Diblock copolymer pattern protection by silver cluster reinforcement.

Pattern fabrication by self-assembly of diblock copolymers is of significant interest due to the simplicity in fabricating complex structures. In particular, polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP) is a fascinating base material as it forms an ordered micellar structure on silicon surfaces. In this work, silver (Ag) is applied using direct current magnetron sputter deposition and high-power impulse magnetron sputter deposition on an ordered micellar PS-b-P4VP layer. The fabricated hybrid materials are structurally analyzed by field emission scanning electron microscopy, atomic force microscopy, and grazing incidence small angle X-ray scattering. When applying simple aqueous posttreatment, the pattern is stable and reinforced by Ag clusters, making micellar PS-b-P4VP ordered layers ideal candidates for lithography.

Superlattice deformation in quantum dot films on flexible substrates via uniaxial strain.

The superlattice in a quantum dot (QD) film on a flexible substrate deformed by uniaxial strain shows a phase transition in unit cell symmetry. With increasing uniaxial strain, the QD superlattice unit cell changes from tetragonal to cubic to tetragonal phase as measured with in situ grazing-incidence small-angle X-ray scattering (GISAXS). The respective changes in the optoelectronic coupling are probed with photoluminescence (PL) measurements. The PL emission intensity follows the phase transition due to the resulting changing inter-dot distances. The changes in PL intensity accompany a redshift in the emission spectrum, which agrees with the Förster resonance energy transfer (FRET) theory. The results are essential for a fundamental understanding of the impact of strain on the performance of flexible devices based on QD films, such as wearable electronics and next-generation solar cells on flexible substrates.

3D Printable Hybrid Gel Made of Polymer Surface-Modified Cellulose Nanofibrils Prepared by Surface-Initiated Controlled Radical Polymerization (SI-SET-LRP) and Upconversion Luminescent Nanoparticles.

A cellulose nanofibril-based hybrid gel material was developed by grafting the polymerized stearyl acrylate (PSA) and upconversion nanoparticles (UCNPs) onto cellulose nanofibrils (CNFs) via Cu0-mediated radical polymerization (SET-LRP) to create a highly cross-linked CNF system. A two-step strategy was exploited to surface-exchange the ligand of the UCNPs from a hydrophobic ligand (oleic acid) to a hydrophilic small-molecule ligand (2-acrylamido-2-methyl-1-propanesulfonic acid, AMPS) and therefore be suitable for SET-LRP. The characteristics and properties of the hybrid material (UCNP-PSA-CNF) were monitored by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), rheology, X-ray diffraction (XRD), and microscopic analysis. Those characterization techniques prove the efficient modification of the CNF, with the presence of 1.8% UCNPs. The luminescence measurement was carried out using a homebuilt confocal microscope with a 980 nm laser source. The nanostructure of UCNPs and their incorporated CNF species were measured by small-angle X-ray scattering (SAXS). In addition, this CNF-based hybrid gel has decisive rheological properties, such as good viscoelasticity (loss tangent was below 0.35 for the UCNP-PSA-CNF gel, while the PSA-CNF gel reached the highest value of 0.42), shear-thinning behavior, and shape retention, and was successfully applied to three-dimensional (3D) gel printing throughout various 3D print models.

Hierarchical propagation of structural features in protein nanomaterials.

Natural high-performance materials have inspired the exploration of novel materials from protein building blocks. The ability of proteins to self-organize into amyloid-like nanofibrils has opened an avenue to new materials by hierarchical assembly processes. As the mechanisms by which proteins form nanofibrils are becoming clear, the challenge now is to understand how the nanofibrils can be designed to form larger structures with defined order. We here report the spontaneous and reproducible formation of ordered microstructure in solution cast films from whey protein nanofibrils. The structural features are directly connected to the nanostructure of the protein fibrils, which is itself determined by the molecular structure of the building blocks. Hence, a hierarchical assembly process ranging over more than six orders of magnitude in size is described. The fibril length distribution is found to be the main determinant of the microstructure and the assembly process originates in restricted capillary flow induced by the solvent evaporation. We demonstrate that the structural features can be switched on and off by controlling the length distribution or the evaporation rate without losing the functional properties of the protein nanofibrils.