Directing macromolecular assemblies by tailored surface functionalizations of nanoporous alumina

Poröse Aluminate (Anodic aluminium oxide (AAO)) bilden Strukturen hoher Ordnung mit parallel angeordneten, hexagonal zylindrischen Poren, welche die Schichtdicke des Materials bestimmen. In dieser Arbeit wurde eine Methode zur Herstellung von hochgeordneten, dünnen Aluminiumoxidfilmen mit variablen Schichtdicken von 1 bis 10 µm auf verschiedenen Oberflächen entwickelt. Die dielektrischen Eigenschaften des AAO ermöglichte in-situ Studien mithilfe von Optischer Wellenleiter Spektroskopie (Optical Waveguide Spectroscopy (OWS)). So konnte die Schicht-für-Schicht (Layer-by-Layer (LbL)) Anlagerung innerhalb der porösen Aluminate von verschiedenen Makromolekülen wie Dendrimer Polyelektrolyte, lineare Polyelektrolyte und Proteine analysiert werden. Experimente bei niedriger Ionenstärke zeigten, dass der molekulare Transport in die zylindrischen Poren inhibiert wird. Grund hierfür ist die elektrostatische Abstoßung der Makromoleküle, welche auf den Porenstegen des AAO adsorbiert sind und den Makromolekülen in Lösung. Unter optimalen Ladungsbedingungen findet die LbL-Ablagerung in gleicher Weise wie auf planaren Oberflächen statt. Das Wachstum der Schichten war demnach lediglich durch die gegebene zylindrische Geometrie begrenzt und konnte bis zur physikalischen Grenze (Reduktion des Porendurchmessers auf 20 bis 35 nm) ungehindert stattfinden. Das Schichtwachstum ist dabei abhängig vom strukturellen Aufbau der Schicht, und wird durch deren Größe, Form und Art der Wechselwirkung zwischen den Makromolekülen bestimmt. Desweiteren wurde in dieser Arbeit eine Methode zur orthogonalen Funktionalisierung der porösen Aluminate entwickelt, mit welcher die silanisierten Porenstege des AAO durch eine dünne Goldschicht geschützt werden können. Die darauffolgende Behandlung des AAO mit Plasma entfernt die ungeschützte Silanisierung innerhalb der zylindrischen Poren, so dass schließlich poröse Aluminate mit unterschiedlicher Oberflächenchemie auf den Porenstegen und im Poreninneren erhalten werden. Diese Meth ode wurde für die Bildung von hybriden sowie fluiden porenüberspannenden Membranen auf Aluminiumoxid durch das Spreiten von Riesenvesikeln (Giant Unilamellar Vesicles (GUVs)) verwendet. Mithilfe dieser Lipidmembranen konnte effektiv das Volumen physikalische des Poreninneren von dem umgebenden Medium abgegrenzt werden, so dass eine physische Barriere entsteht. Dies konnte zum Einen durch den Ausschluss von Protein vom Poreninneren durch die Lipidmembran und zum Anderen durch den Einschluss eines fluoreszierenden Farbstoffs im Poreninneren durch die Lipidmembran gezeigt werden. Schließlich gelang es durch homogene Modifizierung des AAO mit einer lateral beweglichen Lipidmonoschicht, die Menge der Proteinanlagerung innerhalb der dreidimensionalen Strukturen zu verfolgen und zu kontrollieren

Flatland plasmonics and nanophotonics based on graphene and beyond

In this paper, we review and discuss how the recently discovered two-dimensional (2D) Dirac materials, particularly graphene, may be utilized as new efficient platforms for excitations of propagating and localized surface plasmon polaritons (SPPs) in the terahertz (THz) and mid-infrared (MIR) regions. The surface plasmon modes supported by the metallic 2D materials exhibit tunable plasmon resonances that are essential, yet missing, ingredients needed for THz and MIR photonic and optoelectronic devices. We describe how the atomically thin graphene monolayer and metamaterial structures based on it may tailor and control the spectral, spatial, and temporal properties of electromagnetic radiation. In the same frequency range, the newly unveiled nonlocal, nonlinear, and nonequilibrium electrodynamics in graphene show a variety of nonlinear and amplifying electromagnetic responses, whose potential applications are yet unexplored. With these 2D material platforms, virtually all plasmonic, optoelectronic, and nonlinear functions found in near-infrared (NIR) and visible devices can be analogously transferred to the long-wavelength regime, even with enhanced tunability and new functionalities. The spectral range from THz to MIR is particularly compelling because of the many spectral fingerprints of key chemical, gas, and biological agents, as well as a myriad of remote sensing, imaging, communication, and security applications

