Very Intense Distinct Blue and Red Photoluminescence Emission in MgTiO3 Thin Films Prepared by the Polymeric Precursor Method: An Experimental and Theoretical Approach

MgTiO3 (MTO) thin films were prepared by the polymeric precursor method with posterior spin-coating deposition. The films were deposited on Pt(111)/Ti/SiO2/Si(100) substrates and heat treated at 350 degrees C for 2 h and then heat treated at 400, 450, 500, 550, 600, 650 and 700 C for 2 h. The degree of structural order disorder, optical properties, and morphology of the MTO thin films were investigated by X-ray diffraction (XRD), micro-Raman spectroscopy (MR), ultraviolet-visible (UV-vis) absorption spectroscopy, photoluminescence (PL) measurements, and field-emission gun scanning electron microscopy (FEG-SEM) to investigate the morphology. XRD revealed that an increase in the annealing temperature resulted in a structural organization of MTO thin films. First-principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and disordered asymmetric models. The electronic properties were analyzed, and the relevance of the present theoretical and experimental results was discussed in the light of PL behavior. The presence of localized electronic levels and a charge gradient in the band gap due to a break in the symmetry are responsible for the PL in disordered MTO lattice.

The aplication of land use and nighttime lights on the development of high-resolution emission inventories for South America

In this paper, nighttime light data are suggested as a proxy for spatial distribution of vehicles running in urban and nearby areas. Nighttime lights focus on human activities, in contrast to traditional Earth observing systems that focus on natural systems. It is the human activity being visible in the form of brightness of nocturnal lights. Two available nighttime lights dataset were used in this work. The first one was provided by the U.S. Air Force Defense Meteorological Satellite Program (DMSP) Operational Linescan System (OLS), henceforth, DMSO-OLS. The second one is the NASA-NOAA Suomi National Polar-orbiting Polar-orbiting Partnership (NPP) satellite, henceforth, Suomi-NPP. To validate the new proposed methodology, hundreds of urban areas of South America were analyzed in a high degree of resolution. The results of this study showed that night-time lights are very well correlated with vehicle fleet, population, and impervious surfaces but with strong spatial variability. The results of this study suggest a better understanding of the human activities in the context of a vehicular-based city conception.

Spectroscopic investigation and heat generation of Yb3+/Ho3+ codoped aluminosilicate glasses looking for the emission at 2 μm

Energy transfer (ET) and heat generation processes in Yb3+/Ho3+-codoped low-silica calcium aluminosilicate glasses were investigated using thermal lens (TL) and photoluminescence measurements looking for the emission around 2.0 μm. Stepwise ET processes from Yb3+ to Ho3+, upon excitation at 0.976 μm, produced highly efficient emission in the mid-infrared range at around 2.0 μm, with high fluorescence quantum efficiency (η1 ∼ 0.85 and independent of Ho3+ concentration) and relatively very low thermal loading (<0.4) for concentration up to 1.5% of Ho2O3. An equation was deduced for the description of the TL results that provided the absolute value of η1 and the number of emitted photons at 2.0 μm per absorbed pump photon by the Yb3+ ions, the latter reaching 60% for the highest Ho3+ concentration. These results suggest that the studied codoped system would be a promising candidate for the construction of photonic devices, especially for medical applications.

Efficient 1535 nm light emission from an all-Si-based optical micro-cavity containing Er3+ and Yb3+ ions

This work reports on the construction and spectroscopic analyses of optical micro-cavities (OMCs) that efficiently emit at ~1535 nm. The emission wavelength matches the third transmission window of commercial optical fibers and the OMCs were entirely based on silicon. The sputtering deposition method was adopted in the preparation of the OMCs, which comprised two Bragg reflectors and one spacer layer made of either Er- or ErYb-doped amorphous silicon nitride. The luminescence signal extracted from the OMCs originated from the 4I13/2→4I15/2 transition (due to Er3+ ions) and its intensity showed to be highly dependent on the presence of Yb3+ ions.According to the results, the Er3+-related light emission was improved by a factor of 48 when combined with Yb3+ ions and inserted in the spacer layer of the OMC. The results also showed the effectiveness of the present experimental approach in producing Si-based light-emitting structures in which the main characteristics are: (a) compatibility with the actual microelectronics industry, (b) the deposition of optical quality layers with accurate composition control, and (c) no need of uncommon elements-compounds nor extensive thermal treatments. Along with the fundamental characteristics of the OMCs, this work also discusses the impact of the Er3+-Yb3+ ion interaction on the emission intensity as well as the potential of the present findings.

