Frequency-Domain and Wide-Pulse Time-Domain Measurements of Lanthanide Luminescence and Lanthanide-Based Resonance Energy Transfer

Resonance energy transfer (RET) is a non-radiative transfer of the excitation energy from the initially excited luminescent donor to an acceptor. The requirements for the resonance energy transfer are: i) the spectral overlap between the donor emission spectrum and the acceptor absorption spectrum, ii) the close proximity of the donor and the acceptor, and iii) the suitable relative orientations of the donor emission and the acceptor absorption transition dipoles. As a result of the RET process the donor luminescence intensity and the donor lifetime are decreased. If the acceptor is luminescent, a sensitized acceptor emission appears. The rate of RET depends strongly on the donor–acceptor distance (r) and is inversely proportional to r6. The distance dependence of RET is utilized in binding assays. The proximity requirement and the selective detection of the RET-modified emission signal allow homogeneous separation free assays. The term lanthanide-based RET is used when luminescent lanthanide compounds are used as donors. The long luminescence lifetimes, the large Stokes’ shifts and the intense, sharply-spiked emission spectra of the lanthanide donors offer advantages over the conventional organic donor molecules. Both the organic lanthanide chelates and the inorganic up-converting phosphor (UCP) particles have been used as donor labels in the RET based binding assays. In the present work lanthanide luminescence and lanthanide-based resonance energy transfer phenomena were studied. Luminescence lifetime measurements had an essential role in the research. Modular frequency-domain and time-domain luminometers were assembled and used successfully in the lifetime measurements. The frequency-domain luminometer operated in the low frequency domain ( 100 kHz) and utilized a novel dual-phase lock-in detection of the luminescence. One of the studied phenomena was the recently discovered non-overlapping fluorescence resonance energy transfer (nFRET). The studied properties were the distance and temperature dependences of nFRET. The distance dependence was found to deviate from the Förster theory and a clear temperature dependence was observed whereas conventional RET was completely independent of the temperature. Based on the experimental results two thermally activated mechanisms were proposed for the nFRET process. The work with the UCP particles involved the measurement of the luminescence properties of the UCP particles synthesized in our laboratory. The goal of the UCP particle research is to develop UCP donor labels for binding assays. In the present work the effect of the dopant concentrations and the core–shell structure on the total up-conversion luminescence intensity, the red–green emission ratio, and the luminescence lifetime was studied. Also the non-radiative nature of the energy transfer from the UCP particle donors to organic acceptors was demonstrated for the first time in aqueous environment and with a controlled donor–acceptor distance.

Spin-Dynamics in Cold Gases of 87Rb and Atomic Hydrogen. The spins they are a-changin’

In this thesis the dynamics of cold gaseous atoms is studied. Two different atomic species and two different experimental techniques have been used. In the first part of the thesis experiments with Bose-Einstein condensates of Rb-87 are presented. In these experiments the methods of laser cooling and magnetic trapping of atoms were utilized. An atom chip was used as the experimental technique for implementation of magnetic trapping. The atom chip is a small integrated instrument allowing accurate and detailed manipulation of the atoms. The experiments with Rb-87 probed the behaviour of a falling beam of atoms outcoupled from the Bose-Einstein condensate by electromagnetic field induced spin flips. In the experiments a correspondence between the phases of the outcoupling radio frequency field and the falling beam of atoms was found. In the second part of the thesis experiments of spin dynamics in cold atomic hydrogen gas are discussed. The experiments with atomic hydrogen are conducted in a cryostat using a dilution refrigerator as the cooling method. These experiments concentrated on explaining and quantifying modulations in the electron spin resonance spectra of doubly polarized atomic hydrogen. The modifications to the previous experimental setup are described and the observation of electron spin waves is presented. The observed spin wave modes were caused by the identical spin rotation effect. These modes have a strong dependence on the spatial profile of the polarizing magnetic field. We also demonstrated confinement of these modes in regions of strong magnetic field and manipulated their spatial distribution by changing the position of the field maximum.

Side peaks in Nb and NbTi point-contact spectra

Superconductor – normal metal point contacts were investigated, using different combinations of Cu, brass, Nb and NbTi. The resulting spectra contained side peaks. The currents at which these side peaks appeared, depended on the radii of the contacts. For contacts with Nb this dependence was quadratic, while for contacts with NbTi it was linear. Based on this, we argue that the side peaks in the case of the Nb contacts are due to the critical current density being exceeded. In contrast, side peaks of the NbTi contacts are caused by the self-magnetic field exceeding the lower critical field of NbTi. The NbTi contacts did not show the expected contribution from the vanishing Maxwell resistance of the superconductor, a question which remained open.

