Fundamental research on the luminescence of solids. Final report January 1, 1947-July 15, 1949.

At head of title: Office of Naval Research. Contract no. N7onr-284, Task order no. 1"

Sol-gel combustion synthesis and luminescence Of Y4Al2O9 : Eu3+ nanocrystal

Y4Al2O9:EU3+ phosphor was synthesized through a sol-gel combustion method. The Y4Al2O9 phase can form through sintering at 800 degrees C. This temperature is much lower than that required via the solid state reaction method. The average grain size of the phosphor was about 30 run. Compared with the amorphous phosphor, the charge transfer band of crystalline phosphor shows a blue shift. The emission Of Y4Al2O9:Eu3+ indicates the existence of two luminescent centers, in agreement with the crystal structure of Y4Al2O9. Higher doping concentration could be realized in Y4Al2O9 nanocrystal host lattice. This indicates that the sol-gel combustion synthesis method can increase emission intensity and quenching concentration due to a good distribution of EU3+ activators in Y4Al2O9 host. (c) 2005 Elsevier B.V. All rights reserved.

New color centers and photostimulated luminescence of BaFCl : Eu2+

Three new absorption bands, appearing around 670, 865 and 980 nm, are observed in BaFCl:Eu2+ phosphors. They are ascribed to F aggregates formed by association of F centers or by trapping of electrons to the primary F-n(+) (n = 2,3,4) centers. The growth curves of F and F-aggregated centers are similar and may be divided into three stages. The photostimulated luminescence (PSL) decays by stimulation into the absorption bands of F centers and of F aggregates are different; the former decay logarithmically and the latter decay hyperbolically. Some non-radiative processes related to F aggregates, such as electron migration, occur accompanying the PSL process, which may reduce the PSL efficiency and sensitivity of the phosphors. (C) 1997 Published by Elsevier Science Ltd. All rights reserved.

XAFS at Eu-L-3 edge and UV-VUV excited luminescence of europium doped strontium borophosphate prepared in air

The local structure and the valences of europium in SrBPO5:Eu prepared in air were checked by means of XAFS at Eu-L-3 edge. From the EXAFS results, it was discovered that the doped europium atoms were nine-coordinated by oxygen atoms and the distances of bond Eu-O were 2.42 Angstrom in the host. From the XANES data, it was found that the divalent and trivalent europium coexisted in the matrix. The emission spectra excited by VUV or UV exhibited a prominent broad band due to the 4f(6)5d-4f(7) transition of Eu2+ ions, which indicated that the trivalent europium ions were reduced in air in the matrix at high temperature by the defects [V-Sr]" formed by aliovalent substitution between Sr2+ and Eu3+ ions. The VUV excitation spectra in 100-200 nm range showed that the matrix had absorption bands with the maxima at about 130 and 150 nm, respectively.

Luminescence of uranium-doped strontium tetraborate (SrB4O7)

The luminescence and excitation spectra of uranium doped into strontium berate, SrB4O7:U, are reported. The emission spectrum is similar to the structureless green ''uranate' luminescence. The excitation spectrum is assigned to transitions from oxygen-derived orbitals to uranium 5f and 6d orbitals. (C) 1997 Elsevier Science Ltd. All rights reserved.

Role of structural saturation and geometry in the luminescence of silicon-based nanostructured materials

The structural saturation and stability, the energy gap, and the density of states of a series of small, silicon-based clusters have been studied by means of the PM3 and some ab initio (HF/6-31G* and 6-311++G**, CIS/6-31G* and MP2/6-31G*) calculations. It is shown that in order to maintain a stable nanometric and tetrahedral silicon crystallite and remove the gap states, the saturation atom or species such as H, F, Cl, OH, O, or N is necessary, and that both the cluster size and the surface species affect the energetic distribution of the density of states. This research suggests that the visible luminescence in the silicon-based nanostructured material essentially arises from the nanometric and crystalline silicon domains but is affected and protected by the surface species, and we have thus linked most of the proposed mechanisms of luminescence for the porous silicon, e.g., the quantum confinement effect due to the cluster size and the effect of Si-based surface complexes.

