Mechanical metamaterials.

Mechanical metamaterials, also known as architected materials, are rationally designed composites, aiming at elastic behaviors and effective mechanical properties beyond ('meta') those of their individual ingredients-qualitatively and/or quantitatively. Due to advances in computational science and manufacturing, this field has progressed considerably throughout the last decade. Here, we review its mathematical basis in the spirit of a tutorial, and summarize the conceptual as well as experimental state-of-the-art. This summary comprises disordered, periodic, quasi-periodic, and graded anisotropic functional architectures, in one, two, and three dimensions, covering length scales ranging from below one micrometer to tens of meters. Examples include extreme ordinary linear elastic behavior from artificial crystals, e.g. auxetics and pentamodes, 'negative' effective properties, behavior beyond classical linear elasticity, e.g. arising from local resonances, chirality, beyond-nearest-neighbor interactions, quasi-crystalline mechanical metamaterials, topological band gaps, cloaking based on coordinate transformations and on scattering cancelation, seismic protection, nonlinear and programmable metamaterials, as well as space-time-periodic architectures.

Activating Electroluminescence of Charged Naphthalene Diimide Complexes Directly Adsorbed on a Metal Substrate.

Electroluminescence from single molecules adsorbed on a conducting surface imposes conflicting demands for the molecule-electrode coupling. To conduct electrons, the molecular orbitals need to be hybridized with the electrodes. To emit light, they need to be decoupled from the electrodes to prevent fluorescence quenching. Here, we show that fully quenched 2,6-core-substituted naphthalene diimide derivative in a self-assembled monolayer directly deposited on a Au(111) surface can be activated with the tip of a scanning tunneling microscope to decouple the relevant frontier orbitals from the metallic substrate. In this way, individual molecules can be driven from a strongly hybridized state with quenched luminescence to a light-emitting state. The emission performance compares in terms of quantum efficiency, stability, and reproducibility to that of single molecules deposited on thin insulating layers. Quantum chemical calculations suggest that the emitted light originates from the singly charged cationic pair of the molecules.

Action Plots in Action: In-Depth Insights into Photochemical Reactivity.

Predicting wavelength-dependent photochemical reactivity is challenging. Herein, we revive the well-established tool of measuring action spectra and adapt the technique to map wavelength-resolved covalent bond formation and cleavage in what we term "photochemical action plots". Underpinned by tunable lasers, which allow excitation of molecules with near-perfect wavelength precision, the photoinduced reactivity of several reaction classes have been mapped in detail. These include photoinduced cycloadditions and bond formation based on photochemically generated o-quinodimethanes and 1,3-dipoles such as nitrile imines as well as radical photoinitiator cleavage. Organized by reaction class, these data demonstrate that UV/vis spectra fail to act as a predictor for photochemical reactivity at a given wavelength in most of the examined reactions, with the photochemical reactivity being strongly red shifted in comparison to the absorption spectrum. We provide an encompassing perspective of the power of photochemical action plots for bond-forming reactions and their emerging applications in the design of wavelength-selective photoresists and photoresponsive soft-matter materials.

Boosting Light Emission from Single Hydrogen Phthalocyanine Molecules by Charging.

Interest in electroluminescence of single molecules is stimulated by the prospect of possible applications in novel light emitting devices. Recent studies provide valuable insights into the mechanisms leading to single molecule electroluminescence. Concrete information on how to boost the intensity of the emitted light, however, is rare. By combining scanning tunnelling microscopy (STM) and quantum chemical calculations, we show that the light emission efficiencies of an individual hydrogen-phthalocyanine molecule can be increased by a factor of ≈19 upon charging. This boost in intensity can be explained by the development of a vertical dipole moment normal to the substrate facilitating out-coupling of the local excitation to the far field. As this effect is not related to the specific nature of hydrogen-phthalocyanine, it opens up a general way to increase light emission from molecular junctions.

Isotropic Chiral Acoustic Phonons in 3D Quasicrystalline Metamaterials.

The elastic properties of three-dimensional (3D) crystalline mechanical metamaterials, unlike those of amorphous structures, are generally strongly anisotropic-even in the long-wavelength limit and for highly symmetric crystals. Aiming at isotropic linear elastic wave propagation, we therefore study 3D periodic approximants of 3D icosahedral quasicrystalline mechanical metamaterials consisting of uniaxial chiral metarods. Considering the increasing order of the approximants, we approach nearly isotropic effective speeds of sound and isotropic acoustical activity. The latter is directly connected to circularly polarized 3D metamaterial chiral acoustic phonons-for all propagation directions in three dimensions.

