@phdthesis{Benkert2015, author = {Benkert, Thomas}, title = {Neue Steady-State-Techniken in der Magnetresonanztomographie}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-115381}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2015}, abstract = {Die bSSFP-Sequenz kombiniert kurze Akquisitionszeiten mit einem hohen Signal-zu-Rausch-Verh{\"a}ltnis, was sie zu einer vielversprechenden Bildgebungsmethode macht. Im klinischen Alltag ist diese Technik jedoch bisher - abgesehen von vereinzelten Anwendungen - kaum etabliert. Die Hauptgr{\"u}nde hierf{\"u}r sind Signalausl{\"o}schungen in Form von Bandingartefakten sowie der erzielte T2/T1-gewichtete Mischkontrast. Das Ziel dieser Dissertation war die Entwicklung von Methoden zur L{\"o}sung der beiden genannten Limitationen, um so eine umfassendere Verwendung von bSSFP f{\"u}r die MR-Diagnostik zu erm{\"o}glichen. Magnetfeldinhomogenit{\"a}ten, die im Wesentlichen durch Suszeptibilit{\"a}tsunterschiede oder Imperfektionen seitens der Scannerhardware hervorgerufen werden, {\"a}ußern sich bei der bSSFP-Bildgebung in Form von Bandingartefakten. Mit DYPR-SSFP (DYnamically Phase-cycled Radial bSSFP) wurde ein Verfahren vorgestellt, um diese Signalausl{\"o}schungen effizient zu entfernen. W{\"a}hrend f{\"u}r bereits existierende Methoden mehrere separate bSSFP-Bilder akquiriert und anschließend kombiniert werden m{\"u}ssen, ist f{\"u}r die Bandingentfernung mittels DYPR-SSFP lediglich die Aufnahme eines einzelnen Bildes notwendig. Dies wird durch die neuartige Kombination eines dynamischen Phasenzyklus mit einer radialen Trajektorie mit quasizuf{\"a}lligem Abtastschema erm{\"o}glicht. Die notwendigen Bestandteile k{\"o}nnen mit geringem Aufwand implementiert werden. Des Weiteren ist kein spezielles Rekonstruktionsschema notwendig, was die breite Anwendbarkeit des entwickelten Ansatzes erm{\"o}glicht. Konventionelle Methoden zur Entfernung von Bandingartefakten werden sowohl bez{\"u}glich ihrer Robustheit als auch bez{\"u}glich der notwendigen Messzeit {\"u}bertroffen. Um die Anwendbarkeit von DYPR-SSFP auch jenseits der gew{\"o}hnlichen Bildgebung zu demonstrieren, wurde die Methode mit der Fett-Wasser-Separation kombiniert. Basierend auf der Dixon-Technik konnten so hochaufgel{\"o}ste Fett- sowie Wasserbilder erzeugt werden. Aufgrund der Bewegungsinsensitiv{\"a}t der zugrunde liegenden radialen Trajektorie konnten die Messungen unter freier Atmung durchgef{\"u}hrt werden, ohne dass nennenswerte Beeintr{\"a}chtigungen der Bildqualit{\"a}t auftraten. Die erzielten Ergebnisse am Abdomen zeigten weder Fehlzuordnungen von Fett- und Wasserpixeln noch verbleibende Bandingartefakte. Ein Nachteil der gew{\"o}hnlichen Dixon-basierten Fett-Wasser-Separation ist es, dass mehrere separate Bilder zu verschiedenen Echozeiten ben{\"o}tigt werden. Dies f{\"u}hrt zu einer entsprechenden Verl{\"a}ngerung der zugeh{\"o}rigen Messzeit. Abhilfe schafft hier die Verwendung einer Multiecho-Sequenz. Wie gezeigt werden konnte, erm{\"o}glicht eine derartige Kombination die robuste, bandingfreie Fett-Wasser-Separation in klinisch akzeptablen Messzeiten. DYPR-SSFP erlaubt die Entfernung von Bandingartefakten selbst bei starken Magnetfeldinhomogenit{\"a}ten. Dennoch ist es m{\"o}glich, dass Signalausl{\"o}schungen aufgrund des Effekts der Intravoxeldephasierung verbleiben. Dieses Problem tritt prim{\"a}r bei der Bildgebung von Implantaten oder am Ultrahochfeld auf. Als Abhilfe hierf{\"u}r wurde die Kombination von DYPR-SSFP mit der sogenannten z-Shim-Technik untersucht, was die Entfernung dieser Artefakte auf Kosten einer erh{\"o}hten Messzeit erm{\"o}glichte. Die mit DYPR-SSFP akquirierten radialen Projektionen weisen aufgrund des angewendeten dynamischen Phasenzyklus leicht verschiedene Signallevel und Phasen auf. Diese Tatsache zeigt sich durch inkoh{\"a}rente Bildartefakte, die sich jedoch durch eine Erh{\"o}hung der Projektionsanzahl effektiv reduzieren lassen. Folglich bietet es sich in diesem Kontext an, Anwendungen zu w{\"a}hlen, bei denen bereits intrinsisch eine verh{\"a}ltnism{\"a}ßig hohe Anzahl von Projektionen ben{\"o}tigt wird. Hierbei hat sich gezeigt, dass neben der hochaufgel{\"o}sten Bildgebung die Wahl einer 3D radialen Trajektorie eine aussichtsreiche Kombination darstellt. Die in der vorliegenden Arbeit vorgestellte 3D DYPR-SSFP-Technik erlaubte so die isotrope bandingfreie bSSFP-Bildgebung, wobei die Messzeit im Vergleich zu einer gew{\"o}hnlichen bSSFP-Akquisition konstant gehalten werden konnte. Verbleibende, durch den dynamischen Phasenzyklus hervorgerufene Artefakte konnten effektiv mit einem Rauschunterdr{\"u}ckungsalgorithmus reduziert werden. Anhand Probandenmessungen wurde gezeigt, dass 3D DYPR-SSFP einen aussichtsreichen Kandidaten f{\"u}r die Bildgebung von Hirnnerven sowie des Bewegungsapparats darstellt. W{\"a}hrend die DYPR-SSFP-Methode sowie die darauf beruhenden Weiterentwicklungen effiziente L{\"o}sungen f{\"u}r das Problem der Bandingartefakte bei der bSSFP-Bildgebung darstellen, adressiert die vorgestellte RA-TOSSI-Technik (RAdial T-One sensitive and insensitive Steady-State Imaging) das Problem des bSSFP-Mischkontrasts. Die M{\"o}glichkeit der Generierung von T2-Kontrasten basierend auf der bSSFP-Sequenz konnte bereits in vorausgehenden Arbeiten gezeigt werden. Hierbei wurde die Tatsache ausgenutzt, dass der T1-Anteil des Signalverlaufs nach Beginn einer bSSFP-Akquisition durch das Einf{\"u}gen von Inversionspulsen in ungleichm{\"a}ßigen Abst{\"a}nden aufgehoben werden kann. Ein so akquiriertes Bild weist folglich einen reinen, klinisch relevanten T2-Kontrast auf. Die im Rahmen dieser Arbeit vorgestellte Methode basiert auf dem gleichen Prinzip, jedoch wurde anstelle einer gew{\"o}hnlichen kartesischen Trajektorie eine radiale Trajektorie in Kombination mit einer KWIC-Filter-Rekonstruktion verwendet. Somit k{\"o}nnen bei gleichbleibender oder sogar verbesserter Bildqualit{\"a}t aus einem einzelnen, mit RA-TOSSI akquirierten Datensatz verschiedene T2-Wichtungen als auch gew{\"o}hnliche T2/T1-Wichtungen generiert werden. Mittels Variation der Anzahl der eingef{\"u}gten Inversionspulse konnte ferner gezeigt werden, dass es neben den besagten Wichtungen m{\"o}glich ist, zus{\"a}tzliche Kontraste zu generieren, bei denen verschiedene Substanzen im Bild ausgel{\"o}scht sind. Diese Substanzen k{\"o}nnen am Beispiel der Gehirnbildgebung Fett, graue Masse, weiße Masse oder CSF umfassen und zeichnen sich neben den reinen T2-Kontrasten durch eine {\"a}hnlich hohe klinische Relevanz aus. Die m{\"o}gliche Bedeutung der vorgestellten Methode f{\"u}r die klinische Verwendung wurde durch Messungen an einer Gehirntumorpatientin demonstriert. Zusammenfassend l{\"a}sst sich sagen, dass die im Rahmen dieser Dissertation entwickelten Techniken einen wertvollen Beitrag zur L{\"o}sung der eingangs beschriebenen Probleme der bSSFP-Bildgebung darstellen. Mit DYPR-SSFP akquirierte Bilder sind bereits mit bestehender, kommerzieller Rekonstruktionssoftware direkt am Scanner rekonstruierbar. Die Software f{\"u}r die Rekonstruktion von RA-TOSSI-Datens{\"a}tzen wurde f{\"u}r Siemens Scanner implementiert. Folglich sind beide Methoden f{\"u}r klinische Studien einsetzbar, was gleichzeitig den Ausblick dieser Arbeit darstellt.