Reorientational dynamics of highly asymmetric binary non-polymeric mixtures - a dielectric spectroscopy study.

We present an analysis of dielectric spectra measured for a specially designed non-polymeric asymmetric binary glass former characterized by a large difference of the component's Tg (ΔTg = 216 K). We cover the whole additive concentration range from 4% up to 90% (by mass). Two main relaxations α1 and α2 are identified, which are characterized by well separated time scales and are attributed to the dynamics associated with the high-Tg component (α1) and the low-Tg component (α2). Frequency-temperature superposition does not apply. To cope with the extraordinary spectral broadening, we introduce a model consisting of a generalized Cole-Davidson (α1) and a Havriliak-Negami function with a low frequency truncation (α2). Whereas the α1-relaxation reflects essentially homogeneous dynamics and its spectra mainly broaden on the high-frequency flank of the relaxation peak, the α2-relaxation becomes broader on the low-frequency side reflecting pronounced dynamic heterogeneity in a more or less arrested matrix of high-Tg molecules. From the extracted time constants, two glass transition temperatures Tg1 and Tg2 can be derived, showing a non-trivial concentration dependence for Tg2. Supplementary, we find a ß-relaxation. The total relaxation strength Δε strongly deviates from ideal mixing, and therefore care has to be taken interpreting the corresponding Δεαi as representation of molecular populations.

Main and secondary relaxations of non-polymeric high-Tg glass formers as revealed by dielectric spectroscopy.

A series of high-Tg glass formers with Tg values varying between 347 and 390 K and molar masses in the range of 341 and 504 g mol-1 are investigated by dielectric spectroscopy. They are compared to paradigmatic reference systems. Differently polar side groups are attached to a rigid non-polar core unit at different positions. Thereby, the dielectric relaxation strength varies over more than two decades. All the relaxation features typical of molecular glass formers are rediscovered, i.e. stretching of the main (α-) relaxation, a more or less pronounced secondary (ß-) process, and a fragility index quite similar to that of other molecular systems. The position of the polar nitrile side group influences the manifestation of the ß-relaxation. The α-relaxation stretching displays the trend to become less with higher relaxation strength Δεα, confirming recent reports. Typical for a generic ß-process is the increase of its amplitude above Tg, which is found to follow a power-law behaviour as a function of the ratio τα/τß with a universal exponent; yet, its relative amplitude to that of the α-relaxation varies as does the temporal separation of both processes. The mean activation energy of the ß-process as well as the width of the energy distribution gß(E) increases more or less systematically with Tg. The latter is determined from the dielectric spectra subjected to a scaling procedure assuming a thermally activated process. Plotting gß(E) as a function of the reduced energy scale E/Tg, the distributions are centred between 19-35 and their widths differ by a factor 2-3.

Confinement templates for hierarchical nanoparticle alignment prepared by azobenzene-based surface relief gratings.

Alignment of nanoparticles to hierarchical periodic structures is an emerging field in the development of patterned surfaces. Common alignment methods are based on templates that guide particle self-assembly. These can be formed using lithographic methods offering an almost free choice of the motif, while being expensive and time-consuming for large-scale production. Alternatively, template formation by controlled wrinkling offers a low-cost formation, but often suffers from the formation of defect structures like line-defects and cracks. Here, we show a preparation technique for nanoparticle alignment substrates that is based on the inscription of holographic surface relief gratings with a periodic sinusoidal wave pattern on the surface of azobenzene films. As interference patterns are employed for structure formation, very uniform and defect-free gratings with tunable grating height and grating period can be prepared. These substrates were successfully replicated to poly(dimethyl siloxane) and the replicas used for the alignment of polystyrene latex particles. Accordingly produced substrates exhibiting gratings with a variation in grating height allow for efficient screening of nanoparticle alignment in a geometrical confinement in one single experiment. We anticipate our studies as a promising tool for the development of sensors, tunable gratings and metamaterials.

Controlled Wrinkling of Gradient Metal Films.

