@phdthesis{Zeuschner2022, author = {Zeuschner, Steffen Peer}, title = {Magnetoacoustics observed with ultrafast x-ray diffraction}, doi = {10.25932/publishup-56109}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-561098}, school = {Universit{\"a}t Potsdam}, pages = {V, 128, IX}, year = {2022}, abstract = {In the present thesis I investigate the lattice dynamics of thin film hetero structures of magnetically ordered materials upon femtosecond laser excitation as a probing and manipulation scheme for the spin system. The quantitative assessment of laser induced thermal dynamics as well as generated picosecond acoustic pulses and their respective impact on the magnetization dynamics of thin films is a challenging endeavor. All the more, the development and implementation of effective experimental tools and comprehensive models are paramount to propel future academic and technological progress. In all experiments in the scope of this cumulative dissertation, I examine the crystal lattice of nanoscale thin films upon the excitation with femtosecond laser pulses. The relative change of the lattice constant due to thermal expansion or picosecond strain pulses is directly monitored by an ultrafast X-ray diffraction (UXRD) setup with a femtosecond laser-driven plasma X-ray source (PXS). Phonons and spins alike exert stress on the lattice, which responds according to the elastic properties of the material, rendering the lattice a versatile sensor for all sorts of ultrafast interactions. On the one hand, I investigate materials with strong magneto-elastic properties; The highly magnetostrictive rare-earth compound TbFe2, elemental Dysprosium or the technological relevant Invar material FePt. On the other hand I conduct a comprehensive study on the lattice dynamics of Bi1Y2Fe5O12 (Bi:YIG), which exhibits high-frequency coherent spin dynamics upon femtosecond laser excitation according to the literature. Higher order standing spinwaves (SSWs) are triggered by coherent and incoherent motion of atoms, in other words phonons, which I quantified with UXRD. We are able to unite the experimental observations of the lattice and magnetization dynamics qualitatively and quantitatively. This is done with a combination of multi-temperature, elastic, magneto-elastic, anisotropy and micro-magnetic modeling. The collective data from UXRD, to probe the lattice, and time-resolved magneto-optical Kerr effect (tr-MOKE) measurements, to monitor the magnetization, were previously collected at different experimental setups. To improve the precision of the quantitative assessment of lattice and magnetization dynamics alike, our group implemented a combination of UXRD and tr-MOKE in a singular experimental setup, which is to my knowledge, the first of its kind. I helped with the conception and commissioning of this novel experimental station, which allows the simultaneous observation of lattice and magnetization dynamics on an ultrafast timescale under identical excitation conditions. Furthermore, I developed a new X-ray diffraction measurement routine which significantly reduces the measurement time of UXRD experiments by up to an order of magnitude. It is called reciprocal space slicing (RSS) and utilizes an area detector to monitor the angular motion of X-ray diffraction peaks, which is associated with lattice constant changes, without a time-consuming scan of the diffraction angles with the goniometer. RSS is particularly useful for ultrafast diffraction experiments, since measurement time at large scale facilities like synchrotrons and free electron lasers is a scarce and expensive resource. However, RSS is not limited to ultrafast experiments and can even be extended to other diffraction techniques with neutrons or electrons.