Boosting solar energy harvesting with ordered nanostructures fabricated by anodic aluminum oxide templates

To date, technical development has boosted the efficiencies of solar energy conversion devices with conventional planar architectures to be close to the respective theoretical values, which are hard to be further improved without reforming the device structures. Alternatively, ordered nanostructure arrays have recently emerged as efficacious scaffolds to construct devices for converting energy more efficiently due to their advantageous optical effects. To meet the global energy requirements for producing renewable energy efficiently, a general approach is needed to fabricate diverse ordered nanostructure arrays. In the meantime, the approach should allow for fine tuning in every set of nanounits towards obtaining desired properties. Herein, we utilized anodic aluminum oxide (AAO) templates to provide a versatile method for constructing ordered nanostructure arrays from one to two dimensions. Firstly, arrays of one-dimensional Au nanowires comprising two components of pillar and truncated pyramid were fabricated. Then, periodic one-dimensional Janus hetero-nanostructures with programmable morphologies, compositions, dimensions, and interfacial junctions were realized. Finally, two-dimensional superlattice photonic crystals with two sets of nanopores were constructed via a combination of the AAO template and the structural replication technique. Subsequently, these as-obtained nanostructures were integrated into photoelectrochemical water-splitting cells and solar-to-thermal conversion systems, which significantly boosted solar energy harvesting performance. In conjunction with theoretical simulations, we further elucidated that the enhanced light harvesting ability can be ascribed to twofold facts: photonic effects and surface plasmon resonance which thus provide a route to manipulate light at the nanoscale.In dieser Dissertation habe ich drei Arten von hochgeordneten Nanostrukturen realisiert, einschließlich 1D-PTP-Au-Core / CdS-Shell-Array, Au-NW / TiO2-NT-Janus-Hetero-Nanostruktur-Array und 2D-Metall-SPhCs. Diese fortschrittlichen Architekturen könnten als vielseitige Gerüste zum Aufbau energiebezogener Geräte eingesetzt werden und haben ein großes Potenzial, die Gesamtleistung drastisch zu verbessern und die durch die planare Konfiguration auferlegten Grenzen zu durchbrechen. Insbesondere die geordneten Nanostruktur-Arrays mit mehreren Komponenten sind von großer Bedeutung, und die entsprechenden Geräte können die Vorteile dieser nanostrukturierten Komponenten kombinieren, wodurch die relevante Leistung systematisch verbessert wird. Darüber hinaus ermöglichen die hohe Regelmäßigkeit der Nanostrukturverteilung, die Gleichmäßigkeit der Nanounits sowie die steuerbaren Größen und Profile der Nanostruktur die resultierenden Architekturen als leistungsfähige Plattform, um die spezifischen Energieumwandlungsreaktionen mikroskopisch zu untersuchen. Diese Ergebnisse könnten wiederum die weitere Entwicklung der relevanten Geräte leiten

Active Matrix Flexible Sensory Systems: Materials, Design, Fabrication, and Integration

A variety of modern applications including soft robotics, prosthetics, and health monitoring devices that cover electronic skins (e-skins), wearables as well as implants have been developed within the last two decades to bridge the gap between artificial and biological systems. During this development, high-density integration of various sensing modalities into flexible electronic devices becomes vitally important to improve the perception and interaction of the human bodies and robotic appliances with external environment. As a key component in flexible electronics, the flexible thin-film transistors (TFTs) have seen significant advances, allowing for building flexible active matrices. The flexible active matrices have been integrated with distributed arrays of sensing elements, enabling the detection of signals over a large area. The integration of sensors within pixels of flexible active matrices has brought the application scenarios to a higher level of sophistication with many advanced functionalities. Herein, recent progress in the active matrix flexible sensory systems is reviewed. The materials used to construct the semiconductor channels, the dielectric layers, and the flexible substrates for the active matrices are summarized. The pixel designs and fabrication strategies for the active matrix flexible sensory systems are briefly discussed. The applications of the flexible sensory systems are exemplified by reviewing pressure sensors, temperature sensors, photodetectors, magnetic sensors, and biosignal sensors. At the end, the recent development is summarized and the vision on the further advances of flexible active matrix sensory systems is provided

