In order to improve the optical losses of spherical silicon solar cells, new fabrication designs were presented. The new device structures are fabricated based on integration of nanostructures into spherical silicon solar cells. These new device structures include: spherical silicon solar cells integrated with nanostructured antireflection coating layers, spherical silicon solar cells with hemispherical nanopit texturing, and cells integrated with colloidal quantum dots. Silicon spheres were characterized by means of transmission electron microscopy (TEM), single-crystal x-ray diffraction and x-ray powder diffraction to establish the crystallinity nature of the silicon spheres. Furthermore, the material properties of silicon spheres including surface morphology, microwave photoconductivity decay lifetime, and impurity elemental distributions were studied. Silicon nitride antireflection coating layers were developed and deposited onto the spherical silicon solar cells, using a PECVD system. A low temperature hydrogenation plasma technique was developed to improve the passivation quality of the spherical silicon solar cells. The spectral response of silicon spheres with and without a silicon nitride antireflection coating was studied. We have successfully developed and integrated a nanostructured antireflection coating layer into spherical silicon solar cells. The nanostructured porous layer consists of graded-size silicon nanocrystals and quantum-size Si nanoparticles embedded in an oxide matrix. This layer has been characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), Scanning tunneling TEM, energy filtered TEM, transmission electron diffraction (TED), electron energy loss spectroscopy (EELS), energy dispersive x-ray (EDX), Raman spectroscopy and photoluminescence spectroscopy (PL). We developed a novel technique of electrochemical etching for silicon surface texturing using a liquid-phase deposition of oxide mask. Using a focus ion-beam (FIB) technique, cross-sectional TEM samples were prepared to investigate the nature of texturing and the composition of the deposited mask. The hemispherical nanopit texturing was successfully integrated into spherical silicon solar cells and the etching mechanisms and the chemical reactions were discussed. CdSe colloidal quantum dots with diameter of about 2.8nm were integrated into a graded-density nanoporous layer. This structure was implemented on the emitter of the spherical silicon solar cells and the spectral response with and without incorporation of QDs was studied.

This work summarizes results of about 10 years of the author’s own activities in the field of aqueous synthesis and handling of thiol-capped semiconductor nanocrystals. As this field has also been explored by hundreds of other scientists, I have endeavoured to do my utmost to provide a short but comprehensive overview presenting my own results as part of the knowledge framework jointly created by multiple colleagues and collaborators from all over the world. This habilitation thesis consists of an introduction, which provides references to the corresponding literature sources and also links to the corresponding annexes, i.e. original published articles, which are attached to this cumulative script.

This thesis is devoted to the development of microfluidic processes for the controlled self-assembly of quantum dot compound micelles (QDCMs). Microfluidic processes are developed to combine the constituents (cadmium sulfide quantum dots, and block copolymer stabilizing chains) with water to facilitate self-assembly of the composite particles, QDCMs, through initial phase separation, subsequent growth, and eventual quenching. Two genres of microfluidic reactors are developed. The on-chip evolution of QDCM formation and growth is resolved through fluorescence microscopy; QDCM size distributions and associated statistics are determined through off-chip analysis by transmission electron microscopy (TEM). In a flow-focusing reactor, control over the mean size of QDCMs is demonstrated through both the water concentration and the growth time (or reactor channel length). Controlled QDCM self-assembly is also demonstrated in a multiphase gas-liquid reactor. In contrast to the flow-focusing reactor, increasing the multiphase reactor channel length results in a decrease in QDCM size and polydispersity.

