@phdthesis{Bastian2022,
  author    = {Bastian, Philipp U.},
  title     = {Core-shell upconversion nanoparticles - investigation of dopant intermixing and surface modification},
  doi       = {10.25932/publishup-55160},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-551607},
  school      = {Universit{\"a}t Potsdam},
  pages     = {XII, 108, xxiii},
  year      = {2022},
  abstract  = {Frequency upconversion nanoparticles (UCNPs) are inorganic nanocrystals capable to up-convert incident photons of the near-infrared electromagnetic spectrum (NIR) into higher energy photons. These photons are re-emitted in the range of the visible (Vis) and even ultraviolet (UV) light. The frequency upconversion process (UC) is realized with nanocrystals doped with trivalent lanthanoid ions (Ln(III)). The Ln(III) ions provide the electronic (excited) states forming a ladder-like electronic structure for the Ln(III) electrons in the nanocrystals. The absorption of at least two low energy photons by the nanoparticle and the subsequent energy transfer to one Ln(III) ion leads to the promotion of one Ln(III) electron into higher excited electronic states. One high energy photon will be emitted during the radiative relaxation of the electron in the excited state back into the electronic ground state of the Ln(III) ion. The excited state electron is the result of the previous absorption of at least two low energy photons. The UC process is very interesting in the biological/medical context. Biological samples (like organic tissue, blood, urine, and stool) absorb high-energy photons (UV and blue light) more strongly than low-energy photons (red and NIR light). Thanks to a naturally occurring optical window, NIR light can penetrate deeper than UV light into biological samples. Hence, UCNPs in bio-samples can be excited by NIR light. This possibility opens a pathway for in vitro as well as in vivo applications, like optical imaging by cell labeling or staining of specific organic tissue. Furthermore, early detection and diagnosis of diseases by predictive and diagnostic biomarkers can be realized with bio-recognition elements being labeled to the UCNPs. Additionally, "theranostic" becomes possible, in which the identification and the treatment of a disease are tackled simultaneously. For this to succeed, certain parameters for the UCNPs must be met: high upconversion efficiency, high photoluminescence quantum yield, dispersibility, and dispersion stability in aqueous media, as well as availability of functional groups to introduce fast and easy bio-recognition elements. The UCNPs used in this work were prepared with a solvothermal decomposition synthesis yielding in particles with NaYF4 or NaGdF4 as host lattice. They have been doped with the Ln(III) ions Yb3+ and Er3+, which is only one possible upconversion pair. Their upconversion efficiency and photoluminescence quantum yield were improved by adding a passivating shell to reduce surface quenching. However, the brightness of core-shell UCNPs stays behind the expectations compared to their bulk material (being at least μm-sized particles). The core-shell structures are not clearly separated from each other, which is a topic in literature. Instead, there is a transition layer between the core and the shell structure, which relates to the migration of the dopants within the host lattice during the synthesis. The ion migration has been examined by time-resolved laser spectroscopy and the interlanthanoid resonance energy transfer (LRET) in the two different host lattices from above. The results are presented in two publications, which dealt with core-shell-shell structured nanoparticles. The core is doped with the LRET-acceptor (either Nd3+ or Pr3+). The intermediate shell serves as an insulation shell of pure host lattice material, whose shell thickness has been varied within one set of samples having the same composition, so that the spatial separation of LRET-acceptor and -donor changes. The outer shell with the same host lattice is doped with the LRET-donor (Eu3+). The effect of the increasing insulation shell thickness is significant, although the LRET cannot be suppressed completely. Next to the Ln(III) migration within a host lattice, various phase transfer reactions were investigated in order to subsequently perform surface modifications for bioapplications. One result out of this research has been published using a promising ligand, that equips the UCNP with bio-modifiable groups and has good potential for bio-medical applications. This particular ligand mimics natural occurring mechanisms of mussel protein adhesion and of blood coagulation, which is why the UCNPs are encapsulated very effectively. At the same time, bio-functional groups are introduced. In a proof-of-concept, the encapsulated UCNP has been coupled successfully with a dye (which is representative for a biomarker) and the system's photoluminescence properties have been investigated.},
