Localized surface plasmon resonance of metallic nanostructures receives noticeable attention in photonics, electronics, catalysis, and so on. Core-shell nanostructures are particularly attractive due to the versatile tunability of plasmonic properties along with the independent control of core size, shell thickness, and corresponding chemical composition, but they commonly suffer from difficult synthetic procedures. We present a reliable and controllable route to a highly ordered uniform Au@Ag core-shell nanoparticle array via block copolymer lithography and subsequent seeded-shell growth. Size-tunable monodisperse Au nanodot arrays are generated by block copolymer self-assembly and are used as seed layers to grow Ag shells with variable thickness. The resultant Au@Ag core-shell nanoparticle arrays exhibit widely tunable broadband enhancement of plasmonic resonance, greatly surpassing single-element nanoparticle or homogeneous alloy nanoparticle arrays. Surface-enhanced Raman scattering of the core-shell nanoparticle arrays showed an enhancement factor greater than 270 from Au nanoparticle arrays.

Recent advance of high-power laser processing allows for rapid, continuous, area-selective material fabrication, typically represented by laser crystallization of silicon or oxides for display applications. Two-dimensional materials such as graphene exhibit remarkable physical properties and are under intensive development for the manufacture of flexible devices. Here we demonstrate an area-selective ultrafast nanofabrication method using low intensity infrared or visible laser irradiation to direct the self-assembly of block copolymer films into highly ordered manufacturing-relevant architectures at the scale below 12 nm. The fundamental principles underlying this light-induced nanofabrication mechanism include the self-assembly of block copolymers to proceed across the disorder-order transition under large thermal gradients, and the use of chemically modified graphene films as a flexible and conformal light-absorbing layers for transparent, nonplanar, and mechanically flexible surfaces.

No abstract

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.

Nanoscale alloys attract enormous research attentions in catalysis, magnetics, plasmonics and so on. Along with multicomponent synergy, quantum confinement and extreme large surface area of nanoalloys offer novel material properties, precisely and broadly tunable with chemical composition and nanoscale dimension. Despite substantial progress of nanoalloy synthesis, the randomized positional arrangement and dimensional/compositional inhomogeneity of nanoalloys remain significant technological challenges for advanced applications. Here we present a generalized route to synthesize single-crystalline intermetallic nanoalloy arrays with dimensional and compositional uniformity via self-assembly. Specific electrostatic association of multiple ionic metal complexes within self-assembled nanodomains of block copolymers generated patterned monodisperse bimetallic/trimetallic nanoalloy arrays consisting of various elements, including Au, Co, Fe, Pd, and Pt. The precise controllability of size, composition, and intermetallic crystalline structure of nanoalloys facilitated tailored synergistic properties, such as accelerated catalytic growth of vertical carbon nanotubes from Fe-Co nanoalloy arrays.

Effective surface enhancement of Raman scattering (SERS) requires strong near-field enhancement as well as effective light collection of plasmonic structures. To this end, plasmonic nanoparticle (NP) arrays with narrow gaps or sharp tips have been suggested as desirable structures. We present a highly dense and uniform Au nanoscale gap array enabled by the customized design of NP shape and arrangement employing block copolymer self-assembly. Block copolymer selfassembly in thin films offers uniform hexagonally packed nanopost template arrays over the entire surface of a 2 in. wafer. Conventional evaporative metal deposition over the nanotemplate surface allows precise geometric control and positional arrangement of metal NPs, constituting tunable, strong plasmonic near-field enhancement particularly at the "hot spots" near interparticular nanoscale gaps. Underlying field distribution has been investigated by a finite-difference timedomain simulation. In the detection of thiophenol, our Au nanogap array shows a remarkable enhancement of Raman intensity greater than ∼10 4 , a standard deviation as small as 12.3% compared to that of the planar Au thin film. In addition, adenine biomolecules can be detected with a detection limit as low as 100 nM. Our approach proposes highly sensitive and reliable SERS on the basis of a scalable, low-cost bottom-up strategy.

5-nm-scale line and hole patterning is demonstrated by synergistic integration of block copolymer (BCP) lithography with atomic layer deposition (ALD).While directed self-assembly of BCPs generates highly ordered line array or hexagonal dot array with the pattern periodicity of 28 nm and the minimum feature size of 14 nm, pattern density multiplication employing ALD successfully reduces the pattern periodicity down to 14 nm and minimum feature size down to 5 nm. Self-limiting ALD process enable the low temperature, conformal deposition of 5 nm thick spacer layer directly at the surface of organic BCP patterns. This ALD assisted pattern multiplication addresses the intrinsic thermodynamic limitations of low χ BCPs for sub-10-nm scale downscaling. Moreover, this approach offers a general strategy for scalable ultrafi ne nanopatterning without burden for multiple overlay control and high cost lithographic tools.

We investigate the unusually rapid directed self-assembly of block copolymer (BCP) thin films by imposing an in-plane electric field.