NASA SBIR abstracts of 1991 phase 1 projects

The objectives of 301 projects placed under contract by the Small Business Innovation Research (SBIR) program of the National Aeronautics and Space Administration (NASA) are described. These projects were selected competitively from among proposals submitted to NASA in response to the 1991 SBIR Program Solicitation. The basic document consists of edited, non-proprietary abstracts of the winning proposals submitted by small businesses. The abstracts are presented under the 15 technical topics within which Phase 1 proposals were solicited. Each project was assigned a sequential identifying number from 001 to 301, in order of its appearance in the body of the report. Appendixes to provide additional information about the SBIR program and permit cross-reference of the 1991 Phase 1 projects by company name, location by state, principal investigator, NASA Field Center responsible for management of each project, and NASA contract number are included

SYNTHESIS OF TITANIA THIN FILMS WITH CONTROLLED MESOPORE ORIENTATION: NANOSTRUCTURE FOR ENERGY CONVERSION AND STORAGE

This dissertation addresses the synthesis mechanism of mesoporous titania thin films with 2D Hexagonal Close Packed (HCP) cylindrical nanopores by an evaporation-induced self-assembly (EISA) method with Pluronic surfactants P123 and F127 as structure directing agents, and their applications in photovoltaics and lithium ion batteries. To provide orthogonal alignment of the pores, surface modification of substrates with crosslinked surfactant has been used to provide a chemically neutral surface. GISAXS studies show not only that aging at 4°C facilitates ordered mesostructure development, but also that aging at this temperature helps to provide orthogonal orientation of the cylindrical micelles which assemble into an ordered mesophase directly by a disorder-order transition. These films provide pores with 8-9 nm diameter, which is precisely the structure expected to provide short carrier diffusion length and high hole conductivity required for efficient bulk heterojunction solar cells. In addition, anatase titania is a n-type semiconductor with a band gap of +3.2 eV. Therefore, titania readily absorbs UV light with a wavelength below 387 nm. Because of this, these titania films can be used as window layers with a p-type semiconductor incorporated into the pores and at the top surface of the device to synthesize a photovoltaic cell. The pores provide opportunities to increase the surface area for contact between the two semiconductors, to align a p-type semiconductor at the junction, and to induce quantum confinement effects. These titania films with hexagonal phase are infiltrated with a hole conducting polymer, poly(3-hexylthiophene) (P3HT), in order to create a p-n junctions for organic-inorganic hybrid solar cells, by spin coating followed by thermal annealing. This assembly is hypothesized to give better photovoltaic performance compared to disordered or bicontinuous cubic nanopore arrangements; confinement in cylindrical nanopores is expected to provide isolated, regioregular “wires” of conjugated polymers with tunable optoelectronic properties, such as improved hole conductivity over that in bicontinuous cubic structure. The kinetics of infiltration into the pores show that maximum infiltration occurs within less than one hour in these films, and give materials with improved photovoltaic performance relative to planar TiO2/P3HT assemblies. These oriented mesoporous titania films are also used to develop an inorganic solar cell by depositing CdTe at the top using the Close Spaced Sublimation (CSS) technique. A power conversion efficiency of 5.53% is measured for heterostructures built using mesoporous titania films, which is significantly enhanced relative to planar TiO2/CdTe devices and prior reports in the literature. These mesoporous titania films have a great potential in inorganic solar cell development and can potentially replace CdS window layers which are conventionally used in inorganic CdS-CdTe solar cells. The last part of the dissertation addresses layer-by-layer synthesis to increase the thickness of mesoporous titania films with vertically oriented 2D-HCP nanopores, and their use in lithium ion batteries as negative electrodes because of advantages such as good cycling stability, small volume expansion (~3%) during intercalation/extraction and high discharge voltage plateau. The high surface area and small wall thickness of these titania films provide excellent lithium ion insertion and reduced Li-ion diffusion length, resulting in stable capacities as high as 200-250 mAh/g over 200 cycles

Metal Micro-forming

The miniaturization of industrial products is a global trend. Metal forming technology is not only suitable for mass production and excellent in productivity and cost reduction, but it is also a key processing method that is essential for products that utilize advantage of the mechanical and functional properties of metals. However, it is not easy to realize the processing even if the conventional metal forming technology is directly scaled down. This is because the characteristics of materials, processing methods, die and tools, etc., vary greatly with miniaturization. In metal micro forming technology, the size effect of major issues for micro forming have also been clarified academically. New processing methods for metal micro forming have also been developed by introducing new special processing techniques, and it is a new wave of innovation toward high precision, high degree of processing, and high flexibility. To date, several special issues and books have been published on micro-forming technology. This book contains 11 of the latest research results on metal micro forming technology. The editor believes that it will be very useful for understanding the state-of-the-art of metal micro forming technology and for understanding future trends

Production and processing of graphene and related materials

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown