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PVDF thin films prepared under standard processing conditions have a cloudy appearance and are notoriously rough, which prevent microelectronic and photonic applications. On the other hand, high optical quality, smooth films can be prepared either at low relative humidity or at high substrate temperature. Here we systematically investigate the morphology of PVDF thin films by varying the processing conditions. Films are characterized by SEM and AFM and by measurements of clarity, haze and absorption. We show that the cloudy appearance is due to vapor-induced phase separation (VIPS) as is well-documented for the formation of PVDF membranes. Formation of opaque thin films is a general problem of any ternary polymer/solvent/non-solvent system where a high boiling point solvent is used that is fully miscible with a non-solvent, here water from the ambient.

The influence of various experimental parameters on the vertical deposition and structure formation of colloidal crystals on chemically patterned surfaces, with hydrophilic and hydrophobic areas, was investigated. The pattern dimensions range from about 4 to 400 microm, which is much larger than the individual particle size (255 nm), to control the microscopic crystal shape rather than influencing the crystal lattice geometry (as achieved in colloidal epitaxy). The deposition resolution and selectivity were tested by varying the particle concentration in the suspension, the substrate withdrawing speed, pattern size and orientation, and wetting contrast between the hydrophilic and hydrophobic regions. The evolution of colloidal crystal thickness with respect to the pattern dimensions and deposition parameters was further studied. Our results show that the pattern size has a rather strong influence on the deposited number of colloid layers and on the crystal quality. Better results are obtained when the lines of a stripe pattern are oriented parallel to the withdrawing direction rather than perpendicular. The deposition resolution (defined as the minimum feature size on which particles can be deposited) depends on the wetting contrast and increases with lower average hydrophobicity of the substrate.

The morphogenesis, particle size, size distribution, and phase evolution of zinc oxide precipitated in the presence of water-soluble poly(ethylene oxide-block-methacrylic acid) (P(EO-b-MAA)) and poly(ethylene oxide-block-styrene sulfonic acid) (P(EO-b-SSH)) diblock copolymers is reported. Without a polymeric additive, spindlelike particles with a central grain boundary form along with multiply twinned particles. After ∼30 min, the multiple twins are gone, small, needlelike crystals appear, and the sample becomes more polydisperse. With P(EO-b-MAA) copolymers, initially more rounded particles with the same central grain boundary and a narrow size distribution form. They preferentially grow along the crystallographic c-axis and eventually adopt a hexagonal prismatic shape. With P(EO-b-SSH) copolymers, a lamellar intermediate precipitates first. It eventually dissolves and hexagonal prismatic crystals form; in a subsequent growth process unique to these polymeric additives, the crystals grow along the crystallographic a-axis and transform to another morphology termed the "stack of pancakes" shape. Both in the absence of polymer and with P(EO-b-MAA) copolymers, multiple particle generations precipitate. With P(EO-b-SSH) copolymers, no second generation is observed. Nucleation is delayed by the P(EO-b-MAA) copolymers, while P(EOb-SSH) copolymers favor the rapid nucleation of the highly ordered lamellar intermediate.

The site-selective assembly of colloidal polymer particles onto laterally patterned silane layers was studied as a model system for the object assembly process at mesoscale dimensions. The structured silane monolayers on silicon oxide substrates were fabricated by a combination of liquid-and gas-phase deposition of different trialkoxysilanes with a photolithographic patterning technique. By using this method various types of surface functionalizations such as regions with amino functions next to areas of the bare silica surface or positively charged regions of a quaternary ammonium silane surrounded by a hydrophobic octadecylsilane film could be obtained. Furthermore, a triethoxysilane with a photoprotected amino group was synthesized, which allowed direct photopatterning after monolayer preparation, leading to free NH2 groups at the irradiated regions. The different silane monolayer patterns were used to study the surface assembly behavior of carboxylated methacrylate particles by optical and scanning electron microscopy. In dependence of the assembly conditions (different surface functionalizations, pH, and drying conditions), a selective preference of the particles for a specific surface type versus others was found. Site-specific colloid adsorption could be observed also on the photosensitive silane layers after local deprotection with light. From the photosensitive silane and positively charged ammonium silane, molecularly mixed monolayers were prepared, which allowed particle adsorption and photoactivation within the same monolayer as shown by fluorescence labeling.O ne of the major driving forces in modern technology is based on the desire for miniaturization, which leads to smaller and lighter devices and a higher number of functional units per volume element. This tendency is prevalent particularly in microelectronics, optics, and sensors. Fabrication methods for small parts and structuring techniques have been developed very far, entering now the regime of nanoscopic dimensions (1, 2). Integrating individual objects of such dimensions into more complex structures and devices, on the other hand, represents a key challenge. Especially for the interfacing of nanoscopic devices with the macroscopic world, a large number of hierarchical organization levels are required to be implemented and controlled to actually use such small devices. One strategy toward attaining this goal emerges from the application of self-organization and assembly concepts that are ubiquitously present in the biological world and used successfully in supramolecular chemistry. Based on these principles several methods for the assembly of objects into two-and three-dimensional structures have been demonstrated at length scales from several nanometers up to millimeters (3-11). Most of these methods rely on shape complementarity of the objects, the surface tension at the interface of an auxiliary liquid and the object surfaces, and specific molecular interactions between the individual objects.A refined strategy for the assembly of mesos...