}, language = {en} } @phdthesis{Arvind2021, author = {Arvind, Malavika}, title = {Regarding the role of aggregation and structural order on the mechanism of molecular doping of semiconducting polymers}, doi = {10.25932/publishup-50060}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-500606}, school = {Universit{\"a}t Potsdam}, pages = {vii, 153}, year = {2021}, abstract = {Polymeric semiconductors are strong contenders for replacing traditional inorganic semiconductors in electronic applications requiring low power, low cost and flexibility, such as biosensors, flexible solar cells and electronic displays. Molecular doping has the potential to enable this revolution by improving the conductivity and charge transport properties of this class of materials. Despite decades of research in this field, gaps in our understanding of the nature of dopant-polymer interactions has resulted in limited commercialization of this technology. This work aims at providing a deeper insight into the underlying mechanisms of molecular p-doping of semiconducting polymers in the solution and solid-state, and thereby bring the scientific community closer to realizing the dream of making organic semiconductors commonplace in the electronics industry. The role of 1) dopant size/shape, 2) polymer chain aggregation and 3) charge delocalization on the doping mechanism and efficiency is addressed using optical (UV-Vis-NIR) and electron paramagnetic resonance (EPR) spectroscopies. By conducting a comprehensive study of the nature and concentration of the doping-induced species in solutions of the polymer poly(3-hexylthiophene) (P3HT) with 3 different dopants, we identify the unique optical signatures of the delocalized polaron, localized polaron and charge-transfer complex, and report their extinction coefficient values. Furthermore, with X-ray diffraction, atomic force microscopy and electrical conductivity measurements, we study the impact of processing technique and doping mechanism on the morphology and thereby, charge transport through the doped films. This work demonstrates that the doping mechanism and type of doping-induced species formed are strongly influenced by the polymer backbone arrangement rather than dopant shape/size. The ability of the polymer chain to aggregate is found to be crucial for efficient charge transfer (ionization) and polaron delocalization. At the same time, our results suggest that the high ionization efficiency of a dopant-polymer system in solution may subsequently hinder efficient charge transport in the solid-state due to the reduction in the fraction of tie chains, which enable charges to move efficiently between aggregated domains in the films. This study demonstrates the complex multifaceted nature of polymer doping while providing important hints for the future design of dopant-host systems and film fabrication techniques.}, language = {en} } @phdthesis{Cheng2018, author = {Cheng, Xiao}, title = {Controlled solvent vapor annealing of block copolymer films}, doi = {10.25932/publishup-42417}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-424179}, school = {Universit{\"a}t Potsdam}, pages = {X, 166}, year = {2018}, abstract = {This project was focused on exploring the phase behavior of poly(styrene)187000-block-poly(2-vinylpyridine)203000 (SV390) with high molecular weight (390 kg/mol) in thin films, in which the self-assembly of block copolymers (BCPs) was realized via thermo-solvent annealing. The advanced processing technique of solvent vapor treatment provides controlled and stable conditions. In Chapter 3, the factors to influence the annealing process and the swelling behavior of homopolymers are presented and discussed. The swelling behavior of BCP in films is controlled by the temperature of the vapor and of the substrate, on one hand, and variation of the saturation of the solvent vapor atmosphere (different solvents), on the other hand. Additional factors like the geometry and material of the chamber, the type of flow inside the chamber etc. also influence the reproducibility and stability of the processing. The slightly selective solvent vapor of chloroform gives 10\% more swelling of P2VP than PS in films with thickness of ~40 nm. The tunable morphology in ultrathin films of high molecular weight BCP (SV390) was investigated in Chapter 4. First, the swelling behavior can be precisely tuned by temperature and/or vapor flow separately, which provided information for exploring the multiple-parameter-influenced segmental chain mobility of polymer films. The equilibrium state of SV390 in thin films influenced by temperature was realized at various