}, subject = {Kernspintomografie}, language = {de} } @phdthesis{Bendias2018, author = {Bendias, Michel Kalle}, title = {Quantum Spin Hall Effect - A new generation of microstructures}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-168214}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2018}, abstract = {The presented thesis summarizes the results from four and a half years of intense lithography development on (Cd,Hg)Te/HgTe/(Cd,Hg)Te quantum well structures. The effort was motivated by the unique properties of this topological insulator. Previous work from Molenkamp at al.\ has proven that the transport through such a 2D TI is carried by electrons with opposite spin, counter-propagating in 1D channels along the sample edge. However, up to this thesis, the length of quantized spin Hall channels has never been reported to exceed 4 µm. Therefore, the main focus was put on a reproducible and easy-to-handle fabrication process that reveals the intrinsic material parameters. Every single lithography step in macro as well as microscopic sample fabrication has been re-evaluated. In the Development, the process changes have been presented along SEM pictures, microgaphs and, whenever possible, measurement responses. We have proven the conventional ion milling etch method to damage the remaining mesa and result in drastically lower electron mobilities in samples of microscopic size. The novel KI:I2:HBr wet etch method for macro and microstructure mesa fabrication has been shown to leave the crystalline structure intact and result in unprecedented mobilities, as high as in macroscopic characterization Hall bars. Difficulties, such as an irregular etch start and slower etching of the conductive QW have been overcome by concentration, design and etch flow adaptations. In consideration of the diffusive regime, a frame around the EBL write field electrically decouples the structure mesa from the outside wafer. As the smallest structure, the frame is etched first and guarantees a non-different etching of the conductive layer during the redox reaction. A tube-pump method assures reproducible etch results with mesa heights below 300 nm. The PMMA etch mask is easy to strip and leaves a clean mesa with no redeposition. From the very first attempts, to the final etch process, the reader has been provided with the characteristics and design requirements necessary to enable the fabrication of nearly any mesa shape within an EBL write field of 200 µm. Magneto resistance measurement of feed-back samples have been presented along the development chronology of wet etch method and subsequent lithography steps. With increasing feature quality, more and more physics has been revealed enabling detailed evaluation of smallest disturbances. The following lithography improvements have been implemented. They represent a tool-box for high quality macro and microstructure fabrication on (CdHg)Te/HgTe of almost any kind. The optical positive resist ECI 3027 can be used as wet and as dry etch mask for structure sizes larger than 1 µm. It serves to etch mesa structures larger than the EBL write field. The double layer PMMA is used for ohmic contact fabrication within the EBL write field. Its thickness allows to first dry etch the (Cd,Hg)Te cap layer and then evaporate the AuGe contact, in situ and self-aligned. Because of an undercut, up to 300 nm can be metalized without any sidewalls after the lift-off. An edge channel mismatch within the contact leads can be avoided, if the ohmic contacts are designed to reach close to the sample and beneath the later gate electrode. The MIBK cleaning step prior to the gate application removes PMMA residuals and thereby improves gate and potential homogeneity. The novel low HfO2-ALD process enables insulator growth into optical and EBL lift-off masks of any resolvable shape. Directly metalized after the insulator growth, the self-aligned method results in thin and homogeneous gate electrode reproducibly withholding gate voltages to +-10 V. The optical negative resist ARN 4340 exhibits an undercut when developed. Usable as dry etch mask and lift-off resist, it enables an in-situ application of ohmic contacts first etching close to the QW, then metalizing AuGe. Up to 500 nm thickness, the undercut guarantees an a clean lift-off with no sidewalls. The undertaken efforts have led to micro Hall bar measurements with Hall plateaus and SdH-oszillations in up to now unseen levels of detail. The gap resistance of several micro Hall bars with a clear QSH signal have been presented in Quantum Spin Hall. The first to exhibit longitudinal resistances close to the expected h/2e2 since years, they reveal unprecedented details in features and characteristics. It has been shown that their protection against backscattering through time reversal symmetry is not as rigid as previously claimed. Values below and above 12.9 kΩ been explained, introducing backscattering within the Landauer-B{\"u}ttiker formalism of edge channel transport. Possible reasons have been discussed. Kondo, interaction and Rashba-backscattering arising from density inhomogeneities close to the edge are most plausible to explain features on and deviations from a quantized value. Interaction, tunneling and dephasing mechanisms as well as puddle size, density of states and Rashba Fields are gate voltage dependent. Therefore, features in the QSH signal are fingerprints of the characteristic potential landscape. Stable up to 11 K, two distinct but clear power laws have been found in the higher temperature dependence of the QSH in two samples. However, with ΔR = Tα, α = ¼ in one (QC0285) and α = 2 in the other (Q2745), none of the predicted dependencies could be confirmed. Whereas, the gap resistances of QC0285 remains QSH channel dominated up to 3.9 T and thereby confirmed the calculated lifting of the band inversion in magnetic field. The gate-dependent oscillating features in the QSH signal of Q2745 immediately increase in magnetic field. The distinct field dependencies allowed the assumption of two different dominant backscattering mechanisms. Resulting in undisturbed magneto transport and unprecedented QSH measurements The Novel Micro Hall Bar Process has proven to enable the fabrication of a new generation of microstructures.