Probing the antisymmetric Fano interference assisted by a Majorana fermion

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Surface modified Mg-doped ZnO QDs for biological imaging

Fundação Amparo à Pesquisa Estado de São Paulo (FAPESP)

Interferência Fano antissimétrica assistida por um férmion de Majorana

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Filmes de borracha natural com nanopartículas de prata e pontos quânticos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The migration of Mn2+ ions in Cd1-xMnxS nanocrystals: Thermal annealing control

This work reports evidence of the induced migration of Mn2+ ions in Cd(1-x)MnxS nanocrystals (NCs) by selecting a specific thermal treatment for each sample. The growth and characterization of these magnetic dots were investigated by atomic force microscopy (AFM), optical absorption (OA), and electronic paramagnetic resonance (EPR) techniques. The comparison of experimental and simulated EPR spectra confirms the incorporation of Mn2+ ions both in the core and at the dot surface regions. The thermal treatment of a magnetic sample, via selected annealing temperature and/or time, affects the fine and hyperfine interaction constants which modify the shape and the intensity of the EPR transition spectrum. The identification of these changes has allowed tracing the magnetic ion migration from core to surface regions of a dot as well as inferring the local density of the magnetic impurity ions. (C) 2011 Elsevier Ltd. All rights reserved.

SnO2 nanocrystals synthesized by microwave-assisted hydrothermal method: towards a relationship between structural and optical properties

The exploration of novel synthetic methodologies that control both size and shape of functional nanostructure opens new avenues for the functional application of nanomaterials. Here, we report a new and versatile approach to synthesize SnO2 nanocrystals (rutile-type structure) using microwave-assisted hydrothermal method. Broad peaks in the X-ray diffraction spectra indicate the nanosized nature of the samples which were indexed as a pure cassiterite tetragonal phase. Chemically and physically adsorbed water was estimated by TGA data and FT-Raman spectra to account for a new broad peak around 560 cm(-1) which is related to defective surface modes. In addition, the spherical-like morphology and low dispersed distribution size around 3-5 nm were investigated by HR-TEM and FE-SEM microscopies. Room temperature PL emission presents two broad bands at 438 and 764 nm, indicating the existence of different recombination centers. When the size of the nanospheres decreases, the relative intensity of 513 nm emission increases and the 393 nm one decreases. UV-Visible spectra show substantial changes in the optical absorbance of crystalline SnO2 nanoparticles while the existence of a small tail points out the presence of localized levels inside the forbidden band gap and supplies the necessary condition for the PL emission.

Temperature Sensing Using Colloidal-Core Photonic Crystal Fiber

We report on a temperature sensor based on the monitoring of the luminescence spectrum of CdSe/ZnS nanocrystals, dispersed in mineral oil and inserted into the core of a photonic crystal fiber. The high overlap between the pump light and the nanocrystals as well as the luminescence guiding provided by the fiber geometry resulted in relatively high luminescence powers and improved optical signal-to-noise ratio (OSNR). Also, both core end interfaces were sealed so as to generate a more stable and robust waveguide structure. Temperature sensitivity experiments indicated a 70 pm/degrees C spectral shift over the 5 degrees C to 90 degrees C range.

Influence of nanoparticle size on the nonlinear optical properties of magnetite ferrofluids

The nonlinear index of refraction (n(2)) and the two-photon absorption coefficient (beta) of water-based ferrofluids made of magnetite nanocrystals of different sizes and with different coatings have been measured through the Z-scan technique, with ultrashort (femtoseconds) laser pulses. Their third-order susceptibility is calculated from the values of n(2) and beta. The influence of different particles' coatings and sizes on these nonlinear optical properties are investigated. The values of n(2) and beta depend more significantly on the nanoparticles' size than on the particular coating. We observe a decrease of beta as the nanoparticles' diameters decrease, although the optical gap is found to be the same for all samples. The results are interpreted considering modifications in the electronic orbital shape due to the particles' nanosize effect.

