Controlled Segmentation of Metal Nanowire Array by Block Copolymer Lithography and Reversible Ion Loading.

Spatial arrangement of 1D nanomaterials may offer enormous opportunities for advanced electronics and photonics. Moreover, morphological complexity and chemical diversity in the nanoscale components may lead to unique properties that are hardly anticipated in randomly distributed homogeneous nanostructures. Here, controlled chemical segmentation of metal nanowire arrays using block copolymer lithography and subsequent reversible metal ion loading are demonstrated. To impose chemical heterogeneity in the nanowires generated by block copolymer lithography, reversible ion loading method highly specific for one particular polymer block is introduced. Reversibility of the metal ion loading enables area-selective localized replacement of metal ions in the self-assembled patterns and creates segmented metal nanowire arrays with different metallic components. Further integration of this method with shear aligning process produces high aligned segmented metal nanowire array with desired local chemical compositions.

Surface Modification of Block Copolymer Through Sulfur Containing Plasma Treatment.

Some of the important issues of block copolymer (BCP) as an application to the potential low cost next generation lithography are thermal stability and deformation during pattern transfer process in addition to defect density, line edge/width roughness, etc. In this study, sulfur containing plasma treatment was used to modify the BCP and the effects of the plasma on the properties of plasma treated BCP were investigated. The polystyrene hole pattern obtained from polystyrene polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) was initially degraded when the polystyrene hole was annealed at 190 °C for 15 min. However, when the hole pattern was treated using sulfur containing plasmas using H2S or SF6 up to 2 min, possibly due to the sulfurization of the polystyrene hole surface, no change in the hole pattern was observed after the annealing even though there is a slight change in hole shapes during the plasma treatment. The optimized plasma treated polystyrene pattern showed the superior characteristics as the mask layer by showing better thermal stability, higher chemical inertness, and higher etch selectivity during plasma etching.

Nanodomain swelling block copolymer lithography for morphology tunable metal nanopatterning.

Ordered metal nanopatterns are crucial requirements for electronics, magnetics, catalysts, photonics, and so on. Despite considerable progress in the synthetic route to metal nanostructures, highly ordered metal nanopatterning over a large-area is still challenging. Nanodomain swelling block copolymer lithography is presented as a general route to the systematic morphology tuning of metal nanopatterns from amphiphilic diblock copolymer self-assembly. Selective swelling of hydrophilic nanocylinder domains in amphiphilic block copolymer films during metal precursor loading and subsequent oxygen based etching generates diverse shapes of metal nanopatterns, including hexagonal nanoring array and hexagonal nanomesh and double line array in addition to common nanodot and nanowire arrays. Solvent annealing condition of block copolymer templates, selective swelling of hydrophilic cylinder nanodomains, block copolymer template thickness, and oxygen based etching methods are the decisive parameters for systematic morphology evolution. The plasmonic properties of ordered Au nanopatterns are characterized and analyzed with finite differential time domain calculation. This approach offers unprecedented opportunity for diverse metal nanopatterns from commonly used diblock copolymer self-assembly.

Monodisperse pattern nanoalloying for synergistic intermetallic catalysis.

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.

Graphoepitaxy of block-copolymer self-assembly integrated with single-step ZnO nanoimprinting.

A highly efficient, ultralarge-area nanolithography that integrates block-copolymer lithography with single-step ZnO nanoimprinting is introduced. The UV-assisted imprinting of a photosensitive sol-gel precursor creates large-area ZnO topographic patterns with various pattern shapes in a single-step process. This straightforward approach provides a smooth line edge and high thermal stability of the imprinted ZnO pattern; these properties are greatly advantageous for further graphoepitaxial block-copolymer assembly. According to the ZnO pattern shape and depth, the orientation and lateral ordering of self-assembled cylindrical nanodomains in block-copolymer thin films could be directed in a variety of ways. Significantly, the subtle tunability of ZnO trench depth enabled by nanoimprinting, generated complex hierarchical nanopatterns, where surface-parallel and surface-perpendicular nanocylinder arrays are alternately arranged. The stability of this complex morphology is confirmed by self-consistent field theory (SCFT) calculations. The highly ordered graphoepitaxial nanoscale assembly achieved on transparent semiconducting ZnO substrates offers enormous potential for photonics and optoelectronics.

