This thesis discusses the crystal quality and transition of electrons and holes pairs by temperature- and power- dependent Photoluminescence (PL). With the PL spectra, we apply four kinds of Internal Quantum Efficiency (IQE) formulas for c- and m- plane III-nitride and discuss the differences of the four formulas. An analysis of IQE is performed and it is found for m-plane III-nitride being larger than c-plane III-nitride. This result confirms that characteristic m-plane structure can increase its radiative recombination.

Ce travail porte sur la croissance par épitaxie sous jets moléculaires (EJM) et sur les propriétés structurales et optiques de boîtes quantiques (BQs) AlyGa1-yN insérées dans une matrice AlxGa1-xN (0001). L’objectif principal est d’étudier le potentiel des BQs en tant que nouvelle voie pour la réalisation d’émetteurs ultraviolets (UV) efficaces.Tout d'abord, nous avons étudié la croissance des BQs GaN en utilisant soit une source plasma (N2, appelée PAMBE) soit une source ammoniac (NH3, appelée NH3-MBE) afin de choisir la meilleure approche pour former les BQs les plus efficaces. Il a été montré que le procédé de croissance est mieux contrôlé en utilisant l’approche PAMBE, conduisant à la croissance de BQs GaN avec des densités plus élevées, une meilleure uniformité en taille et des intensités de photoluminescence (PL) jusqu’à trois fois plus élevées. En outre, l'influence de la contrainte épitaxiale sur le processus d'auto-assemblage des BQs a été étudiée en fabriquant des BQs GaN sur différentes couche tremplins d’AlxGa1-xN (avec 0,5 ≤ x ≤ 0,7). Nous avons montré que des BQs avec des densités plus élevées et des hauteurs plus faibles sont formées en augmentant le désaccord de paramètre de maille (c.à.d en utilisant des tremplins avec xAl plus élevé). Cependant, les mesures de photoluminescence (PL) indiquent un fort décalage de l'énergie d'émission vers le rouge lorsque xAl augmente, en raison de l'augmentation de la discontinuité du champ électrique interne de 3 à 5,3 MV/cm.Ensuite, des études approfondies sur les conditions de croissance et les propriétés optiques des BQs Al0,1Ga0,9N / Al0,5Ga0,5N ont été présentées, montrant les différents défis pour fabriquer des BQs efficaces. L’optimisation de la procédure de croissance, notamment l’étape de recuit post-croissance, a montré une modification de la forme des BQs. Plus précisément, un changement d’une forme allongée (pour un recuit à 740 °C), à une forme symétrique (pour un recuit à une température proche de ou supérieure à 800°C) a été observé. En plus, une bande d’émission supplémentaire vers les plus grandes longueurs d’onde a également été observée pour les BQs formées avec un recuit à 740°C. Cette bande a été attribuée à une fluctuation de composition des BQs, induisant la formation d’une famille additionnelle de BQs avec des hauteurs plus grandes et une compostions en Al inférieure à 10 %, estimée proche de l’alliage binaire GaN. Enfin, il a été démontré qu’en faisant un recuit à plus haute température (≥ 800°C), l’émission de PL de cette famille supplémentaire de BQs (BQs riche en Ga ou (Al)GaN) diminue très fortement. De plus, cette étape de recuit impacte fortement la forme des BQs et a conduit à une amélioration de leur efficacité radiative d’un facteur 3. Ensuite, la variation de la composition en Al des BQs AlyGa1-yN (0,1 ≤ y ≤ 0,4), ainsi que la quantité de matière déposée ont permis d’évaluer la gamme de longueurs d’onde d’émission accessibles. En ajustant les conditions de croissance, l’émission des BQs a été déplacée de l’UVA vers l’UVC, atteignant une émission autour de 270 - 275 nm (pour les applications de purification de l’eau et de l’air) avec des rendements radiatifs élevés. Les mesures de photoluminescence résolue en temps (TRPL), combinées avec les mesures de PL en fonction de la température, nous ont permis de déterminer les efficacités quantiques internes (IQE) des BQs GaN / AlxGa1-xN (0001). Des valeurs d’IQE