Multiwavelenght study of cluster mergers and consequences for the radio emission properties of galaxy clusters

In the present thesis a thourough multiwavelength analysis of a number of galaxy clusters known to be experiencing a merger event is presented. The bulk of the thesis consists in the analysis of deep radio observations of six merging clusters, which host extended radio emission on the cluster scale. A composite optical and X–ray analysis is performed in order to obtain a detailed and comprehensive picture of the cluster dynamics and possibly derive hints about the properties of the ongoing merger, such as the involved mass ratio, geometry and time scale. The combination of the high quality radio, optical and X–ray data allows us to investigate the implications of the ongoing merger for the cluster radio properties, focusing on the phenomenon of cluster scale diffuse radio sources, known as radio halos and relics. A total number of six merging clusters was selected for the present study: A3562, A697, A209, A521, RXCJ 1314.4–2515 and RXCJ 2003.5–2323. All of them were known, or suspected, to possess extended radio emission on the cluster scale, in the form of a radio halo and/or a relic. High sensitivity radio observations were carried out for all clusters using the Giant Metrewave Radio Telescope (GMRT) at low frequency (i.e. ≤ 610 MHz), in order to test the presence of a diffuse radio source and/or analyse in detail the properties of the hosted extended radio emission. For three clusters, the GMRT information was combined with higher frequency data from Very Large Array (VLA) observations. A re–analysis of the optical and X–ray data available in the public archives was carried out for all sources. Propriety deep XMM–Newton and Chandra observations were used to investigate the merger dynamics in A3562. Thanks to our multiwavelength analysis, we were able to confirm the existence of a radio halo and/or a relic in all clusters, and to connect their properties and origin to the reconstructed merging scenario for most of the investigated cases. • The existence of a small size and low power radio halo in A3562 was successfully explained in the theoretical framework of the particle re–acceleration model for the origin of radio halos, which invokes the re–acceleration of pre–existing relativistic electrons in the intracluster medium by merger–driven turbulence. • A giant radio halo was found in the massive galaxy cluster A209, which has likely undergone a past major merger and is currently experiencing a new merging process in a direction roughly orthogonal to the old merger axis. A giant radio halo was also detected in A697, whose optical and X–ray properties may be suggestive of a strong merger event along the line of sight. Given the cluster mass and the kind of merger, the existence of a giant radio halo in both clusters is expected in the framework of the re–acceleration scenario. • A radio relic was detected at the outskirts of A521, a highly dynamically disturbed cluster which is accreting a number of small mass concentrations. A possible explanation for its origin requires the presence of a merger–driven shock front at the location of the source. The spectral properties of the relic may support such interpretation and require a Mach number M < ∼ 3 for the shock. • The galaxy cluster RXCJ 1314.4–2515 is exceptional and unique in hosting two peripheral relic sources, extending on the Mpc scale, and a central small size radio halo. The existence of these sources requires the presence of an ongoing energetic merger. Our combined optical and X–ray investigation suggests that a strong merging process between two or more massive subclumps may be ongoing in this cluster. Thanks to forthcoming optical and X–ray observations, we will reconstruct in detail the merger dynamics and derive its energetics, to be related to the energy necessary for the particle re–acceleration in this cluster. • Finally, RXCJ 2003.5–2323 was found to possess a giant radio halo. This source is among the largest, most powerful and most distant (z=0.317) halos imaged so far. Unlike other radio halos, it shows a very peculiar morphology with bright clumps and filaments of emission, whose origin might be related to the relatively high redshift of the hosting cluster. Although very little optical and X–ray information is available about the cluster dynamical stage, the results of our optical analysis suggest the presence of two massive substructures which may be interacting with the cluster. Forthcoming observations in the optical and X–ray bands will allow us to confirm the expected high merging activity in this cluster. Throughout the present thesis a cosmology with H0 = 70 km s−1 Mpc−1, m=0.3 and =0.7 is assumed.