Tyrimų tikslas – naudojant kvantinius taškus (KT), kaip tinkamų vaistų pernašai biosuderinamų nanodalelių modelį, in vitro nustatyti bendrus tikslingai nemodifikuotų nanodalelių patekimo į ląsteles ir lokalizacijos jose dėsningumus. Spektroskopiniais metodais ištyrus KT patekimo į ląsteles laikinę dinamiką nustatyta, kad neigiamo krūvio apvalkalo KT patekimo į ląsteles procesą galima suskirstyti į tris etapus, tačiau šie kaupimosi etapai skirtingose ląstelių kultūrose yra nevienodos trukmės. Konfokalinės fluorescencijos mikroskopijos metodu ištyrus neigiamo paviršiaus krūvio KT patekimo į ląsteles procesą, pagal viduląstelinį KT pasiskirstymą ir susiformavusių pūslelių tipus, galima suskirstyti į keturias fazes. Naudojant fluorescencijos gyvavimo trukmės vaizdinimo mikroskopijos metodą užregistruotas nuo endosomų brandos priklausantis viduląstelinių vezikulių vidinės struktūros heterogeniškumas. Skirtingos brandos endosomos gali būti apibūdinamos ir vaizdinamos remiantis jose sukauptų KT savitomis fotoliuminescencijos gyvavimo trukmėmis. Skirtingais fizikiniais ir biocheminiais metodais nustatyta, kad difuzijos būdu KT per ląstelės membraną neprasiskverbia, bet į ląsteles patenka endocitozės būdu. Nepadengti baltymais neigiamo paviršiaus krūvio KT į ląsteles patenka tik vienu nuo kaveolino priklausančiu endocitozės keliu. KT, kaip modelinių diagnostinių priemonių, ir antivėžinio preparato bendras panaudojimas in vitro atskleidė, kad KT, nesukeldami toksinio poveikio ląstelių... [toliau žr. visą tekstą] / The overall aim of the study is to identify the general rules for intracellular uptake and localisation of non-targeted nanoparticles by employing colloid quantum dots (QDs) as a model of biocompatible nanoparticle-based drug carriers. The investigation of intracellular uptake of non-targeted negatively charged QDs with fluorescence spectroscopy method revealed three time-related accumulation stages, which are characteristic for all investigated cell lines, but the stages were of different timing for each of the investigated cell line. The confocal fluorescence microscopy imaging showed four intracellular accumulation phases of QDs based on type and localisation of formed vesicles. The fluorescence lifetime imaging microscopy revealed the inner heterogeneity of intracellular vesicles: the endosomes at particular stage of maturity can be identified by different photoluminescence lifetimes of accumulated QDs. QDs do not penetrate plasma membranes through passive diffusion, but enter a cell through endocytosis. Negatively charged QDs without protein corona enter the cells through the single, caveolin-dependent endocytic pathway. Examination of the possibility to combine QDs, as model diagnostic probes, with anticancer agent in vitro revealed, that despite QDs alone had no cytotoxic effects on cells viability, they increased drug resistance. Therefore, this effect needs profound further research before the application of quantum dots in combined diagnosis and therapy in vivo.

The overall aim of the study is to identify the general rules for intracellular uptake and localisation of non-targeted nanoparticles by employing colloid quantum dots (QDs) as a model of biocompatible nanoparticle-based drug carriers. The investigation of intracellular uptake of non-targeted negatively charged QDs with fluorescence spectroscopy method revealed three time-related accumulation stages, which are characteristic for all investigated cell lines, but the stages were of different timing for each of the investigated cell line. The confocal fluorescence microscopy imaging showed four intracellular accumulation phases of QDs based on type and localisation of formed vesicles. The fluorescence lifetime imaging microscopy revealed the inner heterogeneity of intracellular vesicles: the endosomes at particular stage of maturity can be identified by different photoluminescence lifetimes of accumulated QDs. QDs do not penetrate plasma membranes through passive diffusion, but enter a cell through endocytosis. Negatively charged QDs without protein corona enter the cells through the single, caveolin-dependent endocytic pathway. Examination of the possibility to combine QDs, as model diagnostic probes, with anticancer agent in vitro revealed, that despite QDs alone had no cytotoxic effects on cells viability, they increased drug resistance. Therefore, this effect needs profound further research before the application of quantum dots in combined diagnosis and therapy in vivo. / Tyrimų tikslas – naudojant kvantinius taškus (KT), kaip tinkamų vaistų pernašai biosuderinamų nanodalelių modelį, in vitro nustatyti bendrus tikslingai nemodifikuotų nanodalelių patekimo į ląsteles ir lokalizacijos jose dėsningumus. Spektroskopiniais metodais ištyrus KT patekimo į ląsteles laikinę dinamiką nustatyta, kad neigiamo krūvio apvalkalo KT patekimo į ląsteles procesą galima suskirstyti į tris etapus, tačiau šie kaupimosi etapai skirtingose ląstelių kultūrose yra nevienodos trukmės. Konfokalinės fluorescencijos mikroskopijos metodu ištyrus neigiamo paviršiaus krūvio KT patekimo į ląsteles procesą, pagal viduląstelinį KT pasiskirstymą ir susiformavusių pūslelių tipus, galima suskirstyti į keturias fazes. Naudojant fluorescencijos gyvavimo trukmės vaizdinimo mikroskopijos metodą užregistruotas nuo endosomų brandos priklausantis viduląstelinių vezikulių vidinės struktūros heterogeniškumas. Skirtingos brandos endosomos gali būti apibūdinamos ir vaizdinamos remiantis jose sukauptų KT savitomis fotoliuminescencijos gyvavimo trukmėmis. Skirtingais fizikiniais ir biocheminiais metodais nustatyta, kad difuzijos būdu KT per ląstelės membraną neprasiskverbia, bet į ląsteles patenka endocitozės būdu. Nepadengti baltymais neigiamo paviršiaus krūvio KT į ląsteles patenka tik vienu nuo kaveolino priklausančiu endocitozės keliu. KT, kaip modelinių diagnostinių priemonių, ir antivėžinio preparato bendras panaudojimas in vitro atskleidė, kad KT, nesukeldami toksinio poveikio ląstelių... [toliau žr. visą tekstą]