Controlled wrinkling is a rather simple method of fabricating surface topographies. The production process is based on the spontaneous formation of wrinkles upon compression of a hard film attached to a soft elastic substrate. Controlled wrinkling typically features large-scale wrinkled samples with a discrete wavelength and amplitude. In this report, we employ an approach utilizing linear metal layer thickness gradients for the controlled formation of gradient wrinkle patterns. The observed wavelength modulation was experimentally achieved by preparing layer thickness gradients of gold, chromium, and indium by physical vapor deposition in combination with a poly(dimethyl siloxane) elastomer substrate. In case of chromium and indium, a thin SiO x surface layer was sufficient to ensure adhesion. However, in case of gold, an additional thin chromium adhesion layer was required. For the wrinkled gradient gold film, it was possible to tune the wavelength from 3.4 to 12.2 µm on a single substrate. The experimental data correspond well to the theoretical bilayer model from Stafford et al. Chromium has a significant higher Young's modulus and melting temperature than gold. However, chromium was successfully evaporated and gradient wrinkle patterns with wavelengths from 1.0 to 3.5 µm were realized. In contrast, indium has a considerable lower Young's modulus than gold and chromium, respectively. Consequently, lower wavelengths (0.6-1.0 µm) of the wrinkled gradient indium film were observed. These tunable wrinkled gradient metal films can be envisioned as components in sensors and optical and electro-optical devices.

Fast diffusion-limited lyotropic phase transitions studied in situ using continuous flow microfluidics/microfocus-SAXS.

Fast concentration-induced diffusion-limited lyotropic phase transitions can be studied in situ with millisecond time resolution using continuous flow microfluidics in combination with microfocus small-angle X-ray scattering. The method was applied to follow a classical self-assembly sequence where amphiphiles assemble into micelles, which subsequently assemble into an ordered lattice via a disorder/order transition. As a model system we selected the self-assembly of an amphiphilic block copolymer induced by the addition of a nonsolvent. Using microchannel hydrodynamic flow-focusing, large concentration gradients can be generated, leading to a deep quench from the miscible to the microphase-separated state. Within milliseconds the block copolymers assembly via a spinodal microphase separation into micelles, followed by a disorder/order transition into an FCC liquid-crystalline phase with late-stage domain growth and shear-induced domain orientation into a mesocrystal. A comparison with a slow macroscopic near-equilibrium kinetic experiment shows that the fast structural transitions follow a direct pathway to the equilibrium structure without the trapping of metastable states.

Combinatorial techniques to efficiently investigate and optimize organic thin film processing and properties.

In this article we present several developed and improved combinatorial techniques to optimize processing conditions and material properties of organic thin films. The combinatorial approach allows investigations of multi-variable dependencies and is the perfect tool to investigate organic thin films regarding their high performance purposes. In this context we develop and establish the reliable preparation of gradients of material composition, temperature, exposure, and immersion time. Furthermore we demonstrate the smart application of combinations of composition and processing gradients to create combinatorial libraries. First a binary combinatorial library is created by applying two gradients perpendicular to each other. A third gradient is carried out in very small areas and arranged matrix-like over the entire binary combinatorial library resulting in a ternary combinatorial library. Ternary combinatorial libraries allow identifying precise trends for the optimization of multi-variable dependent processes which is demonstrated on the lithographic patterning process. Here we verify conclusively the strong interaction and thus the interdependency of variables in the preparation and properties of complex organic thin film systems. The established gradient preparation techniques are not limited to lithographic patterning. It is possible to utilize and transfer the reported combinatorial techniques to other multi-variable dependent processes and to investigate and optimize thin film layers and devices for optical, electro-optical, and electronic applications.

Thermo-Mechanical Recyclability of Additively Manufactured Polypropylene and Polylactic Acid Parts and Polypropylene Support Structures.

Polymers have a reputation for several advantageous characteristics like chemical resistance, weight reduction, and simple form-giving processes. The rise of additive manufacturing technologies such as Fused Filament Fabrication (FFF) has introduced an even more versatile production process that supported new product design and material concepts. This led to new investigations and innovations driven by the individualization of customized products. The other side of the coin contains an increasing resource and energy consumption satisfying the growing demand for polymer products. This turns into a magnitude of waste accumulation and increased resource consumption. Therefore, appropriate product and material design, taking into account end-of-life scenarios, is essential to limit or even close the loop of economically driven product systems. In this paper, a comparison of virgin and recycled biodegradable (polylactic acid (PLA)) and petroleum-based (polypropylene (PP) & support) filaments for extrusion-based Additive Manufacturing is presented. For the first time, the thermo-mechanical recycling setup contained a service-life simulation, shredding, and extrusion. Specimens and complex geometries with support materials were manufactured with both, virgin and recycled materials. An empirical assessment was executed through mechanical (ISO 527), rheological (ISO 1133), morphological, and dimensional testing. Furthermore, the surface properties of the PLA and PP printed parts were analyzed. In summary, PP parts and parts from its support structure showed, in consideration of all parameters, suitable recyclability with a marginal parameter variance in comparison to the virgin material. The PLA components showed an acceptable decline in the mechanical values but through thermo-mechanical degradation processes, rheological and dimensional properties of the filament dropped decently. This results in significantly identifiable artifacts of the product optics, based on an increase in surface roughness.