Planktonic potential CO2 emission calculation: preliminary results by applying an adapted enzymatic methodology to marine ecosystems

[EN]Isocitrate Dehydrogenase (IDH) is a key enzyme in the Krebs cycle, being responsible for the production of one of the three CO2 molecules related to cellular respiration. In order to measure the potential CO2 production linked to the marine planktonic community we have adapted an enzymatic methodology. Preliminary results show that different proportions of autotrophs, heterotrophs and mixotrophs and their metabolic pathways, lead to different relationships between potential CO2 emission and potential O2 consumption during cellular respiration. Although more experiments need to be made, this methodology is leading to a better understanding of cellular respiration in marine samples and their impact on the food chain, vertical Carbon flux and the current sequestering capacity for anthropogenic CO2.

Quantitative Aspekte der Anziehungskraft von Straßenbeleuchtungen auf die Emergenz aus nahegelegenen Gewässern (Ephemeroptera, Plecoptera, Trichoptera, Diptera: Simuliidae, Chironomidae, Empididae) unter Berücksichtigung der spektralen Emission ve

Beim Beobachten von nächtlichen Insektenschwärmen an Straßenbeleuchtungen kommt es zur Frage, inwieweit von einer Bedrohung eines geordneten Naturkreislaufes durch dieses Phänomen gesprochen werden kann. Am Beispiel der bedrohten Artenvielfalt aquatischer Insekten im Bereich anthropogen bedingt verschmutzter Fließgewässer wurde die Problematik umfassend untersucht. Die Freilandtests erstreckten sich von Sommer 1998 bis Sommer 2000. Die vorliegende Arbeit geht mehreren Fragestellungen nach:1. - Wie hoch ist der Anteil aquatischer Insekten, der von dem Ort seiner Emergenz aus von einer naheliegenden Straßenlaterne angezogen wird ?2. - Welcher Lampentyp lockt weniger Insekten an: OSRAM HQL (Weiß-Mischlicht) oder PHILIPPS SON (gelbes Licht) ?3. - Welche Wellenlängenbereiche des Lichts sind beim Anflug an die Lampe von besonderer Präferenz ? zu 1. - Aquatische Insekten wiesen kein einheitliches Verhalten im Anflug an künstliches Licht auf. In den Sommermonaten kam es bei einigen Insektengruppen, wie z.B. den Trichopteren, zu einem massenhaften Anflug an die eine, im Untersuchungsgebiet aufgestellte Straßenlaterne. In dieser Zeit ergaben sich im Mittelwert Fangzahlen in einer Nacht am Licht, die der Emergenz von 25 Metern Bachufer/72 Stunden entsprachen. Bei den Dipteren ergab der mittlere Wert eine Emergenz von knapp 10 Metern Uferlänge/72 Stunden. Aufgrund hoher Fangzahlen konnten folgende Ergebnisse auf Artniveau bei den Chironomiden erzielt werden. Bei den zehn häufigsten Arten aus Emergenz und Lichtfang zeigten sich starke Schwankungen: Der Fang am Licht entsprach im Maximum einer Schlupfrate von 61 Metern Ufer/ 72 Stunden bei einer Art, bei einer anderen Art wurde z.B. ein Lichtfang erzielt, der lediglich die Emergenz von 0,3 Metern/72 Stunden umfaßte.zu 2. - In dem ohne Lichtkonkurrenz stattfindenden Vergleich zwischen PHILIPPS SON 70W und OSRAM HQL 125W ergab sich eine Fangrelation von 1:1,6 (SON:HQL). Bei einem Parallelfang (30 Metern Abstand der Leuchten) mit SON/HQL flogen wesentlich mehr Tiere an die HQL: Hier betrug die Relation 1:3,97 (SON:HQL). Es fand somit bei Lichtkonkurrenz eine Abwanderung der Insekten zur 'attraktiveren' Lampe statt.zu 3. - Zuletzt wurde die Anlockwirkung dreier Farbspektren mit den Intensitätsmaxima einer Wellenlänge von 437nm, 579nm und 599nm getestet. 437nm war die in der HQL gemessene Intensitätsspitze im niedrigwelligen Bereich und nach verbreiteter Auffassung von besonderer Anlockwirkung. Der Wellenlängenbereich um 579nm stellte das Intensitätsmaximum der SON-Lampe dar (gelbes Licht); 599nm war als Alternative für anlockschwache Beleuchtungen ausgewählt worden. Hier ergab sich bei abwechselndem Fang (ohne Lichtkonkurrenz) eine Fangrelation von 1,8 : 3,4 : 1 (437nm : 579nm : 599nm).