comprises entre 50 % et 66 % ont été obtenues à basse température, avec la possibilité d’atteindre un rapport d’intensité intégré de PL, entre 300 K et 9 K, allant jusqu’à 75 % pour les BQs GaN et 46 % pour les BQs AlyGa1-yN (contre 0,5 % pour des structures équivalents à base de puits quantiques).Enfin, nous avons montré la possibilité de fabriquer des DELs à base de BQs (Al,Ga)N couvrant une grande gamme de longueurs d’onde allant du bleu-violet jusqu’à l’UVB (de 415 nm à 305 nm). / This PhD deals with the epitaxial growth, structural and optical properties of AlyGa1-yN quantum dots (QDs) grown on AlxGa1-xN (0001) by molecular beam epitaxy (MBE), with the aim to study their potential as a novel route for efficient ultraviolet (UV) emitters.First, we have studied the growth of GaN QDs using either plasma MBE (PAMBE) or ammonia MBE (NH3-MBE) to find the most adapted nitrogen source for the fabrication of UV emitting QDs. It was shown that the growth process is better controlled using PAMBE, leading to the growth of GaN QDs with higher densities, better size uniformity and up to three times higher photoluminescence (PL) intensities. Also, the influence of the epitaxial strain on the QD self-assembling process was studied by fabricating GaN QDs on different AlxGa1-xN surfaces (with 0.5 ≤ x ≤ 0.7). We showed that QDs with higher densities and smaller sizes (heights) are formed by using a larger lattice-mismatch (i.e. a higher xAl composition). However, photoluminescence (PL) measurements indicated a strong redshift in the emission energy as the Al content of the AlxGa1-xN template increases due to the increase of the internal electric field discontinuity from 3 to 5.3 MV/cm.Next, in-depth investigations of the growth conditions and optical properties of Al0.1Ga0.9N QDs / Al0.5Ga0.5N were done presenting the different challenges to be solved to grow efficient QDs. Changing the growth procedure, especially the post-growth annealing step, has shown a modification of the QD shape from elongated QDs, formed with an annealing at 740°C, to symmetric QDs, formed with an annealing at a temperature around or above 800°C. An additional band emission at lower energies was also observed for QDs grown with a lower annealing temperature (740°C). This additional band emission was attributed to the formation of QDs with higher heights and a reduced Al composition less than the nominal one of 10 % (i.e. forming Ga-rich QDs). The influence of the annealing step performed at higher temperature has been shown to strongly decrease the PL emission from this additional QD family. In addition, this annealing step strongly impacted the QD shape and led to an improvement of the QD radiative efficiency by a factor 3. Then, the AlxGa1-xN barrier composition (0.5 ≤ x ≤ 0.7), the AlyGa1-yN QD composition (0.1 ≤ y ≤ 0.4) as well as the deposited amount were varied in order to assess the range of accessible emission energies. Also, the influence of varying the AlxGa1-xN barrier composition on the QD formation was studied. By varying these growth conditions, the QD wavelength emission was shifted from the UVA down to the UVC range, reaching a minimum wavelength emission of 270 - 275 nm (for water and air purification applications) with a high radiative efficiency. Time resolved photoluminescence (TRPL) combined with temperature dependent PL measurements enabled us to determine the internal quantum efficiencies (IQE) of AlyGa1-yN QDs / AlxGa1-xN (0001). IQE values between 50 % and 66 % were found at low temperature, combined with the ability to reach a PL integrated intensity ratio, between 300 K and 9 K, up to 75 % for GaN QDs and 46 % for AlyGa1-yN QDs (versus 0.5 % in a similar quantum well structure emitting in the UVC range).Finally, the demonstration of AlyGa1-yN QD-based light emitting diode prototypes, emitting in the whole UVA range, using GaN and Al0.1Ga0.9N QDs, and in the UVB range down to 305 nm with Al0.2Ga0.8N QDs active regions, was shown.