Cluster carbonilici di platino contenenti fosfine

Nel corso di questa Tesi sono state studiate le reazioni di cluster carbonil anionici di Platino con fosfine. In particolare, sono state investigate nel dettaglio le reazioni dei cluster [Pt3n(CO)6n]2– (n = 3,4) e [Pt19(CO)22]n– (n = 3,4) con PPh3. Sono state poi preliminarmente studiate anche le reazioni di [Pt24(CO)30]2– e [Pt38(CO)44]2– con PPh3. Questo ha portato alla sintesi e alla completa caratterizzazione mediante diffrazione di raggi X su cristallo singolo delle specie [NBu4]2[Pt9(CO)16(PPh3)2] e [NBu4]x[Pt22(CO)22(PPh3)6]2•yCH3CN, contenenti gli anioni [Pt9(CO)16(PPh3)2]2– e [Pt22(CO)22(PPh3)6]2–. È stato inoltre preparato un nuovo composto tentativamente formulato come [Pt19(CO)20(PPh3)2]4–, sulla base dei dati IR, 31P NMR e ESI-MS. Questi rappresentano i primi esempi di cluster carbonilici anionici di Platino contenenti fosfine. Nel caso delle reazioni di [Pt24(CO)30]2– e [Pt38(CO)44]2– con PPh3 i prodotti sono stati caratterizzati al momento solo mediante spettroscopia IR, e quindi è molto difficile ipotizzare una loro struttura. I composti [Pt9(CO)16(PPh3)2]2– e [Pt19(CO)20(PPh3)2]4– sono stati investigati mediante spettroscopia 31P NMR in soluzione a temperatura variabile. Il primo mostra un unico segnale 31P NMR, in accordo con la struttura allo stato solido, mentre [Pt19(CO)20(PPh3)2]4– è risultato essere flussionale. È stato poi studiato nel dettaglio il comportamento fotochimico dei cluster [Pt3n(CO)6n]2– (n = 3-6) in funzione della concentrazione, confermando la loro natura di “Double emitting quantum dots”. Infine è stato preparato e caratterizzato strutturalmente il sale [DAMS]2[Pt9(CO)18]•dmf, contenente il catione [DAMS]+.

Plasmonenresonanzen von sichelförmigen metallischen Nanoobjekten

Metallische Objekte in der Größenordnung der optischen Wellenlänge zeigen Resonanzen im optischen Spektralbereich. Mit einer Kombination aus Kolloidlithographie, Metallfilmbedampfung und reaktivem Ionenstrahl¨atzen wurden Nanosicheln aus Gold bzw. Silber mit identischer Form und Orientierung in Sichelform mit einer Größe von 60nm bis 400nm hergestellt. Der Öffnungswinkel der Nanosicheln lässt sich kontinuierlich einstellen. Durch die einheitliche Orientierung lassen sich Messungen am Ensemble direkt auf das Verhalten des Einzelobjektes übertragen, wie ein Vergleich der Extinktionsspektren einer Ensemblemessung am UV/Vis/NIR-Spektrometer mit einer Einzelpartikelmessung in einem konfokalen Mikroskop zeigt. Die optische Antwort der Nanosicheln wurde als zwei-dimensionales Modell mit einer Finite Elemente Methode berechnet. Das Ergebnis sind mehrere polarisationsabhängige Resonanzen im optischen Spektrum. Diese lassen sich durch Variation des Öffnungswinkels und der Gr¨oße der Nanosichel verschieben. Durch Beleuchten lassen sich plasmonische Schwingungen anregen, die ein stark lokalisiertes Nahfeld an den Spitzen und in der Öffnung der Nanosicheln erzeugen. Das Nahfeld der Partikelresonanz wurde mit einer Fotolackmethode nachgewiesen. Die Untersuchungen am UV/Vis/NIR-Spektrometer zeigen mehrere polarisationsabhängige Resonanzen im Spektralbereich von 300 nm bis 3200 nm. Die Resonanzen der Nanosicheln lassen sich durch den Öffnungswinkel und den Durchmesser in der Größenordnung der Halbwertbreite im optischen Spektrum verschieben. In der Anwendung als Chemo- bzw. Biosensor zeigen Gold-Nanosicheln eine ähnliche Empfindlichkeit wie vergleichbare Sensoren auf der Basis von dünnen Metallstrukturen. Das Nahfeld zeichnet sich durch eine starke Lokalisierung aus und dringt, je nach Multipolordnung, zwischen 14 nm und 70 nm in die Umgebung ein. Quantenpunkte wurden an das Nahfeld der Nanosicheln gekoppelt. Die Emission der Quantenpunkte bei einer Wellenlänge von 860nm wird durch die Resonanz der Nanosicheln verstärkt. Die Nanosicheln wurden als optische Pinzette eingesetzt. Bei einer Anregung mit einem Laser bei einer Wellenlänge von 1064 nm wurden Polystyrolkolloide mit einem Durchmesser von 40 nm von den resonanten Nanosicheln eingefangen. Die Nanosicheln zeigen außergewöhnliche optische Eigenschaften, die mithilfe der Geometrieparameter über einen großen Bereich verändert werden können. Die ersten Anwendungen haben Anknüpfungspunkte zur Verwendung in der Sensorik, Fluoreszenzspektroskopie und als optische Pinzette aufgezeigt.

