Profile simulations of gas chopping etching processes : model development and comparison with experiments

The progress in microsystem technology or nano technology places extended requirements to the fabrication processes. The trend is moving towards structuring within the nanometer scale on the one hand, and towards fabrication of structures with high aspect ratio (ratio of vertical vs. lateral dimensions) and large depths in the 100 µm scale on the other hand. Current procedures for the microstructuring of silicon are wet chemical etching and dry or plasma etching. A modern plasma etching technique for the structuring of silicon is the so-called "gas chopping" etching technique (also called "time-multiplexed etching"). In this etching technique, passivation cycles, which prevent lateral underetching of sidewalls, and etching cycles, which etch preferably in the vertical direction because of the sidewall passivation, are constantly alternated during the complete etching process. To do this, a CHF3/CH4 plasma, which generates CF monomeres is employed during the passivation cycle, and a SF6/Ar, which generates fluorine radicals and ions plasma is employed during the etching cycle. Depending on the requirements on the etched profile, the durations of the individual passivation and etching cycles are in the range of a few seconds up to several minutes. The profiles achieved with this etching process crucially depend on the flow of reactants, i.e. CF monomeres during the passivation cycle, and ions and fluorine radicals during the etching cycle, to the bottom of the profile, especially for profiles with high aspect ratio. With regard to the predictability of the etching processes, knowledge of the fundamental effects taking place during a gas chopping etching process, and their impact onto the resulting profile is required. For this purpose in the context of this work, a model for the description of the profile evolution of such etching processes is proposed, which considers the reactions (etching or deposition) at the sample surface on a phenomenological basis. Furthermore, the reactant transport inside the etching trench is modelled, based on angular distribution functions and on absorption probabilities at the sidewalls and bottom of the trench. A comparison of the simulated profiles with corresponding experimental profiles reveals that the proposed model reproduces the experimental profiles, if the angular distribution functions and absorption probabilities employed in the model is in agreement with data found in the literature. Therefor the model developed in the context of this work is an adequate description of the effects taking place during a gas chopping plasma etching process.

Adsorption of element 112 on a Au surface

Während der letzten 20 Jahre hat sich das Periodensystem bis zu den Elementen 114 und 116 erweitert. Diese sind kernphysikalisch nachgewiesen, so dass jetzt die chemische Untersuchung an erster Selle steht. Nachdem sich das Periodensystem bis zum Element 108 so verhält, wie man es dem Periodensystem nach annimmt, wird in dieser Arbeit die Chemie des Elements 112 untersucht. Dabei geht es um die Adsorptionsenergie auf einer Gold-Ober fläche, weil dies der physikalisch/chemische Prozess ist, der bei der Analyse angewandt wird. Die Methode, die in dieser Arbeit angwandt wird, ist die relativistische Dichtefunktionalmethode. Im ersten Teil wird das Vielkörperproblem in allgemeiner Form behandelt, und im zweiten die grundlegenden Eigenschaften und Formulierungen der Dichtefunktionaltheorie. Die Arbeit beschreibt zwei prinzipiell unterschiedliche Ansätze, wie die Adsorptionsenergie berechnet werden kann. Zum einen ist es die sogenannte Clustermethode, bei der ein Atom auf ein relativ kleines Cluster aufgebracht und dessen Adsorptionsenergie berechnet wird. Wenn es gelingt, die Konvergenz mit der Größe des Clusters zu erreichen, sollte dies zu einem Wert für die Adsorptionsenergie führen. Leider zeigt sich in den Rechnungen, dass aufgrund des zeitlichen Aufwandes die Konvergenz für die Clusterrechnungen nicht erreicht wird. Es werden sehr ausführlich die drei verschiedenen Adsorptionsplätze, die Top-, die Brücken- und die Muldenposition, berechnet. Sehr viel mehr Erfolg erzielt man mit der Einbettungsmethode, bei der ein kleiner Cluster von vielen weiteren Atomen an den Positionen, die sie im Festkörpers auf die Adsorptionsenergie soweit sichergestellt ist, dass physikalisch-chemisch gute Ergebnisse erzielt werden. Alle hier gennanten Rechnungen sowohl mit der Cluster- wie mit der Einbettungsmethode verlangen sehr, sehr lange Rechenzeiten, die, wie oben bereits erwähnt, nicht zu einer Konvergenz für die Clusterrechnungen ausreichten. In der Arbeit wird bei allen Rechnungen sehr detailliert auf die Abhängigkeit von den möglichen Basissätzen eingegangen, die ebenfalls in entscheidender Weise zur Länge und Qualität der Rechnungen beitragen. Die auskonvergierten Rechnungen werden in der Form von Potentialkurven, Density of States (DOS), Overlap Populations sowie Partial Crystal Overlap Populations analysiert. Im Ergebnis zeigt sich, dass die Adsoptionsenergie für das Element 112 auf einer Goldoberfläche ca. 0.2 eV niedriger ist als die Adsorption von Quecksilber auf der gleichen Ober fläche. Mit diesem Ergebnis haben die experimentellen Kernchemiker einen Wert an der Hand, mit dem sie eine Anhaltspunkt haben, wo sie bei den Messungen die wenigen zu erwartenden Ereignisse finden können.

