Parallel Preparation of Densely Packed Arrays of 150‐nm Gold‐Nanocrescent Resonators in Three Dimensions

Metallic nanostructures show interesting optical properties due to their plasmonic resonances, and when arranged in three‐dimensional (3D) arrays hold promise for optical metamaterials with negative refractive index. Towards this goal a simple, cheap, and parallel method to fabricate large‐area, ordered arrays of 150‐nm gold nanocrescents supporting plasmonic resonances in the near‐infrared spectral range is demonstrated. In this process hexagonally ordered monolayers of monodisperse colloids are prepared by a simple floating technique, and subsequently the individual particles are size‐reduced in a plasma process and used as a shadow mask with the initial lattice spacing. The resulting two‐dimensional array of plasmonic resonators is coated with a transparent silica layer, which serves as a support for a second layer prepared by the identical process. The mutual orientation of the nanostructures between the individual layers can be freely adjusted, which determines the polarization‐dependent absorption of the array and opens the possibility to introduce chirality in this type of 3D metamaterial. The iteration of this simple and efficient methodology yields 3D arrays with optical features as sharp as those of the individual nanocrescents, and shows strong potential for large‐scale production of high‐quality optical metamaterials.     

High‐Quality‐Factor Mid‐Infrared Toroidal Excitation in Folded 3D Metamaterials

With unusual electromagnetic radiation properties and great application potentials, optical toroidal moments have received increasing interest in recent years. 3D metamaterials composed of split ring resonators with specific orientations in micro‐/nanoscale are a perfect choice for toroidal moment realization in optical frequency considering the excellent magnetic confinement and quality factor, which, unfortunately, are currently beyond the reach of existing micro‐/nanofabrication techniques. Here, a 3D toroidal metamaterial operating in mid‐infrared region constructed by metal patterns and dielectric frameworks is designed, by which high‐quality‐factor toroidal resonance is observed experimentally. The toroidal dipole excitation is confirmed numerically and further demonstrated by phase analysis. Furthermore, the far‐field radiation intensity of the excited toroidal dipoles can be adjusted to be predominant among other multipoles by just tuning the incident angle. The related processing method expands the capability of focused ion beam folding technologies greatly, especially in 3D metamaterial fabrication, showing great flexibility and nanoscale controllability on structure size, position, and orientation.     

Periodic Large‐Area Metallic Split‐Ring Resonator Metamaterial Fabrication Based on Shadow Nanosphere Lithography

A fast and cheap, large‐area (>1 cm²), high‐coverage fabrication technique for periodic metallic split‐ring resonator metamaterials is presented, which allows control of inner‐ and outer‐ring diameters, gap angles, as well as thickness and periodicity. This method, based on shadow nanosphere lithography, uses tilted‐angle‐rotation thermal evaporation onto Langmuir–Blodgett‐type monolayers of close‐packed polystyrene nanospheres. Excellent agreement of the process parameters with a simplified model is demonstrated. Pronounced, tunable optical metamaterial resonances in the range of 100 THz are consistent with simulations.     

Spatial and Temporal Modulation of Thermal Emission

Precise control of a material's emissivity is critical for thermal‐engineering applications. Metamaterials, which derive their optical properties from sub‐wavelength structures, have emerged as a promising way to tune emissivity over a wide parameter space. However, metamaterial designs have not yet achieved simultaneous spatial and temporal control of emissivity, which is important for advanced engineering applications such as adaptive thermal management and reconfigurable infrared camouflage. Here, spatiotemporal emissivity control is demonstrated by designing and fabricating a large‐area, infrared metamaterial that is modulated with ultraviolet (UV) light. The UV light generates free carriers in a photosensitive ZnO spacer layer, which changes the metamaterial optical properties and causes a localized increase in emissivity. Thermal imaging of the metamaterial during UV illumination reveals an apparent temperature increase as a result of the emissivity change. The imaged temperature fluctuation is recorded under exposure from a temporally modulated and spatially patterned UV illumination source to characterize both the temporal response and spatial resolution of the emissivity change. The results of this work demonstrate new capabilities for thermal metamaterials that could bring about the next generation of thermal‐engineering devices.     

Selective Nanoscale Mass Transport across Atomically Thin Single Crystalline Graphene Membranes

Atomically thin single crystals, without grain boundaries and associated defect clusters, represent ideal systems to study and understand intrinsic defects in materials, but probing them collectively over large area remains nontrivial. In this study, the authors probe nanoscale mass transport across large‐area (≈0.2 cm²) single‐crystalline graphene membranes. A novel, polymer‐free picture frame assisted technique, coupled with a stress‐inducing nickel layer is used to transfer single crystalline graphene grown on silicon carbide substrates to flexible polycarbonate track etched supports with well‐defined cylindrical ≈200 nm pores. Diffusion‐driven flow shows selective transport of ≈0.66 nm hydrated K⁺ and Cl^? ions over ≈1 nm sized small molecules, indicating the presence of selective sub‐nanometer to nanometer sized defects. This work presents a framework to test the barrier properties and intrinsic quality of atomically thin materials at the sub‐nanometer to nanometer scale over technologically relevant large areas, and suggests the potential use of intrinsic defects in atomically thin materials for molecular separations or desalting.     