}, subject = {Quecksilbertellurid}, language = {en} } @phdthesis{Baumgaertner2023, author = {Baumg{\"a}rtner, Kiana Jasmin}, title = {Spectroscopic Investigation of the Transient Interplay at Hybrid Molecule-Substrate Interfaces after Photoexcitation: Ultrafast Electronic and Atomic Rearrangements}, doi = {10.25972/OPUS-33053}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-330531}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2023}, abstract = {This thesis is aimed at establishing modalities of time-resolved photoelectron spectroscopy (tr-PES) conducted at a free-electron laser (FEL) source and at a high harmonic generation (HHG) source for imaging the motion of atoms, charge and energy at photoexcited hybrid organic/inorganic interfaces. Transfer of charge and energy across interfaces lies at the heart of surface science and device physics and involves a complex interplay between the motion of electrons and atoms. At hybrid organic/inorganic interfaces involving planar molecules, such as pentacene and copper(II)-phthalocyanine (CuPc), atomic motions in out-of-plane direction are particularly apparent. Such hybrid interfaces are of importance to, e.g., next-generation functional devices, smart catalytic surfaces and molecular machines. In this work, two hybrid interfaces - pentacene atop Ag(110) and copper(II)-phthalocyanine (CuPc) atop titanium disulfide (1T-TiSe2) - are characterized by means of modalities of tr-PES. The experiments were conducted at a HHG source and at the FEL source FLASH at Deutsches Elektronen-Synchrotron DESY (Hamburg, Germany). Both sources provide photon pulses with temporal widths of ∼ 100 fs and thus allow for resolving the non-equilibrium dynamics at hybrid interfaces involving both electronic and atomic motion on their intrinsic time scales. While the photon energy at this HHG source is limited to the UV-range, photon energies can be tuned from the UV-range to the soft x-ray-range at FLASH. With this increased energy range, not only macroscopic electronic information can be accessed from the sample's valence and conduction states, but also site-specific structural and chemical information encoded in the core-level signatures becomes accessible. Here, the combined information from the valence band and core-level dynamics is obtained by performing time- and angle-resolved photoelectron spectroscopy (tr-ARPES) in the UV-range and subsequently performing time-resolved x-ray photoelectron spectroscopy (tr-XPS) and time-resolved photoelectron diffraction (tr-XPD) in the soft x-ray regime in the same experimental setup. The sample's bandstructure in energy-momentum space and time is captured by a time-of-flight momentum microscope with femtosecond temporal and sub-{\AA}ngstr{\"o}m spatial resolutions. In the investigated systems, out-of-equilibrium dynamics are traced that are connected to the transfer of charge and energy across the hybrid interfaces. While energetic shifts and complementary population dynamics are observed for molecular and substrate states, the shapes of involved molecular orbitals change in energy-momentum space on a subpicosecond time scale. In combination with theory support, these changes are attributed to iiiatomic reorganizations at the interface and transient molecular structures are reconstructed with sub-{\AA}ngstr{\"o}m precision. Unique to the material combination of CuPc/TiSe2, a structural rearrangement on the macroscopic scale is traced simultaneously: ∼ 60 \% of the molecules undergo a concerted, unidirectional in-plane rotation. This surprising observation and its origin are detailed in this thesis and connected to a particularly efficient charge transfer across the CuPc/TiSe2 interface, resulting in a charging of ∼ 45 \% of CuPc molecules.}, subject = {ARPES}, language = {en} } @phdthesis{Schummer2021, author = {Schummer, Bernhard}, title = {Stabilisierung von CdS Nanopartikeln mittels Pluronic P123}, doi = {10.25972/OPUS-23844}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-238443}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2021}, abstract = {Ziel dieser Arbeit war die Stabilisierung von Cadmiumsulfid CdS mit Pluronic P123, einem Polymer. CdS ist ein Halbleiter, der zum Beispiel in der Photonik und bei optischen Anwendungen eingesetzt wird und ist deshalb {\"a}ußerst interessant, da seine Bandl{\"u}cke als Nanopartikel verschiebbar ist. F{\"u}r die Photovoltaik ist es ein attraktives Material, da es im sichtbaren Licht absorbiert und durch die Bandl{\"u}ckenverschiebung effektiver absorbieren kann. Dies ist unter dem Namen Quantum Size Effekt bekannt. Als Feststoff ist CdS f{\"u}r einen solchen Anwendungsbereich weniger geeignet, zumal der Effekt der Bandl{\"u}ckenverschiebung dort nicht auftritt. Wissenschaftler bem{\"u}hen sich deshalb CdS als Nanopartikeln zu stabilisieren, weil CdS in w{\"a}ssrigen L{\"o}sungen ein stark aggregierendes System, also stark hydrophob ist. Es wurden zwei Kriterien f{\"u}r die erfolgreiche Stabilisierung von CdS festgelegt. Zum einen muss das Cds homogen im Medium verteilt sein und darf nicht agglomerieren. Zum anderen, m{\"u}ssen die CdS Nanopartikel kleiner als 100 A sein. In meiner Arbeit habe ich solche Partikel hergestellt und stabilisiert, d.h. verhindert, dass die Partikel weiterwachsen und gleichzeitig ihre Bandl{\"u}cke verschoben wird. Die Herausforderung liegt nicht in der Herstellung, aber in der L{\"o}sung von CdS im Tr{\"a}gerstoff, da CdS in den meisten Fl{\"u}ssigkeiten nicht l{\"o}slich ist und ausf{\"a}llt. Die Stabilisierung in w{\"a}ssrigen L{\"o}sungen wurde das erste Mal durch Herrn Prof. Dr. Rempel mit Ethylendiamintetraessigs{\"a}ure EDTA erfolgreich durchgef{\"u}hrt. Mit EDTA