Title: Recombination study of ions with electrons at temperatures below 300 K Author: Tomáš Kotrík Department: Department of Surface and Plasma Science Supervisor of the doctoral thesis: Prof. RNDr. Juraj Glosík, DrSc. Department of Surface and Plasma Science Abstract: Presented is the study of recombination of ions with electrons performed at low temperatures using the Flowing afterglow with Langmuir probe experimental technique. Studied was the dissociative recombination of H and D ions at temperatures 77 - 300 K. Apart from a two-body also a three-body recombination channel assisted by neutral He atoms was identified and studied. The obtained temperature dependence of the two-body recombination rate coefficient is in a good agreement with findings of other experimental and theoretical works. The dissociative recombination of HCO and DCO ions with electrons was studied in the temperature range 150 - 300 K. The observed temperature dependence of measured recombination rate coefficient for HCO and DCO ions (~T -1.3 and ~T -1.1 , respectively) is in agreement with the majority of previous experimental works and evokes that indirect mechanism governs the recombination process. The electron- assisted collisional-radiative recombination of Ar ions was for the first time studied at temperatures 50 - 300 K. The...

A B S T R A C T Title: Recombination of Ions in Plasma at 50 − 300 K Author: Peter Rubovič Supervisor: Prof. RNDr. Juraj Glosík, DrSc. Abstract: Main part of this doctoral thesis lies in a study of recom- bination of atomic and molecular ions in low temperature plasmatic environment with emphasis on effect of third bodies. Stationary After- glow equipped with Cavity Ring Down Spectrometer and Cryogenic Flowing Afterglow with Langmuir Probe II were used to obtain recom- bination rate coefficients. Electron assisted collisional radiative recom- bination of Ar+ ion was studied in the temperature range of 50−100 K and helium assisted collisional radiative recombination was observed too. Both H+ 3 and its isotopologue D+ 3 were studies in flowing after- glow and spectroscopically in stationary afterglow as well. Binary re- combination rate coefficients and ternary recombination rate coeffi- cients for helium assisted ternary recombination were determined in the temperature range of 50 − 250 K. These coefficients were deter- mined also for pure ortho- and para- nuclear spin configurations of H+ 3 in the temperature range of 80 − 200 K. Keywords: dissociative recombination, collisional radiative recombi- nation, H+ 3 , D+ 3 , Ar+ viii

The inductively coupled plasma mass spectrometer (ICP-MS) has been used in laboratories for many years. The majority of the improvements to the instrument have been done empirically through trial and error. A few fluid models have been made, which have given a general description of the flow through the mass spectrometer interface. However, due to long mean free path effects and other factors, it is very difficult to simulate the flow details well enough to predict how changing the interface design will change the formation of the ion beam. Towards this end, Spencer et al. developed FENIX, a direct simulation Monte Carlo algorithm capable of modeling this transitional flow through the mass spectrometer interface, the transitional flow from disorganized plasma to focused ion beam. Their previous work describes how FENIX simulates the neutral ion flow. While understanding the argon flow is essential to understanding the ICP-MS, the true goal is to improve its analyte detection capabilities. In this work, we develop a model for adding analyte to FENIX and compare it to previously collected experimental data. We also calculate how much ambipolar fields, plasma sheaths, and electron-ion recombination affect the ion beam formation. We find that behind the sampling interface there is no evidence of turbulent mixing. The behavior of the analyte seems to be described simply by convection and diffusion. Also, ambipolar field effects are small and do not significantly affect ion beam formation between the sampler and skimmer cones. We also find that the plasma sheath that forms around the sampling cone does not significantly affect the analyte flow downstream from the skimmer. However, it does thermally insulate the electrons from the sampling cone, which reduces ion-electron recombination. We also develop a model for electron-ion recombination. By comparing it to experimental data, we find that significant amounts of electron-ion recombination occurs just downstream from the sampling interface.