  language  = {en}
}
@phdthesis{Schulze2017,
  author    = {Schulze, Nicole},
  title     = {Neue Templatphasen zur anisotropen Goldnanopartikelherstellung durch den Einsatz strukturbildender Polymere},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-409515},
  school      = {Universit{\"a}t Potsdam},
  pages     = {VI, 117, xv},
  year      = {2017},
  abstract  = {Ziel der vorliegenden Arbeit war die Synthese und Charakterisierung von anisotropen Goldnanopartikeln in einer geeigneten Polyelektrolyt-modifizierten Templatphase. Der Mittelpunkt bildet dabei die Auswahl einer geeigneten Templatphase, zur Synthese von einheitlichen und reproduzierbaren anisotropen Goldnanopartikeln mit den daraus resultierenden besonderen Eigenschaften. Bei der Synthese der anisotropen Goldnanopartikeln lag der Fokus in der Verwendung von Vesikeln als Templatphase, wobei hier der Einfluss unterschiedlicher strukturbildender Polymere (stark alternierende Maleamid-Copolymere PalH, PalPh, PalPhCarb und PalPhBisCarb mit verschiedener Konformation) und Tenside (SDS, AOT - anionische Tenside) bei verschiedenen Synthese- und Abtrennungsbedingungen untersucht werden sollte. Im ersten Teil der Arbeit konnte gezeigt werden, dass PalPhBisCarb bei einem pH-Wert von 9 die Bedingungen eines R{\"o}hrenbildners f{\"u}r eine morphologische Transformation von einer vesikul{\"a}ren Phase in eine r{\"o}hrenf{\"o}rmige Netzwerkstruktur erf{\"u}llt und somit als Templatphase zur formgesteuerten Bildung von Nanopartikeln genutzt werden kann. Im zweiten Teil der Arbeit wurde dargelegt, dass die Templatphase PalPhBisCarb (pH-Wert von 9, Konzentration von 0,01 wt.\%) mit AOT als Tensid und PL90G als Phospholipid (im Verh{\"a}ltnis 1:1) die effektivste Wahl einer Templatphase f{\"u}r die Bildung von anisotropen Strukturen in einem einstufigen Prozess darstellt. Bei einer konstanten Synthesetemperatur von 45 °C wurden die besten Ergebnisse bei einer Goldchloridkonzentration von 2 mM, einem Gold-Templat-Verh{\"a}ltnis von 3:1 und einer Synthesezeit von 30 Minuten erzielt. Ausbeute an anisotropen Strukturen lag bei 52 \% (Anteil an dreieckigen Nanopl{\"a}ttchen von 19 \%). Durch Erh{\"o}hung der Synthesetemperatur konnte die Ausbeute auf 56 \% (29 \%) erh{\"o}ht werden. Im dritten Teil konnte durch zeitabh{\"a}ngige Untersuchungen gezeigt werden, dass bei Vorhandensein von PalPhBisCarb die Bildung der energetisch nicht bevorzugten Pl{\"a}ttchen-Strukturen bei Raumtemperatur initiiert wird und bei 45 °C ein Optimum annimmt. Kintetische Untersuchungen haben gezeigt, dass die Bildung dreieckiger Nanopl{\"a}ttchen bei schrittweiser Zugabe der Goldchlorid-Pr{\"a}kursorl{\"o}sung zur PalPhBisCarb enthaltenden Templatphase durch die Dosierrate der vesikul{\"a}ren Templatphase gesteuert werden kann. In umgekehrter Weise findet bei Zugabe der Templatphase zur Goldchlorid-Pr{\"a}kursorl{\"o}sung bei 45 °C ein {\"a}hnlicher, kinetisch gesteuerter Prozess der Bildung von Nanodreiecken statt mit einer maximalen Ausbeute dreieckigen Nanopl{\"a}ttchen von 29 \%. Im letzten Kapitel erfolgten erste Versuche zur Abtrennung dreieckiger Nanopl{\"a}ttchen von den {\"u}brigen Geometrien der gemischten Nanopartikell{\"o}sung mittels tensidinduzierter Verarmungsf{\"a}llung. Bei Verwendung von AOT mit einer Konzentration von 0,015 M wurde eine Ausbeute an Nanopl{\"a}ttchen von 99 \%, wovon 72 \% dreieckiger Geometrien hatten, erreicht.},
  language  = {de}
}
@phdthesis{Klier2016,
  author    = {Klier, Dennis Tobias},
  title     = {Upconversion luminescence in Er-codoped NaYF4 nanoparticles},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-98486},
  school      = {Universit{\"a}t Potsdam},
  pages     = {ix, 89},
  year      = {2016},
  abstract  = {In the context of an increasing population of aging people and a shift of medical paradigm towards an individualized medicine in health care, nanostructured lanthanides doped sodium yttrium fluoride (NaYF4) represents an exciting class of upconversion nanomaterials (UCNM) which are suitable to bring forward developments in biomedicine and -biodetection. Despite the fact that among various fluoride based upconversion (UC) phosphors lanthanide doped NaYF4 is one of the most studied upconversion nanomaterial, many open questions are still remaining concerning the interplay of the population routes of sensitizer and activator electronic states involved in different luminescence upconversion photophysics as well as the role of phonon coupling. The collective work aims to explore a detailed understanding of the