Laser annealing is a competitive alternative to conventional oven annealing of block copolymer (BCP) thin films enabling rapid acceleration and precise spatial control of the self-assembly process. Localized heating by a moving laser beam (zone annealing), taking advantage of steep temperature gradients, can additionally yield aligned morphologies. In its original implementation it was limited to specialized germanium-coated glass substrates, which absorb visible light and exhibit low-enough thermal conductivity to facilitate heating at relatively low irradiation power density. Here, we demonstrate a recent advance in laser zone annealing, which utilizes a powerful fiber-coupled near-IR laser source allowing rapid BCP annealing over a large area on conventional silicon wafers. The annealing coupled with photothermal shearing yields macroscopically aligned BCP films, which are used as templates for patterning metallic nanowires. We also report a facile method of transferring laser-annealed BCP films onto arbitrary surfaces. The transfer process allows patterning substrates with a highly corrugated surface and single-step rapid fabrication of multilayered nanomaterials with complex morphologies.

We report a facile method of ordering block copolymer (BCP) morphologies in which the conventional two-step casting and annealing steps are replaced by a single-step process where microphase separation and grain coarsening are seamlessly integrated within the casting protocol. This is achieved by slowing down solvent evaporation during casting by introducing a nonvolatile solvent into the BCP casting solution that effectively prolongs the duration of the grain-growth phase. We demonstrate the utility of this solvent evaporation annealing (SEA) method by producing well-ordered large-molecular-weight BCP thin films in a total processing time shorter than 3 min without resorting to any extra laboratory equipment other than a basic casting device, i.e ., spin- or blade-coater. By analyzing the morphologies of the quenched samples, we identify a relatively narrow range of polymer concentration in the wet film, just above the order–disorder concentration, to be critical for obtaining large-grained morphologies. This finding is corroborated by the analysis of the grain-growth kinetics of horizontally oriented cylindrical domains where relatively large growth exponents (1/2) are observed, indicative of a more rapid defect-annihilation mechanism in the concentrated BCP solution than in thermally annealed BCP melts. Furthermore, the analysis of temperature-resolved kinetics data allows us to calculate the Arrhenius activation energy of the grain coarsening in this one-step BCP ordering process.

Solvent-assisted block copolymer self-assembly is a compelling method for processing and advancing practical applications of these materials due to the exceptional level of the control of BCP morphology and significant...

Solvent evaporation annealing (SEA) is a straightforward, single-step casting and annealing method of block copolymers (BCP) processing yielding large-grained morphologies in a very short time. Here, we present a quantitative analysis of BCP graincoarsening in thin films under controlled evaporation of the solvent. Our study is aimed at understanding time and BCP concentration influence on the rate of the lateral growth of BCP grains. By systematically investigating the coarsening kinetics at various BCP concentrations, we observed a steeply decreasing exponential dependence of the kinetics power-law time exponent on polymer concentration. We used this dependence to formulate a mathematical model of BCP ordering under nonstationary conditions and a 2D, time-and concentrationdependent coarsening rate diagram, which can be used as an aid in engineering the BCP processing pathway in SEA and also in other directed self-assembly methods that utilize BCP−solvent interactions such as solvent vapor annealing.

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