânico no solo e diminuição do pH em função da maior geração de nitrato com as doses crescentes dos lodos de esgoto. O potencial de mineralização estimado pelo modelo exponencial simples foi de 28 mg kg-1 de N no tratamento sem lodo, e crescente, de 28 para 100 mg kg-1 de N, nos tratamentos com lodo de Franca, e de 40 para 113 mg kg-1 de N tratamentos com lodo de Barueri. Concluiu-se que os efeitos residuais acumulados no solo devem ser considerados quando se pretender fazer novas aplicações de lodos de esgoto num mesmo local. Os potenciais de mineralização de compostos de N do solo e do lodo que será utilizado, além do acúmulo de nitrato no perfil do solo, devem ser determinados e considerados para o cálculo da dose da próxima aplicação.

Production of fungal volatile organic compounds in bedding materials

Selostus: Haihtuvien orgaanisten yhdisteiden muodostuminen kuivikkeissa

Perpendicular magnetic anisotropy in chemically disordered FePd-FeV(100) alloy thin films

We find that the use of V(100) buffer layers on MgO(001) substrates for the epitaxy of FePd binary alloys yields to the formation at intermediate and high deposition temperatures of a FePd¿FeV mixed phase due to strong V diffusion accompanied by a loss of layer continuity and strong increase of its mosaic spread. Contrary to what is usually found in this kind of systems, these mixed phase structures exhibit perpendicular magnetic anisotropy (PMA) which is not correlated with the presence of chemical order, almost totally absent in all the fabricated structures, even at deposition temperatures where it is usually obtained with other buffer layers. Thus the observed PMA can be ascribed to the V interdiffusion and the formation of a FeV alloy, being the global sample saturation magnetization also reduced.

Raman microprobe characterization of electrodeposited S-rich CuIn(S,Se)2 for photovoltaic applications: Microstructural analysis

This article reports a detailed Raman scattering and microstructural characterization of S-rich CuIn(S,Se)2 absorbers produced by electrodeposition of nanocrystalline CuInSe2 precursors and subsequent reactive annealing under sulfurizing conditions. Surface and in-depth resolved Raman microprobe measurements have been correlated with the analysis of the layers by optical and scanning electron microscopy, x-ray diffraction, and in-depth Auger electron spectroscopy. This has allowed corroboration of the high crystalline quality of the sulfurized layers. The sulfurizing conditions used also lead to the formation of a relatively thick MoS2 intermediate layer between the absorber and the Mo back contact. The analysis of the absorbers has also allowed identification of the presence of In-rich secondary phases, which are likely related to the coexistence in the electrodeposited precursors of ordered vacancy compound domains with the main chalcopyrite phase, in spite of the Cu-rich conditions used in the growth. This points out the higher complexity of the electrodeposition and sulfurization processes in relation to those based in vacuum deposition techniques.

Mineralização de compostos nitrogenados de lodos de esgoto na quinta aplicação em Latossolo