Helicity-Preserving Optical Cavity Modes for Enhanced Sensing of Chiral Molecules.

Researchers routinely sense molecules by their infrared vibrational "fingerprint" absorption resonances. In addition, the dominant handedness of chiral molecules can be detected by circular dichroism (CD), the normalized difference between their optical response to incident left- and right- handed circularly polarized light. Here, we introduce a cavity composed of two parallel arrays of helicity-preserving silicon disks that allows one to enhance the CD signal by more than 2 orders of magnitude for a given molecule concentration and given thickness of the cell containing the molecules. The underlying principle is first-order diffraction into helicity-preserving modes with large transverse momentum and long lifetimes. In sharp contrast, in a conventional Fabry-Perot cavity, each reflection flips the handedness of light, leading to large intensity enhancements inside the cavity, yet to smaller CD signals than without the cavity.

It's in the Fine Print: Erasable Three-Dimensional Laser-Printed Micro- and Nanostructures.

3D printing, on all scales, is currently a vibrant topic in scientific and industrial research as it has enormous potential to radically change manufacturing. Owing to the inherent nature of the manufacturing process, 3D printed structures may require additional material to structurally support complex features. Such support material must be removed after printing-sometimes termed subtractive manufacturing-without adversely affecting the remaining structure. An elegant solution is the use of photoresists containing labile bonds that allow for controlled cleavage with specific triggers. Herein, we explore state-of-the-art cleavable photoresists for 3D direct laser writing, as well as their potential to combine additive and subtractive manufacturing in a hybrid technology. We discuss photoresist design, feature resolution, cleavage properties, and current limitations of selected examples. Furthermore, we share our perspective on possible labile bonds, and their corresponding cleavage trigger, which we believe will have a critical impact on future applications and expand the toolbox of available cleavable photoresists.

On the limits of laminates in diffusive optics.

Laminate metamaterials lead to anisotropic material properties, which can be tailored by the contrast between the two ingredient materials within the laminate. Such tailored anisotropies are, for example, required to realize advanced invisibility cloaks, wormhole architectures, or analogues of negative refraction. The physics and mathematics of laminates is very well established in the context of the diffusion equation and mathematical equivalents thereof, such as the heat conduction equation, the electrical conduction equation, electrostatics, magnetostatics, and laminar fluid dynamics. However, the validity of the diffusion equation is often stressed for disordered optical media, because sufficiently large transmission of light is requested. As a result, the condition that all relevant transport mean free path lengths need to be small compared to all relevant geometrical dimensions, may not be fulfilled. Monte Carlo simulations can grasp the physics of this transition regime between diffusive and ballistic optics. Here, we present corresponding numerical simulations for laminates. On this basis, we discuss the resulting fundamental limitations and trade-offs for laminates.

Polarizing beam splitter integrated onto an optical fiber facet.

When light either leaves or enters an optical fiber, one often needs free-space optical components to manipulate the state of polarization or the light's phase profile. It is therefore desirable to integrate such components onto a fiber end facet. In this paper, we realize, for the first time, a polarizing beam splitter fabricated directly onto the end facet of a single-mode optical fiber. The element is composed of a refractive prism, intentionally slightly displaced from the core of the fiber, and an elevated and suspended sub-wavelength diffraction grating, the lamellae of which have an aspect ratio of about 5. This integrated micro-optical component is characterized experimentally at 1550 nm wavelength. We find that the two emerging output beams exhibit a degree of polarization of 81 percent and 82 percent for Transverse Magnetic (TM) and Transverse Electric (TE) polarization, respectively.

Cloaking of metal grid electrodes on Lambertian emitters by free-form refractive surfaces.

We discuss invisibility cloaking of metal grid electrodes on Lambertian light emitters by using dielectric free-form surfaces. We show that cloaking can be ideal in geometrical optics for all viewing directions if reflections at the dielectric-air interface are negligible. We also present corresponding white-light proof-of-principle experiments that demonstrate close-to-ideal cloaking for a wide range of viewing angles. Remaining imperfections are analyzed by ray-tracing calculations. The concept can potentially be used to enhance the luminance homogeneity of large-area organic light-emitting diodes.

Mechanical cloak design by direct lattice transformation.

