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Institute
Die Materialklasse der transparenten leitenden Metalloxide (engl. transparent conducting oxides (TCO)) und amorphen oxidischen Dünnschichtsysteme (engl. amorphous oxidic semiconductors (AOS)) sind überaus faszinierend, da sie gegensätzliche physikalische Eigenschaften, wie Transparenz und hohe Leitfähigkeit in sich vereinen. Die zugrunde liegenden physikalischen Mechanismen sind immer noch unklar und werden in dieser Dissertation beleuchtet. Dazu wurde die resonante Photoelektronenspektroskopie (resPES)gewählt, da sie sich in den letzten Jahren als vielseitiges Werkzeug für die detaillierte Untersuchung der elektronischen Struktur und der Identifikation von Defekten ausgezeichnet hat. Im Rahmen dieser Arbeit ergab sie die einmalige Möglichkeit, sowohl hoch qualitative TCO-Einkristalle (ZnO, Ga2O3, In2O3 und SnO2) als auch amorphe oxidische Dünnschichtsysteme (GIZO und SnOx) photeelektronenspektroskopisch zu untersuchen und zu vergleichen. Somit wird gezeigt, dass die elektronische Struktur der Materialklasse der TCO und ihrer korrespondierenden AOS mehr Gemeinsamkeiten aufweisen, als bisher erwartet wurde.
Es zeigt sich, dass die Bandlücke, im eigentlichen Sinne, in der Materialklasse der TCO und AOS nicht existiert. Lokalisierte Zustände füllen den gesamten Bereich dieser Bandlücke aus und reichen zum Teil in das Valenzband (VB) und Leitungsband (CB) hinein. Dies führt dazu, dass es keine, wie bisher gedacht, scharfen Grenzen zwischen lokalisierten und delokalisierten Zuständen gibt. Um dies zu verdeutlichen wird ein neuartiges Modell eingeführt, das aufzeigt, dass die Wechselwirkung von metallischen d- und s-Niveaus in einer Öffnung der d-Schale resultiert. Durch Charge-Transfer (CT)-Mechanismen und weitere Hybridisierung mit metallischen unbesetzten p-Zuständen folgt eine stärkere Lokalisierung. Die Diskussion wird begonnen mit der Klärung der Elementeverhältnisse der untersuchten Materialsysteme. Darauf folgt die Charakterisierung von intrinsischen Defekten und ihren Beiträgen auf die elektronische Struktur. Abschließend werden die elektronischen Strukturen der AOS mit denen der korrespondierenden TCO verglichen.
The method of microscopic imaging using X-rays and diffractive lenses was developed at synchrotron radiation facilities and it was recently transferred to systems with laboratory X-ray sources. The first part of this thesis focuses on instrumentation, in particular on the fabrication, characterization, and application of multilayer Laue lenses (MLL). The second part describes a micromechanical in-situ test that is used to study crack propagation with X-ray microscopy in microchips in a dedicated fracture mechanics experiment called micro double cantilever beam test (MicroDCB).
MLLs were fabricated from WSi2/Si multilayer coatings using mechanical preparation and focused ion beam milling. Initial characterization of the obtained lenses using scanning electron microscopy and X-ray microscopy was used to evaluate the quality of the multilayer stack and particularly to identify geometrical imperfections of individual lens elements. Crossed partial MLLs were assembled as a compact lens device for two-dimensional operation, i.e. point focusing of synchrotron radiation or full-field transmission imaging. The optical properties were simulated using a geometrical optics approximation and a physical optics model. Experimental results verify full-field imaging using crossed partial MLLs with a focal length of 8.0 mm for Cu-Ka radiation in a laboratory X-ray microscope. Sub-100 nm resolution is shown and remaining aberrations are discussed. So-called wedged MLLs employ dynamic diffraction to increase the diffraction efficiency. A fabrication process is presented that allows a subsequent geometrical modification of the lens element using a stress layer. Thus, the wedged geometry is realized independently of the multilayer coating. The resulting layer tilt is measured using a laboratory X-ray microscope. First investigations of such wedged MLLs with synchrotron radiation at a photon energy E=15.25 keV show an enhancement of the diffraction efficiency of 57 % in comparison to a tilted MLL with the same dimensions.