Em sistemas agrícolas em que se aplica lodo de esgoto, devem ser consideradas as necessidades de N das plantas e, simultaneamente, evitar a geração de excesso de nitrato, poluente potencial de águas subsuperficiais. Para isso, na determinação das quantidades máximas a serem aplicadas em determinado cultivo, devem-se conhecer algumas propriedades do lodo de esgoto e do solo. Uma delas é a fração de mineralização de compostos nitrogenados orgânicos (FMN) contidos nos resíduos que serão mineralizados durante o ciclo da cultura. Essa quantidade, somada ao N na forma mineral contido no lodo, fornece a quantidade de N do lodo de esgoto que ficará disponível durante a safra. Este trabalho teve como objetivo determinar se as aplicações anteriores de lodo de esgoto, feitas em um Latossolo, alteram a FMN do resíduo recentemente aplicado. O solo foi previamente tratado, em quatro cultivos sucessivos de milho, com quatro doses e dois tipos de lodo de esgoto, um de origem urbana (Franca, SP) e outro de origem urbano-industrial (Barueri, SP). O experimento de mineralização foi instalado em laboratório, com delineamento experimental em blocos casualizados e três repetições, realizado durante 15 semanas. As doses dos lodos de esgoto estudadas, na quinta aplicação, corresponderam a 160, 320, 640 e 1.280 mg kg-1 de N orgânico. Em sete épocas, foram determinados o pH e os teores de N nas formas amoniacal e nítrica. A FMN foi calculada com os dados obtidos para a mineralização líquida medida 105 dias após o início da incubação. Os comportamentos dos dois tipos de lodo foram similares, com taxa de mineralização inicial elevada. Os teores de amônio mantiveram-se baixos logo após o início da incubação até o final, com aumento linear nos teores de nitrato. Houve maior acúmulo de nitrato para as maiores doses aplicadas. O potencial de mineralização dos tratamentos, estimado pelo modelo exponencial simples, variou entre 58 e 284 mg kg-1 de N. Não houve efeito das quantidades de resíduos previamente aplicadas ao Latossolo sobre a fração de mineralização do N orgânico recentemente aplicado via lodo de esgoto, com confiabilidade de 95 %. Os resultados mostraram que, em reaplicações na mesma área, as doses de lodo de esgoto devem ser menores do que as doses calculadas para aplicação única, devido ao N residual acumulado no solo, tanto na forma orgânica quanto inorgânica.

Size effects in the magneto-optical response of Co nanoparticles

A study of the magneto-optical (MO) spectral response of Co nanoparticles embedded in MgO as a function of their size and concentration in the spectral range from 1.4 to 4.3 eV is presented. The nanoparticle layers were obtained by sputtering at different deposition temperatures. Transmission electron microscopy measurements show that the nanoparticles have a complex structure which consists of a crystalline core having a hexagonal close-packed structure and an amorphous crust. Using an effective-medium approximation we have obtained the MO constants of the Co nanoparticles. These MO constants are different from those of continuous Co layers and depend on the size of the crystalline core. We associate these changes with the size effect of the intraband contribution to the MO constants, related to a reduction of the relaxation time of the electrons into the nanoparticles.

Growth, optical characterization, and laser operation of a stoichiometric crystal KYb(WO4)(2)

We present our recent achievements in the growing and optical characterization of KYb(WO4)2 (hereafter KYbW) crystals and demonstrate laser operation in this stoichiometric material. Single crystals of KYbW with optimal crystalline quality have been grown by the top-seeded-solution growth slow-cooling method. The optical anisotropy of this monoclinic crystal has been characterized, locating the tensor of the optical indicatrix and measuring the dispersion of the principal values of the refractive indices as well as the thermo-optic coefficients. Sellmeier equations have been constructed valid in the visible and near-IR spectral range. Raman scattering has been used to determine the phonon energies of KYbW and a simple physical model is applied for classification of the lattice vibration modes. Spectroscopic studies (absorption and emission measurements at room and low temperature) have been carried out in the spectral region near 1 µm characteristic for the ytterbium transition. Energy positions of the Stark sublevels of the ground and the excited state manifolds have been determined and the vibronic substructure has been identified. The intrinsic lifetime of the upper laser level has been measured taking care to suppress the effect of reabsorption and the intrinsic quantum efficiency has been estimated. Lasing has been demonstrated near 1074 nm with 41% slope efficiency at room temperature using a 0.5 mm thin plate of KYbW. This laser material holds great promise for diode pumped high-power lasers, thin disk and waveguide designs as well as for ultrashort (ps/fs) pulse laser systems.

Influence of average size and interface passivation on the spectral emission of Si nanocrystals embedded in SiO2