In this thesis, I will present and discuss research performed on InGaN/GaN multiple quantum well (QW) structures. The results of which were taken using photoluminescence (PL) spectroscopy and PL time decay spectroscopy. In the first two experimental chapters, I report on the effects of QW growth methodology on the optical properties of c-plane InGaN/GaN QWs. I compare structures grown using the single temperature (1T), quasi-two temperature (Q2T), temperature bounced (T-bounced) and two temperature (2T) QW growth methodologies. The T-bounced and 2T structures are observed to have gross well width fluctuations (GWWF), where the QW width varies from 0 to 100 % created when the QWs are exposed to a temperature ramp. Whereas, the 1T and Q2T structures have continuous QWs with only one or two monolayer well width fluctuations. The structures with GWWFs are observed to have a larger room temperature internal quantum efficiency (RT-IQE) at low excitation conditions i.e. below efficiency droop compared to those without. The larger RT-IQE is ascribed to several factors which include an increased radiative recombination rate, increased thermal activation energy of non-radiative recombination and reduced defect density of the QWs. The effect of barrier growth temperature is also investigated. No clear trend is observed between barrier growth temperature and RT-IQE.In the last experimental chapter I report on studies of carrier localisation in InGaN/GaN QWs using resonant PL spectroscopy. The effect of carrier localisation on the independently localised electrons and holes are investigated and the resonant PL spectrum is studied in detail. The InGaN/GaN QW structure is observed to exhibit an effective mobility edge at 12 K where delocalised carriers are created above a particular excitation energy. The emission from the resonantly excited localised states which are accompanied by the emission of a longitudinal optical phonon (resonant LO feature) is investigated as a function of temperature and excitation energy. The integrated PL intensity of the resonant LO feature is observed to quench rapidly with temperature up to around 45 K, independent of excitation energy. The integrated PL intensity of the resonant LO feature is fitted to an Arrhenius model and a thermal activation energy of ∼ 1(±1) meV is extracted. This activation energy is speculated to be consistent with the localisation energy of electrons.

Title: Advanced spectroscopic characterization of quantum dot ensembles Author: Michael Greben Department: Department of Chemical Physics and Optics Supervisor of the doctoral thesis: Prof. Jan Valenta, Ph.D. Abstract: Semiconductor quantum dots (QDs) are small crystallites whose sizes (of the order of nm) cause spatial confinement of carriers in all 3 dimensions. As result, QDs often reveal very different physical properties in comparison with their bulk counterparts. From the optical point of view, the broadening of bandgap with QD-size shrinking is particularly interesting. It is a purely quantum mechanical effect that results from quantum confinement (QC), i.e. dimensional limitations of excitons. A strong spatial confinement leads to a relaxation of momentum (Heisenberg uncertainty principle), consequently, larger overlap of the wave-functions of carriers results in significant increase of probability of radiative recombination. Therefore ensembles of QDs are promising candidates for new generations of photonic and photovoltaic devices. This PhD thesis is primary focused on detailed spectroscopic characterization of ensembles of direct (PbS) and indirect (Si) semiconductor QDs in both colloidal (toluene) and matrix-embedded (oxide or oxinitrides multilayers) forms. The oleic- acid capped PbS QDs were...