Organic Glasses of High Glass Transition Temperatures Due To Substitution with Nitrile Groups.

The glass transition temperature (Tg) of a molecular glass depends on its molar mass. However, the nature of intermolecular interactions also plays a major role in both the glass transition temperature and its glass-forming ability. In this context, we report on novel molecular glasses containing nitrile groups and investigate the influence of this highly polar group on Tg and the glass-forming ability. As reference compounds, we studied the thermal properties of synthesized molecular glasses with C-C-bonded phenyl rings. The molar mass of the studied compounds ranges from 341 to 568 g/mol. Despite their relatively low molar mass, glass transition temperatures from 347 K (74 °C) to 471 K (198 °C) were observed. Most of the compounds possess high Tg/Tmratios between 0.7 and 0.8. By introducing highly interacting nitrile groups, the dependence of the molar mass on Tg could be increased by a factor of 2-3.

Combinatorial preparation and characterization of thin-film multilayer electro-optical devices.

In this article we present a setup for the combinatorial vapor deposition of thin-film multilayer devices as well as methods for the fast and efficient analytic screening of the libraries obtained. The preparation setup is based on a commercially available evaporation chamber equipped with various evaporation sources for both organic and metallic materials. The combinatorial approach is realized by the combination of a rotation stage for the substrate, a five-mask sampler, and an additional mask whose position can be deliberately varied along one axis during the evaporation process. The latter is used to evaporate linear as well as step gradients by continuous or stepwise movement of a shutter mask. The mask sampler allows to define the sectors of the library and to evaporate more complex structures, e.g., an electrode layout. Finally, the simultaneous evaporation of two or more materials enables us to produce layers of varying composition ratio in general and doped materials, in particular. For the control of the evaporation process we have developed an automation software, which is particularly helpful for complex library designs and which grants excellent repeatability of experiments. Efficient and fast characterization of the obtained libraries is realized by (i) a purely optical setup and (ii) an electro-optical setup. (i) The UV/vis reader FLASHScan 530 permits to map out the UV/vis absorbance or fluorescence of the whole library. The UV/vis absorbance is primarily used to determine layer thicknesses and to confirm thickness uniformity across larger regions. The fluorescence measurements are used to determine the composition of layers containing fluorescent dyes. (ii) For a detailed short- and long-term electro-optical analysis we have developed an automated measurement system, which allows the characterization of 8x8 optoelectronic devices and to study their degradation behavior. Both solar cells and organic light-emitting diodes can be tested. Finally, we have developed a data analysis software to extract characteristic values from the huge amount of data and with this facilitate the finding of systematic dependencies.

Athermal Azobenzene-Based Nanoimprint Lithography.

A novel nanoimprint lithography technique based on the photofluidization effect of azobenzene materials is presented. The tunable process allows for imprinting under ambient conditions without crosslinking reactions, so that shrinkage of the resist is avoided. Patterning of surfaces in the regime from micrometers down to 100 nm is demonstrated.

Tailored star block copolymer architecture for high performance chemically amplified resists.

Star block copolymers are demonstrated for their application as a high-performance resist material. This new resist material shows advanced progress in sensitivity and solubility contrast and is finally combinatorially optimized to achieve a 66 nm line/space pattern. The tailored molecular architecture of the star block copolymer is synthesized via core-first atom transfer radical polymerization (ATRP) and shows narrow polydispersity indices below 1.2.

Combinatorial optimization of a molecular glass photoresist system for electron beam lithography.

Electron beam lithography is a powerful technique for the production of nanostructures but pattern quality depends on numerous interacting process variables. Orthogonal gradients of resist composition, baking temperatures, and development time as well as dose variations inside writing fields are used to prepare ternary combinatorial libraries for an efficient stepwise optimization of a molecular glass negative tone resist system.

Towards environmentally friendly, dry deposited, water developable molecular glass photoresists.

Photoresists based on molecular glasses are gaining more and more importance as resist material to replace polymer based photoresist. In addition environmental issues have to be considered in the long-term. Therefore the paper describes novel negative photoresists containing a ternary mixture of a glassy low molecular functional polyphenol where the film preparation is possible by solvent-free physical vapor deposition. After UV light exposure and a thermal annealing process to enable acid catalyzed crosslinking between the molecular glass and the crosslinker, the photoresist was developed using only water to give well-defined patterns. In order to experimentally study efficiently the multiple parameters such as composition, exposure dose, and development times combinatorial PVD techniques were utilized.