FG Angewandte Physik und Halbleiterspektroskopie
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Dark and light current–voltage characteristics of perovskite solar absorbers are analyzed in terms of their carrier densities. The analysis reveals p-type large polarons as a dominant carrier type in the investigated perovskite solar cells. The mechanism causing photosensitivity is attributed to the dissociation (and pairing) of bipolarons to large polarons (and vice versa) that are controlled by the internal potential Γ. As an example, the polaron concept is tested for a formamidinium lead triiodide perovskite solar cell. The individual steps of the data analysis are demonstrated and determine the ionicity factor of this perovskite film, quantify the density of the large polarons, and predict the gain and loss of photo-induced carriers. It is deduced that a reversible light-on/off operation can only occur when the bias voltage never exceeds a critical value of the internal potential. The results gained in this study suggest that the novel analysis can be successively applied on different hybrid perovskite materials, too.
Thermal atomic layer deposition (ALD) of cerium oxide using commercial Ce(thd)4 precursor and O₃ on SiO₂ substrates is studied employing in-situ X-ray photoelectron spectroscopy (XPS). The system presents a complex growth behavior determined by the change in the reaction mechanism when the precursor interacts with the substrate or the cerium oxide surface. During the first growth stage, non-ALD side reactions promoted by the substrate affect the growth per cycle, the amount of carbon residue on the surface, and the oxidation degree of cerium oxide. On the contrary, the second growth stage is characterized by a constant growth per cycle in good agreement with the literature, low carbon residues, and almost fully oxidized cerium oxide films. This distinction between two growth regimes is not unique to the CeOx/SiO₂ system but can be generalized to other metal oxide substrates. Furthermore, the film growth deviates from the ideal layer-by-layer mode, forming micrometric inhomogeneous and defective flakes that eventually coalesce for deposit thicknesses above 10 nm. The ALD-cerium oxide films present less order and a higher density of defects than films grown by physical vapor deposition techniques, likely affecting their reactivity in
oxidizing and reducing conditions.
This study comprehensively investigated the thermal properties and phase behavior of lithium niobate-tantalate (𝐿𝑖𝑁𝑏𝑥𝑇𝑎1−𝑥𝑂3, LNT) solid solutions. The research used experimental techniques to explore the variation of the ferroelectric Curie temperature (Tc) as a function of composition. LNT single crystals were grown using the Czochralski method. The elemental composition of niobium (Nb) and tantalum (Ta) in these crystals was determined using X-ray fluorescence (XRF) analysis. Small, compositionally homogeneous samples were then selected for differential scanning calorimetry (DSC) measurements to determine specific heat capacities (Cp). The DSC measurements revealed a linear decrease in Tc with increasing Ta concentration in the LNT solid solution crystals. Additionally, the ferroelectric transition width was observed to be narrower in mixed crystals compared to pure LT. Differential Thermal Analysis (DTA) and crystal growth experiments were performed further to understand the phase behavior of LNT solid solutions. The heats of fusion for the end members, LN and LT, were measured using DTA, yielding values of 103 kJ/mol at 1531 K for LN and 289 kJ/mol at 1913 K for LT. These values were used as input parameters in a thermodynamic solution model implemented in the Factsage
software. The solution model enabled the calculation of a phase diagram for LNT solid solutions, which was further optimized in the Calphad Factsage. Thermodynamic parameters for the Gibbs free energy of mixing of the solid solution were also generated. The resulting phase diagram showed good agreement with the experimental data. Additionally, the temperature-dependent thermal conductivity of pure LN, LT, and LNT solid solutions and selected doped LN and LT crystals (Mg, Zn) was investigated. Measurements were conducted across a temperature range from 300 K to 1300 K. The findings indicated that thermal conductivity increases with temperature, especially above 800 K, with a more pronounced effect in tantalum-rich solutions. The interplay of the Nb/Ta ratio and doping effects was particularly significant at high temperatures. These insights into the thermal conductivity of LNT and doped LN and LT crystals are crucial for optimizing growth conditions. Understanding thermal conductivity helps ensure homogeneous crystallization during the growth process, which remains a challenge in the production of LNT single crystals.