k{\"o}nnen jedoch nur sehr kleine Konzentrationen stabilisiert werden. Zudem k{\"o}nnen Parameter wie Gr{\"o}ße und Geschwindigkeit der Reaktion beim Stabilisieren der CdS-Nanopartikel nicht angepasst oder beeinflusst werden. Dieses Problem ist dem, vieler medizinischer Wirkstoffe sehr {\"a}hnlich, die in hohen Konzentrationen verabreicht werden sollen, aber nicht oder nur schwer in Wasser l{\"o}slich sind (Bsp. Kurkumin). Ein vielversprechender L{\"o}sungsweg ist dort, die Wirkstoffe in große Tr{\"a}gerpartikel (sog. Mizellen) einzuschleusen, die ihrerseits gut l{\"o}slich sind. In meiner Arbeit habe ich genau diesen Ansatz f{\"u}r CdS verfolgt. Als Tr{\"a}gerpartikel/Mizelle wurde das bekannte Copolymer Pluronic P123 verwendet. Aus dieser Pluronic Produktreihe wird P123 gew{\"a}hlt, da es die gr{\"o}ßte Masse bei gleichzeitig h{\"o}chstem Anteil von Polypropylenoxid PPO im Vergleich zur Gesamtkettenl{\"a}nge hat. P123 ist ein tern{\"a}res Polyether oder Dreiblockkopolymer und wird von BASAF industriell produziert. Es besteht aus drei B{\"o}cken, dem mittlere Block Polypropylenoxid PPO und den beiden {\"a}ußeren Bl{\"o}cken Polyethylenoxid PEO. Der Buchstabe P steht f{\"u}r past{\"o}s, die ersten beiden Ziffern in P123 mit 300 multipliziert ergeben das molare Gewicht und die letzte Ziffer mit 10 multipliziert entspricht dem prozentualen Gewichtsanteil PEO. Die Bildung von Mizellen aus den P123 Molek{\"u}len kann bewusst {\"u}ber geringe Temperatur{\"a}nderungen gesteuert werden. Bei ungef{\"a}hr Raumtemperatur liegen Mizellen vor, die sich bei h{\"o}heren Temperaturen von sph{\"a}rischen in wurmartige Mizellen umwandeln. Oberhalb einer Konzentration von 30 Gewichtsprozent wtp bilden die Mizellen außerdem einen Fl{\"u}ssigkristall. Ich habe in meiner Arbeit zun{\"a}chst P123 mit Hilfe von R{\"o}ntgenstreuung untersucht. Anders als andere Methoden gibt R{\"o}ntgenstreuung direkten Aufschluss {\"u}ber die Morphologie der Stoffe. R{\"o}ntgenstreuung kann die Mischung von P123 mit CdS abbilden und l{\"a}sst darauf schließen, ob das Ziel erreicht werden konnte, stabile CdS Nanopartikel in P123 zu binden. F{\"u}r die Stabilisierung der Nanopartikel ist es zun{\"a}chst notwendig die richtigen Temperaturen f{\"u}r die Ausgangsl{\"o}sungen und gemischten L{\"o}sungen zu finden. Dazu muss P123 viel genauer untersucht werden, als der momentane Kenntnisstand in der Literatur. Zu diesem Zweck als auch f{\"u}r die Analyse des stabilisierten CdS habe ich ein neues Instrument am LRM entwickelt, sowie eine temperierbare Probenumgebung f{\"u}r Fl{\"u}ssigkeiten f{\"u}rs Vakuum, um morphologische Eigenschaften aus Streuamplituden und -winkeln zu entschl{\"u}sseln. Diese R{\"o}ntgenstreuanlage wurde konzipiert und gebaut, um auch im Labor P123 in kleinen Konzentrationen messen zu k{\"o}nnen. R{\"o}ntgenkleinwinkelstreuung eignet sich besonders als Messmethode, da die Probe mit einer hohen statistischen Relevanz in Fl{\"u}ssigkeit und in verschiedenen Konzentrationen analysiert werden kann. F{\"u}r die Konzentrationen 5, 10 und 30 wtp konnte das temperaturabh{\"a}ngige Verhalten von P123 pr{\"a}zise mit R{\"o}ntgenkleinwinkelstreuung SAXS gemessen und dargestellt werden. F{\"u}r 5 wtp konnten die Gr{\"o}ßen der Unimere und Mizellen bestimmt werden. Trotz der nicht vorhandenen Absolutkalibration f{\"u}r diese Konzentration konnten dank des neu eingef{\"u}hrten Parameters kappa eine Dehydrierung der Mizellen mit steigender Temperatur abgesch{\"a}tzt, sowie eine Hysterese zwischen dem Heizen und Abk{\"u}hlen festgestellt werden. F{\"u}r die Konzentration von 10 wtp wurden kleinere Temperaturschritte gew{\"a}hlt und die Messungen zus{\"a}tzlich absolut kalibriert. Es wurden die Gr{\"o}ßen und Streul{\"a}ngendichten SLD der Unimere und Mizellen pr{\"a}zise bestimmt und ein vollst{\"a}ndiges Form-Phasendiagramm erstellt. Auch f{\"u}r diese Konzentration konnte eine Hysterese eindeutig an der Gr{\"o}ße, SLD und am Parameter kappa gezeigt werden, sowie eine Dehydrierung des Mizellenkerns. Dies beweist, dass der Parameter kappa geeignet ist, um bei nicht absolut kalibrierten Messungen, Aussagen {\"u}ber die Hydrierung und Hysterese komplexer Kern-H{\"u}lle Modelle zu machen. F{\"u}r die Konzentration von 30 wtp konnte zwischen 23°C und 35°C eine FCC Struktur nachgewiesen werden. Dabei vergr{\"o}ßert sich die Gitterkonstante der FCC Struktur von 260 A auf 289 A in Abh{\"a}ngigkeit der Temperatur. Durch das Mischen zweier L{\"o}sungen, zum einen CdCl2 und 30 wtp P123 und zum anderen Na2S und 30 wtp P123, konnte CdS erfolgreich stabilisiert werden. Mit einer Kamera wurde die Gelbf{\"a}rbung der L{\"o}sung, und somit die Bildung des CdS, in Abh{\"a}ngigkeit der Zeit untersucht. Es konnte festgestellt werden, dass das Bilden der CdS Nanopartikel je nach Konzentration und Temperierprogramm zwischen 30 und 300 Sekunden dauert und einer logistischen Wachstumsfunktion folgt. H{\"o}here Konzentrationen CdS bewirken einen schnelleren Anstieg der Wachstumsfunktion. Mittels UV-Vis Spektroskopie konnte gezeigt werden, dass die Bandl{\"u}cke von CdS mit steigender Konzentration konstant bei 2,52 eV bleibt. Eine solche Verschiebung der Bandl{\"u}cke von ungef{\"a}hr 0,05 eV im Vergleich zum Festk{\"o}rper, deutet auf einen CdS Partikeldurchmesser von 80A hin. Mit SAXS konnte gezeigt werden, dass sich die fl{\"u}ssigkristalline Struktur des P123 bei zwei verschiedenen Konzentrationen CdS, von 0,005 und 0,1 M, nicht {\"a}ndert. Das CdS wird zwischen den Mizellen, also durch die Bildung des Fl{\"u}ssigkristalls, und im Kern der Mizelle aufgrund seiner Hydrophobizit{\"a}t stabilisiert. Die Anfangs definierten Kriterien f{\"u}r eine erfolgreiche Stabilisierung wurden erf{\"u}llt. P123 ist ein hervorragend geeignetes Polymer, um hydrophobes CdS, sowohl durch die Bildung eines Fl{\"u}ssigkristalls, als auch im Kern der Mizelle zu stabilisieren.