Development of the optimal estimation method for inversion of stratospheric emission spectra and validation of HNO3 profiles

This doctoral thesis focuses on ground-based measurements of stratospheric nitric acid (HNO3)concentrations obtained by means of the Ground-Based Millimeter-wave Spectrometer (GBMS). Pressure broadened HNO3 emission spectra are analyzed using a new inversion algorithm developed as part of this thesis work and the retrieved vertical profiles are extensively compared to satellite-based data. This comparison effort I carried out has a key role in establishing a long-term (1991-2010), global data record of stratospheric HNO3, with an expected impact on studies concerning ozone decline and recovery. The first part of this work is focused on the development of an ad hoc version of the Optimal Estimation Method (Rodgers, 2000) in order to retrieve HNO3 spectra observed by means of GBMS. I also performed a comparison between HNO3 vertical profiles retrieved with the OEM and those obtained with the old iterative Matrix Inversion method. Results show no significant differences in retrieved profiles and error estimates, with the OEM providing however additional information needed to better characterize the retrievals. A final section of this first part of the work is dedicated to a brief review on the application of the OEM to other trace gases observed by GBMS, namely O3 and N2O. The second part of this study deals with the validation of HNO3 profiles obtained with the new inversion method. The first step has been the validation of GBMS measurements of tropospheric opacity, which is a necessary tool in the calibration of any GBMS spectra. This was achieved by means of comparisons among correlative measurements of water vapor column content (or Precipitable Water Vapor, PWV) since, in the spectral region observed by GBMS, the tropospheric opacity is almost entirely due to water vapor absorption. In particular, I compared GBMS PWV measurements collected during the primary field campaign of the ECOWAR project (Bhawar et al., 2008) with simultaneous PWV observations obtained with Vaisala RS92k radiosondes, a Raman lidar, and an IR Fourier transform spectrometer. I found that GBMS PWV measurements are in good agreement with the other three data sets exhibiting a mean difference between observations of ~9%. After this initial validation, GBMS HNO3 retrievals have been compared to two sets of satellite data produced by the two NASA/JPL Microwave Limb Sounder (MLS) experiments (aboard the Upper Atmosphere Research Satellite (UARS) from 1991 to 1999, and on the Earth Observing System (EOS) Aura mission from 2004 to date). This part of my thesis is inserted in GOZCARDS (Global Ozone Chemistry and Related Trace gas Data Records for the Stratosphere), a multi-year project, aimed at developing a long-term data record of stratospheric constituents relevant to the issues of ozone decline and expected recovery. This data record will be based mainly on satellite-derived measurements but ground-based observations will be pivotal for assessing offsets between satellite data sets. Since the GBMS has been operated for more than 15 years, its nitric acid data record offers a unique opportunity for cross-calibrating HNO3 measurements from the two MLS experiments. I compare GBMS HNO3 measurements obtained from the Italian Alpine station of Testa Grigia (45.9° N, 7.7° E, elev. 3500 m), during the period February 2004 - March 2007, and from Thule Air Base, Greenland (76.5°N 68.8°W), during polar winter 2008/09, and Aura MLS observations. A similar intercomparison is made between UARS MLS HNO3 measurements with those carried out from the GBMS at South Pole, Antarctica (90°S), during the most part of 1993 and 1995. I assess systematic differences between GBMS and both UARS and Aura HNO3 data sets at seven potential temperature levels. Results show that, except for measurements carried out at Thule, ground based and satellite data sets are consistent within the errors, at all potential temperature levels.