Spatial coordinate transformations have helped simplifying mathematical issues and solving complex boundary-value problems in physics for decades already. More recently, material-parameter transformations have also become an intuitive and powerful engineering tool for designing inhomogeneous and anisotropic material distributions that perform wanted functions, e.g., invisibility cloaking. A necessary mathematical prerequisite for this approach to work is that the underlying equations are form invariant with respect to general coordinate transformations. Unfortunately, this condition is not fulfilled in elastic-solid mechanics for materials that can be described by ordinary elasticity tensors. Here, we introduce a different and simpler approach. We directly transform the lattice points of a 2D discrete lattice composed of a single constituent material, while keeping the properties of the elements connecting the lattice points the same. After showing that the approach works in various areas, we focus on elastic-solid mechanics. As a demanding example, we cloak a void in an effective elastic material with respect to static uniaxial compression. Corresponding numerical calculations and experiments on polymer structures made by 3D printing are presented. The cloaking quality is quantified by comparing the average relative SD of the strain vectors outside of the cloaked void with respect to the homogeneous reference lattice. Theory and experiment agree and exhibit very good cloaking performance.

Simultaneous wavelength and orbital angular momentum demultiplexing using tunable MEMS-based Fabry-Perot filter.

In this paper, we experimentally demonstrate simultaneous wavelength and orbital angular momentum (OAM) multiplexing/demultiplexing of 10 Gbit/s data streams using a new on-chip micro-component-tunable MEMS-based Fabry-Perot filter integrated with a spiral phase plate. In the experiment, two wavelengths, each of them carrying two channels with zero and nonzero OAMs, form four independent information channels. In case of spacing between wavelength channels of 0.8 nm and intensity modulation, power penalties relative to the transmission of one channel do not exceed 1.45, 0.79 and 0.46 dB at the hard-decision forward-error correction (HD-FEC) bit-error-rate (BER) limit 3.8 × 10-3 when multiplexing a Gaussian beam and OAM beams of azimuthal orders 1, 2 and 3 respectively. In case of phase modulation, power penalties do not exceed 1.77, 0.54 and 0.79 dB respectively. At the 0.4 nm wavelength grid, maximum power penalties at the HD-FEC BER threshold relative to the 0.8 nm wavelength spacing read 0.83, 0.84 and 1.15 dB when multiplexing a Gaussian beam and OAM beams of 1st, 2nd and 3rd orders respectively. The novelty and impact of the proposed filter design is in providing practical, integrable, cheap, and reliable transformation of OAM states simultaneously with the selection of a particular wavelength in wavelength division multiplexing (WDM). The proposed on-chip device can be useful in future high-capacity optical communications with spatial- and wavelength-division multiplexing, especially for short-range communication links and optical interconnects.

Uncloaking diffusive-light invisibility cloaks by speckle analysis.

Within the range of validity of the stationary diffusion equation, an ideal diffusive-light invisibility cloak can make an arbitrary macroscopic object hidden inside of the cloak indistinguishable from the surroundings for all colors, polarizations, and directions of incident visible light. However, the diffusion equation for light is an approximation which becomes exact only in the limit of small coherence length. Thus, one expects that the cloak can be revealed by illumination with coherent light. The experiments presented here show that the cloaks are robust in the limit of large coherence length but can be revealed by analysis of the speckle patterns under illumination with partially coherent light. Experiments on cylindrical core-shell cloaks and corresponding theory are in good agreement.

Experimental Evidence for Sign Reversal of the Hall Coefficient in Three-Dimensional Metamaterials.

Effectively inverting the sign of material parameters is a striking possibility arising from the concept of metamaterials. Here, we show that the electrical properties of a p-type semiconductor can be mimicked by a metamaterial solely made of an n-type semiconductor. By fabricating and characterizing three-dimensional simple-cubic microlattices composed of interlocked hollow semiconducting tori, we demonstrate that sign and magnitude of the effective metamaterial Hall coefficient can be adjusted via a tori separation parameter-in agreement with previous theoretical and numerical predictions.

Photo-Induced Click Chemistry for DNA Surface Structuring by Direct Laser Writing.

Oligonucleotides containing photo-caged dienes were prepared and shown to react quantitatively in a light-induced Diels-Alder cycloaddition with functional maleimides in aqueous solution within minutes. Due to its high yield and fast rate, the reaction was exploited for DNA surface patterning with sub-micrometer resolution employing direct laser writing (DLW). Functional DNA arrays were written by direct laser writing (DLW) in variable patterns, which were further encoded with fluorophores and proteins through DNA directed immobilization. This mild and efficient light-driven platform technology holds promise for the fabrication of complex bioarrays with sub-micron resolution.

