RESUMEN
Enabled by surface-mediated equilibration, physical vapour deposition can create high-density stable glasses comparable with liquid-quenched glasses aged for millions of years. Deposition is often performed at various rates and temperatures on rigid substrates to control the glass properties. Here we demonstrate that on soft, rubbery substrates, surface-mediated equilibration is enhanced up to 170 nm away from the interface, forming stable glasses with densities up to 2.5% higher than liquid-quenched glasses within 2.5 h of deposition. Gaining similar properties on rigid substrates would require 10 million times slower deposition, taking ~3,000 years. Controlling the modulus of the rubbery substrate provides control over the glass structure and density at constant deposition conditions. These results underscore the significance of substrate elasticity in manipulating the properties of the mobile surface layer and thus the glass structure and properties, allowing access to deeper states of the energy landscape without prohibitively slow deposition rates.
RESUMEN
This study establishes a comprehensive library of nanopatterns achievable by a single block copolymer (BCP), ranging from spheres to complex structures like split micelles, flower-like clusters, toroids, disordered micelle arrays, and unspecified unique shapes. The ordinary nanostructures of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) surface micelles deposited on a SiOx surface undergo a unique morphology transformation when immersed directly in solvents. Investigating parameters such as immersion solvents, BCP molecular weight, substrate interactions, and temperature, this work reveals the influence of these parameters on the thermodynamics and kinetics governing the morphology transformation. Additionally, the practical application of BCP nanopattern templates for fabricating metal nanostructures through direct solvent immersion of surface micelles is demonstrated. This approach offers an efficient and effective method for producing diverse nanostructures, with the potential to be employed in nanolithography, catalysts, electronics, membranes, plasmonics, and photonics.
RESUMEN
Polymers under confinement exhibit different structures and properties from the bulk. While block copolymers (BCPs) create well-defined micelles in solution, two-dimensional (2D) spatial confinement at the air-water interface constrains the chain conformations and deforms the micellar structure, thus forming a surface micelle. The BCP surface micelles open up an opportunity in nanoscience and engineering by serving as an interfacial modifier and structural platform. Nevertheless, a scaling law, a principle governing the micellar structure, is absent. Herein, we report a unified scaling relation to describe the combinational structure of BCP surface micelles in two and three dimensions and further reveal their formation mechanism in line with the suggested scaling relation. We investigated the intrinsic scaling relations in a surface pressure-free environment by introducing a concept of excluded volume-dependent scaling exponent based on the scaling theory of 2D polymers. In addition, an extrinsic scaling relation is derived for the surface pressure-dependent corona scaling.
RESUMEN
Directed self-assembly (DSA) of block copolymer (BCP) thin films is of particular interest in nanoscience and nanotechnology due to its superior ability to form various well-aligned nanopatterns. Herein, nanoscratch-DSA is introduced as a simple and scalable DSA strategy allowing highly aligned BCP nanopatterns over a large area. A gentle scratching on the target substrate with a commercial diamond lapping film can form uniaxially aligned nanoscratches. As applied in BCP thin films, the nanoscratch effectively guides the self-assembly of overlying BCPs and provides highly aligned nanopatterns along the direction of the nanoscratch. The nanoscratch-DSA is not material-specific, allowing more versatile nanofabrication for various functional nanomaterials. In addition, we demonstrate that the nanoscratch-DSA can be utilized as a direction-controllable and area-selective nanofabrication method.
RESUMEN
The employment of self-assembly of soft materials has been accepted as an inexpensive, robust, and reliable patterning method. As their self-assembly relies on the delicate molecular interactions near the substrate, a precise prediction/control of the interface structure and dynamics is critical to achieve desired nanostructures. Herein, a polymeric nanomosaic (PNM) pattern is created from the air/water interfacial self-assembly of a block copolymer (BCP) and introduced as an effective interfacial energy control for substrates. As a demonstration, the PNM coating is employed to control the BCP film structures. The perpendicular orientation of BCP self-assembly, which requires neutral wetting conditions for both blocks, is difficult to achieve but can readily be obtained with the PNM coating upon a fine resolution of the pattern quality. The universal applicability of the PNM coating as an interfacial control has been confirmed on curved, flexible, and three-dimensional substrates. In addition, the PNM is introduced as an etching-free and reusable topcoat imparting free surface neutralization even for the high-χ BCP nanopatterning.
