Directed Self‐Assembly of Templatable Block Copolymers by Easily Accessible Magnetic Control

Magnetic control has been a prosperous and powerful contactless approach in arraying materials into high‐order nanostructures. However, it is tremendously difficult to control organic polymers in this way on account of the weak magnetic response. The preparation of block copolymers (BCPs) with high magnetostatic energy is reported here, relying on an effective electrostatic coupling between paramagnetic ions and polymer side chains. As a result, the BCPs undergo a magnetically directed self‐assembly to form microphase‐segregated nanostructures with long‐range order. It is emphasized that such a precisely controlled alignment of the BCPs is performed upon a single commercial magnet with low‐intensity field (0.35 Tesla). This strategy is profoundly easy‐to‐handle in contrast to routine electromagnetic methods with high‐intensity field (5–10 Tesla). More significantly, the paramagnetic metal component in the BCP samples can be smartly removed, providing a template effect with a preservation of the directed self‐assembled nanofeatures for patterning follow‐up functionalized species through the original binding site.     

Flash Light Millisecond Self‐Assembly of High χ Block Copolymers for Wafer‐Scale Sub‐10 nm Nanopatterning

One of the fundamental challenges encountered in successful incorporation of directed self‐assembly in sub‐10 nm scale practical nanolithography is the process compatibility of block copolymers with a high Flory–Huggins interaction parameter (χ). Herein, reliable, fab‐compatible, and ultrafast directed self‐assembly of high‐χ block copolymers is achieved with intense flash light. The instantaneous heating/quenching process over an extremely high temperature (over 600 °C) by flash light irradiation enables large grain growth of sub‐10 nm scale self‐assembled nanopatterns without thermal degradation or dewetting in a millisecond time scale. A rapid self‐assembly mechanism for a highly ordered morphology is identified based on the kinetics and thermodynamics of the block copolymers with strong segregation. Furthermore, this novel self‐assembly mechanism is combined with graphoepitaxy to demonstrate the feasibility of ultrafast directed self‐assembly of sub‐10 nm nanopatterns over a large area. A chemically modified graphene film is used as a flexible and conformal light‐absorbing layer. Subsequently, transparent and mechanically flexible nanolithography with a millisecond photothermal process is achieved leading the way for roll‐to‐roll processability.     

Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

The thin‐film directed self‐assembly of molecular building blocks into oriented nanostructure arrays enables next‐generation lithography at the sub‐5 nm scale. Currently, the fabrication of inorganic arrays from molecular building blocks is restricted by the limited long‐range order and orientation of the materials, as well as suitable methodologies for creating lithographic templates at sub‐5 nm dimensions. In recent years, higher‐order liquid crystals have emerged as functional thin films for organic electronics, nanoporous membranes, and templated synthesis, which provide opportunities for their use as lithographic templates. By choosing examples from these fields, recent progress toward the design of molecular building blocks is highlighted, with an emphasis on liquid crystals, to access sub‐5 nm features, their directed self‐assembly into oriented thin films, and, importantly, the fabrication of inorganic arrays. Finally, future challenges regarding sub‐5 nm patterning with liquid crystals are discussed.     

Photopatterning of Cross‐Linkable Epoxide‐Functionalized Block Copolymers and Dual‐Tone Nanostructure Development for Fabrication Across the Nano‐ and Microscales

The self‐assembly of block copolymers in thin films provides an attractive approach to patterning 5–100 nm structures. Cross‐linking and photopatterning of the self‐assembled block copolymer morphologies provide further opportunities to structure such materials for lithographic applications, and to also enhance the thermal, chemical, or mechanical stability of such nanostructures to achieve robust templates for subsequent fabrication processes. Here, model lamellar‐forming diblock copolymers of polystyrene and poly(methyl methacrylate) with an epoxide functionality are synthesized by atom transfer radical polymerization. We demonstrate that self‐assembly and cross‐linking of the reactive block copolymer materials in thin films can be decoupled into distinct, controlled process steps using solvent annealing and thermal treatment/ultraviolet exposure, respectively. Conventional optical lithography approaches can also be applied to the cross‐linkable block copolymer materials in thin films and enable simultaneous structure formation across scales—micrometer scale patterns achieved by photolithography and nanostructures via self‐assembly of the block copolymer. Such materials and processes are thus shown to be capable of self‐assembling distinct block copolymers (e.g., lamellae of significantly different periodicity) in adjacent regions of a continuous thin film.     

Graphoepitaxial Directed Self‐Assembly of Polystyrene‐Block‐Polydimethylsiloxane Block Copolymer on Substrates Functionalized with Hexamethyldisilazane to Fabricate Nanoscale Silicon Patterns

In block copolymer (BCP) nanolithography, microphase separated polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) thin films are particularly attractive as they can form small features and the two blocks can be readily differentiated during pattern transfer. However, PS‐b‐PDMS is challenging because the chemical differences in the blocks can result in poor surface‐wetting, poor pattern orientation control and structural instabilities. Usually the interfacial energies at substrate surface are engineered with the use of a hydroxyl‐terminated polydimethylsiloxane (PDMS‐OH) homopolymer brush. Herein, we report a facile, rapid and tuneable molecular functionalization approach using hexamethyldisilazane (HMDS). The work is applied to both planar and topographically patterned substrates and investigation of graphoepitaxial methods for directed self‐assembly and long‐range translational alignment of BCP domains is reported. The hexagonally arranged in‐plane and out‐of‐plane PDMS cylinders structures formed by microphase separation were successfully used as on‐chip etch masks for pattern transfer to the underlying silicon substrate. The molecular approach developed here affords significant advantages when compared to the more usual PDMS‐OH brushes used.     

Templated Self‐Assembly of Block Copolymers: Top‐Down Helps Bottom‐Up

One of the key challenges in nanotechnology is to control a self‐assembling system to create a specific structure. Self‐organizing block copolymers offer a rich variety of periodic nanoscale patterns, and researchers have succeeded in finding conditions that lead to very long range order of the domains. However, the array of microdomains typically still contains some uncontrolled defects and lacks global registration and orientation. Recent efforts in templated self‐assembly of block copolymers have demonstrated a promising route to control bottom‐up self‐organization processes through top‐down lithographic templates. The orientation and placement of block‐copolymer domains can be directed by topographically or chemically patterned templates. This templated self‐assembly method provides a path towards the rational design of hierarchical device structures with periodic features that cover several length scales.