Effect of the ytterbium concentration on the upconversion luminescence of Yb3+/Er3+ co-doped PbO-GeO2-Ga2O3 glasses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study of Hybrid Silica-Polyethyleneglycol Xerogels by Eu3+ Luminescence Spectroscopy

Good optical quality Eu3+-doped silica-polyethyleneglycol hybrids were prepared by the sol-gel process. Thermomechanical analysis showed an increase of the glass transition temperature, due to the stiffness of the polymeric network, as the amount of Eu3+ increased. Europium luminescent properties were used to study structural evolution during the sol-gel transition. For lower doping concentrations dried gels present statistical distributions of Eu3+, typical of an amorphous environment, while for higher concentrations a crystalline-like environment of Eu3+ was observed. A broad emission band was observed in the visible part of the electromagnetic spectrum and assigned to the intrinsic emission from the hybrid polymeric network.

Influence of physical and chemical properties of solids on heavy metal adsorption

Partition of heavy metals between particulate and dissolve fraction of stormwater primarily depends on the adsorption characteristics of solids particles. Moreover, the bioavailability of heavy metals is also influenced by the adsorption behaviour of solids. However, due to the lack of fundamental knowledge in relation to the heavy metals adsorption processes of road deposited solids, the effectiveness of stormwater management strategies can be limited. The research study focused on the investigation of the physical and chemical parameters of solids on urban road surfaces and, more specifically, on heavy metal adsorption to solids. Due to the complex nature of heavy metal interaction with solids, a substantial database was generated through a series of field investigations and laboratory experiments. The study sites for the build-up pollutant sample collection were selected from four urbanised suburbs located in a major river catchment. Sixteen road sites were selected from these suburbs and represented typical industrial, commercial and residential land uses. Build-up pollutants were collected using a wet and dry vacuum collection technique which was specially designed to improve fine particle collection. Roadside soil samples were also collected from each suburb for comparison with the road surface solids. The collected build-up solids samples were separated into four particle size ranges and tested for a range of physical and chemical parameters. The solids build-up on road surfaces contained a high fraction (70%) of particles smaller than 150ìm, which are favourable for heavy metal adsorption. These solids particles predominantly consist of soil derived minerals which included quartz, albite, microcline, muscovite and chlorite. Additionally, a high percentage of amorphous content was also identified in road deposited solids. In comparing the mineralogical data of surrounding soil and road deposited solids, it was found that about 30% of the solids consisted of particles generated from traffic related activities on road surfaces. Significant difference in mineralogical composition was noted in different particle sizes of build-up solids. Fine solids particles (<150ìm) consisted of a clayey matrix and high amorphous content (in the region of 40%) while coarse particles (>150ìm) consisted of a sandy matrix at all study sites, with about 60% quartz content. Due to these differences in mineralogical components, particles larger than and smaller than 150ìm had significant differences in their specific surface area (SSA) and effective cation exchange capacity (ECEC). These parameters, in turn, exert a significant influence on heavy metal adsorption. Consequently, heavy metal content in >150ìm particles was lower than in the case of fine particles. The particle size range <75ìm had the highest heavy metal content, corresponding with its high clay forming minerals, high organic matter and low quartz content which increased the SSA, ECEC and the presence of Fe, Al and Mn oxides. The clay forming minerals, high organic matter and Fe, Al and Mn oxides create distinct groups of charge sites on solids surfaces and exhibit different adsorption mechanisms and bond strength, between heavy metal elements and charge sites. Therefore, the predominance of these factors in different particle sizes leads to different heavy metal adsorption characteristics. Heavy metals show preference for association with clay forming minerals in fine solids particles, whilst in coarse particles heavy metals preferentially associate with organic matter. Although heavy metal adsorption to amorphous material is very low, the heavy metals embedded in traffic related materials have a potential impact on stormwater quality.Adsorption of heavy metals is not confined to an individual type of charge site in solids, whereas specific heavy metal elements show preference for adsorption to several different types of charge sites in solids. This is attributed to the dearth of preferred binding sites and the inability to reach the preferred binding sites due to competition between different heavy metal species. This confirms that heavy metal adsorption is significantly influenced by the physical and chemical parameters of solids that lead to a heterogeneity of surface charge sites. The research study highlighted the importance of removal of solids particles from stormwater runoff before they enter into receiving waters to reduce the potential risk posed by the bioavailability of heavy metals. The bioavailability of heavy metals not only results from the easily mobile fraction bound to the solids particles, but can also occur as a result of the dissolution of other forms of bonds by chemical changes in stormwater or microbial activity. Due to the diversity in the composition of the different particle sizes of solids and the characteristics and amount of charge sites on the particle surfaces, investigations using bulk solids are not adequate to gain an understanding of the heavy metal adsorption processes of solids particles. Therefore, the investigation of different particle size ranges is recommended for enhancing stormwater quality management practices.