The long working distance of the X-ray microscope facilitates the integration of customized equipment to perform in-situ experiments. The MicroDCB tester was designed and built to drive a crack in an appropriately prepared specimen. It is compatible with the X-ray microscope and it allows tomographic studies under load. In particular, the method was applied to investigate crack propagation in the on-chip interconnect stack of advanced microelectronics products. Stable crack propagation at this location was achieved. Subsequent tomographies were acquired at several load steps. The reconstructed datasets show no critical distortions. This test is assumed to provide valuable information about crack propagation such heterogeneous structures, what is of interest to address reliability issues.
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.
Role of substrates morphology and chemistry in ALD HfO₂ on Si(111)-H terminated surfaces as model
(2017)
This work presents an approach to investigate fundamental aspects concerning the early stage of the atomic layer deposition (ALD) growth process on stepped surfaces. The first interaction between precursors and surface is strongly important for the ALD growth that it is still far away from the status to be completely understood.
For this purpose, a few ALD-cycles withtetrakis(dimethylamido)hafnium (TDMAH) and trimethylaluminum (TMA) as metallic precursors and water (H₂O) as oxidant has been performed in order to study the initial metal oxide film growth on stepped surfaces such as silicon Si(111)-H terminated, highly oriented pyrolytic graphite (HOPG) and silver deposited HOPG (Ag-HOPG). These investigations have been carried out at various substrate temperatures, where scanning tunneling microscopy (STM) has been used systematically to probe the ALD features. This technique is delivering unique knowledge about the locality and the density of nucleation’s sites on the different substrates. The data collected are then subjected to a mathematical model to understand the growth and to determine the effect of the surface morphology and chemistry on the behavior of the nucleation.
The in-situ cycle-by-cycle STM investigation of 4 initial ALD cycles of TDMAH and H₂O on Si(111)-H terminated at room temperature (RT) and at 280°C displays two regimes of growth: In Regime I (1st - 2nd cycle) an increase in roughness in the first cycle to 0.2nm and 0.34nm respectively for RT and 280°C with a partial surface coverage of 71% and 54% is observed. In the 2nd cycle, the coverage increased to ~98% and 94% maintaining the same film height of the 1st cycle. A complete layer is formed in this regime. The results are discussed in reference to the Puurunen model. Following this model, the determination of the reaction mechanism in relation to the number of Hf atoms/nm² attached to the surface reveals that two ligands exchanges occur at RT and one ligand exchange at 280°C in the first regime. In addition, the origin of the reaction saturation was determined to be caused by the steric hindrance effect. In this first regime, the growth model is governed by random deposition followed by Mullins diffusion as determined from the universal values found for the roughness dynamic exponents (α, β, 1/z) of the film.
In the framework of this thesis, synchrotron radiation based spectroscopy methods are applied to study the electronic structures of stoichiometric Rutile single crystals and TiO2 thin films, and the initial stage of chromium and cobalt growth on TiO2 thin films. Resonance photoemission spectroscopy of clean TiO2 at the Ti L2,3 edges led to Auger-like features, with kinetic energies corresponding to the Ti L2,3M4,5M4,5 Auger decay channels. The presence of these features is assigned to origin from a d2L2 charge transfer state. The resonance of the Ti L3M2,3V Auger channel at the Ti L2 edge is assigned to the L2L3V Coster-Kronig Auger, followed by the normal L3M2,3V Auger decay. The deposition of chromium on the TiO2 film causes a strong interaction at the interface, in which TiO(2-x) is formed together with chromium in the Cr 3+ state. Besides the oxidized component, contribution of metallic chromium is found as well. In the ultra-low coverage regime, post-deposition oxidation is observed, in which metallic chromium is oxidized to Cr2O3, accompanied by re-oxidation of the substrate to TiO2. The interface reaction is also reflected by the appearance of two defect states in the band gap. Resonant photo-emission at the Cr 2p and Ti 2p edges shows well distinguishable Cr 3d respectively Ti 3d character of the respective states. Indications for self-cleaning properties are found by removal of surface carbon during storage in UHV, but the influence of chromium on these properties is not studied in detail. The interaction between cobalt and TiO2 is weaker than that of chromium and TiO2. Nevertheless, an interface reaction is found, in which some of the deposited cobalt is oxidized, while the oxide support is partly reduced. The particular oxidation state of Cobalt is identified by means of multiplet calculation including charge transfer and crystal field effects. The calculated XAS and XPS spectra indicate Co 2+ in a tetrahedral coordination with four oxygen atoms. The metallic component of cobalt gives rise to a broad resonance in the valence band down to -20 eV, with a pronounced satellite feature that reflects the oxidized component.