Synthesis and surface modification of semiconductor nanocrystals

The last decade has witnessed an exponential growth of activities in the field of nanoscience and nanotechnology worldwide, driven both by the excitement of understanding new science and by the potential hope for applications and economic impacts. The largest activity in this field up to date has been in the synthesis and characterization of new materials consisting of particles with dimensions in the order of a few nanometers, so-called nanocrystalline materials. [1-8] Semiconductor nanomaterials such as III/V or II/VI compound semiconductors exhibit strong quantum confinement behavior in the size range from 1 to 10 nm. Therefore, preparation of high quality semiconductor nanocrystals has been a challenge for synthetic chemists, leading to the recent rapid progress in delivering a wide variety of semiconducting nanomaterials. Semiconductor nanocrystals, also called quantum dots, possess physical properties distinctly different from those of the bulk material. Typically, in the size range from 1 to 10 nm, when the particle size is changed, the band gap between the valence and the conduction band will change, too. In a simple approximation a particle in a box model has been used to describe the phenomenon[9]: at nanoscale dimensions the degenerate energy states of a semiconductor separate into discrete states and the system behaves like one big molecule. The size-dependent transformation of the energy levels of the particles is called “quantum size-effect”. Quantum confinement of both the electron and hole in all three dimensions leads to an increase in the effective bandgap of the material with decreasing crystallite size. Consequently, both the optical absorption and emission of semiconductor nanaocrystals shift to the blue (higher energies) as the size of the particles gets smaller. This color tuning is well documented for CdSe nanocrystals whose absorption and emission covers almost the whole visible spectral range. As particle sizes become smaller the ratio of surface atoms to those in the interior increases, which has a strong impact on particle properties, too. Prominent examples are the low melting point [8] and size/shape dependent pressure resistance [10] of semiconductor nanocrystals. Given the size dependence of particle properties, chemists and material scientists now have the unique opportunity to change the electronic and chemical properties of a material by simply controlling the particle size. In particular, CdSe nanocrystals have been widely investigated. Mainly due to their size-dependent optoelectronic properties [11, 12] and flexible chemical processibility [13], they have played a distinguished role for a number of seminal studies [11, 12, 14, 15]. Potential technical applications have been discussed, too. [8, 16-27] Improvement of the optoelectronic properties of semiconductor nanocrystals is still a prominent research topic. One of the most important approaches is fabricating composite type-I core-shell structures which exhibit improved properties, making them attractive from both a fundamental and a practical point of view. Overcoating of nanocrystallites with higher band gap inorganic materials has been shown to increase the photoluminescence quantum yields by eliminating surface nonradiative recombination sites. [28] Particles passivated with inorganic shells are more robust than nanocrystals covered by organic ligands only and have greater tolerance to processing conditions necessary for incorporation into solid state structures or for other applications. Some examples of core-shell nanocrystals reported earlier include CdS on CdSe [29], CdSe on CdS, [30], ZnS on CdS, [31] ZnS on CdSe[28, 32], ZnSe on CdSe [33] and CdS/HgS/CdS [34]. The characterization and preparation of a new core-shell structure, CdSe nanocrystals overcoated by different shells (CdS, ZnS), is presented in chapter 4. Type-I core-shell structures as mentioned above greatly improve the photoluminescence quantum yield and chemical and photochemical stability of nanocrystals. The emission wavelengths of type-I core/shell