upconversion mechanism in nanoscaled NaYF4 based materials co-doped with several lanthanides, e.g. Yb3+ and Er3+ as the "standard" type upconversion nanoparticles (UCNP) up to advanced UCNP with Gd3+ and Nd3+. Especially the impact of the crystal lattice structure as well as the resulting lattice phonons on the upconversion luminescence was investigated in detail based on different mixtures of cubic and hexagonal NaYF4 nanoscaled crystals. Three synthesis methods, depending on the attempt of the respective central spectroscopic questions, could be accomplished in the following work. NaYF4 based upconversion nanoparticles doped with several combination of lanthanides (Yb3+, Er3+, Gd3+ and Nd3+) were synthesized successfully using a hydrothermal synthesis method under mild conditions as well as a co-precipitation and a high temperature co-precipitation technique. Structural information were gathered by means of X-ray diffraction (XRD), electron microscopy (TEM), dynamic light scattering (DLS), Raman spectroscopy and inductively coupled plasma atomic emission spectrometry (ICP-OES). The results were discussed in detail with relation to the spectroscopic results. A variable spectroscopic setup was developed for multi parameter upconversion luminescence studies at various temperature 4 K to 328 K. Especially, the study of the thermal behavior of upconversion luminescence as well as time resolved area normalized emission spectra were a prerequisite for the detailed understanding of intramolecular deactivation processes, structural changes upon annealing or Gd3+ concentration, and the role of phonon coupling for the upconversion efficiency. Subsequently it became possible to synthesize UCNP with tailored upconversion luminescence properties. In the end, the potential of UCNP for life science application should be enunciated in context of current needs and improvements of a nanomaterial based optical sensors, whereas the "standard" UCNP design was attuned according to the special conditions in the biological matrix. In terms of a better biocompatibility due to a lower impact on biological tissue and higher penetrability for the excitation light. The first step into this direction was to use Nd3+ ions as a new sensitizer in tridoped NaYF4 based UCNP, whereas the achieved absolute and relative temperature sensitivity is comparable to other types of local temperature sensors in the literature.},
  language  = {en}
}
@phdthesis{Mitzscherling2015,
  author    = {Mitzscherling, Steffen},
  title     = {Polyelectrolyte multilayers for plasmonics and picosecond ultrasonics},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-80833},
  school      = {Universit{\"a}t Potsdam},
  pages     = {93},
  year      = {2015},
  abstract  = {This thesis investigates the application of polyelectrolyte multilayers in plasmonics and picosecond acoustics. The observed samples were fabricated by the spin-assisted layer-by-layer deposition technique that allowed a precise tuning of layer thickness in the range of few nanometers. The first field of interest deals with the interaction of light-induced localized surface plasmons (LSP) of rod-shaped gold nanoparticles with the particles' environment. The environment consists of an air phase and a phase of polyelectrolytes, whose ratio affects the spectral position of the LSP resonance. Measured UV-VIS spectra showed the shift of the LSP absorption peak as a function of the cover layer thickness of the particles. The data are modeled using an average dielectric function instead of the dielectric functions of air and polyelectrolytes. In addition using a measured dielectric function of the gold nanoparticles, the position of the LSP absorption peak could be simulated with good agreement to the data. The analytic model helps to understand the optical properties of metal nanoparticles in an inhomogeneous environment. The second part of this work discusses the applicability of PAzo/PAH and dye-doped PSS/PAH polyelectrolyte multilayers as transducers to generate hypersound pulses. The generated strain pulses were detected by time-domain Brillouin scattering (TDBS) using a pump-probe laser setup. Transducer layers made of polyelectrolytes were compared qualitatively to common aluminum transducers in terms of measured TDBS signal amplitude, degradation due to laser excitation, and sample preparation. The measurements proved that fast and easy prepared polyelectrolyte transducers provided stronger TDBS signals than the aluminum transducer. AFM topography measurements showed a degradation of the polyelectrolyte structures, especially for the PAzo/PAH sample. To quantify the induced strain, optical barriers were introduced to separate the transducer material from the medium of the hypersound propagation. Difficulties in the sample preparation prohibited a reliable quantification. But the experiments showed that a coating with transparent polyelectrolytes increases the efficiency of aluminum transducers and modifies the excited phonon distribution. The adoption of polyelectrolytes to the scientific field of picosecond acoustics enables a cheap and fast fabrication of transducer layers on most surfaces. In contrast to aluminum layers the polyelectrolytes are transparent over a wide spectral range. Thus, the strain modulation can be probed from surface and back.},