This thesis describes observations, techniques and strategies, which contribute towards the development of nanoparticle based detection and treatment of cancer. Quantum dots and biorecognition molecules were studied towards applications in detection and microgels were used in the rational design of a targeted drug delivery vehicle. The fluorescence intensity of quantum dots was examined in buffers commonly used in molecular biology. The fluorescence intensity of ZnS-capped CdSe quantum dots (QDs) was found to vary significantly, depending on the amount of ZnS capping on the QDs or the concentration, pH and type of buffer the QDs were in. Since fluorescence cannot reliably be used to quantify QDs, an alternative quantification method was developed, which does not rely on their fluorescence. This method employs phage display to identify nanoparticle-specific bacteriophage which were then applied in an assay to quantify QDs in environments where absorbance or fluorescence spectroscopy are ineffective. Biorecognition molecules, which can direct nanoparticles to a molecular target, were also identified through phage display. Phage display on whole cells was used to identify a peptide, which was conjugated with QDs to stain HeLa (cervical cancer) cells. A high-throughput phage display screening strategy was also developed, which could enable the simultaneous identification of multiple biorecognition molecules from a single library. QD-encoded microbead barcodes were conjugated to protein targets and then used to screen a phage display library. The beads and the binding phage were then separated using flow cytometry and fluorescence assisted cell sorting. Finally, biorecognition molecules were combined with nanoparticles to create drug delivery vehicles, which were designed to protect, deliver and then release chemotherapeutic drugs through an intracellular pH trigger. PolyNIPAAm and chitosan hydrogels, under 200 nm in diameter, were loaded with chemotherapeutic drugs, conjugated to transferrin and tested in vitro on HeLa cells. These projects demonstrate the great potential in this growing field as well as some of the many challenges that have yet to be overcome.

This thesis describes observations, techniques and strategies, which contribute towards the development of nanoparticle based detection and treatment of cancer. Quantum dots and biorecognition molecules were studied towards applications in detection and microgels were used in the rational design of a targeted drug delivery vehicle. The fluorescence intensity of quantum dots was examined in buffers commonly used in molecular biology. The fluorescence intensity of ZnS-capped CdSe quantum dots (QDs) was found to vary significantly, depending on the amount of ZnS capping on the QDs or the concentration, pH and type of buffer the QDs were in. Since fluorescence cannot reliably be used to quantify QDs, an alternative quantification method was developed, which does not rely on their fluorescence. This method employs phage display to identify nanoparticle-specific bacteriophage which were then applied in an assay to quantify QDs in environments where absorbance or fluorescence spectroscopy are ineffective. Biorecognition molecules, which can direct nanoparticles to a molecular target, were also identified through phage display. Phage display on whole cells was used to identify a peptide, which was conjugated with QDs to stain HeLa (cervical cancer) cells. A high-throughput phage display screening strategy was also developed, which could enable the simultaneous identification of multiple biorecognition molecules from a single library. QD-encoded microbead barcodes were conjugated to protein targets and then used to screen a phage display library. The beads and the binding phage were then separated using flow cytometry and fluorescence assisted cell sorting. Finally, biorecognition molecules were combined with nanoparticles to create drug delivery vehicles, which were designed to protect, deliver and then release chemotherapeutic drugs through an intracellular pH trigger. PolyNIPAAm and chitosan hydrogels, under 200 nm in diameter, were loaded with chemotherapeutic drugs, conjugated to transferrin and tested in vitro on HeLa cells. These projects demonstrate the great potential in this growing field as well as some of the many challenges that have yet to be overcome.