Electronic energy transfer processes and charge carrier transport in pi-conjugated polymers

Conjugated polymers have attracted tremendous academical and industrial research interest over the past decades due to the appealing advantages that organic / polymeric materials offer for electronic applications and devices such as organic light emitting diodes (OLED), organic field effect transistors (OFET), organic solar cells (OSC), photodiodes and plastic lasers. The optimization of organic materials for applications in optoelectronic devices requires detailed knowledge of their photophysical properties, for instance energy levels of excited singlet and triplet states, excited state decay mechanisms and charge carrier mobilities. In the present work a variety of different conjugated (co)polymers, mainly polyspirobifluorene- and polyfluorene-type materials, was investigated using time-resolved photoluminescence spectroscopy in the picosecond to second time domain to study their elementary photophysical properties and to get a deeper insight into structure-property relationships. The experiments cover fluorescence spectroscopy using Streak Camera techniques as well as time-delayed gated detection techniques for the investigation of delayed fluorescence and phosphorescence. All measurements were performed on the solid state, i.e. thin polymer films and on diluted solutions. Starting from the elementary photophysical properties of conjugated polymers the experiments were extended to studies of singlet and triplet energy transfer processes in polymer blends, polymer-triplet emitter blends and copolymers. The phenomenon of photonenergy upconversion was investigated in blue light-emitting polymer matrices doped with metallated porphyrin derivatives supposing an bimolecular annihilation upconversion mechanism which could be experimentally verified on a series of copolymers. This mechanism allows for more efficient photonenergy upconversion than previously reported for polyfluorene derivatives. In addition to the above described spectroscopical experiments, amplified spontaneous emission (ASE) in thin film polymer waveguides was studied employing a fully-arylated poly(indenofluorene) as the gain medium. It was found that the material exhibits a very low threshold value for amplification of blue light combined with an excellent oxidative stability, which makes it interesting as active material for organic solid state lasers. Apart from spectroscopical experiments, transient photocurrent measurements on conjugated polymers were performed as well to elucidate the charge carrier mobility in the solid state, which is an important material parameter for device applications. A modified time-of-flight (TOF) technique using a charge carrier generation layer allowed to study hole transport in a series of spirobifluorene copolymers to unravel the structure-mobility relationship by comparison with the homopolymer. Not only the charge carrier mobility could be determined for the series of polymers but also field- and temperature-dependent measurements analyzed in the framework of the Gaussian disorder model showed that results coincide very well with the predictions of the model. Thus, the validity of the disorder concept for charge carrier transport in amorphous glassy materials could be verified for the investigated series of copolymers.

Size-selective investigations of spectral and emission properties of small particles and nanotubes