Influence of reactant absorption and dissolution in heterogeneous precipitation processes

In this research work, the aim was to investigate the volumetric mass transfer coefficient [kLa] of oxygen in stirred tank in the presence of solid particle experimentally. The kLa correlations as a function of propeller rotation speed and flow rate of gas feed were studied. The O2 and CO2 absorption in water and in solid-liquid suspensions and heterogeneous precipitation of MgCO3 were thoroughly examined. The absorption experiments of oxygen were conducted in various systems like pure water and in aqueous suspensions of quartz and calcium carbonate particles. Secondly, the precipitation kinetics of magnesium carbonate was also investigated. The experiments were performed to study the reactive crystallization with magnesium hydroxide slurry and carbon dioxide gas by varying the feed rates of carbon dioxide and rotation speeds of mixer. The results of absorption and precipitation are evaluated by titration, total carbon (TC analysis), and ionic chromatrography (IC). For calcium carbonate, the particle concentration was varied from 17.4 g to 2382 g with two size fractions: 5 µm and 45-63 µm sieves. The kLa and P/V values of 17.4 g CaCO3 with particle size of 5µm and 45-63 µm were 0.016 s-1 and 2400 W/m3. At 69.9 g concentration of CaCO3, the achieved kLa is 0.014 s-1 with particle size of 5 µm and 0.017 s-1 with particle size of 45 to 63 µm. Further increase in concentration of calcium carbonate, i.e. 870g and 2382g , does not affect volumetric mass transfer coeffienct of oxygen. It could be concluded from absorption results that maximum value of kLa is 0.016 s-1. Also particle size and concentration does affect the transfer rate to some extend. For precipitation experiments, the constant concentration of Mg(OH)2 was 100 g and the rotation speed varied from 560 to 750 rpm, whereas the used feed rates of CO2 were 1 and 9 L/min. At 560 rpm and feed rate of CO2 is 1 L/min, the maximum value of Mg ion and TC were 0.25 mol/litre and 0.12 mol/litre with the residence time of 40 min. When flow rate of CO2 increased to 9 L/min with same 560 rpm, the achieved value of Mg and TC were 0.3 mol/litre and 0.12 mol/L with shorter residence time of 30 min. It is concluded that feed rate of CO2 is dominant in precipitation experiments and it has a key role in dissociation and reaction of magnesium hydroxide in precipitation of magnesium carbonate.

Spin-electromagnetic waves spectra in multiferroic heterostructures

This work devotes to the theoretical investigations of spin-electromagnetic waves (SEW) propagating in a thin-film multiferroic structures that were composed of a slot-line and structures with several ferrite films. In contrast to earlier works, the spin-electromagnetic waves in the investigated structures are originated from two different electrodynamics coupling. The first one is coupling of the electromagnetic wave localized mainly in the slot-line with the spin wave excited mostly in the ferrite film. The second one is coupling of two spin waves in the different ferrite films separated by a thin ferroelectric film. For theoretical analysis of SEWs propagation in such kind of structures theories of their eigen-wave spectra were developed. Spectra of SEW in the investigated structures were calculated and analyzed. The range of electric and magnetic tunability of dispersion characteristic were investigated. Spectra of SEW in the investigated multiferroic structures are used for investigation of transfer function of periodic structures.

Inverkan av indirekt rekombination på fotoinducerad absorption

I organiska halvledare påverkas mängden laddningsbärare kraftigt av indirekt rekombination, det vill säga processen då fria laddningsbärare försvinner genom att kombineras med orörliga laddningsbärare av motsatt laddning. De orörliga laddningsbärarna uppstår när laddningsbärare fastnar i fällor, som är energitillstånd med låg energi och densitet. Utöver indirekt rekombination sker även direkt rekombination mellan fria laddningsbärare. Då man tillverkar solceller av organiska halvledare påverkas effektiviteten av energidistributionen och rekombinationsprocesserna i materialen. Utveckling av olika metoder för undersökning av dessa egenskaper är således till nytta i jakten på bättre solcellsmaterial. Målet med detta arbete var att vidareutveckla dataanalysen för cwPA-mätningar(från engelska continuous-wave Photoinduced Absorption) för att ur resultaten få information om indirekt rekombination och fälldistributioner. I cwPA-mätningar studerar man fotoinducerad absorption, det vill säga förändringen i absorption hos ett prov då densiteten av fotogenererade laddningsbärare varierar. Laddningsbärarna genereras av ett pumpljus vars intensitet ges av en fyrkantsvåg som växlar mellan 0 och I med vinkelfrekvensen omega. Resultaten fås i form av i-fas-signal (PAI), som har samma frekvens och fas som pumpljuset, och kvadratur (PAQ), som har samma frekvens som pumpljuset men är fasförskjuten 90 grader. Fördelen med denna mätning är förutom känsligheten att den är kontaktlös, vilket gör att den visar egenskaperna hos det undersökta materialet utan att påverkas av elektriska kontakter. För att undersöka inverkan av indirekt rekombination på cwPA-mätningar simulerades mätresultat genom att använda numeriska beräkningar. Grunden för simuleringarna var att lösa differentialekvationer för densiteter av laddningsbärare i olika tillstånd. Beräkningarna använde en modell med transporttillstånd och fällor placerade så att energidistributionen var symmetrisk för elektroner och hål. Modellen antog att laddningsbärare inte kunde röra sig direkt mellan fällor utan endast via transporttillstånd. Från simuleringarna erhölls användbara samband mellan fotoinducerad absorption och olika fälldistributioner. Särskilt påverkade distributionerna i-fas-signalen för hög intensitet på pumpljuset och kvadraturen för låg frekvens på fyrkantsvågen. För en exponentiell fälldistribution hittades samband mellan mätresultat och distributionens karakteristiska energi (Ech) i förhållande till temperaturen (T). Dessa är för hög intensitet PAI~I^(1+Ech/kT) och för låg frekvens PAQ~omega^(kT/Ech). Resultaten visade att man kan skilja på en exponentiell fälldistribution, en gaussisk fälldistribution och ett system som domineras av direkt rekombination genom att göra cwPA-mätningar vid olika temperaturer.