Role of solids in heavy metals build-up on urban road surfaces

Solids are widely identified as a carrier of harmful pollutants in stormwater runoff exerting a significant risk to receiving waters. This paper outlines the findings of an in-depth investigation on heavy metal adsorption to solids surfaces. Pollutant build-up samples collected from sixteen road sites in residential, industrial and commercial land uses were separated into four particle size ranges and analysed for a range of physico-chemical parameters and nine heavy metals including Iron (Fe), Aluminum (Al), Lead (Pb), Zinc (Zn), Cadmium (Cd), Chromium (Cr), Manganese (Mn), Nickel (Ni) and Copper (Cu). High specific surface area (SSA) and total organic carbon (TOC) content in finer particle size ranges was noted, thus confirming strong correlations with heavy metals. Based on their physico-chemical characteristics, two different types of solids originating from traffic and soil sources were identified. Solids generated by traffic were associated with high loads of heavy metals such as Cd and Cr with strong correlation with SSA. This suggested the existence of surface dependent bonds such as cation exchange between heavy metals and solids. In contrast, Fe, Al and Mn which can be attributed to soil inputs showed strong correlation with TOC suggesting strong bonds such as chemsorption. Zn was found to be primarily attached to solids by bonding with the oxides of Fe, Al and Mn. The data analysis also confirmed the predominance of the finer fraction, with 70% of the solids being finer than 150 µm and containing 60% of the heavy metal pollutant load.

Study of electron states of solids by techniques of electron spectroscopy

Studies of valence bands and core levels of solids by photoelectron spectroscopy are described at length. Satellite phenomena in the core level spectra have been discussed in some detail and it has been pointed out that the intensity of satellites appearing next to metal and ligand core levels critically depends on the metal-ligand overlap. Use of photoelectron spectroscopy in investigating metal-insulator transitions and spin-state transitions in solids is examined. It is shown that relative intensities of metal Auger lines in transition metal oxides and other systems provide valuable information on the valence bands. Occurrence of interatomic Auger transitions in competition with intraatomic transitions is discussed. Applications of electron energy loss spectroscopy and other techniques of electron spectroscopy in the study of gas-solid interactions are briefly presented.

Studies of Solids and Surfaces by Auger Electron Spectroscopy

Although the applications of Auger electron spectroscopy in surface analysis have by far outweighed its use as a tool to investigate electron states of solids and surfaces, there are a variety of situations where Auger spectroscopy provides unique information. Apart from the chemical shifts, Auger intensities are useful in determining the number of d-electron states in transition metal systems. Auger spectroscopy is a good probe to investigate the surface oxidation of metals. In addition to the intra-atomic Auger transitions, inter-atomic transitions observed in oxides and other systems reveal the nature of electron states of surfaces. Charge-transfer and hybridization effects in alloys are also usefully studied by Auger spectroscopy. Auger electron spectroscopy has not been a popular technique to investigate adsorption of molecules on surfaces, but the technique is useful to obtain fingerprints of surface species.