In this work, growth and characterisation of 3C-SiC thin films, investigation of oxidation of thus prepared layers and Pr-silicate and AlON based interface with SiC have been studied. Chemical vapor deposition of 3C-SiC thin films on Si(001) and Si(111) substrates has been investigated. Prior to the actual SiC growth, preparation of initial buffer layers of SiC was done. Using such a buffer layer, epitaxial growth of 3C-SiC has been achieved on Si(111) and Si(001) substrates. The temperature of 1100°C and 1150°C has been determined to be the optimal temperature for 3C-SiC growth on Si (111) and Si(001) substrates respectively. The oxidation studies on SiC revealed that a slow oxidation process at moderate temperatures in steps was useful in reducing and suppressing the g-C at the SiO2/SiC interface. Clean, graphitefree SiO2 has been successfully grown on 3C-SiC by silicon evaporation and UHV anneal. For the application of high-k Pr2O3 on silicon carbide, plausible interlayer, Pr-Silicate and AlON, have been investigated. Praseodymium silicate has been prepared successfully completely consuming the SiO2 and simultaneously suppressing the graphitic carbon formation. A comparatively more stable interlayer using AlON has been achieved. This interlayer mainly consists of stable phases of AlN along with some amount of Pr-aluminates and CN. Such layers act as a reaction barrier between Pr2O3 and SiC, and simultaneously provide higher band offsets.
Die vorliegende Arbeit behandelt CuInS2-Filme, die mittels Molekularstrahlepitaxie auf einkristallinen Si- und GaAs-Substraten unterschiedlicher Orientierung abgeschieden wurden. In-situ kamen dabei photoelektronenspektroskopische Analysemethoden und die Beugung niederenergetischer Elektronen zum Einsatz. Ex-situ wurden die Filme mittels Röntgenstrukturanalyse, Ionenrückstreuung und Photolumineszenz untersucht. Zunächst wurde die Bandanpassung des Si(111)/CuInS2(112)-Heteroübergangs bestimmt, wobei die Grenzfläche durch das Auftreten von Fremdphasen und durch Interdiffusion nicht ideal und stark gestört erscheint. Es wurde ein Grenzflächendipol von etwa 1 eV ermittelt. Der Vergleich der chemischen Zusammensetzung an der Filmoberfläche und im Filmvolumen deutet auf einen Konzentrationsgradienten in der Schicht hin. Unabhängig vom Cu/In-Verhältnis wurde eine schwefelarme Oberfläche gefunden. Zudem zeigen Cu-reiche CuInS2-Filme unabhängig von der Substratorientierung ein [112]-orientiertes Wachstum, wogegen im In-reichen Präparationsregime die Kristallorientierung des Substrates übernommen wird.
The chemical and electronic structure of chalcopyrite absorbers with different bulk band gap energies, Egbulk, [i.e., low-gap Cu(In,Ga)Se2 (CIGSe, Egbulk ~ 1.2 eV) and wide-gap CuInS2 (CIS, Egbulk ~ 1.5 eV)] and of buffer/absorber heterointerfaces based on these materials are studied with soft and hard x-ray spectroscopy techniques. Mechanisms that benefit (limit) the performance of low(wide)-gap chalcopyrite-based solar cells are identified. This knowledge is used to develop surface tailoring treatments to optimize buffer/absorber heterointerfaces based on wide-gap chalcopyrites and improve the performance of their solar cells.
Photoemission spectroscopy (PES) characterization of the two absorbers (i.e., CIGSe and CIS) reveal compositional-depth profiles. The changes detected in CIGSe include: a near surface Ga-depletion, a strongly Cu-poor surface and a strong presence of surface Na that (likely) occupies Cu vacancies. A similar Cu-deficiency is found in CIS. The depth-composition changes result in significant widening of the band gap at the surface, Egsurf, (i.e., CIGSe, Egsurf: 1.70 ± 0.2 eV and CIS, Egsurf: 1.88 ± 0.2 eV) as evident by ultraviolet photoelectron spectroscopy (UPS) and inverse photoemission spectroscopy (IPES) measurements. Differences in the interaction of the CIGSe and CIS surfaces with deposited buffer materials are identified. PES and modified Auger parameter studies reveal strong intermixing at the CdS/CIGSe and ZnS/CIGSe heterointerfaces. S L2,3 x-ray emission spectroscopy (XES) measurements of CIGSe substrates submitted to CdS chemical bath deposition (CBD-CdS) treatments show the formation of In2S3 and defect-rich/nanostructured CdS at the interface, compounds with higher band gap values than the measured Egsurf for CIGSe. S L2,3 XES spectra of CIGSe substrates submitted to CBD-ZnS treatments reveal the formation of (Zn,In)(S,Se)2 chemical analogs at the interface. PES and XES measurement series show that the CdS/CIS heterointerface is more abrupt, with no detected interface chemical species. Direct measurement of the band alignment of these heterointerfaces reveals: an ideal conduction band offset (CBO) configuration for CdS/CIGSe (i.e., CBO: +0.11 ± 0.25 eV), a spike CBO configuration for ZnS/CIGSe (i.e., CBO: +1.06 ± 0.4 eV), and a highly unfavorable cliff CBO configuration for CdS/CIS (i.e., CBO: -0.42 ± 0.25 eV). The performance of solar cell devices based on these heterointerfaces is correlated to their CBO configuration.