Cleaving Direct-Laser-Written Microstructures on Demand.

Using an advanced functional photoresist we introduce direct-laser-written (DLW) 3D microstructures capable of complete degradation on demand. The networks consist exclusively of reversible bonds, formed by irradiation of a phenacyl sulfide linker, giving disulfide bonds in a radical-free step-growth polymerization via a reactive thioaldehyde. The bond formation was verified in solution by ESI-MS. To induce cleavage, dithiothreitol causes a thiol-disulfide exchange, erasing the written structure. The mild cleavage of the disulfide network is highly orthogonal to other, for example, acrylate-based DLW structures. To emphasize this aspect, DLW structures were prepared incorporating reversible structural elements into a non-reversible acrylate-based standard scaffold, confirming subsequent selective cleavage. The high lateral resolution achievable was verified by the preparation of well-defined line gratings with line separations of down to 300 nm.

3D Laser Micro- and Nanoprinting: Challenges for Chemistry.

3D printing is a powerful emerging technology for the tailored fabrication of advanced functional materials. This Review summarizes the state-of-the art with regard to 3D laser micro- and nanoprinting and explores the chemical challenges limiting its full exploitation: from the development of advanced functional materials for applications in cell biology and electronics to the chemical barriers that need to be overcome to enable fast writing velocities with resolution below the diffraction limit. We further explore chemical means to enable direct laser writing of multiple materials in one resist by highly wavelength selective (λ-orthogonal) photochemical processes. Finally, chemical processes to construct adaptive 3D written structures that are able to respond to external stimuli, such as light, heat, pH value, or specific molecules, are highlighted, and advanced concepts for degradable scaffolds are explored.

Enhancement of second-harmonic generation in nonlinear nanolaminate metamaterials by nanophotonic resonances.

Nanolaminate metamaterials recently attracted a lot of attention as a novel second-order nonlinear material that can be used in integrated photonic circuits. Here, we explore theoretically and numerically the opportunity to enhance the nonlinear response from such nanolaminates by exploiting Fano resonances supported in grating-coupled waveguides. The enhancement factor of the radiated second harmonic signal compared to a flat nanolaminate can reach values as large as 35 for gold gratings and even 7000 for MgF2 gratings. For the MgF2 grating, extremely high-Q Fano resonances are excited in such all-dielectric system that result in strong local fields in the nonlinear waveguide layer to boost the nonlinear conversion. A significant portion of the nonlinear signal is also strongly coupled to a dark waveguide mode, which remains guided in the nanolaminate. The strong excitation of a dark mode at the second harmonic frequency provides a viable method for utilizing second-order nonlinearities for light generation and manipulation in integrated photonic circuits.

Wavelength-selective orbital-angular-momentum beam generation using MEMS tunable Fabry-Perot filter.

We demonstrate an on-chip device capable of wavelength-selective generation of vortex beams, which is realized by a spiral phase plate integrated onto a microelectromechanical system (MEMS) tunable filter. This vortex MEMS filter, being capable of functioning simultaneously in both wavelength and orbital-angular-momentum (OAM) domains at the 1550 nm wavelength regime, is considered as a compact, robust, and cost-effective solution for simultaneous OAM- and wavelength-division multiplexed optical communications. The experimental OAM spectra for azimuthal orders 1, 2, and 3 show an OAM state purity >92% across a wavelength range of more than 30 nm.

Simultaneous Dual Encoding of Three-Dimensional Structures by Light-Induced Modular Ligation.

A highly efficient strategy for the simultaneous dual surface encoding of 2D and 3D microscaffolds is reported. The combination of an oligo(ethylene glycol)-based network with two novel and readily synthesized monomers with photoreactive side chains yields two new photoresists, which can be used for the fabrication of microstructures (by two-photon polymerization) that exhibit a dual-photoreactive surface. By combining both functional photoresists into one scaffold, a dual functionalization pattern can be obtained by a single irradiation step in the presence of adequate reaction partners based on a self-sorting mechanism. The versatility of the approach is shown by the dual patterning of halogenated and fluorescent markers as well as proteins. Furthermore, we introduce a new ToF-SIMS mode ("delayed extraction") for the characterization of the obtained microstructures that combines high mass resolution with improved lateral resolution.