Photoluminescence of the Eu-doped thin film heterojunction GaAs/SnO2 and rare-earth doping distribution

Tin dioxide (SnO2) thin films doped with Eu3+, are deposited by the sol-gel-dip-coating process on top of GaAs films, which is deposited by resistive evaporation on glass substrate. This heterojunction assembly presents luminescence from the rare-earth ion, unlike the SnO2 deposition directly on a glass substrate, where emissions from the Eu3+ transitions are absent. The Eu3+ transitions are clearly identified and are similar to the observation on SnO2 pressed powder (pellets), thermally treated at much higher temperatures. However, in the form of heterojunction films, the Eu emission comes along a broad band, located at higher energy compared to Eu3+ transitions, which is blue-shifted as the thermal annealing temperature increases. The size of nanocrystallites points toward quantum confinement or electron transfer between oxygen vacancies, originated from the disorder in the material, and trivalent rare-earth ions, which present acceptor-like character in this matrix. This electron transfer may relax for higher temperatures in the case of pellets, and the broad band is eliminated.

Structural properties of cerium doped siloxane-PMMA hybrid coatings with high anticorrosive performance

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

Porous silica matrix obtained from pyrex class by hydrothermal treatment: Characterization and nature of the porosity

A novel porous silica matrix has been prepared from Pyrex glass, using hydrothermal treatment under saturated-steam condition. This process makes it possible to obtain, in one step, a silica support formed of a homogeneously distributed and interconnected macropore microstructure. The new matrix contains silanol groups that can be used in reactions of surface modification to provide a hybrid material and a selective macrofiltration membrane, and also it can improve chemical inertness. The porous matrix is noncrystalline as obtained and, after thermal treatment at temperatures higher than 950degreesC, exhibits an X-ray pattern characteristic of alpha-cristobalite and low volume contraction. The present samples were characterized by scanning electron microscopy, mercury intrusion porosimetry, nitrogen adsorption-desorption isotherms, infrared spectroscopy, X-ray powder diffractometry, atomic absorption, and high-resolution solid-state nuclear magnetic resonance. The results present a new way of producing a macroporous silica matrix.

Frequency upconversion involving triads and quartets of ions in a Pr3+/Nd3+ codoped fluoroindate glass

Frequency upconversion (UC) processes involving energy transfer (ET) among Nd 3+ and Pr 3+ ions in a fluoroindate glass are reported. In a first experiment, the excitation of Pr 3+ [transition 3H 4→ 1D 2] and of Nd 3+ [transition 4I 9/2→( 2G 7/2+ 4G 5/2)] was achieved with a dye laser operating in the 575-590 nm range. In a second experiment, the Nd 3+ ions were excited with the second harmonic of a Nd: YAG laser at 532 nm. The ET processes leading to UC in both experiments were studied by monitoring the blue fluorescence decay at 480 nm due to the transition 3P 0→ 3H 4 in Pr 3+. In the more relevant UC process, quartets of ions (Nd-Nd-Pr-Pr) are excited due to absorption of three laser photons by two Nd 3+ ions which transfer their energy to two Pr 3+ ions. Each Pr 3+ ion promoted to the 3P 0 level decays to the ground state emitting one photon in the blue region. This conclusion was achieved investigating the dependence of the UC fluorescence intensity as a function of laser intensity, samples concentrations, and temporal behavior of the UC signal. Other UC processes involving nonisoionic groups of three ions are also reported. © 2002 American Institute of Physics.