Two surface tailoring approaches intended to correct the CBO configuration of the CdS/CIS heterointerface are presented. One method is based on rapid thermal processing (RTP) selenization treatments of CIS absorbers, aiming to exchange Se for S in treated samples. The idea behind this approach is to modify the surface of a wide-gap chalcopyrite so that it forms a more favorable heterointerface with CdS, such as heterointerfaces within low-gap chalcopyrite devices. X-ray fluorescence analysis and PES measurements of RTP-treated CIS samples show a greater treatment effect at the surface of the sample compared to the bulk (i.e., surface [Se]/[S+Se] range: 0.23 ± 0.05 to 0.83 ± 0.05, compared to bulk [Se]/[S+Se] range: 0.01 ± 0.03 to 0.24 ± 0.03). Tuning of the Cu:In:(S+Se) surface composition from a Cu-poor 1:3:5 to a 1:1:2 stoichiometry is observed in RTP-treated CIS samples with lower to higher surface Se contents, respectively. UPS measurements show a shift in valence band maximum toward the Fermi level in samples with higher surface Se content (i.e., -0.88 ± 0.1 to -0.51 ± 0.1 eV), as expected for a reduction in Egsurf due to exchange of Se for S. Ultraviolet-visible spectrophotometry reveals a reduction in the optical band gap of samples with greater Se incorporation (i.e., from 1.47 ± 0.05 to 1.08 ± 0.05 eV), allowing for a working window for optimization purposes.
The second tailoring method involves surface functionalization of CIS absorbers with dipole-charge-inducing self-assembled monolayers (SAM) of benzoic acid derivatives and thiol molecules. The introduction of dipole charges between a heterointerface can tune the relative alignment of the electronic bands composing its electronic structure; thus, use of a suitable dipole-inducing SAM could correct the CBO misalignment in the CdS/CIS heterointerface. UPS measurements of the secondary electron cut-off region of CIS samples treated with a selected set of SAMs show a work function modulation of CIS (i.e., 4.4 ± 0.2 eV - 5.2 ± 0.2 eV). Small gains in solar cell parameters of solar cells based on SAM-modified heterointerfaces are measured.
An overview of the performance of chalcopyrite(kesterite)-based solar cells in relation to the electronic properties of their corresponding buffer/absorber heterointerface suggests that optimization approaches extending beyond the buffer/absorber heterointerface may be needed for further performance gains in wide-gap chalcopyrite-based solar cell devices.
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.
Als Modellsystem für gleichrichtende Heterokontakte von Dünnschichtsolarzellen wurden polykristalline ZnO-Filme auf Si mittels Magnetron-Sputtern und metallorganischer Gasstrahldeposition (MOCBD) abgeschieden. Mit Photoelektronenspektroskopie wurden bis zu 3 chemische Grenzflächenkomponenten gefunden: SiOx, eine Willemit-artige Mischphase und reduziertes Zn0. Letzteres kann über die Sputterparameter Bias-Potenzial und O2-Partialdruck kontrolliert werden. Mit MOCBD wurden auf Si(111):H abrupte Heterokontakte präpariert. Ferner tritt an Korngrenzen und der Oberfläche Hydroxid auf. Dies kann durch Heizen entfernt werden. Während der Messungen traten energetische Verschiebungen der Spektren auf, die die Auswertung der Grenzflächenenergetik stören. Zur Erklärung wurde folgendes Modell entwickelt: In einem schnellen Oberflächenprozess findet Photolyse von Hydroxid statt, wodurch H2O oder mobile OH-Gruppen gebildet werden, die Sauerstoffvakanzen ausheilen und so die n-Dotierung vermindern. In einem langsameren Volumenprozess wird durch Photolyse von ZnO die n-Dotierung erhöht.