In this thesis I present and discuss the results of optical spectroscopy performed on InGaN/GaN single and multiple quantum well (QW) structures. I report on the optical properties of InGaN/GaN single and multiple QW structures, measured at high excitation power densities. I show a correlation exists between the reduction in PL efficiency at high excitation power densities, the phenomenon so-called ``efficiency-droop'', and a broadening of the PL spectra. I also show a distinct change in recombination dynamics, measured by time-resolved photoluminescence (PL), which occurs at the excitation power densities for which efficiency droop is measured. The broadening of the PL spectra at high excitation power densities is shown to occur due to a rapidly redshifting, short-lived high energy emission band. The high energy emission band is proposed to be due to the recombination of weakly localised/delocalised carriers occurring as a consequence of the progressive saturation of the local potential fluctuations responsible for carrier localisation, at high excitation power densities. I report on the effects of varying threading dislocation (TD) density on the optical properties of InGaN/GaN multiple QW structures. No systematic relationship exists between the room temperature internal quantum efficiency (IQE) and the TD density, in a series of nominally identical InGaN/GaN multiple QWs deposited on GaN templates of varying TD density. I also show the excitation power density dependence of the PL efficiency, at room temperatures, is unaffected for variation in the TD density between 2 x107 and 5 x109 cm-2. The independence of the optical properties to TD density is proposed to be a consequence of the strong carrier localisation, and hence short carrier diffusion lengths. I report on the effects of including an InGaN underlayer on the optical and microstructural properties of InGaN/GaN multiple QW structures. I show an increase in the room temperature IQE occurs for the structure containing the InGaN underlayer, compared to the reference. I show using PL excitation spectroscopy that an additional carrier transfer and recombination process occurs on the high energy side of the PL spectrum associated with the InGaN underlayer. Using PL decay time measurements I show the additional recombination process for carriers excited in the underlayer occurs on a faster timescale than the recombination at the peak of the PL spectrum. The additional contribution to the spectrum from the faster recombination process is proposed as responsible for the increase in room temperature IQE.

General lighting with InGaN light emitting diodes (LEDs) as light sources is of particular interest in terms of energy savings and related environmental benefits due to high lighting efficiency, long lifetime, and Hg-free nature. Incandescent and fluorescent light sources are used for general lighting almost everywhere. But their lighting efficiency is very limited: only 20-30 lm/W for incandescent lighting bulb, approximately 100 lm/W for fluorescent lighting. State-of-the-art InGaN LEDs with a luminous efficacy of over 200 lm/W at room temperature have been reported. However, the goal of replacing the incandescent and fluorescent lights with InGaN LEDs is still elusive since their lighting efficiency decreases substantially when the injection current increases beyond certain values (typically 10-50 Acm-2). In order to improve the electroluminescence (EL) performance at high currents for InGaN LEDs, two approaches have been undertaken in this thesis. First, we explored the preparation and characterization of non-polar and semi-polar GaN substrates (including a-plane, m-plane and semi-polar planes). These substrates serve as promising alternatives to the commonly used c-plane, with the benefit of a reduced polarization-induced electric field and therefore higher quantum efficiency. It is demonstrated that LEDs on m-plane GaN substrates have inherently higher EL quantum efficiency and better efficiency retention ability at high injection currents than their c-plane counterparts. Secondly, from a device structure level, we explored the possible origins of the EL efficiency degradation at high currents in InGaN LEDs and investigated the effect of hot electrons on EL of LEDs by varying the barrier height of electron blocking layer. A first-order theoretical model is proposed to explain the effect of electron overflow caused by hot electron transport across the LED active region on LED EL performance. The calculation results are in agreement with experimental observations. Furthermore, a novel structure called a “staircase electron injector” (SEI) is demonstrated to effectively thermalize hot electrons, thereby reducing the reduction of EL efficiency due to electron overflow. The SEI features several InyGa1-yN layers, with their In fraction (y) increasing in a stepwise manner, starting with a low value at the first step near the junction with n-GaN.

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.

