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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.
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.
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.
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.
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 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 this thesis the detailed investigations concerning processing and stability of thin films including carbon species and their possible application as materials of a low dielectric constant (low k) are presented. In order to gather a complex information regarding the chemical, morphological and dielectric properties of the produced layer a combination of the spectroscopy: X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and Fourier transform infrared spectroscopy (FTIR), microscopy: atomic force microscopy (AFM) and electrical characterization: capacitance-voltage technique (CV) have been applied. The films deposited by means of variety of techniques have been described, ranging from evaporation, through spraying and dropping to spin-coating. Regarding the possible low-k application, a considerable attention has been paid to the hybrid organic-inorganic 3-aminopropyl-trimethoxysilane (APTMS) based composite materials enriched with carbon species coming from the following dopants: C60 fullerenes, [6,6]-phenyl-C61-butyric acid (PCBM), copper phthalocyanine (CuPc), and tris(dimethylvinylsilyloxy)-POSS (POSS). In the following thesis progressive steps leading to gradual decreasing of the resulting permittivity of the hybrid material is presented. As revealed by the performed investigations, the replacement of C60 within the APTMS based matrix by its better soluble derivative PCBM allows the increase of the concentration of the carbon species within the composite films. The introduction of POSS as an additional dopant gave the opportunity of increasing the resistance of the produced material against the ambient influence. With the excess of the POSS concentration an original fractal-shaped cluster formation has been observed. Finally, the dispersion of the properly chosen low concentration of CuPc and POSS molecules within the APTMS based matrix led to the fabrication of homogenous layer with an ultra-low dielectric constant of 1.8.
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.
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.
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.