This thesis focuses on the deposition of thin TiO₂ films on p-type Si using atomic layer deposition (ALD) technique, on the study of the electronic proprieties of the grown films and on the electrochemical characterization of TiO₂/Si photoelectrodes. The deposition parameters, electronic properties and electrochemical performance and stability of the TiO₂/Si samples are correlated.
The ALD technique is used to deposit TiO₂ with two different precursors namely Titanium isopropoxide and Titanium methoxide onto Si substrates. Laboratory as well as synchrotron based X-ray spectroscopy techniques are used to characterize these films. The growth quality of the TiO₂ ALD films is determined by analyzing X-Ray photoelectron spectroscopy (XPS) data in terms of stoichiometry, defect states and Ti³⁺:Ti⁴⁺ ratios. The ALD technique was modified with different heating arrangements to obtain various polymorphs of TiO₂.
The ALD and anatase TiO₂ films are characterized using synchrotron radiation to study their electronic properties and these films are compared with single crystal rutile TiO₂. X-ray absorption spectroscopy (XAS) and resonant photoelectron spectroscopy (res-PES) measurements are performed with synchrotron radiation. XAS measurements are used to determine the polymorphs as well as the electronic structure of TiO₂ Res-PES measurements are conducted at the O1s and Ti2p edges to study multiple hole Auger decay processes and polaronic and charge transfer states as well as to determine the electronic band gap of the TiO₂ layers. One of the main findings of this thesis is the determination of the partial density of states (pDOS) of O and Ti in the conduction and valence band. The combination of the pDOS and the band edge positions obtained from res-PES measurements are used to calculate the charge neutrality level of the TiO₂ polymorphs.
The photoelectrochemical measurements are conducted on bare-Si and TiO₂/Si photoelectrodes. The electrochemical performance of these photoelectrodes is studied in electrolytes having pH values ranging from 1 to 13. The deposition of TiO₂ on Si enhances the photoelectrochemical performance of the Si photoelectrode. The TiO₂ increases the stability of the photoelectrode in all electrochemical media over 12 hours of experimental condition. Moreover, it is also observed that the TiO₂/Si photoelectrode is less responsive to the pH value of the electrolyte. The electrochemical findings are explained on the basis of the electronic properties of the TiO₂ layer. The electronic band gap obtained from spectroscopic measurement and the photoelectrochemical measurements are used to explain the performance and stability of the TiO₂/Si photoelectrodes. The thesis also addresses the stability of Si microstructured photoelectrodes (SiMPs) prepared by an electrochemical method. The stability of the SiMPs deteriorates more rapidly than that one of the planar Si photoelectrode. However, using a protective ALD TiO₂ layer on these SiMPs the overall performance is even more enhanced than on the TiO₂/planar Si system.
Als eine Folge der Miniaturisierung aller integrierten elektrischen Bauteile wird der spezifische Widerstand der TaN/Ta Doppelsperrschichten ein zunehmend wichtiger Parameter für die Schaltgeschwindigkeit beim 32 nm Technologieknoten. In Rahmen dieser Arbeit wird die Optimierung der Abscheidung von TaN/Ta Stapeln durchgeführt, mit dem Ziel die Tantalnitridschichtdicke zu minimieren und das Tantal in der leitfähigeren alpha-Phase wachsen zu lassen. Im ersten Teil der Studie wurde in situ ARXPS verwendet, um das Wachstum von verschiedenen Tantalnitridschichten auf SiO2 und SiCOH in Abhängigkeit der Abscheidezeit, des Stickstoffflusses und der Abscheideleistung zu untersuchen. Im zweiten Teil wurde die kristalline Phase 20 nm dicken Tantal Schichten abgeschieden auf verschiedenen Tantalnitridschichten, die in der Wachstumsstudie vorgestellt worden sind, untersucht. Die wichtigsten Erkenntnisse sind das Auftreten von Tantalkarbid und Tantalsilizid als Zwischenschichtverbindungen bei der Abscheidung auf SiCOH und nur Tantalsilizid für die Abscheidung auf SiO2. Demzufolge wächst alpha-Tantal vorzugsweise auf Tantalkarbid und stickstoffreichen Zwischenschichten, während Silizid an der Schnittstelle das Wachstum von beta-Tantal fördert. Um die Ergebnisse zu überprüfen, wurden zwei weitere Modifikationen des Interfaces untersucht. So wurde eine kleinere Bias-Leistung für eine Abscheidung von Tantalnitrid auf SiO2 benutzt, um die Rolle des Tantalsilizids zu bestätigen. Außerdem wurde eine thermische Behandlung einer dünnen Tantalschicht auf SiCOH durchgeführt, um die Rolle des Tantalkarbids zu bestätigen. Schließlich ergab die Kontaktwiderstandsmessung in Viaketten auf strukturierten Wafern für vier ausgewählte Prozesse tendenziell den gleichen Verlauf wie die Schichtwiderstandsergebnisse der entsprechenden Barrierenaufbauten der Experimente auf blanken Testwafern.