High-resolution imaging of buried metal interconnect structures in advanced microelectronic products with full-field X-ray microscopy is demonstrated in the hard X-ray regime, i.e., at photon energies > 10 keV. The combination of two multilayer optics—a side-by-side Montel (or nested Kirkpatrick–Baez) condenser optic and a high aspect-ratio multilayer Laue lens—results in an asymmetric optical path in the transmission X-ray microscope. This optics arrangement allows the imaging of 3D nanostructures in opaque objects at a photon energy of 24.2 keV (In-Kα X-ray line). Using a Siemens star test pattern with a minimal feature size of 150 nm, it was proven that features < 150 nm can be resolved. In-Kα radiation is generated from a Ga-In alloy target using a laboratory X-ray source that employs the liquid-metal-jet technology. Since the penetration depth of X-rays into the samples is significantly larger compared to 8 keV photons used in state-of-the-art laboratory X-ray microscopes (Cu-Kα radiation), 3D-nanopattered materials and structures can be imaged nondestructively in mm to cm thick samples. This means that destructive de-processing, thinning or cross-sectioning of the samples are not needed for the visualization of interconnect structures in microelectronic products manufactured using advanced packaging technologies. The application of laboratory transmission X-ray microscopy in the hard X-ray regime is demonstrated for Cu/Cu6Sn5/Cu microbump interconnects fabricated using solid–liquid interdiffusion (SLID) bonding.
In this work, a reliable kinetic reaction mechanism was revised to accurately reproduce the detailed reaction paths of steam reforming of methane over a Ni/Al2O3 catalyst. A steadystate fixed-bed reactor experiment and a 1D reactor catalyst model were utilized for this task. The distinctive feature of this experiment is the possibility to measure the axially resolved temperature profile of the catalyst bed, which makes the reaction kinetics inside the reactor visible. This allows for understanding the actual influence of the reaction kinetics on the system; while pure gas concentration measurements at the catalytic reactor outlet show near-equilibrium conditions, the inhere presented temperature profile shows that it is insufficient to base a reaction mechanism development on close equilibrium data. The new experimental data allow for achieving much higher quality in the modeling efforts. Additionally, by carefully controlling the available active surface via dilution in the experiment, it was possible to slow down the catalyst conversion rate, which helped during the adjustment of the reaction kinetics. To assess the accuracy of the revised mechanism, a monolith experiment from the literature was simulated. The results show that the fitted reaction mechanism was able to accurately predict the experimental outcomes for various inlet mass flows, temperatures, and steam-to-carbon ratios.
In-situ study of crack propagation in patterned structures of microchips using X-ray microscopy
(2023)
The motivation of this thesis was to control crack steering into regions of engineered 3D-nanopatterned structures with high fracture toughness and to determine the local critical energy release rate for crack propagation in 3D-nanopatterned systems. On-chip copper interconnect structures of advanced microchips, insulated by organosilicate glasses, were chosen as an example system to study fracture on small scale, since this is a well-defined 3D- nanopatterned system and since a high mechanical robustness is requested for microchips. An experiment for in-situ high-resolution 3D imaging of the fracture behavior of 3D-nanopatterned structures and of the kinetics of microcrack propagation in solids was designed and applied, combining a miniaturized micromechanical test and high-resolution X-ray imaging. Particularly, a miniaturized piezo-driven double cantilever beam test set-up (micro- DCB) was integrated in a laboratory X-ray microscope, and nano X-ray computed tomography was applied for high-resolution 3D imaging of the microcrack evolution in the on-chip interconnect stack of microchips manufactured in the 14 nm technology node. The measured geometry of the microcrack at several loading steps during the micro-DCB test and the subsequent data analysis based on linear elastic fracture mechanics and the Euler-Bernoulli beam model were the basis for the development and application of a new methodology to determine the critical energy release rate for crack propagation in sub- 100 nm regions of a processed wafer quantitatively. It was experimentally proven that specially designed metallic guard ring structures at the rim of the microchips dissipate energy in such a way that the microcrack propagation is efficiently slowed down and eventually stopped, i.e. they are effective to prevent mechanical damage of microchips. It was demonstrated that it is possible to steer the microcrack in a controlled way by tuning the fracture mode mixity locally at the crack tip. The established concept for a controlled crack propagation provides the basis for further fundamental studies of the fracture behavior of nanoscale materials and structures. The results have significant effects for the understanding of fracture mechanics at small scales, e.g. in microchips, but also in other nanopatterned materials, e.g. in bio-inspired, hierarchically structured engineered materials. The experimental results gathered at realistic microelectronic products provide valuable information to control the crack path in on-chip interconnect stacks for design-for-reliability in semiconductor industry and to manufacture mechanically robust microchips in leading-edge technology nodes. The experimental study of controlled microcrack steering into regions with high fracture toughness provides knowledge for the design of guard ring structures in microchips to stop the propagation of microcracks, e.g. generated during the wafer dicing process.