}, subject = {R{\"o}ntgen-Kleinwinkelstreuung}, language = {de} } @phdthesis{Betzold2022, author = {Betzold, Simon}, title = {Starke Licht-Materie-Wechselwirkung und Polaritonkondensation in hemisph{\"a}rischen Mikrokavit{\"a}ten mit eingebetteten organischen Halbleitern}, doi = {10.25972/OPUS-26665}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-266654}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2022}, abstract = {Kavit{\"a}ts-Exziton-Polaritonen (Polaritonen) sind hybride Quasiteilchen, die sich aufgrund starker Kopplung von Halbleiter-Exzitonen mit Kavit{\"a}tsphotonen ausbilden. Diese Quasiteilchen weisen eine Reihe interessanter Eigenschaften auf, was sie einerseits f{\"u}r die Grundlagenforschung, andererseits auch f{\"u}r die Entwicklung neuartiger Bauteile sehr vielversprechend macht. Bei Erreichen einer ausreichend großen Teilchendichte geht das System in den Exziton-Polariton-Kondensationszustand {\"u}ber, was zur Emission von laserartigem Licht f{\"u}hrt. Organische Halbleiter als aktives Emittermaterial zeigen in diesem Kontext großes Potential, da deren Exzitonen neben großen Oszillatorst{\"a}rken auch hohe Bindungsenergien aufweisen. Deshalb ist es m{\"o}glich, unter Verwendung organischer Halbleiter selbst bei Umgebungsbedingungen {\"a}ußerst stabile Polaritonen zu erzeugen. Eine wichtige Voraussetzung zur Umsetzung von integrierten opto-elektronischen Bauteilen basierend auf Polaritonen ist der kontrollierte r{\"a}umliche Einschluss sowie die Realisierung von frei konfigurierbaren Potentiallandschaften. Diese Arbeit besch{\"a}ftigt sich mit der Entwicklung und der Untersuchung geeigneter Plattformen zur Erzeugung von Exziton-Polaritonen und Polaritonkondensaten in hemisph{\"a}rischen Mikrokavit{\"a}ten, in die organische Halbleiter eingebettet sind.}, subject = {Exziton-Polariton}, language = {de} } @phdthesis{Bollmann2013, author = {Bollmann, Stefan}, title = {Structural Dynamics of Oligopeptides determined by Fluorescence Quenching of Organic Dyes}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-92191}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2013}, abstract = {For determination of structures and structural dynamics of proteins organic fluorophores are a standard instrument. Intra- and intermolecular contact of biomolecular structures are determined in time-resolved and stationary fluorescence microscopy experiments by quenching of organic fluorophores due to Photoinduced Electron Transfer (PET) and dimerization interactions. Using PET we show in this work that end-to-end contact dynamics of serine-glycine peptides are slowed down by glycosylation. This slow down is due to a change in reaction enthalpy for end-to-end contact and is partly compensated by entropic effects. In a second step we test how dimerization of MR121 fluorophore pairs reports on end-to-end contact dynamics. We show that in aqueous solutions containing strong denaturants MR121 dimerization reports advantageously on contact dynamics for glycine-serine oligopeptides compared to the previously used MR121/tryptophane PET reporters. Then we analyze dimer interactions and quenching properties of different commercially available fluorophores being standards in F{\"o}rster Resonance Energy Transfer (FRET) measurements. Distances in biomolecules are determinable using FRET, but for very flexible biomolecules the analysis of masurement data can be distorted if contact of the two FRET fluorophores is likely. We quantify how strong the quenching of fluorophore pairs with two different or two identical fluorophores is. Dimer spectra and association constants are quantified to estimate if fluophores are applicable in various applications, e.g. in FRET measurements with unstructured peptides and proteins.}, subject = {Fluorophore}, language = {en} } @phdthesis{Liess2017, author = {Liess, Andreas}, title = {Structure-Property Relationships of Merocyanine Dyes in the Solid State: Charge Transport and Exciton Coupling}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-152900}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2017}, abstract = {The present thesis demonstrates the importance of the solid state packing of dipolar merocyanine dyes with regard to charge transport and exciton coupling. Due to the charge transport theory for disordered materials, it is expected that high ground state dipole moments in amorphous thin films lead to low mobility values due to a broadening of the density of states. However, due to their inherent dipolarity, merocyanine dyes usually align in antiparallel dimers in an ordered fashion. The examination of twenty different molecules with ground state dipole moments up to 15.0 D shows that by a high dipolarity and well-defined sterics, the molecules pack in a highly regular two-dimensional brickwork-type structure, which is beneficial for hole transport. Utilization of these molecules for organic thin-film transistors (OTFTs) leads to hole mobility values up to 0.21 cm²/Vs. By fabrication of single crystal field-effect transistors (SCFETs) for the derivative showing the highest mobility values in OTFTs, even hole mobilities up to 2.34 cm²/Vs are achieved. Hence, merocyanine based transistors show hole mobility values comparable to those of conventional p-type organic semiconductors and therefore high ground state dipole moments are not necessarily disadvantageous regarding high mobility applications. By examination of a different series of ten merocyanine dyes with the same chromophore backbone but different donor substituents, it is demonstrated that the size of the donor has a significant influence on the optical properties of thin films. For small and rigid donor substituents, a hypsochromic shift of the absorption compared to the monomer absorption in solution is observed due to the card stack like packing of the molecules in the solid state. By utilization of sterical demanding or flexible donor substituents, a zig-zag type packing is observed, leading to a bathochromical shift of the absorption. These packing motifs and spectral shifts with an offset of 0.93 eV of the H- and J-bands comply with the archetype examples of H- and J-aggregates from Kasha's exciton theory.