GaN-Nanodrähte können mit einer hohen strukturellen Perfektion auf verschiedenen kristallinen und amorphen Substraten gewachsen werden. Sie bieten somit faszinierende Möglichkeiten, sowohl zur Untersuchung von fundamentalen Eigenschaften des Materialsystems, als auch in der Anwendung in optoelektronischen Bauteilen. Obwohl bereits verschiedene Prototypen solcher Bauteile vorgestellt wurden, sind viele grundlegende Eigenschaften von GaN-Nanodrähten noch ungeklärt, darunter die interne Quanteneffizienz (IQE), welche ein wichtiges Merkmal für optoelektronische Anwendungen darstellt. Die vorliegende Arbeit präsentiert eine detaillierte Untersuchung der Rekombinationsdynamik von Exzitonen, in selbst-induzierten und selektiv gewachsenen GaN Nanodraht-Proben, welche mit Molekularstrahlepitaxie hergestellt wurden. Die zeitaufgelösten Photolumineszenz (PL)-Experimente werden durch Simulationen ergänzt, welche auf Ratengleichungs-Modellen basieren. Es stellt sich heraus, dass die Populationen von freien und gebundenen Exzitonen gekoppelt sind und zwischen 10 und 300 K von einem nichtstrahlenden Kanal beeinflusst werden. Die Untersuchung von Proben mit unterschiedlichem Nanodraht-Durchmesser und Koaleszenzgrad zeigt, dass weder die Nanodraht-Oberfläche, noch Defekte als Folge von Koaleszenz diesen nichtstrahlenden Kanal induzieren. Daraus lässt sich folgern, dass die kurze Zerfallszeit von Exzitonen in GaN-Nanodrähten durch Punktdefekte verursacht wird, welche die IQE bei 10 K auf 20% limitieren. Der häufig beobachtete biexponentiellen PL-Zerfall des Donator-gebundenen Exzitons wird analysiert und es zeigt sich, dass die langsame Komponente durch eine Kopplung mit Akzeptoren verursacht wird. Motiviert durch Experimente, welche eine starke Abhängigkeit der PL-Intensität vom Nanodraht-Durchmesser zeigen, wird die externen Quanteneffizienz von geordneten Nanodraht-Feldern mit Hilfe numerischer Simulationen der Absorption und Extraktion von Licht in diesen Strukturen untersucht. / GaN nanowires (NWs) can be fabricated with a high structural perfection on various crystalline and amorphous substrates. They offer intriguing possibilities for both fundamental investigations of the GaN material system as well as applications in optoelectronic devices. Although prototype devices based on GaN NWs have been presented already, several fundamental questions remain unresolved to date. In particular, the internal quantum efficiency (IQE), an important basic figure of merit for optoelectronic applications, is essentially unknown for GaN NWs. This thesis presents a detailed investigation of the exciton dynamics in GaN NWs using continuous-wave and time-resolved photoluminescence (PL) spectroscopy. Spontaneously formed ensembles and ordered arrays of GaN NWs grown by molecular-beam epitaxy are examined. The experiments are combined with simulations based on the solution of rate equation systems to obtain new insights into the recombination dynamics in GaN NWs at low temperatures. In particular, the free and bound exciton states in GaN NWs are found to be coupled and affected by a nonradiative channel between 10 and 300 K. The investigation of samples with different NW diameters and coalescence degrees conclusively shows that the dominating nonradiative channel is neither related to the NW surface nor to coalescence-induced defects. Hence, we conclude that nonradiative point defects are the origin of the fast recombination dynamics in GaN NWs, and limit the IQE of the investigated samples to about 20% at cryogenic temperatures. We also demonstrate that the frequently observed biexponential decay for the donor-bound exciton originates from a coupling with the acceptor-bound exciton state in the GaN NWs. Motivated by an experimentally observed, strong dependence of the PL intensity of ordered GaN NW arrays on the NW diameter, we perform numerical simulations of the light absorption and extraction to explore the external quantum efficiency of these samples.