  language  = {en}
}
@phdthesis{Note2006,
  author    = {Note, Carine},
  title     = {Influence of hydrophobically modified polyelectrolytes on nanoparticle synthesis in self-organized systems and in water},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-11670},
  school      = {Universit{\"a}t Potsdam},
  year      = {2006},
  abstract  = {The formation of colloids by the controlled reduction, nucleation, and growth of inorganic precursor salts in different media has been investigated for more than a century. Recently, the preparation of ultrafine particles has received much attention since they can offer highly promising and novel options for a wide range of technical applications (nanotechnology, electrooptical devices, pharmaceutics, etc). The interest derives from the well-known fact that properties of advanced materials are critically dependent on the microstructure of the sample. Control of size, size distribution and morphology of the individual grains or crystallites is of the utmost importance in order to obtain the material characteristics desired. Several methods can be employed for the synthesis of nanoparticles. On the one hand, the reduction can occur in diluted aqueous or alcoholic solutions. On the other hand, the reduction process can be realized in a template phase, e.g. in well-defined microemulsion droplets. However, the stability of the nanoparticles formed mainly depends on their surface charge and it can be influenced with some added protective components. Quite different types of polymers, including polyelectrolytes and amphiphilic block copolymers, can for instance be used as protecting agents. The reduction and stabilization of metal colloids in aqueous solution by adding self-synthesized hydrophobically modified polyelectrolytes were studied in much more details. The polymers used are hydrophobically modified derivatives of poly(sodium acrylate) and of maleamic acid copolymers as well as the commercially available branched poly(ethyleneimine). The first notable result is that the polyelectrolytes used can act alone as both reducing and stabilizing agent for the preparation of gold nanoparticles. The investigation was then focused on the influence of the hydrophobic substitution of the polymer backbone on the reduction and stabilization processes. First of all, the polymers were added at room temperature and the reduction process was investigated over a longer time period (up to 8 days). In comparison, the reduction process was realized faster at higher temperature, i.e. 100°C. In both cases metal nanoparticles of colloidal dimensions can be produced. However, the size and shape of the individual nanoparticles mainly depends on the polymer added and the temperature procedure used. In a second part, the influence of the prior mentioned polyelectrolytes was investigated on the phase behaviour as well as on the properties of the inverse micellar region (L2 phase) of quaternary systems consisting of a surfactant, toluene-pentanol (1:1) and water. The majority of the present work has been made with the anionic surfactant sodium dodecylsulfate (SDS) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) since they can interact with the oppositely charged polyelectrolytes and the microemulsions formed using these surfactants present a large water-in-oil region. Subsequently, the polymer-modified microemulsions were used as new templates for the synthesis of inorganic particles, ranging from metals to complex crystallites, of very small size. The water droplets can indeed act as nanoreactors for the nucleation and growth of the particles, and the added polymer can influence the droplet size, the droplet-droplet interactions, as well as the stability of the surfactant film by the formation of polymer-surfactant complexes. One further advantage of the polymer-modified microemulsions is the possibility to stabilize the primary formed nanoparticles via a polymer adsorption (steric and/or electrostatic stabilization). Thus, the polyelectrolyte-modified nanoparticles formed can be redispersed without flocculation after solvent evaporation.},
  subject      = {Mikroemulsion},
  language  = {en}
}