nanocrystals typically only shows a small red-shift when compared to the plain core nanocrystals. [30, 31, 35] In contrast to type-I core-shell nanocrystals, only few studies have been conducted on colloidal type-II core/shell structures [36-38] which are characterized by a staggered alignment of conduction and valence bands giving rise to a broad tunability of absorption and emission wavelengths, as was shown for CdTe/CdSe core-shell nanocrystals. [36] The emission of type-II core/shell nanocrystals mainly originates from the radiative recombination of electron-hole pairs across the core-shell interface leading to a long photoluminescence lifetime. Type-II core/shell nanocrystals are promising with respect to photoconduction or photovoltaic applications as has been discussed in the literature.[39] Novel type-II core-shell structures with ZnTe cores are reported in chapter 5. The recent progress in the shape control of semiconductor nanocrystals opens new fields of applications. For instance, rod shaped CdSe nanocrystals can enhance the photo-electro conversion efficiency of photovoltaic cells, [40, 41] and also allow for polarized emission in light emitting diodes. [42, 43] Shape control of anisotropic nanocrystals can be achieved by the use of surfactants, [44, 45] regular or inverse micelles as regulating agents, [46, 47] electrochemical processes, [48] template-assisted [49, 50] and solution-liquid-solution (SLS) growth mechnism. [51-53] Recently, formation of various CdSe nanocrystal shapes has been reported by the groups of Alivisatos [54] and Peng, [55] respectively. Furthermore, it has been reported by the group of Prasad [56] that noble metal nanoparticles can induce anisotropic growth of CdSe nanocrystals at lower temperatures than typically used in other methods for preparing anisotropic CdSe structures. Although several approaches for anisotropic crystal growth have been reported by now, developing new synthetic methods for the shape control of colloidal semiconductor nanocrystals remains an important goal. Accordingly, we have attempted to utilize a crystal phase control approach for the controllable synthesis of colloidal ZnE/CdSe (E = S, Se, Te) heterostructures in a variety of morphologies. The complex heterostructures obtained are presented in chapter 6. The unique optical properties of nanocrystals make them appealing as in vivo and in vitro fluorophores in a variety of biological and chemical investigations, in which traditional fluorescence labels based on organic molecules fall short of providing long-term stability and simultaneous detection of multiple emission colours [References]. The ability to prepare water soluble nanocrystals with high stability and quantum yield has led to promising applications in cellular labeling, [57, 58] deep-tissue imaging, [59, 60] and assay labeling [61, 62]. Furthermore, appropriately solubilized nanocrystals have been used as donors in fluorescence resonance energy transfer (FRET) couples. [63-65] Despite recent progress, much work still needs to be done to achieve reproducible and robust surface functionalization and develop flexible (bio-) conjugation techniques. Based on multi-shell CdSe nanocrystals, several new solubilization and ligand exchange protocols have been developed which are presented in chapter 7. The organization of this thesis is as follows: A short overview describing synthesis and properties of CdSe nanocrystals is given in chapter 2. Chapter 3 is the experimental part providing some background information about the optical and analytical methods used in this thesis. The following chapters report the results of this work: synthesis and characterization of type-I multi-shell and type-II core/shell nanocrystals are described in chapter 4 and chapter 5, respectively. In chapter 6, a high–yield synthesis of various CdSe architectures by crystal phase control is reported. Experiments about surface modification of nanocrystals are described in chapter 7. At last, a short summary of the results is given in chapter 8.

Surface-plasmon optical and electrochemical characterization of biofunctional surface architectures