RESUMEN
In polymer thin films, the bottom polymer chains are irreversibly adsorbed onto the substrates creating an ultrathin layer. Although this thin layer (only a few nanometers thick) governs all film properties, an understanding of this adsorbed layer remains elusive, and thus, its effective control has yet to be achieved, particularly in block copolymer (BCP) thin films. Herein, we employ self-assembled copolymer adsorption layers (SCALs), transferred from the air/water interfacial self-assembly of BCPs, as an effective control of the adsorbed layer in BCP thin films. SCALs replace the natural adsorbed layer, irreversibly adsorbing onto the substrates when other BCP is additionally coated on the SCALs. We further show that SCALs guide the thin film nanostructures because they provide topological restrictions and enthalpic/entropic preferences for a BCP self-assembly. The SCAL-induced self-assembly enables unprecedented control of nanostructures, creating novel nanopatterns such as spacing-controlled hole/dot patterns, dotted-line patterns, dash-line patterns, and anisotropic cluster patterns with exceptional controllability.
RESUMEN
Over the past several decades, tremendous efforts have been made to understand the fundamental physics of block copolymer (BCP) self-assembly in bulk or thin films, and this has led to the development of BCP-based bottom-up nanofabrication. BCPs also form periodic nanostructures at the air/water interface, which has potential application to ultrathin-film nanopatterning with molecular-level precision. Nonetheless, controlling the nanostructure formation at the air/water interface is restricted by the inherent parameters of BCPs; BCP morphology is determined by the hydrophilic-to-hydrophobic block ratio. Here we show that controlling the spreading area of BCPs at the air/water interface can tune the shape and size of BCP structures, suggesting a new phase diagram of BCP structures as a function of the relative block fraction and spreading area. A neat polystyrene-b-poly(2-vinylpyridine), known to form a dot morphology, instead forms a strand or planar morphology when the spreading area is varied with Langmuir-Blodgett technique.
RESUMEN
OBJECTIVE: We report here the case of a 52-year-old Korean woman who was initially diagnosed with non-fluent/global crossed aphasia. METHODS AND RESULTS: Initial computed tomography of the brain revealed a haematoma of approximately 40 ml in the right basal ganglia area and cavitation around the right lateral ventricle. Three years after onset the aphasia was resolved to a conduction aphasia and she had an ongoing left-sided gait disturbance. Follow-up anatomical magnetic resonance imaging found no recurrence of haemorrhage. Language functional magnetic resonance imaging was examined before and after repetitive transcranial magnetic stimulation treatment. A 90-mm round coil stimulator was used and the repetitive transcranial magnetic stimulation treatment location was P3 on the 10-20 International electrode placement system (1 Hz, 20 min per day for 10 days over a 2-week period). Functional magnetic resonance imaging results before repetitive transcranial magnetic stimulation treatment showed no significant activity in either the ipsilesional or contralesional hemispheres for noun generation and sentence completion paradigms (p < 0.001, cluster size 128). Compared with the pre-treatment phase, following repetitive transcranial magnetic stimulation treatment the data from functional magnetic resonance imaging revealed significant activations in the right inferior frontal lobe (Broca's area), posterior temporal gyrus (Wernicke's area), and parietal lobe for both the noun generation and sentence completion tasks (p < 0.001, cluster size 128). CONCLUSION: This functional magnetic resonance imaging case study is the first to suggest the use of repetitive transcranial magnetic stimulation for improving language outcome in a patient with crossed aphasia. In addition, we report the value of language functional magnetic resonance imaging before and after repetitive transcranial magnetic stimulation treatment for determining the effect of treatment and the underlying neurobiological mechanism of functional recovery following repetitive transcranial magnetic stimulation treatment.