This thesis describes low temperature growth of wide band gap metal oxide thin films deposited by thermal (T-) and plasma-enhanced (PE-) atomic layer deposition (ALD) techniques in which high quality materials are grown with atomic level precision.
Metal oxides are extensively investigated due to their exceptional physical and chemical properties, including relatively wide band gap, high dielectric constant and high thermal stability. This variety of properties results in a wide range of different applications. Thin films of indium oxide (InOx), gallium oxide (GaOx), zinc oxide (ZnOx), and quaternary InOx/GaOx/ZnOx (IGZO), in addition to the well-known aluminum oxide (AlOx), and the catalyst cerium oxide (CeOx), have proven to be superior candidates for many applications; from microelectronics and optoelectronics to gas sensor devices. The demanding requirements of low-temperature deposition processes for thermal sensitive substrates, which include high layer homogeneity and conformality over large areas, makes ALD a pioneer deposition technique. Although many oxides have been grown by TALD and PEALD, the deposition of wide band gap oxides at low temperatures are rarely reported and/or being investigated.
In this work, the deposition method of the individual binary oxide films and combining the respective binary processes into the developed super-cycle growth of quaternary compound have been investigated at relatively low-temperatures by TALD and PEALD. Besides, the growth characteristics and chemical properties of the deposited films were evaluated by in-situ and ex-situ characterization techniques such as spectroscopic ellipsometry (SE) and X-ray photoelectron spectroscopy (XPS), where the influence of ALD process parameters on the growth mechanism and films composition are discussed in detail for any potential applications.
Due to the unique electronic band structure, graphene has opened the great potential to extend the functionality of a large variety of graphene-based devices in health and environment, energy storage, or various microelectronic applications, to mention a few. At this point, the implementation of graphene into Silicon (Si) semiconductor technology is strongly dependent on several key challenges. Among them, high-quality and wafer-scale graphene synthesis on CMOS compatible substrates is of the highest importance. Though large-area graphene can be achieved on substrates like copper, platinum, silicon carbide, or single-crystal Ni, however, high growth temperatures, unavailability of large scale, or contamination issues are the main drawbacks of their usage. In this PhD work, 8-inch scale graphene synthesis is attempted on alternative substrates such as epitaxial Germanium on Si and polycrystalline Nickel on Si. To achieve the growth of the highest quality of graphene, this work focuses on the investigations of various nucleation and growth mechanisms, substrate–graphene interfaces, effects of different substrate orientations, and detailed microscopic and macroscopic characterization of the grown films. Finally, it should also be stressed that the experiments in this work were carried out in a standard BiCMOS pilot-line, making this study unique, as its results might directly pave the way to further graphene integration and graphene-based device prototyping in mainstream Si technologies.
The chemical and electronic structure of hybrid organometallic (CH₃NH₃PbI₍₃₋ₓ₎Clₓ) and inorganic (CsSnBr₃) perovskite materials on compact TiO₂ (c-TiO₂) is studied using x-ray and electron based spectroscopic techniques. The morphology and local elemental composition of CH₃NH₃PbI₍₃₋ₓ₎Clₓ, used as absorbers in PV devices, defining the film quality and influencing the performance of respective solar cells is studied in detail by using photoemission electron microscopy (PEEM). An incomplete coverage, with holes reaching down to the c-TiO₂ was revealed; three different topological regions with different degrees of coverage and chemical composition were identified. Depending on the degree of coverage a variation in I oxidation and the formation of Pb⁰ in the vicinity of the c-TiO₂ is found. The valence band maxima (VBM) derived from experimental data for the perovskite and c-TiO₂, combined with information from literature on spiro-MeOTAD suggests an energy level alignment resulting in an excellent charge selectivity at the absorber/spiro-MeOTAD and absorber/c-TiO₂ interfaces respectively. Further, the derived energy level alignment indicates a large recombination barrier (~2 eV), preventing shunts due to direct contact between c-TiO₂ and spiro-MeOTAD in the pin-holes.