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.     

Adlayer‐Free Large‐Area Single Crystal Graphene Grown on a Cu(111) Foil

To date, thousands of publications have reported chemical vapor deposition growth of “single layer” graphene, but none of them has described truly single layer graphene over large area because a fraction of the area has adlayers. It is found that the amount of subsurface carbon (leading to additional nuclei) in Cu foils directly correlates with the extent of adlayer growth. Annealing in hydrogen gas atmosphere depletes the subsurface carbon in the Cu foil. Adlayer‐free single crystal and polycrystalline single layer graphene films are grown on Cu(111) and polycrystalline Cu foils containing no subsurface carbon, respectively. This single crystal graphene contains parallel, centimeter‐long ≈100 nm wide “folds,” separated by 20 to 50 µm, while folds (and wrinkles) are distributed quasi‐randomly in the polycrystalline graphene film. High‐performance field‐effect transistors are readily fabricated in the large regions between adjacent parallel folds in the adlayer‐free single crystal graphene film.     

Anisotropic Nanoscale Wrinkling in Solid‐State Substrates

Pattern formation induced by wrinkling is a very common phenomenon exhibited in soft‐matter substrates. In all these systems, wrinkles develop in the presence of compressively stressed thin films lying on compliant substrates. Here, the controlled growth of self‐organized nanopatterns exploiting a wrinkling instability on a solid‐state substrate is demonstrated. Soda‐lime glasses are modified in the surface layers by a defocused ion beam, which triggers the formation of a compressively stressed surface layer deprived of alkali ions. When the substrate is heated up near its glass transition temperature, the wrinkling instability boosts the growth rate of the pattern by about two orders of magnitude. High‐aspect‐ratio anisotropic ripples bound by faceted ridges are thus formed, which represent an optimal template for guiding the growth of large‐area arrays of functional nanostructures. The engineering over large square centimeter areas of quasi‐1D arrays of Au nanostripe dimers endowed with tunable plasmonic response, strong optical dichroism, and high electrical conductivity is demonstrated. These peculiar functionalities allow these large‐area substrates to be exploited as active metamaterials in nanophotonics, biosensing, and optoelectronics.     

Infrared metamaterial phase holograms

As a result of advances in nanotechnology and the burgeoning capabilities for fabricating materials with controlled nanoscale geometries, the traditional notion of what constitutes an optical device continues to evolve. The fusion of maturing low-cost lithographic techniques with newer optical design strategies has enabled the introduction of artificially structured metamaterials in place of conventional materials for improving optical components as well as realizing new optical functionality. Here we demonstrate multilayer, lithographically patterned, subwavelength, metal elements, whose distribution forms a computer-generated phase hologram in the infrared region (10.6 μm). Metal inclusions exhibit extremely large scattering and can be implemented in metamaterials that exhibit a wide range of effective medium response, including anomalously large or negative refractive index; optical magnetism; and controlled anisotropy. This large palette of metamaterial responses can be leveraged to achieve greater control over the propagation of light, leading to more compact, efficient and versatile optical components.     

Level set‐based topology optimization targeting dielectric resonator‐based composite right‐ and left‐handed transmission lines

In the last decade, metamaterials have been gaining attention and have been investigated because of their unique characteristics, which conventional materials do not have, such as negative refraction indexes. However, it is sometimes difficult to design metamaterials on the basis of experience and theoretical considerations because the relationship between their electromagnetic characteristics and structure is often vague. A mathematical structural design methodology targeting metamaterials may therefore be useful for expanding the engineering applications of metamaterials in industry. In this paper, a new level set‐based topology optimization method is proposed for designing composite right‐ and left‐handed transmission lines, each of which consists of a waveguide and periodically located dielectric resonators. Such transmission lines function as a fundamental metamaterial. In the proposed method, the shape and topology of the dielectric resonators are represented by the level set function, and topology optimization problems are formulated on the basis of the level set‐based representation. Copyright © 2011 John Wiley & Sons, Ltd.     