The development and characterization of biomolecule sensor formats based on the optical technique Surface Plasmon Resonance (SPR) Spectroscopy and electrochemical methods were investigated. The study can be divided into two parts of different scope. In the first part new novel detection schemes for labeled targets were developed on the basis of the investigations in Surface-plamon Field Enhanced Spectroscopy (SPFS). The first one is SPR fluorescence imaging formats, Surface-plamon Field Enhanced Fluorescence Microscopy (SPFM). Patterned self assembled monolayers (SAMs) were prepared and used to direct the spatial distribution of biomolecules immobilized on surfaces. Here the patterned monolayers would serve as molecular templates to secure different biomolecules to known locations on a surface. The binding processed of labeled target biomolecules from solution to sensor surface were visually and kinetically recorded by the fluorescence microscope, in which fluorescence was excited by the evanescent field of propagating plasmon surface polaritons. The second format which also originates from SPFS technique, Surface-plamon Field Enhanced Fluorescence Spectrometry (SPFSm), concerns the coupling of a fluorometry to normal SPR setup. A spectrograph mounted in place of photomultiplier or microscope can provide the information of fluorescence spectrum as well as fluorescence intensity. This study also firstly demonstrated the analytical combination of surface plasmon enhanced fluorescence detection with analyte tagged by semiconducting nano- crystals (QDs). Electrochemically addressable fabrication of DNA biosensor arrays in aqueous environment was also developed. An electrochemical method was introduced for the directed in-situ assembly of various specific oligonucleotide catcher probes onto different sensing elements of a multi-electrode array in the aqueous environment of a flow cell. Surface plasmon microscopy (SPM) is utilized for the on-line recording of the various functionalization steps. Hybridization reactions between targets from solution to the different surface-bound complementary probes are monitored by surface-plasmon field-enhanced fluorescence microscopy (SPFM) using targets that are either labeled with organic dyes or with semiconducting quantum dots for color-multiplexing. This study provides a new approach for the fabrication of (small) DNA arrays and the recording and quantitative evaluation of parallel hybridization reactions. In the second part of this work, the ideas of combining the SP optical and electrochemical characterization were extended to tethered bilayer lipid membrane (tBLM) format. Tethered bilayer lipid membranes provide a versatile model platform for the study of many membrane related processes. The thiolipids were firstly self-assembled on ultraflat gold substrates. Fusion of the monolayers with small unilamellar vesicles (SUVs) formed the distal layer and the membranes thus obtained have the sealing properties comparable to those of natural membranes. The fusion could be monitored optically by SPR as an increase in reflectivity (thickness) upon formation of the outer leaflet of the bilayer. With EIS, a drop in capacitance and a steady increase in resistance could be observed leading to a tightly sealing membrane with low leakage currents. The assembly of tBLMs and the subsequent incorporation of membrane proteins were investigated with respect to their potential use as a biosensing system. In the case of valinomycin the potassium transport mediated by the ion carrier could be shown by a decrease in resistance upon increasing potassium concentration. Potential mediation of membrane pores could be shown for the ion channel forming peptide alamethicin (Alm). It was shown that at high positive dc bias (cis negative) Alm channels stay at relatively low conductance levels and show higher permeability to potassium than to tetramethylammonium. The addition of inhibitor amiloride can partially block the Alm channels and results in increase of membrane resistance. tBLMs are robust and versatile model membrane architectures that can mimic certain properties of biological membranes. tBLMs with incorporated lipopolysaccharide (LPS) and lipid A mimicking bacteria membranes were used to probe the interactions of antibodies against LPS and to investigate the binding and incorporation of the small antimicrobial peptide V4. The influence of membrane composition and charge on the behavior of V4 was also probed. This study displays the possibility of using tBLM platform to record and valuate the efficiency or potency of numerous synthesized antimicrobial peptides as potential drug candidates.

Designed functional defects in colloidal photonic crystals: switching, biomonitoring and modified photoluminescence