}, subject = {Exziton}, language = {en} } @phdthesis{Genheimer2023, author = {Genheimer, Ulrich}, title = {The Photophysics of Small Organic Molecules for Novel Light Emitting Devices}, doi = {10.25972/OPUS-32031}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-320313}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2023}, abstract = {This PhD thesis addresses the photophysics of selected small organic molecules with the purpose of using them for efficient and even novel light sources. In particular, the studies presented focused on revealing the underlying exciton dynamics and determining the transition rates between different molecular states. It was shown how the specific properties and mechanisms of light emission in fluorescent molecules, molecules with phosphorescence or thermally activated delayed fluorescence (TADF), biradicals, and multichromophores can be utilized to build novel light-emitting devices. The main tool employed here was the analysis of the emitters' photon statistics, i.e. the analysis of the temporal distribution of emitted photons, during electrical or optical excitation. In the introduction of this work, the working principle of an organic light-emitting diode (OLED) was introduced, while Chapter 2 provided the physical background of the relevant properties of organic molecules and their interaction with light. In particular, the occurrence of discrete energy levels in organic semiconductors and the process of spontaneous light emission were discussed. Furthermore, in this chapter a mathematical formalism was elaborated with the goal to find out what kind of information about the studied molecule can be obtained by analyzing its photon statistics. It was deduced that the intensity correlation function g (2)(t) contains information about the first two factorial moments of the photon statistics and that higher order factorial moments do not contain any additional information about the system under study if the system is always in the same state after the emission of a photon. To conclude the introductory part, Chapter 3 introduced the utilized characterization methods including confocal microscopy of single molecules, time correlated single photon counting and temperature dependent photoluminescence measurements. To provide the background necessary for an understanding of for the following result chapters, in Section 4.1 a closer look was taken at the phenomenon of blinking and photobleaching of individual molecules. For a squaraine-based fluorescent emitter rapid switching between a bright and dark state was observed during photoexcitation. Using literature transition rates between the molecular states, a consistent model was developed that is able to explain the distribution of the residence times of the molecule in the bright and dark states. In particular, an exponential and a power-law probability distribution was measured for the time the molecule resides in tis bright and dark state, respectively. This behavior as well as the change in photoluminescence intensity between the two states was conclusively explained by diffusion of residual oxygen within the sample, which had been prepared in a nitrogen-filled glovebox. For subsequent samples of this work, thin strips of atomic aluminum were deposited on the matrices to serve as oxygen getter material. This not only suppressed the efficiency of photobleaching, but also noticeably prolonged the time prior to photobleaching, which made many of the following investigations possible in the first place. For emitters used in displays, emission properties such as narrow-band luminescence and short fluorescence lifetimes are desired. These properties can be influenced not only by the emitter molecule itself, but also by the interaction with the chosen environment. Therefore, before focusing on the photophysics of individual small organic molecules, Section 4.2 highlighted the interaction of a perylene bisimide-based molecular species with its local environment in a disordered polymethyl methacrylate matrix. In a statistical approach, individual photophysical properties were measured for 32 single molecules and correlations in the variation of the properties were analyzed. This revealed how the local polarity of the molecules' environment influences their photophysics. In particular, it was shown how an increase in local polarity leads to a red-shifted emission, narrower emission lines, broader vibronic splitting between different emission lines in combination with a smaller Huang-Rhys parameter, and a longer fluorescence lifetime. In the future, these results may help to embed individual chromophores into larger macromolecules to provide the chromophore with the optimal local environment to exhibit the desired emission properties. The next two sections focused on a novel and promising class of chromophores, namely linear coordinated copper complexes, synthesized in the group of Dr. Andreas Steffen at the Institute of Inorganic Chemistry at the University of W{\"u}rzburg. In copper atoms, the d-orbitals are fully occupied, which prevents undesirable metal-centered d-d⋆ states, which tend to lie low in energy and recombine non-radiatively. Simultaneously, the copper atom provides a flexible coordination geometry, while complexes in their linear form are expected to exhibit the least amount of excited state distortions. Depending on the chosen ligands, these copper complexes can exhibit phosphorescence as well as temperature activated delayed fluorescence. In Section 4.3, a phosphorescent copper complex with a chlorine atom and a 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethyl-2-pyrrolidine-ylidene- ligand was tested for its suitability as an optically active material in an OLED. For this purpose, an OLED with a polyspirobifluorene-based copolymer matrix and the dopant at a concentration of 20 wt\% was electrically excited. Deconvolution of the emission spectrum in contributions from the matrix and the dopant revealed that 60 \% of the OLEDs emission was due to the copper complex. It was also shown that the shape of the emission spectrum of the copper complex remains unchanged upon incorporation into the OLED, but is red-shifted by about 233 meV. In Section 4.4, a second copper complex exhibiting thermally activated delayed fluorescence was analyzed. This complex comprised a carbazolate as well as a 2-(2,6- diisopropyl)-phenyl-1,1-diphenyl-isoindol-2-ium-3-ide ligand and was examined in the solid state and at the single-molecule level, where single photon emission was recorded up to an intensity of 78'000 counts per second. The evaluation of the second-order autocorrelation function of the emitted light proved an efficient transition between singlet and triplet excited states on the picosecond time scale. In the solid state, the temperature- dependent fluorescence decay of the complex was analyzed after pulsed photoexcitation in the temperature range between 300 K and 5 K. From these measurements, a small singlet-triplet energy gap of only 65 meV and a triplet sublevel splitting of 3.0 meV were derived. The transition rates between molecular states could also