Sebastian Krolikowski

Luminescence from Bi2+-activated alkali earth borophosphates for white LEDs.

Bi(2+)-doped MBPO(5) (M = Ba(2+), Sr(2+), Ca(2+)), synthesized in air via solid state reaction, are considered as novel orange and red phosphors for white light emitting diodes with improved colour quality. Absorption of Bi(2+) due to (2)P(1/2)-->(2)S(1/2) and (2)P(1/2)-->(2)P(3/2) could be observed and quantified. Excitation to (2)P(3/2) is accompanied by vibronic sidebands, and corresponding emission behaviour is found. The electron-phonon coupling strength increases in the order M = Ba(2+)-->Sr(2+)-->Ca(2+). In the case of MBPO(5):Bi(2+), one-, two- and even three-phonon sidebands could clearly be observed. The crystal structure of all three compounds belongs to space group P3(1)21. Bi(2+) is incorporated on M(2+) sites, and reduction of Bi(3+) to Bi(2+) occurs for reasons of charge compensation. In accordance with crystallographic data, fluorescence decay behaviour indicates that only one type of Bi(2+)-emission centers is present.

Intense red photoluminescence from Mn 2+ -doped (Na + ; Zn 2+ ) sulfophosphate glasses and glass ceramics as LED converters

We report on intense red fluorescence from Mn(2+)-doped sulfophosphate glasses and glass ceramics of the type ZnO-Na(2)O-SO(3)-P(2)O(5). As a hypothesis, controlled internal crystallization of as-melted glasses is achieved on the basis of thermally-induced bimodal separation of an SO(3)-rich phase. Crystal formation is then confined to the relict structure of phase separation. The whole synthesis procedure is performed in air at <or= 800 degrees C. Electron spin resonance and Raman spectroscopy indicate that Mn(2+) species are incorporated on Zn(2+) sites with increasingly ionic character for increasing concentration. Correspondingly, in the glasses, increasing MnO content results in decreasing network polymerization. Stable glasses and continuously increasing emission intensity are observed for relatively high dopant concentration of up to 3 mol.%. Recrystallization of the glass results in strongly increasing emission intensity. Dynamic emission spectroscopy reveals only on type of emission centers in the glassy material, whereas three different centers are observed in the glass ceramic. These are attributed to octahedrally coordinated Mn(2+) in the residual glass phase and in crystalline phosphate and sulfate lattices, respectively. Relatively low crystal field strength results in almost ideal red emission, peaking around 625 nm. Excitation bands lie in the blue-to-green spectral range and exhibit strong overlap. The optimum excitation range matches the emission properties of GaN- and InGaN-based light emitting devices.

Structural heterogeneity and pressure-relaxation in compressed borosilicate glasses by in situ small angle X-ray scattering

We report on Brillouin and in situ small angle X-ray scattering (SAXS) analyses of topological heterogeneity in compressed sodium borosilicate glasses. SAXS intensity extrapolated to very low angular regimes, I(q = 0), is related to compressibility. From Brillouin scattering and analyses of the elastic properties of the glass, the Landau-Placzek ratio is determined and taken as a direct reflection of the amplitude of frozen-in density fluctuations. It is demonstrated that with increasing fictive pressure, topological (mid- and long-range) homogeneity of the glass increases significantly. Heating and cooling as well as isothermal scans were performed to follow the evolution of density fluctuations upon pressure recovery. For a sample with a fictive pressure p(f) of 470 MPa, complete recovery to p(f) = 0.1 MPa was observed to occur close to the glass transition temperature. The values of fictive and apparent fictive temperature, respectively, as obtained via the intersection method from plots of I(q = 0) vs. temperature were found in good agreement with previous calorimetric analyses. Isothermal scans suggest that mid- and long-range recovery govern macroscopic density relaxation.

Europium partitioning, luminescence re-absorption and quantum efficiency in (Sr,Ca) åkermanite–feldspar bi-phasic glass ceramics

We report on partitioning of europium in bi-phasic akermanite–feldspar glass ceramics with broadly tunable photoluminescence. Conditions for precipitating Eu-doped microcrystalline (Sr,Ca)-akermanite from supercooled liquids of the type MO–B2O3–SiO2–Al2O3 (M = Mg, Ca and Sr) were evaluated. Formation of secondary anorthite and slawsonite feldspar is controlled by chemical composition and crystallization kinetics. Eu2+ precipitates on Sr2+ and, to a lesser extent, on Ca2+ sites. Static and dynamic Eu2+ luminescence spectroscopy and spatially resolved cathodoluminescence spectroscopy are used to explore the distribution of europium between crystallite species and the residual glass phase. It was found that akermanite precipitation occurs congruently with respect to Sr and Ca partitioning for liquids with Sr/(Sr + Ca) ≥ 0.4. Due to kinetic selection, the Ca-rich side of the (Ca,Sr)2MgSi2O7 solid solution is favored and less strontium is incorporated into the crystal phase relative to the precursor material for liquids with lower strontium content, meaning that strontium enriches in the residual glass phase. Using a selective etching process, the crystalline feldspar phase was separated from the residual glass and akermanite phases, respectively. In this way, the spectroscopic contributions of each phase could be distinguished from each other, clarifying the problem of external quantum efficiency of photoluminescence and re-absorption in glass ceramics relative to the spectroscopic properties of pure crystals.

Relaxation and Prigogine-Defay ratio of compressed glasses with negative viscosity-pressure dependence.

Differential scanning calorimetry and density measurements were employed to study relaxation processes in compressed NaAlSi(3)O(8) and Na(0.34)Ca(0.31)Al(0.96)Si(3.04)O(8) glasses with negative dependence of viscosity (eta) on pressure (p). Isobaric configurational heat capacities, coefficients of thermal expansion and compressibility of the melts, and real and apparent fictive temperatures are reported for the pressure regime from 0.1 to 700 MPa and cooling rates from 0.1 to 400 K/min. The onset of glass transition, measured on the compressed glass under normal pressure, is found to shift with increasing pressure of freezing in accordance with in situ viscosity data. Based on the pressure-derivative of the compression-induced excess enthalpy (or apparent fictive temperature), a condition for which a negative dependence of fictive temperature on pressure occurs is developed. It is further shown that in this case, also d eta/d p is negative. We suggest that in the region of glass transition, glasses with large Prigogine-Defay (PD) ratio have a high probability to also exhibit a negative dependence of viscosity on pressure. However, the criterion cannot be applied inversely: particularly glasses with a high sensitivity of short-range structural parameters to pressure may exhibit a relatively low PD ratio, but negative d eta/d p.