Einige Effekte von Silizium sind bis heute ungeklärt. Dazu zählt Oxidation von hoch-dotiertem n-Si in Fluor-haltigen Säuren im Dunkeln. Diese Oxidation wurde erstmals systematisch untersucht und zur Grundlage eines Modells für Elektroneninjektion gemacht. Die angenommenen Oberflächenkomplexen erklären den Einsatz der Kennlinien. Weitere Untersuchungen zur Identifizierung des Komplexes sowie seiner energetischen Position bieten sich an. Mit zyklischen Voltammogrammen wurde gezeigt, dass die Vorschubgeschwindigkeit des Potentials entscheidend für die Gestalt der Kennlinien ist. Schon 20mV/s ist für das untersuchte System zu schnell, um einen Gleichgewichtszustand zu erreichen. Dies wird durch die Ausbildung von Hysteresen klar erkennbar. Der initielle Strompuls zeigt eine vielfache Stromdichte gegenüber den bekannten Werten der nachfolgenden Oszillationspulse. Die Wasserstoff-terminierte Grenzfläche wird innerhalb weniger Zehntelsekunden oxidiert und passiviert. Alle nachfolgenden Strompulse können als weniger gut synchronisierte Oxidationen verstanden werden.
A series of two-dimensional and three-dimensional quasi-steady state numerical simulations have been performed for the initial stages (seeding process) of the Czochralski (CZ) growth of oxide crystals using the finite element method (FEM). We have considered different cases and configurations with respect to real systems in the CZ-dielectrics laboratory of the Institute for Crystal Growth (IKZ). Using induction heating in metallic parts as heat source the fluid flow and temperature field were determined in the whole CZ system. The aim of these calculations was to investigate and reveal the effect of several parameters such as the geometry and location of an active afterheater with respect to the crucible, arrangement and design of thermal insulation, crucible bottom shape, and seed rotation rate on the flow and temperature field of the system and the seed-melt interface shape. The results demonstrate that the temperature and fluid flow in the gas domain is strongly affected by an active afterheater and its insulation as well as their geometry and position. The results also show the important role played by the seed rotation rate for influencing the shape of the seed-melt interface.
The thesis discusses a fundamental question of reconstruction on the Si(100) surface as well as three material combinations, which are important for perspective microelectronics technologies: Si/Pr2O3/Si(100), W/WNx/poly-Si/SiO2/Si(100), and CoSix/Si(100). A refined mixed ad-dimer model is developed for the Si(100)-c(4´4) reconstruction on the basis of scanning tunnelling microscopy investigations. A thermal stability of Pr2O3/Si(100) and Si/Pr2O3/Si(100) structures is studied with ion sputtering assisted Auger electron spectroscopy. The latter technique is also applied for precise determination of O and N content in the new W/WNx/poly-Si/SiO2/Si(100) structure, and to study the preferential sputtering of Si in CoSi2, CoSi, and Co2Si phases on Si(100) surface. The WSix/poly-Si/SiO2/Si(100) system, which was previously used in microelectronics, is studied for comparison. The preferential sputtering of Si in WSix is shown to be qualitatively similar as in the CoSix case.
Aluminium based micro mirrors exposed to UV laser light – in situ performance and degradation
(2014)
The present thesis characterises aluminium based micro mirrors exposed to UV laser light. Such micro mirrors, used in highly integrated spatial light modulators, can for example be used as programmable masks in DUV micro lithography. Therefore they are sensitive to any performance loss arising from material degradation or changes in the mirror curvature. The key question addressed in this thesis is the investigation of the in situ curvature change, which means characterisation during a real laser irradiation. For this purpose a measuring station was designed, combining a phase-shift interferometer, an optical microscope and the laser irradiation of the sample at 248nm. The Phase-shift interferometry technique used is a very sensitive contactless optical measurement principle, which allows a resolution of the sample surface in the single-digit nanometer range.