temperatures with the same degree of swelling. Various methods including characterization with SFM, metallization and RIE were used to identify the morphology of films as porous half-layer with PS dots and P2VP matrix. The kinetic investigations demonstrate that on substrates with either weak or strong interaction the original morphology of the BCP with high molecular weight is changed very fast within 5 min, and the further annealing serves for annihilation of defects. The morphological development of symmetric BCP in films with thickness increasing from half-layer to one-layer influenced by confinement factors of gradient film thicknesses and various surface properties of substrates was studied in Chapter 5. SV390 and SV99 films show bulk lamella-forming morphology after slightly selective solvent vapor (chloroform) treatment. SV99 films show cylinder-forming morphology under strongly selective solvent vapor (toluene) treatment since the asymmetric structure (caused by toluene uptake in PS blocks only) of SV99 block copolymer during annealing. Both kinds of morphology (lamella and cylinder) are influenced by the film thickness. The annealed morphology of SV390 and SV99 influenced by the combination of confined film and substrate property is similar to the morphology on flat silicon wafers. In this chapter the gradients in the film thickness and surface properties of the substrates with regard to their influence on the morphological development in thin BCP films are presented. Directed self-assembly (graphoepitaxy) of this SV390 was also investigated to compare with systematically reported SV99. In Chapter 6 an approach to induced oriented microphase separation in thick block copolymer films via treatment with the oriented vapor flow using mini-extruder is envisaged to be an alternative to existing methodologies, e.g. via non-solvent-induced phase separation. The preliminary tests performed in this study confirm potential perspective of this method, which alters the structure through the bulk of the film (as revealed by SAXS measurements), but more detailed studies have to be conducted in order to optimize the preparation.}, language = {en} } @phdthesis{Stephan2007, author = {Stephan, Niels}, title = {Ph{\"a}nomenologische Untersuchungen zur Feuchteempfindlichkeit der elektrischen Eigenschaften von d{\"u}nnen Polymerfilmen und deren Verwendung f{\"u}r neuartige Feuchtesensoren}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-13853}, school = {Universit{\"a}t Potsdam}, year = {2007}, abstract = {Ziel dieser Arbeit ist die ph{\"a}nomenologische Untersuchung der Feuchteempfindlichkeit der elektrischen Eigenschaften d{\"u}nner Polymerschichten. Diese Untersuchungen stellen gleichzeitig Vorarbeiten zur Entwicklung von Prototypen von zwei polymeren D{\"u}nnschicht-Feuchtesensoren dar, die sich durch die spezielle Auswahl der feuchtesensitiven Materialien jeweils durch eine besondere Eigenschaft gegen{\"u}ber kommerziellen Massenprodukten auszeichnen. Ziel der Entwicklungsarbeiten f{\"u}r den ersten Prototypen war die Konstruktion eines schnellen Feuchtesensors, der pl{\"o}tzliche und sprunghafte Feuchte{\"a}nderungen in der umgebenden Atmosph{\"a}re m{\"o}glichst rasch detektieren kann. Daf{\"u}r wurden d{\"u}nne Schichten von Poly-DADMAC auf Interdigitalstrukturen aufgebracht, die einen m{\"o}glichst direkten Kontakt zwischen feuchtesensitiver Schicht und umgebender, feuchter Atmosph{\"a}re gew{\"a}hrleisten. Als Messgr{\"o}ßen dienten die Wechselstromgr{\"o}ßen Widerstand und Kapazit{\"a}t der Schichten. Die Feuchtekennlinien der Schichten zeigen gute Konstanz und hohe Reproduzierbarkeit. Der Widerstand der Schichten {\"a}ndert sich durch den Einfluss von Feuchte je nach Schichtdicke um 3 bis 5 Gr{\"o}ßenordnungen und eignet sich als Messgr{\"o}ße f{\"u}r die Feuchtigkeit im gesamten Feuchtebereich. Die Hysterese der Filme konnte auf kleiner als 2,5\% r.F. bestimmt werden, die Reproduzierbarkeit auf besser als 1\% r.F. Die Ansprechzeit der Schichten l{\"a}sst sich schichtdickenabh{\"a}ngig zu 1 bis 10 Sekunden bestimmen. Hierbei zeigen besonders die d{\"u}nnen Schichten kurze Ansprechzeiten. Zielstellung f{\"u}r den zweiten Feuchtesensor war