Delocalization of a hole in van der Waals clusters: Ionization potential of rare-gas and small Hg_n clusters

The size dependence of the ionization potential I_p(n) of van der Waals (vdW) bound clusters has been calculated by using a model Hamiltonian, which includes electron hopping, vdW interactions, and charge-dipole interactions. The charge-density and dipole-density distributions for both neutral and ionized n-atom clusters are determined self-consistently. The competition between the polarization energy of the neutral atoms surrounding a partially localized hole and the tendency toward hole delocalization in the ionized clusters is found to dominate the size dependence of I_p(n). To test our theory, we culculate I_p(Xe_n) and I_p(Kr_n) for n \le 300. Good quantitative agreement with experiment is obtained. The theory is also applied to calculate I_p(Hg_n). Comparison with experiments suggests that in Hg_n^+ clusters with n \le 20 the positive charge is mainly distributed within a trimer which is situated at the center of the cluster and which polarizes the n - 3 surrounding neutral atoms.

On the localization of electrons and holes in Hg_n and rare-gas clusters

We have used a microscopic theory to study the size dependence of the degree of localization of the valence electrons and holes in neutral an ionized rare-gas and Hg_n clusters. We discuss under which circumstances localization of the electrons and holes is favoured. We have calculated the ionization potential of Xe_n, Kr_n and small Hg_n clusters. Good agreement with experiments is obtained. We have also determined the dependence of the ionization potential on cluster structure.

An attempt on the calculation of relativistic potential energy curves: noble gas difluorides

Total energy SCF calculations were performed for noble gas difluorides in a relativistic procedure and compared with analogous non-relativistic calculations. The discrete variational method with numerical basis functions was used. Rather smooth potential energy curves could be obtained. The theoretical Kr - F and Xe - F bond distances were calculated to be 3.5 a.u. and 3.6 a.u. which should be compared with the experimental values of 3.54 a.u. and 3.7 a.u. Although the dissociation energies are off by a factor of about five it was found that ArF_2 may be a stable molecule. Theoretical ionization energies for the outer levels reproduce the experimental values for KrF_2 and XeF_2 to within 2 eV.

Chemical gas sensors based on functionalized self-actuated piezo-resistive cantilevers

Der Schwerpunkt dieser Arbeit liegt in der Anwendung funktionalisierter Mikrocantilever mit integrierter bimorpher Aktuation und piezo-resistiver Detektion als chemische Gassensoren für den schnellen, tragbaren und preisgünstigen Nachweis verschiedener flüchtiger Substanzen. Besondere Beachtung erfährt die Verbesserung der Cantilever-Arbeitsleistung durch den Betrieb in speziellen Modi. Weiterer Schwerpunkt liegt in der Untersuchung von spezifischen Sorptionswechselwirkungen und Anwendung von innovativen Funktionsschichten, die bedeutend auf die Sensorselektivität wirken.

High-Speed Semiconductor Lasers based on Low-Dimensional Active Materials for Optical Telecommunication