(In,Ga)N/GaN-Leuchtdioden wurden vor mehr als 10 Jahren kommerzialisiert, dennoch ist das Verständnis über den Einfluss von Lokalisierung auf die Rekombinationsdynamik in den (In,Ga)N/GaN Quantengräben (QG) unvollständig. In dieser Arbeit nutzen wir die temperaturabhängige stationäre und zeitaufgelöste Spektroskopie der Photolumineszenz (PL), um diesen Einfluss in einer typischen Ga-polaren, planaren (In,Ga)N/GaN-QG-Struktur zu untersuchen. Zusätzlich dehnen wir unsere Studie auf N-polare, axiale (In,Ga)N/GaN Quantumscheiben, nichtpolare Kern/Mantel GaN/(In,Ga)N µ-Drähte und Ga-polare, submonolage InN/GaN Übergitter aus. Während wir einen einfach exponentiellen Abfall der PL-Intensität in den nichtpolaren QG beobachten (Hinweise auf die Rekombination von Exzitonen), folgen die PL-Transienten in polaren QG asymptotisch einem Potenzgesetz. Dieses Potenzgesetz weist auf eine Rekombination zwischen individuell lokalisierten, räumlich getrennten Elektronen und Löchern hin. Für einen solchen Zerfall kann keine eindeutige PL-Lebensdauer definiert werden, was die Schätzung der internen Quanteneffizienz und die Bestimmung einer Diffusionslänge erschwert. Um nützliche Rekombinationsparameter und Diffusivitäten für die polaren QG zu extrahieren, analysieren wir die PL-Transienten mit positionsabhängigen Diffusionsreaktionsgleichungen, die durch einen Monte-Carlo-Algorithmus effizient gelöst werden. Aus diesen Simulationen ergibt sich, dass das asymptotische Potenzgesetz auch bei effizienter nichtstrahlender Rekombination (z. B. in den Nanodrähten) erhalten bleibt. Zudem stellen wir fest, dass sich die InN/GaN Übergitter elektronisch wie konventionelle (In,Ga)N/GaN QG verhalten, aber mit starkem, thermisch aktiviertem nichtstrahlenden Kanal. Des Weiteren zeigen wir, dass das Verhältnis von Lokalisierungs- und Exzitonenbindungsenergie bestimmt, dass die Rekombination entweder durch das Tunneln von Elektronen und Löchern oder durch den Zerfall von Exzitonen dominiert wird. / (In,Ga)N/GaN light-emitting diodes have been commercialized more than one decade ago. However, the knowledge about the influence of the localization on the recombination dynamics and on the diffusivity in the (In,Ga)N/GaN quantum wells (QWs) is still incomplete. In this thesis, we employ temperature-dependent steady-state and time-resolved photoluminescence (PL) spectroscopy to investigate the impact of localization on the recombination dynamics of a typical Ga-polar, planar (In,Ga)N/GaN QW structure. In addition, we extend our study to N-polar, axial (In,Ga)N/GaN quantum disks, nonpolar core/shell GaN/(In,Ga)N µ-rods, and Ga-polar, sub-monolayer InN/GaN superlattices. While we observe a single exponential decay of the PL intensity in the nonpolar QWs, indicating the recombination of excitons, the decay of the PL intensity in polar QWs asymptotically obeys a power law. This power law reveals that recombination occurs between individually localized, spatially separated electrons and holes. No unique PL lifetime can be defined for such a decay, which impedes the estimation of the internal quantum efficiency and the determination of a diffusion length. In order to extract useful recombination parameters and diffusivities for the polar QWs, we analyze the PL transients with position-dependent diffusion-reaction equations, efficiently solved by a Monte Carlo algorithm. From these simulations, we conclude that the power law asymptote is preserved despite efficient nonradiative recombination in the nanowires. Moreover, we find that the InN/GaN superlattices behave electronically as conventional (In,Ga)N/GaN QWs, but with a strong, thermally-activated nonradiative channel. Furthermore, we demonstrate that the ratio of localization and exciton binding energy, both of which are influenced by the magnitude of the internal electric fields in the QWs, determines the recombination mechanism to be either dominated by tunneling of electrons and holes or by the decay of excitons.