Scanning Nanowelding Lithography for Rewritable One‐Step Patterning of Sub‐50 nm High‐Aspect‐Ratio Metal Nanostructures

The development of a new nanolithographic strategy, named scanning nanowelding lithography (SNWL), for the one‐step fabrication of arbitrary high‐aspect‐ratio nanostructures of metal is reported in this study. Different from conventional pattern transfer and additive printing strategies which require subtraction or addition of materials, SNWL makes use of a sharp scanning tip to reshape metal thin films or existing nanostructures into desirable high‐aspect‐ratio patterns, through a cold‐welding effect of metal at the nanoscale. As a consequence, SNWL can easily fabricate, in one step and at ambient conditions, sub‐50 nm metal nanowalls with remarkable aspect ratio >5, which are found to be strong waveguide of light. More importantly, SNWL outweighs the existing strategies in terms of the unique ability to erase the as‐made nanostructures and rewrite them into other shapes and orientations on‐demand. Taking advantages of the serial and rewriting capabilities of SNWL, the smart information storage–erasure of Morse codes is demonstrated. SNWL is a promising method to construct arbitrary high‐aspect‐ratio nanostructure arrays that are highly desirable for biological, medical, optical, electronic, and information applications.     

Camphor‐Enabled Transfer and Mechanical Testing of Centimeter‐Scale Ultrathin Films

Camphor is used to transfer centimeter‐scale ultrathin films onto custom‐designed substrates for mechanical (tensile) testing. Compared to traditional transfer methods using dissolving/peeling to remove the support‐layers, camphor is sublimed away in air at low temperature, thereby avoiding additional stress on the as‐transferred films. Large‐area ultrathin films can be transferred onto hollow substrates without damage by this method. Tensile measurements are made on centimeter‐scale 300 nm‐thick graphene oxide film specimens, much thinner than the ≈2 μm minimum thickness of macroscale graphene‐oxide films previously reported. Tensile tests were also done on two different types of large‐area samples of adlayer free CVD‐grown single‐layer graphene supported by a ≈100 nm thick polycarbonate film; graphene stiffens this sample significantly, thus the intrinsic mechanical response of the graphene can be extracted. This is the first tensile measurement of centimeter‐scale monolayer graphene films. The Young's modulus of polycrystalline graphene ranges from 637 to 793 GPa, while for near single‐crystal graphene, it ranges from 728 to 908 GPa (folds parallel to the tensile loading direction) and from 683 to 775 GPa (folds orthogonal to the tensile loading direction), demonstrating the mechanical performance of large‐area graphene in a size scale relevant to many applications.     

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.     

Modern Scattering‐Type Scanning Near‐Field Optical Microscopy for Advanced Material Research

Infrared and optical spectroscopy represents one of the most informative methods in advanced materials research. As an important branch of modern optical techniques that has blossomed in the past decade, scattering‐type scanning near‐field optical microscopy (s‐SNOM) promises deterministic characterization of optical properties over a broad spectral range at the nanoscale. It allows ultrabroadband optical (0.5–3000 µm) nanoimaging, and nanospectroscopy with fine spatial (<10 nm), spectral (<1 cm^?1), and temporal (<10 fs) resolution. The history of s‐SNOM is briefly introduced and recent advances which broaden the horizons of this technique in novel material research are summarized. In particular, this includes the pioneering efforts to study the nanoscale electrodynamic properties of plasmonic metamaterials, strongly correlated quantum materials, and polaritonic systems at room or cryogenic temperatures. Technical details, theoretical modeling, and new experimental methods are also discussed extensively, aiming to identify clear technology trends and unsolved challenges in this exciting field of research.     

Resistless Nanoimprinting in Metal for Plasmonic Nanostructures

Metal nanostructures are the main building blocks of metamaterials and plasmonics which show many extraordinary properties not existing in nature. A simple and widely applicable method that can directly pattern metals with silicon molds without the need of resists, using pressures of <4 MPa and temperatures of 25–150 °C is reported. Three‐dimensional structures with smooth and vertical sidewalls, down to sub‐10 nm resolution, are generated in silver and gold films in a single patterning step. Using this nanopatterning scheme, large‐scale vivid images through extraordinary optical transmission and strong surface‐enhanced Raman scattering substrates are realized. Resistless nanoimprinting in metal (RNIM) is a new class of metal patterning that allows plasmonic nanostructures to be fabricated quickly, repeatedly, and at a low‐cost.     

Nanofountain‐Probe‐Based High‐Resolution Patterning and Single‐Cell Injection of Functionalized Nanodiamonds

Nanodiamonds are rapidly emerging as promising carriers for next‐generation therapeutics and drug delivery. However, developing future nanoscale devices and arrays that harness these nanoparticles will require unrealized spatial control. Furthermore, single‐cell in vitro transfection methods lack an instrument that simultaneously offers the advantages of having nanoscale dimensions and control and continuous delivery via microfluidic components. To address this, two modes of controlled delivery of functionalized diamond nanoparticles are demonstrated using a broadly applicable nanofountain probe, a tool for direct‐write nanopatterning with sub‐100‐nm resolution and direct in vitro single‐cell injection. This study demonstrates the versatility of the nanofountain probe as a tool for high‐fidelity delivery of functionalized nanodiamonds and other agents in nanomanufacturing and single‐cell biological studies. These initial demonstrations of controlled delivery open the door to future studies examining the nanofountain probe's potential in delivering specific doses of DNA, viruses, and other therapeutically relevant biomolecules.     