The scope of this work is the fundamental growth, tailoring and characterization of self-organized indium arsenide quantum dots (QDs) and their exploitation as active region for diode lasers emitting in the 1.55 µm range. This wavelength regime is especially interesting for long-haul telecommunications as optical fibers made from silica glass have the lowest optical absorption. Molecular Beam Epitaxy is utilized as fabrication technique for the quantum dots and laser structures. The results presented in this thesis depict the first experimental work for which this reactor was used at the University of Kassel. Most research in the field of self-organized quantum dots has been conducted in the InAs/GaAs material system. It can be seen as the model system of self-organized quantum dots, but is not suitable for the targeted emission wavelength. Light emission from this system at 1.55 µm is hard to accomplish. To stay as close as possible to existing processing technology, the In(AlGa)As/InP (100) material system is deployed. Depending on the epitaxial growth technique and growth parameters this system has the drawback of producing a wide range of nano species besides quantum dots. Best known are the elongated quantum dashes (QDash). Such structures are preferentially formed, if InAs is deposited on InP. This is related to the low lattice-mismatch of 3.2 %, which is less than half of the value in the InAs/GaAs system. The task of creating round-shaped and uniform QDs is rendered more complex considering exchange effects of arsenic and phosphorus as well as anisotropic effects on the surface that do not need to be dealt with in the InAs/GaAs case. While QDash structures haven been studied fundamentally as well as in laser structures, they do not represent the theoretical ideal case of a zero-dimensional material. Creating round-shaped quantum dots on the InP(100) substrate remains a challenging task. Details of the self-organization process are still unknown and the formation of the QDs is not fully understood yet. In the course of the experimental work a novel growth concept was discovered and analyzed that eases the fabrication of QDs. It is based on different crystal growth and ad-atom diffusion processes under supply of different modifications of the arsenic atmosphere in the MBE reactor. The reactor is equipped with special valved cracking effusion cells for arsenic and phosphorus. It represents an all-solid source configuration that does not rely on toxic gas supply. The cracking effusion cell are able to create different species of arsenic and phosphorus. This constitutes the basis of the growth concept. With this method round-shaped QD ensembles with superior optical properties and record-low photoluminescence linewidth were achieved. By systematically varying the growth parameters and working out a detailed analysis of the experimental data a range of parameter values, for which the formation of QDs is favored, was found. A qualitative explanation of the formation characteristics based on the surface migration of In ad-atoms is developed. Such tailored QDs are finally implemented as active region in a self-designed diode laser structure. A basic characterization of the static and temperature-dependent properties was carried out. The QD lasers exceed a reference quantum well laser in terms of inversion conditions and temperature-dependent characteristics. Pulsed output powers of several hundred milli watt were measured at room temperature. In particular, the lasers feature a high modal gain that even allowed cw-emission at room temperature of a processed ridge wave guide device as short as 340 µm with output powers of 17 mW. Modulation experiments performed at the Israel Institute of Technology (Technion) showed a complex behavior of the QDs in the laser cavity. Despite the fact that the laser structure is not fully optimized for a high-speed device, data transmission capabilities of 15 Gb/s combined with low noise were achieved. To the best of the author`s knowledge, this renders the lasers the fastest QD devices operating at 1.55 µm. The thesis starts with an introductory chapter that pronounces the advantages of optical fiber communication in general. Chapter 2 will introduce the fundamental knowledge that is necessary to understand the importance of the active region`s dimensions for the performance of a diode laser. The novel growth concept and its experimental analysis are presented in chapter 3. Chapter 4 finally contains the work on diode lasers.

Effects of red brick production on land use, household income, and greenhouse gas emissions in Khartoum, Sudan

In Khartoum (Sudan) a particular factor shaping urban land use is the rapid expansion of red brick making (BM) for the construction of houses which occurs on the most fertile agricultural Gerif soils along the Nile banks. The objectives of this study were to assess the profitability of BM, to explore the income distribution among farmers and kiln owners, to measure the dry matter (DM), nitrogen (N), phosphorus (P), potassium (K) and organic carbon (C_org) in cow dung used for BM, and to estimate the greenhouse gas (GHG) emissions from burned biomass fuel (cow dung and fuel wood). About 49 kiln owners were interviewed in 2009 using a semi-structured questionnaire that allowed to record socio-economic and variable cost data for budget calculations, and determination of Gini coefficients. Samples of cow dung were collected directly from the kilns and analyzed for their nutrients concentrations. To estimate GHG emissions a modified approach of the Intergovernmental Panel on Climate Change (IPCC) was used. The land rental value from red brick kilns was estimated at 5-fold the rental value from agriculture and the land rent to total cost ratio was 29% for urban farms compared to 6% for BM. The Gini coefficients indicated that income distribution among kiln owners was more equal than among urban farmers. Using IPCC default values the 475, 381, and 36 t DM of loose dung, compacted dung, and fuel wood used for BM emit annually 688, 548, and 60 t of GHGs, respectively.