The self-assembly of a single layer of organic molecules on a substrate is a powerful strategy to modify surfaces and interfacial properties. The detailed interplay of molecule-to-substrate and molecule-molecule interactions are crucial for the preparation of stable and uniform monomolecular coatings. Thiolates, silanes, phosphonates and carboxylates are widely used head-groups to link organic molecules to specific surfaces study we show that self-assembly of stable and highly compact monolayers of perfluorocarbons. Remarkably, the lowest ever reported surface energy of 2.6 mJ m-2 was measured for a perfluorododecyl iodide monolayer on a silicon nitride substrate. As a convenient, flexible and simple method, the self-assembly of halogen-bond driven perfluorocarbon monolayers is compatible with several applications, ranging from biosensing to electronics and microfluidics. Compared to other methods used to functionalise surfaces and interfaces, our procedure offers the unique advantage to work with extremely inert perfluorinated solvents. We demonstrate that surfaces commonly unstable in contact with many common organic solvents, such as organic-inorganic perovskites, can be functionalized via halogen bonding.

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The efficacy with which solvent vapor annealing (SVA) can control block copolymer self-assembly has so far been demonstrated primarily for the simplest class of copolymer, the linear diblock copolymer. Adding a third distinct block-thereby creating a triblock terpolymer-not only provides convenient access to complex continuous network morphologies, particularly the gyroid phases, but also opens up a route toward the fabrication of novel nanoscale devices such as optical metamaterials. Such applications, however, require the generation of well-ordered 3D continuous networks, which in turn requires a detailed understanding of the SVA process in terpolymer network morphologies. Here, in situ grazing-incidence small-angle X-ray scattering (GISAXS) is employed to study the self-assembly of a gyroid-forming triblock terpolymer during SVA, revealing the effects of several key SVA parameters on the morphology, lateral order, and, in particular, its preservation in the dried film. The robustness of the terpolymer gyroid morphology is a key requirement for successful SVA, allowing the exploration of annealing parameters which may enable the generation of films with long-range order, e.g., for optical metamaterial applications.

Metamaterials are artificially engineered materials whose optical properties are dependent on both the geometry of their structural units and their chemical com-position. [1] The ability to design an effective permittivity ε eff ( ω ) and permeability μ eff ( ω ) by careful choice of these subwavelength structural units offers the potential for intriguing applications, such as super-lenses and cloaking devices. [2,3] Associated material properties include those otherwise unavailable in nature, such as a negative refractive index and extreme “hyperbolic” optical anisotropy. [4] The observation of these unique properties at optical frequencies, however, requires structural control on the length scale of just a few nano meters. “Top down” techniques are either unable to produce bulk 3D structures (e.g., electron beam lithography [5,6] ), or cannot produce such structures on the nanoscale (e.g., direct laser writing [7–9] ), with the uniformity and efficiency necessary for a truly macroscopic ε eff ( ω ) and μ eff ( ω ). [10,11] Optical metamaterials offer the tantalizing possibility of creating extraordinary optical properties through the careful design and arrangement of subwavelength structural units. Gyroid-structured optical metamaterials possess a chiral, cubic, and triply periodic bulk morphology that exhibits a redshifted effective plasma frequency. They also exhibit a strong linear dichroism, the origin of which is not yet understood. Here, the interaction of light with gold gyroid optical metamaterials is studied and a strong correlation between the surface morphology and its linear dichroism is found. The termination of the gyroid surface breaks the cubic symmetry of the bulk lattice and gives rise to the observed wavelength- and polarization-dependent reflection. The results show that light couples into both localized and propagating plasmon modes associated with anisotropic surface protrusions and the gaps between such protrusions. The localized surface modes give rise to the anisotropic optical response, creating the linear dichroism. Simulated reflection spectra are highly sensitive to minute details of these surface terminations, down to the nanometer level, and can be understood with analogy to the optical properties of a 2D anisotropic metasurface atop a 3D isotropic metamaterial. This pronounced sensitivity to the subwavelength surface morphology has significant consequences for both the design and application of optical metamaterials.