Evaluation of hollow fiberoptic tips for the conduction of Er : YAG laser

Objective: The use of Er:YAG laser operating in the 3 μm range with adjustable power and pulses has become popular for dental and medical practice due to its high photoablative capacity, surgical precision and antimicrobial action. Background data: The existing fiberoptic tips irradiate lasers parallel to the long axes of the tooth limiting its efficiency in the root canal. Methods: We evaluated hollow fiberoptic tips obtained from silicate glass as a means of Er:YAG laser conduction in dental procedures. The fiber tips were molded from capillary tubes with different profiles so that their ends would have cylindric, conical or spherical shapes. The performance of the three fibers as a means of propagation of Er:YAG (λ = 2.94 μm) laser radiation was compared to that of a solid sapphire fiber at 10 Hz and 200 mJ and of 20 Hz and 500 mJ. The profiles of frontal and lateral burning were visualized on thermal paper. Results: Analysis of these profiles demonstrated that the sapphire tip and the hollow fiber of cylindric section did not differ significantly in the profiles of frontal burning, and no lateral burning was detected. The fibers of the conical and spherical sections, although presenting attenuation in the frontal output power, showed a larger burning area in the frontal profile, in addition to producing lateral burning. Conclusions: The results indicate that commercial hollow fiberoptics have advantages such as easy manufacture of the different tip shapes, great adaptability, low cost, and a low loss of transmission. © Mary Ann Liebert, Inc.

Comparison among different pH values of Rhodamine B solution impregnated into mesoporous silica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural and Luminescence Properties of Silica-Based Hybrids Containing New Silylated-Diketonato Europium(III) Complex

A new betadiketonate ligand displaying a trimethoxysilyl group as grafting function and a diketone moiety as complexing site (TTA-Si = 4,4,4-trifluoro-2-(3-trimethoxysilyl)propyl)-1-3-butanedione (C4H3S)COCH[(CH2)(3)Si(OCH3)(3)]COCF3) and its highly luminescent europium(III) complex [Eu(TTA-Si)(3)] have been synthesized and fully characterized. Luminescent silica-based hybrids have been prepared as well with this new complex grafted on the surface of dense silica nanoparticles (28 +/- 3 nm) or on mesoporous silica particles. The covalent bonding of Eu(TTA-Si)(3) inside the core of uniform silica nanoparticles (40 +/- 5 nm) was also achieved. Luminescence properties are discussed in relation to the europium chemical environment involved in each of the three hybrids. The general methodology proposed allowed high grafting ratios and overcame chelate release and tendency to agglomeration, and it could be applied to any silica matrix (in the core or at the surface, nanosized or not, dense or mesoporous) and therefore numerous applications such as luminescent markers and luminophors could be foreseen.

Quantum critical scaling at a Bose-glass/superfluid transition: Theory and experiment for a model quantum magnet

In this paper we investigate the quantum phase transition from magnetic Bose Glass to magnetic Bose-Einstein condensation induced by amagnetic field in NiCl2 center dot 4SC(NH2)(2) (dichloro-tetrakis-thiourea-nickel, or DTN), doped with Br (Br-DTN) or site diluted. Quantum Monte Carlo simulations for the quantum phase transition of the model Hamiltonian for Br-DTN, as well as for site-diluted DTN, are consistent with conventional scaling at the quantum critical point and with a critical exponent z verifying the prediction z = d; moreover the correlation length exponent is found to be nu = 0.75(10), and the order parameter exponent to be beta = 0.95(10). We investigate the low-temperature thermodynamics at the quantum critical field of Br-DTN both numerically and experimentally, and extract the power-law behavior of the magnetization and of the specific heat. Our results for the exponents of the power laws, as well as previous results for the scaling of the critical temperature to magnetic ordering with the applied field, are incompatible with the conventional crossover-scaling Ansatz proposed by Fisher et al. [Phys. Rev. B 40, 546 (1989)]. However they can all be reconciled within a phenomenological Ansatz in the presence of a dangerously irrelevant operator.

The influence of SiO2 content on spectroscopic properties and laser emission efficiency of Yb3+-Er3+ co-doped calcium aluminosilicate glasses

We have studied the influence of SiO2 content on the spectroscopic properties and laser emission efficiency of Yb3+-Er3+ co-doped calcium aluminosilicate glasses. An increase in SiO2 content resulted in higher phonon energy, which reduced the up-conversion emission, enhanced the energy transfer efficiency up to 70 % from Yb3+ to Er3+, and enhanced the optical quality. All these results led to an increase from 20 to 30 % in the laser emission efficiency.