Compositional effect of two-dimensional monodisperse AuPd bimetallic nanoparticle arrays fabricated by block copolymer nanopatterning on catalytic activity of CO oxidation.

We present a straightforward approach for fabricating AuPd nanocatalysts based on self-assembled block copolymer nanopatterning. CO oxidation was carried out on AuPd alloy nanoparticles and the activity increased with increasing Pd content; this synergistic activity can be precisely tuned by varying the chemical composition. Theoretical calculations suggest that Pd clusters are required to bind and dissociate O2 for oxidation of coadsorbed CO molecules. Our results suggest that the geometric configuration of the Pd atoms on the surface are a key factor in the catalytic activity.

Self-Assembly of Complex Multimetal Nanostructures from Perforated Lamellar Block Copolymer Thin Films.

We introduce a facile and effective fabrication of complex multimetallic nanostructures through block copolymer self-assembly. Two- and three-dimensional complex nanostructures, such as "nanomesh," "double-layered nanomeshes," and "surface parallel cylinders on nanomesh," can be fabricated using the self-assembly of perforated lamellar morphology in block copolymer thin films. Simultaneous integration of various metallic elements, including Pt, Au, and Co, into the self-assembled morphologies generates multimetal complex nanostructures with highly interconnected morphology and a large surface. The resultant metal nanostructures with a large surface area, robust electrical connectivity, and well-defined alloy composition demonstrate a high-performance electrochemical catalysis for hydrogen evolution reaction (current density: 6.27 mA/cm2@0.1 V and Tafel slope: 43 mV/dec).

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.

Laser Writing Block Copolymer Self-Assembly on Graphene Light-Absorbing Layer.

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.

Highly tunable refractive index visible-light metasurface from block copolymer self-assembly.

The refractive index of natural transparent materials is limited to 2-3 throughout the visible wavelength range. Wider controllability of the refractive index is desired for novel optical applications such as nanoimaging and integrated photonics. We report that metamaterials consisting of period and symmetry-tunable self-assembled nanopatterns can provide a controllable refractive index medium for a broad wavelength range, including the visible region. Our approach exploits the independent control of permeability and permittivity with nanoscale objects smaller than the skin depth. The precise manipulation of the interobject distance in block copolymer nanopatterns via pattern shrinkage increased the effective refractive index up to 5.10. The effective refractive index remains above 3.0 over more than 1,000 nm wavelength bandwidth. Spatially graded and anisotropic refractive indices are also obtained with the design of transitional and rotational symmetry modification.

Au-Ag core-shell nanoparticle array by block copolymer lithography for synergistic broadband plasmonic properties.

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.

Multicomponent nanopatterns by directed block copolymer self-assembly.

Complex nanopatterns integrating diverse nanocomponents are crucial requirements for advanced photonics and electronics. Currently, such multicomponent nanopatterns are principally created by colloidal nanoparticle assembly, where large-area processing of highly ordered nanostructures raises significant challenge. We present multicomponent nanopatterns enabled by block copolymer (BCP) self-assembly, which offers device oriented sub-10-nm scale nanopatterns with arbitrary large-area scalability. In this approach, BCP nanopatterns direct the nanoscale lateral ordering of the overlaid second level BCP nanopatterns to create the superimposed multicomponent nanopatterns incorporating nanowires and nanodots. This approach introduces diverse chemical composition of metallic elements including Au, Pt, Fe, Pd, and Co into sub-10-nm scale nanopatterns. As immediate applications of multicomponent nanopatterns, we demonstrate multilevel charge-trap memory device with Pt-Au binary nanodot pattern and synergistic plasmonic properties of Au nanowire-Pt nanodot pattern.