In dieser Arbeit wurde die Elektronenemission von Nanopartikeln auf Oberflächen mittels spektroskopischen Photoelektronenmikroskopie untersucht. Speziell wurden metallische Nanocluster untersucht, als selbstorganisierte Ensembles auf Silizium oder Glassubstraten, sowie ferner ein Metall-Chalcogenid (MoS2) Nanoröhren-Prototyp auf Silizium. Der Hauptteil der Untersuchungen war auf die Wechselwirkung von fs-Laserstrahlung mit den Nanopartikeln konzentriert. Die Energie der Lichtquanten war kleiner als die Austrittsarbeit der untersuchten Proben, so dass Ein-Photonen-Photoemission ausgeschlossen werden konnte. Unsere Untersuchungen zeigten, dass ausgehend von einem kontinuierlichen Metallfilm bis hin zu Clusterfilmen ein anderer Emissionsmechanismus konkurrierend zur Multiphotonen-Photoemission auftritt und für kleine Cluster zu dominieren beginnt. Die Natur dieses neuen Mechanismus` wurde durch verschiedenartige Experimente untersucht. Der Übergang von einem kontinuierlichen zu einem Nanopartikelfilm ist begleitet von einer Zunahme des Emissionsstroms von mehr als eine Größenordnung. Die Photoemissions-Intensität wächst mit abnehmender zeitlicher Breite des Laserpulses, aber diese Abhängigkeit wird weniger steil mit sinkender Partikelgröße. Die experimentellen Resultate wurden durch verschiedene Elektronenemissions-Mechanismen erklärt, z.B. Multiphotonen-Photoemission (nPPE), thermionische Emission und thermisch unterstützte nPPE sowie optische Feldemission. Der erste Mechanismus überwiegt für kontinuierliche Filme und Partikel mit Größen oberhalb von mehreren zehn Nanometern, der zweite und dritte für Filme von Nanopartikeln von einer Größe von wenigen Nanometern. Die mikrospektroskopischen Messungen bestätigten den 2PPE-Emissionsmechanismus von dünnen Silberfilmen bei „blauer“ Laseranregung (hν=375-425nm). Das Einsetzen des Ferminiveaus ist relativ scharf und verschiebt sich um 2hν, wenn die Quantenenergie erhöht wird, wogegen es bei „roter“ Laseranregung (hν=750-850nm) deutlich verbreitert ist. Es zeigte sich, dass mit zunehmender Laserleistung die Ausbeute von niederenergetischen Elektronen schwächer zunimmt als die Ausbeute von höherenergetischen Elektronen nahe der Fermikante in einem Spektrum. Das ist ein klarer Hinweis auf eine Koexistenz verschiedener Emissionsmechanismen in einem Spektrum. Um die Größenabhängigkeit des Emissionsverhaltens theoretisch zu verstehen, wurde ein statistischer Zugang zur Lichtabsorption kleiner Metallpartikel abgeleitet und diskutiert. Die Elektronenemissionseigenschaften bei Laseranregung wurden in zusätzlichen Untersuchungen mit einer anderen Anregungsart verglichen, der Passage eines Tunnelstroms durch einen Metall-Clusterfilm nahe der Perkolationsschwelle. Die elektrischen und Emissionseigenschaften von stromtragenden Silberclusterfilmen, welche in einer schmalen Lücke (5-25 µm Breite) zwischen Silberkontakten auf einem Isolator hergestellt wurden, wurden zum ersten Mal mit einem Emissions-Elektronenmikroskop (EEM) untersucht. Die Elektronenemission beginnt im nicht-Ohmschen Bereich der Leitungsstrom-Spannungskurve des Clusterfilms. Wir untersuchten das Verhalten eines einzigen Emissionszentrums im EEM. Es zeigte sich, dass die Emissionszentren in einem stromleitenden Silberclusterfilm Punktquellen für Elektronen sind, welche hohe Emissions-Stromdichten (mehr als 100 A/cm2) tragen können. Die Breite der Energieverteilung der Elektronen von einem einzelnen Emissionszentrum wurde auf etwa 0.5-0.6 eV abgeschätzt. Als Emissionsmechanismus wird die thermionische Emission von dem „steady-state“ heißen Elektronengas in stromdurchflossenen metallischen Partikeln vorgeschlagen. Größenselektierte, einzelne auf Si-Substraten deponierte MoS2-Nanoröhren wurden mit einer Flugzeit-basierten Zweiphotonen-Photoemissions-Spektromikroskopie untersucht. Die Nanoröhren-Spektren wiesen bei fs-Laser Anregung eine erstaunlich hohe Emissionsintensität auf, deutlich höher als die SiOx Substratoberfläche. Dagegen waren die Röhren unsichtbar bei VUV-Anregung bei hν=21.2 eV. Eine ab-initio-Rechnung für einen MoS2-Slab erklärt die hohe Intensität durch eine hohe Dichte freier intermediärer Zustände beim Zweiphotonen-Übergang bei hν=3.1 eV.