A multitude of irradiation tests were performed to describe the change of mirror curvature as a function of different irradiation parameters such as the pulse energy, the laser repetition rate or the ambient atmosphere. The most significant effect was detected by the variation of the applied pulse energy, which was in the range of 10⁻⁵J/cm²-10⁻²J/cm². A general conclusion was that a minimum energy of 10⁻⁵J/cm² at a repetition rate of 1kHz is required to detect any laser induced change of the mirror curvature. At higher energy levels two characteristic behaviours can be distinguished. Up to a level of 10⁻³J/cm² the mirrors show a permanent concave bowing in the range of λ/100. A further increase of the pulse energy causes an accumulating bowing in the opposite direction (convex) of λ/10 within some ten million laser pulses. However this convex bowing partially relaxes after the irradiation is stopped.
Another aspect of the thesis was the determination of laser induced material degradation. For this purpose irradiated mirrors were investigated by means of different devices and analytical techniques such as atomic force microscopy (AFM), reflectometry and transmission electron microscopy (TEM). The AFM analysis showed a slight increase of surface roughness and a directional change of the grain size. As a result of the TEM analysis it turned out that arrangement and shape of the grains seems not to have changed. But after the irradiation the growth of a porous oxide layer up to 20nm on the upper mirror surface was noticed.
Finally different hypotheses are proposed to explain the mechanisms behind the observed concave and convex bowing at particular pulse energies. In this connection it is assumed that the mirrors at pulse energies larger than 10⁻³J/cm² do not show a static bowing at all. It is rather assumed that the mirror bow oscillates with the laser repetition rate.
Aggressive scaling of the complementary metal-oxide-semiconductor (CMOS) transistors resulted in the silicon dioxide (SiO2) gate dielectrics being as thin as 1.2 nm in the state-of-the-art high performance transistors. In consequence, the leakage current due to direct tunneling of electrons through the gate oxide increased significantly resulting in an unacceptably high level of power dissipation. For this reason, it is very desirable to replace the SiO2 gate dielectric with an insulator of a higher dielectric constant (high-k). The higher dielectric constant allows for the use of physically thicker dielectric layers with high capacitance densities but strongly reduced tunneling currents. This work focuses on the preparation and characterization of Praseodymium silicate high-k dielectric layers on Si(001) and evaluates the potential of this material to replace SiO2 as a gate dielectric in the state-of-the-art and future CMOS technology generations.
Im Mittelpunkt der vorliegenden Arbeit stehen die Untersuchung von Fanointerferenzen innerhalb der wissenschaftlichen Methode der resonanten Photoelektronenspektroskopie. Basis dieser Methode ist die Interpretation aus dem Festkörper emittierter Elektronen. Die detektierten Elektronen können dabei aus direkten Photoemissionen oder Deaktivierungsprozessen (Spectator-/Participator-Zerfälle) nach resonanten Anregungen von Rumpfelektronen stammen. Führen beide Prozesse zum selben Systemendzustand, können die emittierten Elektronen interferieren, was sich in der Ausprägung eines charakteristischen Intensitätsprofils, dem Fano-Profil, äußert. Die Form des Intensitätsprofils kann dabei über den Fanoparameter q beschrieben werden.
Im Rahmen dieser Arbeit erfolgte die Diskussion von Fanointerferenzen an organischen (HOPG, Graphenflocken) und oxidischen (CuO, In2O3, SiO2) Materialsystemen.
Im HOPG und den untersuchten Graphenflocken konnten mittels der Analyse der Fanoprofile exzitonische Zustände innerhalb der Bandlücke nachgewiesen werden.
Durch die Untersuchungen am CuO konnte die Variation des Fanoparameters in Abhängigkeit vom Grundzustand des Systems gezeigt werden.
Die für die untersuchten In2O3 Einristalle beobachteten Interferenzen beruhen auf der Existenz besetzter Zustände an der Fermienergie.
Abschließend konnte eine Korrelation des jeweils auftretenden Fanoparameters mit den beobachteten multi-hole-Auger-Zerfällen nachgewiesen werden.