Direct Growth of Ultrafast Transparent Single‐Layer Graphene Defoggers

The idea flat surface, superb thermal conductivity and excellent optical transmittance of single‐layer graphene promise tremendous potential for graphene as a material for transparent defoggers. However, the resistance of defoggers made from conventional transferred graphene increases sharply once both sides of the film are covered by water molecules which, in turn, leads to a temperature drop that is inefficient for fog removal. Here, the direct growth of large‐area and continuous graphene films on quartz is reported, and the first practical single‐layer graphene defogger is fabricated. The advantages of this single‐layer graphene defogger lie in its ultrafast defogging time for relatively low input voltages and excellent defogging robustness. It can completely remove fog within 6 s when supplied a safe voltage of 32 V. No visible changes in the full defogging time after 50 defogging cycles are observed. This outstanding performance is attributed to the strong interaction forces between the graphene films and the substrates, which prevents the permeation of water molecules. These directly grown transparent graphene defoggers are expected to have excellent prospects in various applications such as anti‐fog glasses, auto window and mirror defogging.     

Chalcogenide Phase Change Material for Active Terahertz Photonics

The strikingly contrasting optical properties of various phases of chalcogenide phase change materials (PCM) has recently led to the development of novel photonic devices such as all‐optical non‐von Neumann memory, nanopixel displays, color rendering, and reconfigurable nanoplasmonics. However, the exploration of chalcogenide photonics is currently limited to optical and infrared frequencies. Here, a phase change material integrated terahertz metamaterial for multilevel nonvolatile resonance switching with spatial and temporal selectivity is demonstrated. By controlling the crystalline proportion of the PCM film, multilevel, non‐volatile, terahertz resonance switching states with long retention time at zero hold power are realized. Spatially selective reconfiguration at sub‐metamaterial scale is shown by delivering electrical stimulus locally through designer interconnect architecture. The PCM metamaterial also features ultrafast optical modulation of terahertz resonances with tunable switching speed based on the crystalline order of the PCM film. The multilevel nonvolatile, spatially selective, and temporally tunable PCM metamaterial will provide a pathway toward development of novel and disruptive terahertz technologies including spatio‐temporal terahertz modulators for high speed wireless communication, neuromorphic photonics, and machine‐learning metamaterials.     

Fano-resonant asymmetric metamaterials for ultrasensitive spectroscopy and identification of molecular monolayers

Engineered optical metamaterials present a unique platform for biosensing applications owing to their ability to confine light to nanoscale regions and to their spectral selectivity. Infrared plasmonic metamaterials are especially attractive because their resonant response can be accurately tuned to that of the vibrational modes of the target biomolecules. Here we introduce an infrared plasmonic surface based on a Fano-resonant asymmetric metamaterial exhibiting sharp resonances caused by the interference between subradiant and superradiant plasmonic resonances. Owing to the metamaterial's asymmetry, the frequency of the subradiant resonance can be precisely determined and matched to the molecule's vibrational fingerprints. A multipixel array of Fano-resonant asymmetric metamaterials is used as a platform for multispectral biosensing of nanometre-scale monolayers of recognition proteins and their surface orientation, as well as for detecting chemical binding of target antibodies to recognition proteins.     

Microfluidics: Nanostructuring of Titania Thin Films by a Combination of Microfluidics and Block‐Copolymer‐Based Sol–Gel Templating (Small 7/2011)

Sol–gel templating of titania thin films with the amphiphilic diblock copolymer poly(dimethyl siloxane)‐block‐methyl methacrylate poly(ethylene oxide) is combined with microfluidic technology to control the structure formation. Due to the laminar flow conditions in the microfluidic cell, a better control of the local composition of the reactive fluid is achieved. The resulting titania films exhibit mesopores and macropores, as determined with scanning electron microscopy, X‐ray reflectivity, and grazing incidence small angle X‐ray scattering. The titania morphology has three features that are beneficial for application in photovoltaics: 1) a large surface‐to‐volume ratio important for charge generation with disordered hexagonally arranged mesopores of 25 nm size and a film porosity of up to 0.79, 2) enhanced light scattering that enables the absorption of more light, and 3) a dense titania layer with a thickness of about 6 nm at the substrate (bottom electrode) to prevent short circuits. An optical characterization complements the structural investigation.