Es werden zwei komplementäre "bottom-up" Methoden präsentiert, die den kontrollierten Einbau von "intelligenten" planaren Defekten in selbstorganisierte kolloidale photonische Kristalle (KPKs) ermöglichen. Die Defektschicht basiert auf einem funktionellen, nanometer-skalierten dünnen Film, der entweder durch schichtweise ("layer-by-layer") Selbstorganisation und Mikrokontakttransferübertragung oder durch Aufschleudern und einer KPK-Opferfüllung hergestellt wird. Die entwickelten Techniken gestatten die Integration von maßgeschneiderten dünnen Defektfilmen bestehend aus einer enorm großen Vielfalt an Materialien; sie sind kostengünstig und können im größeren Maßstab angewendet werden. Optische Untersuchungen zeigen einen engen, durch den Defekt hervorgerufenen Transmissionszustand in der photonischen Bandlücke. Die Defektwellenlänge hängt von der optischen Dicke der Defektschicht ab. Aktives Schalten der Defektwellenlänge wird erreicht, indem Defektschichten aus Makromolekülen hergestellt werden, die über externe Erreger wie Licht, Temperatur, Redoxzyklen und mechanischen Druck adressiert werden können. Die Ergebnisse der Untersuchungen sind im Einklang mit separat durchgeführten Ellipsometrie-Messungen und theoretischen "scalar wave approximation"-Berechnungen. Darüber hinaus werden KPKs mit funktionellen biomolekularen Defekten vorgestellt. Über Verschiebungen der Defektmode können DNA-Konformationsänderungen, die enantioselektive Einlagerung eines chiralen Antitumormedikaments sowie Enzymaktivitäten optisch beobachtet werden. Die Einlagerung von fluoreszierenden Farbstoffen und Quantenpunkten in Defekt-KPKs führt zu einer eindeutigen, durch die photonische Bandlücke und den Defektzustand hervorgerufenen Modifizierung der Photolumineszenz (PL)-Spektren. Schaltbare PL-Modifizierungen werden detektiert, wenn adressierbare Defekt-KPKs verwendet werden.

Hydrophobe und hydrophile Beladung polymerer Vesikel

Polymere Vesikel, gebildet durch Selbstorganisation des amphiphilen Blockcopolymers Polybutadien-b-Polyethylenoxid in Wasser, wurden in der vorliegenden Arbeit erfolgreich mit hydrophoben und hydrophilen Substraten beladen und detailliert charakterisiert. Über verschiedene Präparationsmethoden sind unilamellare PB130-PEO66-Vesikel unterschiedlicher Größen und Verteilungsbreiten zugänglich, die aber alle eine konstante hydrophobe Schalendicke von etwa 15nm aufweisen, wie aus TEM-Messungen hervorgeht. Die hydrophoben Farbstoffe Oil Red EGN, Oil Blue N, Nilrot sowie ein Perylen-Derivat wurden in diese hydrophobe Schale eingelagert. Durch Absorptions-, Emissions-, (cryo)TEM- und Fluoreszenzmikroskopie-Messungen konnte gezeigt werden, dass die selbstorganisierte Struktur durch die Einlagerung der hydrophoben Farbstoffe in die Schale nicht beeinflusst wird. Als zusätzliche hydrophobe Modell-Substrate wurden Halbleiter-Nanokristalle, sogenannte Quantum Dots (QDs, d=5.7nm), erfolgreich in die polymere Vesikelschale eingelagert und durch Fluoreszenz-Korrelations-Spektroskopie (FCS) in Kombination mit dynamischer Lichtstreuung (DLS) nachgewiesen. Die Position der QDs in der Mitte der polymeren Doppelmembran konnte durch cryogene TEM-Abbildungen aufgezeigt werden. Darüber hinaus wurde die hydrophile Beladung des Vesikelkerns mit dem wasserlöslichen Farbstoff Phloxin B erfolgreich realisiert.

Triphenylene-based polymers for organic electronics

An efficient synthesis has been developed toward a novel series of conjugated blue emitting polymers containing triphenylene as repeating unit for polymer light emitting diodes (PLEDs). Soluble triphenylene-based co- and homo-polymers have been synthesized by the palladium-catalyzed Suzuki-Miyaura and the nickel-catalysed Yamamoto polycondensation reactions, respectively. The photophysical properties as well as the application of the polymers in PLED devices are presented here.rnIn addition a simple GNR fabrication method that allows for the production of atomically precise GNRs of different topologies and widths is introduced. This bottom-up approach consists in the surface-assisted coupling of suitably designed molecular triphenylene precursors into linear polyphenylenes and their subsequent cyclodehydrogenation and results in GNRs whose topology, width and edge periphery are defined by the precursor monomers. Various types of atomically precise GNRs thus eventually become available for experimental investigation and exploitation of their many predicted and technologically highly interesting properties. Furthermore, it is anticipated that this bottom-up approach of GNR fabrication will allow the engineering of chemical and electronic properties and the yet elusive realization of theoretically predicted structures such as intraribbon quantum dots, superlattice structures, or magnetic devices based on specific GNR edge states.rn