Wachstumsphänomene und Stickstoffdotierung bei der Sublimationszüchtung von 6H-Siliciumcarbid
(2001)
Die Keimoberfläche ist durch das Vorhandensein einer Störschicht charakterisiert, die durch die mechanische Kristallbearbeitung hervorgerufen wird. Diese Schicht kann die Ursache für zusätzliche Defekte sein. Die Untersuchungen der Oberflächenmorphologie zeigen, daß ein Überschuß an Silicium im Quellmaterial notwendig ist, um ein defektfreies Wachstum in den ersten Stadien zu ermöglichen. Sowohl ein Oxidationsschritt vor dem Wachstum als auch die Anwendung von fehlorientierten Keimen führten nicht zum gewünschten Stufenfluß. Im Konzentrationsbereich von 1x10^18 <= c_N (cm^-3) <= 3x10^19 wurden 6H-SiC-Einkristalle gezüchtet, sowohl auf (0001)- als auch (000-1)-Keimen. Der Einbau von Stickstoff bewirkt das Absinken der Wachstumsgeschwindigkeit, was mit dem ''site-competition''-Modell erklärt werden kann. Die Sättigung der Stickstoffkonzentration im Kristall in Abhängigkeit vom N_2/Ar-Verhältnis konnte durch eine Langmuir-Isotherme beschrieben werden. Die Polarität der Keimoberfläche beeinflußt den Stickstoffeinbau. Die Stickstoffkonzentration im gewachsenen Kristall ist auf der C-terminierten Fläche ca. doppelt so hoch wie auf der Si-terminierten. Es wurde gezeigt, daß die Oberflächenmorphologie zusätzlich zur Keimpolarität den Stickstoffeinbau beeinflußt.
Spin-cast films of the ferroelectric copolymer P(VDF-TrFE) are attractive for various applications. For such films the question arises whether there exists a depending on film thickness of ferroelectric functionality. In this work, ultra-thin films of P(VDF-TrFE) up to 0.35nm of thickness have been successfully spin coated, which is quite promising in respect of low cost approach in the electronic industry. This thesis focuses on the preparation of the ultra-thin P(VDF-TrFE) copolymer film and its characterizations to find out a scientific guideline for the suitable application as a non-volatile memory element. Therefore, the ultra-thin film preparations have been investigated initially. Optimization of annealing parameters has been done to get the ferroelectric beta phase and thickness determination is also done carefully. The copolymer layer thickness could be determined down to about 0.35 nm. Photoelectron spectroscopy is used extensively for the characterization of the thin film. Eventually, longer time X-ray irradiation of the P(VDF-TrFE) sample may cause a phase change from ferroelectric to paraelectric. Therefore the X-ray irradiation time was also optimized. With photoelectron spectroscopy, the interface chemistry of the P(VDF-TrFE) copolymer and different electrode materials was studied. The interfaces aluminum/P(VDF-TrFE) and PEDOT:PSS/P(VDF-TrFE) are compared. PEDOT:PSS is a conducting polymer, Poly(3,4-ethylenedioxidethiophene): poly(styrenesulfonate). This data suggested that an interface layer is formed for electrodes, made of aluminum. An interface reaction occurs in both cases: for aluminum as top and as bottom electrode. In contract, the organic PEDOT:PSS electrode shows no chemical interaction with the P(VDF-TrFE) copolymer. The much lower reactivity of organic electrode, compare to aluminum, gives a direct hint to improved functional properties of thin organic ferroelectric films. In terms of a low cost approach for electronics, based on organic devices, the introduction of organic non volatile memories is of great importance. P(VDF-TrFE) copolymer is the material with a very hopeful perspective. In next part electrical measurements with P(VDF-TrFE) have been done. By capacitance voltage measurements, the ferroelectric behavior of the polymer by measurements at elevated temperatures (Curie-Point) is confirmed, a threshold for remanent poalrization for films below 100 nm is found, if aluminum electrodes are used, but with inert electrodes, a downscaling of a low coercitive field was possible down to ten nm. This is very important, because due to the high coercitive field of the copolymer (>50 MV/m), ultrathin films for low operation voltages are needed. A prerequisite for memory applications is a high retention time, this was also confirmed. By the help of Near edge X-ray Absorption Spectroscopy (NEXAFS) the possible ferroelectric dipole orientation have been also investigated. The average dipole orientation (perpendicular to the substrate) is observed up to 0.35 nm P(VDF-TrFE) copolymer films when PEDOT:PSS/Si substrate is used. The ferroelectric properties of ultrathin films down to a layer thickness of 10nm were characterized using spectroscopic (F1s NEXAFS) and electrical methods (Capacitance voltage). The results indicates an extrinsic switching mechanism with a much lower opera-tion voltage than for a collective intrinsic switching. Both independent methods agree that there is no critical thickness for spincoated copolymer films down to 10 nm, if an adapted system of electrodes is used.