Optical metamaterials offer the tantalizing possibility of creating extraordinary optical properties through the careful design and arrangement of subwavelength structural units. Gyroid-structured optical metamaterials possess a chiral, cubic, and triply periodic bulk morphology that exhibits a redshifted effective plasma frequency. They also exhibit a strong linear dichroism, the origin of which is not yet understood. Here, the interaction of light with gold gyroid optical metamaterials is studied and a strong correlation between the surface morphology and its linear dichroism is found. The termination of the gyroid surface breaks the cubic symmetry of the bulk lattice and gives rise to the observed wavelength- and polarization-dependent reflection. The results show that light couples into both localized and propagating plasmon modes associated with anisotropic surface protrusions and the gaps between such protrusions. The localized surface modes give rise to the anisotropic optical response, creating the linear dichroism. Simulated reflection spectra are highly sensitive to minute details of these surface terminations, down to the nanometer level, and can be understood with analogy to the optical properties of a 2D anisotropic metasurface atop a 3D isotropic metamaterial. This pronounced sensitivity to the subwavelength surface morphology has significant consequences for both the design and application of optical metamaterials.

Solvent vapor annealing (SVA) is an excellent means to anneal block copolymer thin films, thereby controlling the self-assembly processes from molecular to macroscopic length scales. Triblock terpolymers are excellent candidate materials to generate ordered 3D continuous interpenetrating network morphologies, particularly the gyroid phases, which form over a much wider composition range compared to diblock copolymers. Here, we present the results of in situ grazing-incidence small-angle X-ray scattering (GISAXS) experiments on a gyroid-forming triblock terpolymer, polyisopreneb-polystyrene-b-poly(ethylene oxide) (ISO), revealing the effects of several key SVA parameters on the morphology, lateral order and, particularly, its preservation in the dried film. The robustness of the terpolymer gyroid morphology is a key requirements for successful SVA, allowing the exploration of annealing parameters which may enable the generation of films with long-range order, e.g. for optical metamaterial applications.

In this work, a variant of a Kretschmann-type surface plasmon resonance (SPR) sensor is introduced. k-space imaging is combined with half-ball glass optics to facilitate the measurement of SPRs across the visible spectral range. In contrast to current state-of-the-art techniques, which are widely utilized in commercially available systems, the presented method allows single-shot-acquisition of the full angular reflection without any moving parts, as well as mapping of the surface plasmon dispersion by scanning across the entire visible wavelength range. Measurements on various thin metallic films demonstrate the sensitivity of the system towards minute changes of the metal surface and its close vicinity. The fast and precise measurement of surface plasmon resonances paves the way for improved detection in applications such as immunoassays or gas-sensors, especially for real-time in situ measurements.

Block copolymer (BCP) self-assembly is a promising route to manufacture functional nanomaterials for applications from nanolithography to optical metamaterials. Self-assembled cubic morphologies cannot, however, be conveniently optically characterized in the lab due to their structural isotropy. Here, the aligned crystallization behavior of a semicrystalline-amorphous polyisoprene-b-polystyrene-b-poly(ethylene oxide) (ISO) triblock terpolymer was utilized to visualize the grain structure of the cubic microphase-separated morphology. Upon quenching from a solvent swollen state, ISO first self-assembles into an alternating gyroid morphology, in the confinement of which the PEO crystallizes preferentially along the least tortuous pathways of the single gyroid morphology with grain sizes of hundreds of micrometers. Strikingly, the resulting anisotropic alignment of PEO crystallites gives rise to a unique optical birefringence of the alternating gyroid domains, which allows imaging of the self-assembled grain structure by optical microscopy alone. This study provides insight into polymer crystallization within a tortuous three-dimensional network and establishes a useful method for the optical visualization of cubic BCP morphologies that serve as functional nanomaterial templates.