In-situ ambient pressure hard x-ray photoelectron spectroscopy (AP-HAXPES) studies of 60 and 300 nm CH₃NH₃PbI₍₃₋ₓ₎Clₓ have been performed under varies conditions (i.e. vacuum/water and dark/UV light) to gain insight into the degradation mechanism responsible for the short lifetime of the absorber. The 60 nm perovskite forms Pb⁰ in water vapor (non-defined illumination) in presence of x-rays. The 300 nm perovskite sample shows a complex behavior under illumination/dark. In water vapor/dark the perovskite dissolves into its organic (MAI) and inorganic (PbI₂) components. Under illumination PbI₂ further decomposes to Pb⁰ induced by UV light and x-rays.
For alternative inorganic CsSnBr₃ perovskites, the impact of SnF₂ on the chemical and electronic structure is studied to identify its role for the improved performance of the solar cell. HAXPES and lab-XPS measurements performed on CsSnBr₃ with and without SnF₂ indicate two Sn, Cs, and Br species in all samples, where the second Sn species is attributed to oxidized Sn (Sn⁴⁺). When adding SnF₂ to the precursor solution, the coverage is improved and less Sn⁴⁺ and Cs and Br secondary species can be observed, revealing an oxidation inhibiting effect of SnF₂. Additionally, SnF₂ impacts the electronic structure, enhancing the density of states close to the VBM.
In dieser Arbeit konnte gezeigt werden, dass eine direkte Methanisierung von CO₂, die über die Sabatier-Gleichung, CO₂ + 4H₂ ↔ CH₄ + 2H₂O, beschrieben wird, im Labor- und im Technikums-Maßstab unter Variation verschiedenster Bedingungen realisierbar ist. Die Sabatier-Reaktion findet beschleunigt unter dem Einsatz von Katalysatoren statt. Unterschiedliche kommerzielle Katalysatoren auf Nickel und Ruthenium-Basis konnten auf ihrer Eignung für die Methanisierung untersucht werden und mit im Labor präparierte Katalysatoren verglichen werden. Relevante Größen zur Beschreibung der Aktivität der Katalysatoren ist der Umsatz an CO₂, die Ausbeute an CH₄ und die Selektivität bezüglich der Sabatier-Reaktion. Im Labor wurden Umsätze und Ausbeuten von über 90% und Selektivitäten von nahezu 100% gemessen. Durch eine Änderung der Temperatur, der Eingangsmenge an Gasen, der Katalysatormenge und des Druckes können die optimalen Prozessbedingungen für die Reaktion spezifiziert werden. Eine weitere Betrachtung galt der Messung mit synthetischen und realen Abgasen (Oxyfuel, CCS) und darauf bezogen, der Einfluss einer Verdünnung des CO₂ durch Stickstoff und Sauerstoff und der Rolle von bekannten Katalysatorgiften wie Schwefel- oder Stickoxiden. Es konnte ein Zusammenhang zwischen der Stärke der Verunreinigung an Schwefel, der Reaktortemperatur und der Abnahme der katalytischen Aktivität ermittelt werden. Die Produktion von Kohlenmonoxid gibt zusätzlich Aufschluss über stattfinden Teil-und Nebenreaktionen.
Ergebnisse in der Laboranlage konnten zum Teil für den Aufbau einer Technikumsanlage, welche eine Vergrößerung zum Labor um den Faktor 5000 darstellt, genutzt werden. Eine Zahl von Experimenten wurde im Technikum wiederholt. Die Technikumsanlage ist dabei in der Lage ca. 250 kg CO₂ pro Tag aus CO₂-haltigen Abgasen in Methan umzuwandeln. Ein erweiterter Praxisbezug stellte die Einbindung des Technikums in einem Kraftwerk dar und die Messung mit realem Rauchgas. Ohne zusätzliche Reinigungsschritte des Abgases konnten auch hier Umsätze von 90% erreicht werden. Eine komplexe Temperaturentwicklung und Erhöhung auf 600°C im Reaktor wurde aufgezeichnet und führt dabei zur Abnahme des Umsatzes auf ca. 60%. Bei diesen Temperaturen stellt sich ein Gleichgewicht zwischen, durch die exotherme Reaktion, erzeugter und abgeführter Wärme ein. Als Reaktionsprodukt wird ein Schwachgas erhalten, welches für die Rückverstromung eingesetzt werden kann.
In der Methanisierung von CO₂ besteht die Möglichkeit das CO₂ in einen Kreislauf (Power-to-Gas) zu binden und so die Emission von Treibhausgasen zu mindern. Das erzeugte Methan fungiert als chemischer Energiespeicher und trägt zur Stabilisierung des Stromnetzes bei.