The correlation between the structural (average size and density) and optoelectronic properties [band gap and photoluminescence (PL)] of Si nanocrystals embedded in SiO2 is among the essential factors in understanding their emission mechanism. This correlation has been difficult to establish in the past due to the lack of reliable methods for measuring the size distribution of nanocrystals from electron microscopy, mainly because of the insufficient contrast between Si and SiO2. With this aim, we have recently developed a successful method for imaging Si nanocrystals in SiO2 matrices. This is done by using high-resolution electron microscopy in conjunction with conventional electron microscopy in dark field conditions. Then, by varying the time of annealing in a large time scale we have been able to track the nucleation, pure growth, and ripening stages of the nanocrystal population. The nucleation and pure growth stages are almost completed after a few minutes of annealing time at 1100°C in N2 and afterward the ensemble undergoes an asymptotic ripening process. In contrast, the PL intensity steadily increases and reaches saturation after 3-4 h of annealing at 1100°C. Forming gas postannealing considerably enhances the PL intensity but only for samples annealed previously in less time than that needed for PL saturation. The effects of forming gas are reversible and do not modify the spectral shape of the PL emission. The PL intensity shows at all times an inverse correlation with the amount of Pb paramagnetic centers at the Si-SiO2 nanocrystal-matrix interfaces, which have been measured by electron spin resonance. Consequently, the Pb centers or other centers associated with them are interfacial nonradiative channels for recombination and the emission yield largely depends on the interface passivation. We have correlated as well the average size of the nanocrystals with their optical band gap and PL emission energy. The band gap and emission energy shift to the blue as the nanocrystal size shrinks, in agreement with models based on quantum confinement. As a main result, we have found that the Stokes shift is independent of the average size of nanocrystals and has a constant value of 0.26±0.03 eV, which is almost twice the energy of the Si¿O vibration. This finding suggests that among the possible channels for radiative recombination, the dominant one for Si nanocrystals embedded in SiO2 is a fundamental transition spatially located at the Si¿SiO2 interface with the assistance of a local Si-O vibration.

Magnetization reversal and magnetic anisotropies in epitaxial Fe/MgO and Fe/MgO/Fe heterostructures grown on Si(001)

Epitaxial Fe/MgO heterostructures have been grown on Si(001) by a combination of sputtering and laser ablation deposition techniques. The growth of MgO on Si(001) is mainly determined by the nature of the interface, with large lattice mismatch and the presence of an amorphous layer of unclear origin. Reflection high energy electron diffraction patterns of this MgO buffer layer are characteristic of an epitaxial, but disordered, structure. The structural quality of subsequent Fe and MgO layers continuously improves due to the better lattice match and the burial of defects. A weak uniaxial in-plane magnetic anisotropy is found superimposed on the expected cubic biaxial anisotropy. This additional anisotropy, of interfacial nature and often found in Fe/MgO and Fe/MgO/GaAs(001) systems, is less intense here due to the poorer MgO/Si interface quality compared with that of other systems. From the evolution of the anisotropy field with film thickness, magnetic anisotropy is also found to depend on the crystal quality. Kerr measurements of a Fe/MgO multilayered structure grown on Si show two different switching fields, suggesting magnetic coupling of two of the three Fe layers. Nevertheless, due to the little sensitivity to the bottom Fe film, independent switching of the three layers cannot be ruled out.

Influence of premetallization surface treatment on the formation of Schottky Au-nGaN contacts

The influence of premetallization surface preparation on the structural, chemical, and electrical properties of Au-nGaN interfaces has been investigated by x-ray photoemission spectroscopy (XPS), current-voltage measurement (I-V) and cross-section transmission electron microscopy (TEM). XPS analysis showed that the three GaN substrate treatments investigated i.e., ex situ hydrofluoric acid etch, in situ anneal in ultrahigh-vacuum (UHV), and in situ Ga reflux cleaning in UHV result in surfaces increasingly free of oxygen contamination. XPS and TEM characterization of Au-nGaN formed after the three premetallization surface treatments show that HF etching and UHV annealing produce abrupt, well-defined interfaces. Conversely, GaN substrate cleaning in a Ga flux results in Au/GaN intermixing. I-V characterization of Au¿nGaN contacts yields a Schottky barrier height of 1.25 eV with a very low-ideality factor and very good contact uniformity for the premetallization UHV anneal, while the Ga reflux cleaning results in a much lower barrier (0.85 eV), with poor ideality and uniformity. I-V and XPS results suggest a high density of acceptor states at the surface, which is further enhanced by UHV annealing. These results are discussed in the context of current models of Schottky barrier formation.