be determined. Here, the fast singlet decay time of τS1 = 9.8ns proved the efficient thermally activated delayed fluorescence process, which was demonstrated for the first time for this new class of copper(I) complexes thus. While the use of thermally activated delayed fluorescence is a potential way to harness otherwise long-living dark triplet states, radicals completely avoid dark triplet states. However, this usually comes with the huge drawback of the molecules being chemically unstable. Therefore, two chemically stable biradical species were synthesized in the framework of the DFG research training school GRK 2112 on Molecular biradicals: structure, properties and reactivity, by Yohei Hattori in the group of Prof. Dr. Christoph Lambert and Rodger Rausch in the group of Prof. Dr. Frank W{\"u}rthner at the Institute of Organic Chemistry at the University of W{\"u}rzburg, respectively. In Section 4.5, it was investigated how these molecules can be used in OLEDs. In the first isoindigo based biradical (6,6'-bis(3,5-di-tert-butyl-4-phenoxyl)-1,1'-bis(2- ethylhexyl)-[3,3'-biindolinyl-idene]-2,2'-dione) two tert-butyl moieties kinetically block chemical reactions at the place of the lone electrons and an electron-withdrawing core shifts the electron density into the center of the chromophore. With these properties, it was possible to realize a poly(p-phenylene vinylene) copolymer based OLED doped with the biradical and to observe luminescence during optical as well as electrical excitation. Analyzing shapes of the photo- and electroluminescence spectra at different doping concentrations, F{\"o}rster resonance energy transfer was determined to be the dominant transition mechanism for excitons from the matrix to the biradical dopants. Likewise, OLEDs could be realized with the second diphenylmethylpyridine based birad- ical (4-(5-(bis(2,4,6-trichlorophenyl)methyl)-4,6-dichloropyridin-2-yl)-N-(4-(5-(bis(2,4,6- -trichlorophenyl)methyl)-4,6-dichloropyridin-2-yl)phenyl)-N-(4-methoxyphenyl)aniline) as dopant. In this biradical, chlorinated diphenylmethyl groups protect the two unpaired electrons. Photo- and electroluminescence spectra showed an emission in the near in- frared spectral range between 750 nm and 1000 nm. Also, F{\"o}rster resonance energy trans- fer was the dominant energy transfer mechanism with an transfer efficiency close to 100 \% even at doping concentrations of only 5 wt\%. In addition to demonstrating the working OLEDs based in biradicals, the detection of luminescence of the two biradical species in devices also constitutes an important step toward making use of experimental techniques such as optically detected electron spin resonance, which could provide information about the electronic states of the emitter and their spin manifold during OLED operation. Another class of emitters studied are molecules in which several chromophores are co- valently linked to form a macrocyclic system. The properties of these multichromophores were highlighted in Section 4.6. Here, it was analyzed how the photophysical behavior of the molecules is affected by the covalent linking, which determines the interaction be- tween the chromophores. The first multichromophore, 2,2'-ditetracene, was synthesized by Lena Ross in the group of Prof. Dr. Anke Kr{\"u}ger at the Institute of Organic Chemistry at the University of W{\"u}rzburg and was analyzed in this work both at the single-molecule level and in its aggregated crystalline form. While the single crystals were purified and grown in a vertical sublimation oven, the samples for the single molecule studies were prepared in matrices of amorphous polymethyl methacrylate and crystalline anthracene. Tetracene was analyzed concurrently to evaluate the effects of covalent linking. In samples where the distance between two molecules is sufficiently large, tetracene and 2,2'-ditracene show matching emission profiles with the only difference in the Franck-Condon factors and a de- creased photoluminescence decay time constant from 14 ns for tetracene to 5 ns for 2,2'- ditracene, which can be attributed to the increased density of the vibrational modes in 2,2'-ditracene. Evaluation of the photon statistics of individual 2,2'-ditracene molecules however showed that the system does not behave as two individual chromophores but as a collective state, preserving the spectral properties of the two tetracene chromophores. Complementary calculations performed by Marian Deutsch in the group of Prof. Dr. Bernd Engels at the Institute of Physical and Theoretical Chemistry at the University of W{\"u}rzburg helped to understand the processes in the materials and could show that the electronic and vibronic modes of 2,2'-ditracene are superpositions of the modes occurring in tetracene. In contrast, single-crystalline 2,2'-ditetracene behaves significantly different than tetracene, namely exhibiting a red shift in photoluminescence of 150 meV, caused by an altered crys- talline packing that lowers the S1-state energy level. Temperature-dependent photolu- minescence measurements revealed a rich emission pattern from 2,2'-ditetracene single crystals. The mechanisms behind this were unraveled using photoluminescence lifetime density analysis in different spectral regions of the emission spectrum and at different tem- peratures. An excimer state was identified that is located about 5 meV below the S1-state, separated by a 1 meV barrier, and which can decay to the ground state with a time constant of 9 ns. Also, as the S1-state energy level is lowered below the E(S1) ≥ 2 ×E(T1) threshold, singlet fission is suppressed in 2,2'-ditetracene in contrast to tetracene. Therefore, at low temperatures, photoluminescence is enhanced by a factor of 46, which could make 2,2'- ditetracene a useful material for future applications in devices such as OLEDs or lasers. The second multichromophore species, para-xylylene bridged perylene bisimide macrocycles, were synthesized by Peter Spenst in the group of Prof. Dr. Frank W{\"u}rthner at the Institute of Organic Chemistry at the University of W{\"u}rzburg, by linking three and four perylene bisimides, respectively. To reveal the exciton dynamics in these macrocycles, highly diluted monomers as well as trimers and tetramers were doped into matrices of polymethyl methacrylate to create thin films in which individual macrocycles could be analyzed. The emission spectra of the