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The development of solid materials which are able to upconvert optical radiation into photons of higher energy is attractive for many applications such as photocatalytic cells and photovoltaic devices. However, to fully exploit triplet-triplet annihilation photon energy upconversion (TTA-UC), oxygen protection is imperative because molecular oxygen is an ultimate quencher of the photon upconversion process. So far, reported solid TTA-UC materials have focused mainly on elastomeric matrices with low barrier properties because the TTA-UC efficiency generally drops significantly in glassy and semicrystalline matrices. To overcome this limit, for example, combine effective and sustainable annihilation upconversion with exhaustive oxygen protection of dyes, we prepare a sustainable solid-state-like material based on nanocellulose. Inspired by the structural buildup of leaves in Nature, we compartmentalize the dyes in the liquid core of nanocellulose-based capsules which are then further embedded in a cellulose nanofibers (NFC) matrix. Using pristine cellulose nanofibers, a sustainable and environmentally friendly functional nanomaterial with ultrahigh barrier properties is achieved. Also, an ensemble of sensitizers and emitter compounds are encapsulated, which allow harvesting of the energy of the whole deep-red sunlight region. The films demonstrate excellent lifetime in synthetic air (20.5/79.5, O2/N2)-even after 1 h operation, the intensity of the TTA-UC signal decreased only 7.8% for the film with 8.8 μm thick NFC coating. The lifetime can be further modulated by the thickness of the protective NFC coating. For comparison, the lifetime of TTA-UC in liquids exposed to air is on the level of seconds to minutes due to fast oxygen quenching.

Biosilica is a natural polymer, synthesized by the poriferan enzyme silicatein from monomeric silicate substrates. Biosilica stimulates mineralizing activity and gene expression of SaOS-2 cells. To study its effect on the formation of hydroxyapatite (HA), SaOS-2 cells were grown on different silicatein/biosilica-modified substrates (bone slices, Ca-P-coated coverslips, glass coverslips). Growth on these substrates induced the formation of HA nodules, organized in longitudinal arrays or spherical spots. Nodules of sizes above 1 μm were composed of irregularly arranged HA prism-like nanorods, formed by aggregates of three to eight SaOS-2 cells. Moreover, growth on silicatein/biosilica-modified substrates elicited increased [(3)H]dT incorporation into DNA, indicative of enhanced cell proliferation. Consequently, an in vitro-based bioassay was established to determine the ratio between [(3)H]dT incorporation and HA formation. This ratio was significantly higher for cells that grew on silicatein/biosilica-modified substrates than for cells on Ca-P-coated coverslips or plain glass slips. Hence, we propose that this ratio of in vitro-determined parameters reflects the osteogenic effect of different substrates on bone-forming cells. Finally, qRT-PCR analyses demonstrated that growth of SaOS-2 cells on a silicatein/biosilica matrix upregulated BMP2 (bone morphogenetic protein 2, inducer of bone formation) expression. In contrast, TRAP (tartrate-resistant acid phosphatase, modulator of bone resorption) expression remained unaffected. We conclude that biosilica shows pronounced osteogenicity in vitro, qualifying this material for studies of bone replacement also in vivo.