Semiconductor quantum dots (QDs) and gold nanoparticles (AuNPs) have gained tremendous attention in the last decade as a result of their size-dependent spectroscopic properties. These nanoparticles have been a subject of intense study to bridge the gap between macroscopic and atomic behavior, as well as to generate new materials for novel applications in therapeutics, biological sensing, light emitting devices, microelectronics, lasers, and solar cells. One of the most promising areas for the use of these nanoparticles is in biotechnology, where their size-dependent optical properties are harnessed for imaging and sensing applications. However, these nanoparticles, as synthesized, are often not stable in aqueous media and lack simple and reliable means of covalently linking to biomolecules. The focus of this work is to advance the progress of these nanomaterials for biotechnology by synthesizing them, characterizing their optical properties and rendering them water-soluble and functional while maintaining their coveted optical properties. QDs were synthesized by an organometallic chemical procedure that utilizes coordinating solvents to provide brightly luminescent nanoparticles. The optical interactions of these QDs were studied as a function of concentration to identify particle size-dependent optimal concentrations, where scattering and indirection excitation are minimized and the amount light observed per particle is maximized. Both QDs and AuNPs were rendered water-soluble and stable in a broad range of biologically relevant conditions by using a series of ligands composed of dihydrolipoic acid (DHLA) appended to poly(ethylene glycol) methyl ether. By studying the stability of the surface modified AuNPs, we revealed some interesting information regarding the role of the surface ligand on the nanoparticle stability (i.e. solubility in high salt concentration, resistance to dithiothreitol competition and cyanide decomposition). Furthermore, the nanoparticles were functionalized using a series of bifunctional ligands that contain a dithiol group (DHLA) for surface binding, a PEG segment to instill water-solubility and a terminal functional group for easy bioconjugation (i.e. NH 2 , COOH, or biotin). Finally, a sensing application was demonstrated to detect the presence of microbial DNA (unmethlylated CpG) by using Toll-like receptor 9 proteins as the recognition components and the QDs as the transduction elements via Förster Resonance Energy Transfer.