We report chemical vapor deposition and cryogenic photoluminescence studies of narrow-diameter single-wall carbon nanotubes. Our systematic study of synthesis parameters identifies means to control the average length, diameter, and areal density of carbon nanotubes grown on silica substrates. Using synthesis conditions that favor the growth of carbon nanotubes with sub-nanometer diameters, we fabricate samples with spatially isolated suspended nanotubes ideally suited for optical studies. Photoluminescence spectroscopy of individual nanotubes reveals two classes: spectrally broad and narrow single-peak emission at the temperature of liquid helium. The latter class with spectral line widths down to the resolution limit of our spectrometer of 40 meV indicates that exciton coherence in carbon nanotubes can be substantially improved by controlling the growth conditions and utilized in sources of indistinguishable single photons. (C) 2016 The Author(s). Published by Elsevier Ltd.

Gold gyroid optical metamaterials are known to possess a reduced plasma frequency and linear dichroism imparted by their intricate subwavelength single gyroid morphology. The anisotropic optical properties are, however, only evident when a large individual gyroid domain is investigated. Multidomain gyroid metamaterials, fabricated using a polyisoprene-b-polystyrene-b-poly(ethylene oxide) triblock terpolymer and consisting of multiple small gyroid domains with random orientation and handedness, instead exhibit isotropic optical properties. Comparing three effective medium models, we here show that the specular reflectance spectra of such multidomain gyroid optical metamaterials can be accurately modeled over a broad range of incident angles by a Bruggeman effective medium consisting of a random wire array. This model accurately reproduces previously published results tracking the variation in normal incidence reflectance spectra of gold gyroid optical metamaterials as a function of host refractive index and volume fill fraction of gold. The effective permittivity derived from this theory confirms the change in sign of the real part of the permittivity in the visible spectral region (so, that gold gyroid metamaterials exhibit both dielectric and metallic behavior at optical wavelengths). That a Bruggeman effective medium can accurately model the experimental reflectance spectra implies that small multidomain gold gyroid optical metamaterials behave both qualitatively and quantitatively as an amorphous composite of gold and air (i.e., nanoporous gold) and that coherent electromagnetic contributions arising from the subwavelength gyroid symmetry are not dominant.

The self assembly of block‐copolymers into the gyroid morphology is replicated into 3D nanostructured conjugated polymers. Voided styrenic gyroidal networks are used as scaffolds for the electrodeposition of two poly(3,4‐ethylenedioxythiophene) derivatives and poly(pyrrole). The careful choice of solvents and electrolytes allows the excellent replication of the initial self‐assembled morphology into self‐supporting gyroidal conjugated polymer networks. The nanostructured films are employed to fabricate electrochromic devices, exhibiting excellent color contrast upon switching, with fast switching speeds. The versatility and reliability of this method are demonstrated by the creation of switchable Fresnel zone plates, with which the focussing of light can be switched on and off.

Carbon nanotubes exhibit a wealth of unique physical properties. By virtue of their exceptionally low mass and extreme stiffness they provide ultrahigh-quality mechanical resonances, promise long electron spin coherence times in a nuclear-spin free lattice for quantum information processing and spintronics, and feature unprecedented tunability of optical transitions for optoelectronic applications. Excitons in semiconducting single-walled carbon nanotubes could facilitate the upconversion of spin, mechanical or hybrid spin-mechanical degrees of freedom to optical frequencies for efficient manipulation and detection. However, successful implementation of such schemes with carbon nanotubes has been impeded by rapid exciton decoherence at non-radiative quenching sites, environmental dephasing and emission intermittence. Here we demonstrate that these limitations may be overcome by exciton localization in suspended carbon nanotubes. For excitons localized in nanotube quantum dots we found narrow optical lines free of spectral wandering, radiative exciton lifetimes and effectively suppressed blinking. Our findings identify the great potential of localized excitons for efficient and spectrally precise interfacing of photons, phonons and spins in novel carbon nanotube-based quantum devices.