Infrared-to-visible upconversion emission in Er3+ doped TeO2-WO3-Bi2O3 glasses with silver nanoparticles

The influence of silver nanoparticles (NPs) on the frequency upconversion luminescence in Er3+ doped TeO2-WO3-Bi2O3 glasses is reported. The effect of the NPs on the Er3+ luminescence was controlled by appropriate heat-treatment of the samples. Enhancement up to 700% was obtained for the upconverted emissions at 527, 550, and 660 nm, when a laser at 980 nm is used for excitation. Since the laser frequency is far from the NPs surface plasmon resonance frequency, the luminescence enhancement is attributed to the local field increase in the proximity of the NPs and not to energy transfer from the NPs to the emitters as is usually reported. This is the first time that the effect is investigated for tellurite-tungstate-bismutate glasses and the enhancement observed is the largest reported for a tellurium oxide based glass. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4754468]

Microtensile bond strength of resin composite to dentin treated with Er:YAG laser of bleached teeth

The objective of this study was to evaluate the influence of Er:YAG laser (lambda = 2.94 mu m) on microtensile bond strength (mu TBS) and superficial morphology of bovine dentin bleached with 16% carbamide peroxide. Forty bovine teeth blocks (7 x 3 x 3 mm(3)) were randomly assigned to four groups: G1- bleaching and Er:YAG irradiation with energy density of 25.56 J/cm(2) (focused mode); G2 - bleaching; G3 - no-bleaching and Er:YAG irradiation (25.56 J/cm(2)); G4 - control, non-treated. G1 and G2 were bleached with 16% carbamide peroxide for 6 h during 21 days. Afterwards, all blocks were abraded with 320 to 600-grit abrasive papers to obtain flat standardized dentin surfaces. G1 and G3 were Er:YAG irradiated. Blocks were immediately restored with 4-mm-high composite resin (Adper Single Bond 2, Z-250-3 M/ESPE). After 24 h, the restored blocks (n = 9) were serially sectioned and trimmed to an hour-glass shape of approximately 1 mm(2) at the bonded interface area, and tested in tension in a universal testing machine (1 mm/ min). Failure mode was determined at a magnification of 100x using a stereomicroscope. One block of each group was selected for scanning electron microscope (SEM) analysis. mu TBS data was analyzed by two-way ANOVA and Tukey test (alpha = 0.05). Mean bond strengths (SD) in MPa were: G1- 32.7 (5.9)(A); G2- 31.1 (6.3)(A); G3- 25.2 (8.3)(B); G4- 36.7 (9.9).(A) Groups with different uppercase letters were significantly different from each other (p < .05). Enamel bleaching procedure did not affect mu TBS values for dentin adhesion. Er:YAG laser irradiation with 25.56 J/cm(2) prior to adhesive procedure of bleached teeth did not affect mu TBS at dentin and promoted a dentin surface with no smear layer and opened dentin tubules observed under SEM. On the other hand, Er:YAG laser irradiation prior to adhesive procedure of non-bleached surface impaired mu TBS compared to the control group.

Synthesis, characterization, optical absorption, luminescence and defect centres in Er3+ and Yb3+ co-doped MgAl2O4 phosphors

The Er3+-Yb3+ co-doped MgAl2O4 phosphor powders have been prepared by the combustion method. The phosphor powders are well characterized by X-ray diffraction (XRD) and energy dispersive (EDX) techniques. The absorption spectrum of Er3+/Er3+-Yb3+ doped/co-doped phosphor powder has been recorded in the UV-Vis-NIR region of the electro-magnetic spectrum. The evidence for indirect pumping under 980 nm excitation of Er3+ from Yb3+ was observed in the MgAl2O4 matrix material. Electron spin resonance (ESR) studies were carried out to identify the defect centres responsible for the thermally stimulated luminescence (TSL) process in MgAl2O4:Er3+ phosphor. Three defect centres were identified in irradiated phosphor by ESR measurements which were carried out at room temperature and these were assigned to an O- ion and F+ centres. O- ion (hole centre) appears to correlate with the low temperature TSL peak at 210 A degrees C and one of the F+ centres (electron centre) is related to the high temperature peak at 460 A degrees C.