macrocycles remained identical to those of the monomers, indicating weak coupling between the chromophores. Single photon emission could be verified for monomers as well as macrocycles, as exciton-exciton annihilation processes suppress the simultaneous emission of two photons from one macrocycle. Nevertheless, the proof of the occurrence of a doubly excited state was obtained by excitation power dependent photon statistics measurements. The formalism developed in the theory part of this thesis for calculating the photon statistics of multichromophore systems was used here to find a theoretical model that matches the experimental results. The main features of this model are a doubly excited state, fast singlet-singlet annihilation, and an efficient transition from the doubly excited state to a dark triplet state. The occurrence of triplet-triplet annihilation was demonstrated in a subsequent experiment in which the macrocycles were excited at a laser intensity well above the saturation intensity of the monomer species. In contrast to the monomers, the trimers and tetramers exhibited neither a complete dark state nor saturation of photoluminescence. Both processes, efficient singlet-singlet and triplet-triplet annihilation make perylene bisimide macrocycles exceptionally bright single photon emitters. These advantages were utilized to realize a room temperature electrically driven fluorescent single photon source. For this purpose, OLEDs were fabricated using polyvinylcarbazole and 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazol blends as a host material for perylene bisimide trimers. Photon antibunching could be observed in both optically and electrically driven devices, representing the first demonstration of electrically driven single photon sources using fluorescent emitters at room temperature. As expected from the previous optical experiments, the electroluminescence of the molecules was exceptionally bright, emitting about 105 photons per second, which could be seen even by eye under the microscope. Finally, in the last section 4.7 of this thesis, two additional measurement schemes were proposed as an alternative to the measurement of the second-order correlation function g (2)(t) of single molecules, which only provides information about the first two factorial moments of the molecules' photon statistics. In the first scheme, the g (3)(t) function was measured with three photodiodes, which is a consequential extension of the Hanbury Brown and Twiss measurement with two photodiodes. It was demonstrated how measuring the g (3)(t) function is able to identify interfering emitters with non-Poisson statistics in the experiment. The second setup was designed with an electro-optic modulator that repeatedly gen- erates photoexcitation in the form of a step function. The recording of luminescence transients for different excitation intensities yields the same results as the correspond- ing g (2)-functions measured on single emitters, both in their shape and in their depen- dence on excitation power. To demonstrate this concept, the TADF emitter TXO-TPA (2- [4-(diphenylamino)phenyl]-10,10-dioxide-9H-thioxanthen-9-one) was doped at a concen- tration of 10-4 wt\% in a mCP (1,3-Bis(N-carbazolyl)benzene) matrix. This concentration was low enough that TXO-TPA molecules did not interact with each other, but an ensem- ble of molecules was still present in the detection volume. The intramolecular transition rates between singlet and triplet states of TXO-TPA could be derived with an error of at most 5 \%. Other experimental techniques designed to obtain this information require ei- ther lengthy measurements on single molecules, where sample preparation is also often a challenge, or temperature-dependent fluorescence lifetime measurements, which require a cryostat, which in turn places constraints on the sample design used. In future, this ap- proach could establish a powerful method to study external factors influencing molecular transition rates. Overall, this thesis has introduced new molecular materials, revealed their photophys- ical properties, and demonstrated how they can be used to fabricate efficient and even novel light sources.}, subject = {Fotophysik}, language = {en} } @phdthesis{Seifert2022, author = {Seifert, Annika Kristina}, title = {Unidirectional freezing of soft and hard matter for biomedical applications}, doi = {10.25972/OPUS-27728}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-277281}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2022}, abstract = {A multitude of human tissues, such as bones, tendons, or muscles, are characterized by a hierarchical and highly ordered structure. In many cases, the loss of these tissues requires reconstruction using biocompatible replacement materials. In the field of bone replacement, the pore structure of the material has a crucial influence. Anisotropic porosity would have the advantage of facilitating the ingrowth of cells and newly formed blood vessels as well as the transport of nutrients. In this thesis, scaffolds with a highly ordered and anisotropic pore structure were fabricated using unidirectional freezing. Systematic investigations were carried out on biopolymer solutions (alginate and chitosan) to gain a deeper understanding of the freeze-structuring process. The knowledge gained was then applied to the development of anisotropically structured bone substitute materials. Here, the previously existing material platform for anisotropically structured calcium phosphates was extended to low-temperature phases such as calcium deficient hydroxyapatite (CDHA) or the secondary phosphates monetite and brushite. After the implantation of a biomaterial, the inevitably triggered initial immune response plays a key role in the success of a graft, with immune cells such as neutrophils or macrophages being of particular importance. In this thesis, the influence of anisotropically structured alpha-TCP and CDHA scaffolds as well as their unstructured references on human monocytes/macrophages was investigated. Macrophages produced extracellular traps (ETs) due to mineral nanoparticles formed by the binding of phosphate and calcium ions to human platelet lysate. In particular, incubation of alpha-TCP samples in lysate containing cell culture medium resulted in pronounced particle formation and enhanced release of ETs.}, subject = {Freezing}, language = {en} }