Die vorliegende Arbeit beschäftigt sich mit dem Aufbau von Nanokristall-LEDs. Dazu werden der Synthese, der Abscheidung und dem Aufbau und der Charakterisierung von Nanopartikeln und LEDs Platz eingeräumt. CdTe-Nanopartikel werden über eine wässrige Synthese, die auf elektrochemisch erzeugten Tellurwasserstoff beruhte, hergestellt. Der Vorteil besteht im geringen Aufwand und der guten Reproduzierbarkeit. Es konnte festgestellt werden, dass sich ein hoher Überschuss an Cadmiumionen in der Lösung positiv auf die Wachstumsgeschwindigkeit der Nanopartikel auswirkt. Statt des anfänglich benutzten Layer-by-Layer-Tauchverfahrens wurde ein Layer-by-Layer-Sprühverfahren entwickelt, das die schnelle Herstellung homogener Filme, bestehend aus alternierenden Schichten einer Matrix und der Nanopartikel, ermöglichte. Nachteilig ist der hohe Verbrauch an Nanopartikeln gegenüber dem Tauchverfahren. Dem Tauchverfahren lastet der Umstand an, die kolloidalen Lösungen durch häufiges Eintauchen des Substrats zu verunreinigen. Dies wird beim Sprühverfahren vermieden, da alles nicht adsorbierte Material nach unten abfließt. Es wurde gezeigt, dass sich Polyelektrolyte durch anorganische Gele ersetzen lassen, die über einen Sol-Gel-Prozess darstellbar sind, wobei es möglich wurde „All inorganic“-LEDs aufzubauen mit dem Vorteil der hohen Temperaturstabilität. Wobei sich die Reinheit der dargestellten Aluminiumoxid-Sole stark auf das Bestreben Aluminiumoxid-Kristalle zu bilden, auswirkt, die die Funktionsfähigkeit der LED behindern können. Die Verwendung einer isolierenden Matrix wie Poly-(diallyldimethylammoniumchlorid) oder Aluminiumoxid als Zwischenschicht zum Aufbau von mehrlagigen Nanopartikelschichten stellte sich als unproblematisch heraus, da sich Ladungsträger über einen „hopping“-Mechanismus zwischen den Halbleiternanopartikeln bewegen können. Größere Probleme bereitete die Verwendung von Nanopartikeln größerer Bandlücken wie ZnSe (2,7eV) als Elektrolumineszenz-Emitter. Es konnte nur eine weissbläuliche Emission beobachtet werden. Mit Nanopartikeln kleiner Bandlücke wie CdTe (1,6eV) wurde eine schmalbandige rote Emission festgestellt. Vorteilhaft erwies sich die Verwendung von Kern-Schale-Teilchen wie CdSe/CdS. Mit einer Matrix aus Aluminiumoxid-Gel konnte eine LED mit sehr niedriger Onset-Spannung (2,3V) hergestellt werden, die eine Lebensdauer von 33,5h besaß und noch bei einer Temperatur von 150°C emittierte. Ein weiterer Weg Nanopartikel zu stabilisieren, stellt der Einbau in makrokristalline Einkristalle durch Mischkristallbildung in Wasser oder organischen Lösungsmitteln dar. Die erhaltenen Kristalle zeichnen sich durch hohe photochemische und thermische Stabilität aus. Sie zeigen die Emissionseigenschaften der Nanopartikel, die nach Auflösung der Matrix wieder kolloidal in Lösung gehen. Allerdings liegen die Nanopartikel in der Kristallmatrix nicht regulär verteilt vor. Die Mischkristalle wurden erfolgreich als Luminophor in einer Gasentladungslampe und als Konversionsschicht einer kommerziellen LED getestet, die die Emission der Nanopartikel aufwies.

This thesis describes the development and demonstration of a new technique for the fabrication of well-defined quantum dots in a bulk silicon substrate, for potential applications such as quantum computation in coupled quantum dots. Hall characterisation was performed on double-gated mesaMetal-Oxide- Semiconductor Field-Effect Transistors (MOSFETs) on a silicon-on-insulator (SOI) substrate, for the purpose of silicon quantum dots in etched nanowires on SOI. Carrier density and mobility results are presented, demonstrating top- and backgate control over the two inversion layers created at the upper and lower surfaces of the superficial silicon mesa. A new technique is developed enabling effective depletion gating of quantum dots in a bulk silicon substrate. A lower layer of aluminium gates is defined using electron beam lithography; the surface of these gates is oxidised using a plasma oxidation technique; and a further layer of aluminium gates is deposited. The lower gates form tunable tunnel barriers in the narrow inversion layer channel created by the upper MOSFET gate. The two layers of gates are electrically isolated by the localised layer of aluminium oxide. Low-temperature transport spectroscopy has been performed in both the many electron (∼100 electrons) and the few electron (∼10 electrons) regimes.Excited states in the bias spectroscopy provide evidence of quantum confinement. Preliminary temperature and magnetic field dependence data are presented. These results demonstrate that depletion gates are an effective technique for defining quantum dots in silicon. Furthermore, the demonstration of the first silicon radio-frequency single electron transistor is reported. The island is again defined by electrostatically tunable tunnel barriers in a narrow channel field effect transistor. Charge sensitivities of better than 10μe/√Hz are demonstrated at MHz bandwidth. These results establish that silicon may be used to fabricate fast, sensitive electrometers.