die Entwicklung eines Prototypen, dessen sensitive Schicht sich biostatisch und biozid verh{\"a}lt, so dass er in biotischen Umgebungen eingesetzt werden kann. Es wurden f{\"u}nf Polysulfobetaine synthetisiert, deren Biozidit{\"a}t und Biostatik mit dem Kontakttest nach R{\"o}nnpagel, dem ISO846-Test und Abbautests bestimmt wurde. Zwei Polymere - Poly-DMMAAPS (BT2) und Poly-[MSA-Styren-Sulfobetain] (BT5) - erwiesen sich als ausreichend biozid und biostatisch. Schichten dieser Polymere wurden auf Interdigitalstrukturen aufgezogen, anschließend wurden die Kennlinien dieser Proben aufgenommen. Die Messwerte zeigen f{\"u}r beide Polymere gute Konstanz und eine hohe Reproduzierbarkeit. BT2-Proben sind zwischen 20\% und 80\% r.F. besonders empfindlich und zeigen {\"u}ber einen Monat keine Langzeitdrift. Vernetzte Proben zeigen bis 50°C keinen temperaturbedingten Abfall der Feuchteempfindlichkeit. Der Einsatz vernetzter BT5-Schichten als kapazitiver Feuchtesensor ist bis etwa 70°C m{\"o}glich, die Schichten sind selbst nach Lagerung im Hochvakuum und mehrfacher Betauung stabil. Damit liegen zwei funktionsf{\"a}hige Prototypen von Feuchtesensoren vor, f{\"u}r die die meisten Kennwerte denen von vergleichbaren kommerziellen Feuchtesensoren entsprechen. Gleichzeitig zeichnen sie sich aber durch eine sehr niedrige Ansprechzeit bzw. eine ausreichende Lebensdauer unter biotischen Bedingungen aus.}, language = {de} } @phdthesis{Jung2004, author = {Jung, Carl Christoph}, title = {Lichtinduzierte Generierung und Charakterisierung optischer Anisotropie}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0001390}, school = {Universit{\"a}t Potsdam}, year = {2004}, abstract = {Eine Nutzung der optischen Anisotropie d{\"u}nner Schichten ist vor allem f{\"u}r die Displaytechnologie, die optische Datenspeicherung und f{\"u}r optische Sicherheitselemente von hoher Bedeutung. Diese Doktorarbeit befasst sich mit theoretischen und experimentellen Untersuchung von dreidimensionaler Anisotropie und dabei insbesondere mit der Untersuchung von lichtinduzierter dreidimensionaler Anisotropie in organischen d{\"u}nnen Polymer-Schichten. Die gewonnenen Erkentnisse und entwickelten Methoden k{\"o}nnen wertvolle Beitr{\"a}ge f{\"u}r Optimierungsprozesse, wie bei der Kompensation der Blickwinkelabh{\"a}ngigkeit von Fl{\"u}ssigkristall-Displays, liefern. Die neue Methode der Immersions-Transmissions-Ellipsometrie (ITE) zur Untersuchung von d{\"u}nneren Schichten wurde im Rahmen dieser Dissertation entwickelt. Diese Methode gestattet es, in Kombination mit konventioneller Reflexions- und Transmissionsellipsometrie, die absoluten dreidimensionalen Brechungsindices einer biaxialen Schicht zu bestimmen. Erstmals gelang es damit, das dreidimensionale Brechungsindexellipsoid von transparenten, d{\"u}nneren (150 nm) Filmen hochgenau (drei Stellen hinter dem Komma) zu bestimmen. Die ITE-Methode hat demzufolge das Potential, auch bei noch d{\"u}nneren Schichten mit Gewinn eingesetzt werden zu k{\"o}nnen. Die lichtinduzierte Generierung von dreidimensionaler Anisotropie wurde in d{\"u}nnen Schichten von azobenzenhaltigen und zimts{\"a}urehaltigen, amorphen und fl{\"u}ssig-kristallinen Homo- und Copolymeren untersucht. Erstmals wurden quantitative Untersuchungen zur {\"A}nderung von lichtinduzierten, dreidimensionalen Anisotropien in d{\"u}nnen Schichten von azobenzenhaltigen und zimts{\"a}urehaltigen Polymeren bei Tempern oberhalb der Glastemperatur durchgef{\"u}hrt. Bei vielen der untersuchten Polymere war die dreidimensionale Ordnung nach dem Bestrahlen mit polarisiertem Licht und anschließendem Tempern oberhalb der Glastemperatur scheinbar von der Schichtdicke abh{\"a}ngig. Die Ursache liegt wohl in der, mit der neuentwickelten ITE-Methode detektierten, planaren Ausgangsorientierung der aufgeschleuderten d{\"u}nneren Schichten. Um Verkippungs-Gradienten in dickeren Polymerschichten in ihrem Verlauf zu bestimmen, wurde eine spezielle Methode unter Benutzung der Wellenleitermoden-Spektroskopie entwickelt. Quantenchemisch bestimmte, maximal induzierbare Doppelbrechungen in fl{\"u}ssig-kristallinen Polymeren wurden mit den experimentell gefundenen Ordnungen verglichen.}, language = {de} }