Molekulardynamiksimulationen zur Untersuchung des Mischalkali-Effektes in silikatischen Gläsern

In der vorliegenden Arbeit wird mittels Molekulardynamik(MD)-Computersimulationen die Dynamik von verschiedenen Alkalisilikaten in der Schmelze und im Glas untersucht. Es ist bekannt, daß diese Systeme ionenleitend sind, was auf eine hohe Mobilität der Alkaliionen im Vergleich zu den glasbildenden Komponenten Si und O zurückzuführen ist. Im Mittelpunkt des Interesses steht der sog. Mischalkalieffekt (MAE), der in ternären Mischungen aus Siliziumdioxid mit zwei Alkalioxiden auftritt. Gegenüber Mischungen mit nur einer Alkaliionensorte weisen letztere Systeme eine signifikante Verlangsamung der Alkaliionendiffusion auf. Zunächst werden zwei binäre Alkalisilikate simuliert, nämlich Lithiumdisilikat (LS2) und Kaliumdisilikat (KS2). Die Simulationen zeigen, daß der Ursprung der hohen Mobilität der Alkaliionen in der Struktur begründet ist. KS2 und LS2 weisen auf intermediären Längenskalen Ordnung auf, die in partiellen statischen Strukturfaktoren durch Prepeaks reflektiert ist. Die den Prepeaks zugrundeliegende Struktur erklärt sich durch perkolierende Netzwerke aus alkalioxidreichen Kanälen, die als Diffusionskanäle für die mobilen Alkaliionen fungieren. In diesen Kanälen bewegen sich die Ionen mittels Sprüngen (Hopping) zwischen ausgezeichneten Plätzen. In der Simulation beobachtet man für die hohen Temperaturen (4000K>=1500K) eine ähnliche Aktivierungsenergie wie im Experiment. Im Experiment findet allerdings unterhalb von ca.1200K ein Crossover in ein Arrheniusverhalten mit höherer Aktivierungsenergie statt, welches von der Simulation nicht nachvollzogen wird. Das kann mit der in der Simulation nicht im Gleichgewicht befindlichen Si-O-Matrix erklärt werden, bei der Alterungseffekte beobachtet werden. Am stärksten ist der MAE für eine Alkalikomponente, wenn deren Konzentrationsanteil in einem ternären Mischalkalisystem gegen 0 geht. Daher wird ein LS2-System untersucht, in dem ein Li-Ion gegen ein K-Ion getauscht wird. Der Einfluß des K-Ions ist sowohl lokal in den charakteristischen Abständen zu den ersten nächsten Nachbarn (NN) zu sehen, als auch in der ortsaufgelösten Koordinationszahlverteilung bis zu Längenskalen von ca. 8,5 Angstrom. Die Untersuchung der Dynamik des eingesetzten K-Ions zeigt, daß die Sprungwahrscheinlichkeit nicht mit der Lokalisierung, einem Maß für die Bewegung eines Teilchens um seine Ruheposition, korreliert ist, aber daß eine chemische Umgebung mit wenig Li- und vielen O-NN oder vielen Li- und wenig O-NN ein Sprungereignis begünstigt. Zuletzt wird ein ternäres Alkalisilikat (LKS2) untersucht, dessen Struktur alle charakteristischen Längenskalen von LS2 und KS2 aufweist. Es stellt sich also eine komplexe Struktur mit zwei perkolierenden Subnetzwerken für Alkaliionen ein. Die Untersuchung der Dynamik zeigt eine geringe Wahrscheinlichkeit dafür auf, daß Ionen in ein Subnetzwerk andersnamiger Ionen springen. Auch kann gezeigt werden, daß das Modellpotential den MAE reproduzieren kann, daß also die Diffusionskonstanten in LKS2 bei bis zu einer Größenordnung langsamer sind als in KS2 bzw. LS2. Der beobachtete Effekt stellt sich zudem vom funktionalen Verlauf her so dar, wie er beim MAE erwartet wird. Es wurde auch festgestellt, daß trotz der zeitlichen Verzögerung in den dynamischen Größen die Anzahl der Sprünge pro Zeit nicht geringer ist und daß für niedrige Temperaturen (d.h.im Glas) Sprünge auf den Nachbarplatz mit anschließendem Rücksprung auf die vorherige Position deutlich wahrscheinlicher sind als bei hohen Temperaturen (also in der Schmelze). Die vorliegenden Resultate geben Aufschluß über die Details der Mechanismen mikroskopischer Ionenleitung in binären und ternären Alkalisilikaten sowie dem MAE.

Development of empirical potentials for amorphous silica

Development of empirical potentials for amorphous silica Amorphous silica (SiO2) is of great importance in geoscience and mineralogy as well as a raw material in glass industry. Its structure is characterized as a disordered continuous network of SiO4 tetrahedra. Many efforts have been undertaken to understand the microscopic properties of silica by classical molecular dynamics (MD) simulations. In this method the interatomic interactions are modeled by an effective potential that does not take explicitely into account the electronic degrees of freedom. In this work, we propose a new methodology to parameterize such a potential for silica using ab initio simulations, namely Car-Parrinello (CP) method [Phys. Rev. Lett. 55, 2471 (1985)]. The new potential proposed is compared to the BKS potential [Phys. Rev. Lett. 64, 1955 (1990)] that is considered as the benchmark potential for silica. First, CP simulations have been performed on a liquid silica sample at 3600 K. The structural features so obtained have been compared to the ones predicted by the classical BKS potential. Regarding the bond lengths the BKS tends to underestimate the Si-O bond whereas the Si-Si bond is overestimated. The inter-tetrahedral angular distribution functions are also not well described by the BKS potential. The corresponding mean value of theSiOSi angle is found to be ≃ 147◦, while the CP yields to aSiOSi angle centered around 135◦. Our aim is to fit a classical Born-Mayer/Coulomb pair potential using ab initio calculations. To this end, we use the force-matching method proposed by Ercolessi and Adams [Europhys. Lett. 26, 583 (1994)]. The CP configurations and their corresponding interatomic forces have been considered for a least square fitting procedure. The classical MD simulations with the resulting potential have lead to a structure that is very different from the CP one. Therefore, a different fitting criterion based on the CP partial pair correlation functions was applied. Using this approach the resulting potential shows a better agreement with the CP data than the BKS ones: pair correlation functions, angular distribution functions, structure factors, density of states and pressure/density were improved. At low temperature, the diffusion coefficients appear to be three times higher than those predicted by the BKS model, however showing a similar temperature dependence. Calculations have also been carried out on crystalline samples in order to check the transferability of the potential. The equilibrium geometry as well as the elastic constants of α-quartz at 0 K are well described by our new potential although the crystalline phases have not been considered for the parameterization. We have developed a new potential for silica which represents an improvement over the pair potentials class proposed so far. Furthermore, the fitting methodology that has been developed in this work can be applied to other network forming systems such as germania as well as mixtures of SiO2 with other oxides (e.g. Al2O3, K2O, Na2O).

Microbiologic results after non-surgical erbium-doped:yttrium, aluminum, and garnet laser or air-abrasive treatment of peri-implantitis: a randomized clinical trial

The purpose of this study is to assess clinical and microbiologic effects of the non-surgical treatment of peri-implantitis lesions using either an erbium-doped:yttrium, aluminum, and garnet (Er:YAG) laser or an air-abrasive subgingival polishing method.