Absorption and scattering in perfect thermal radiation absorber-emitter metasurfaces.

Detailed spectral analysis of radiation absorption and scattering behaviors of metasurfaces was carried out via finite-difference time-domain (FDTD) photonic simulations. It revealed that, for typical metal-insulator-metal (MIM) nanodisc metasurfaces, absorbance and scattering cross-sections exhibit a ratio of σabs/σsca = 1 at the absorption peak spectral position. This relationship was likewise found to limit the attainable photo-thermal conversion efficiency in experimental and application contexts. By increasing the absorption due to optical materials, such as Cr metal nano-films typically used as an adhesion layer, it is possible to control the total absorption efficiency η = σabs/σsca and to make it the dominant extinction mechanism. This guided the design of MIM metasurfaces tailored for near-perfect-absorption and emission of thermal radiation. We present the fabrication as well as the numerical and experimental spectral characterisation of such optical surfaces.

Synthetic dimension band structures on a Si CMOS photonic platform.

Synthetic dimensions, which simulate spatial coordinates using nonspatial degrees of freedom, are drawing interest in topological science and other fields for modeling higher-dimensional phenomena on simple structures. We present the first realization of a synthetic frequency dimension on a silicon ring resonator integrated photonic device fabricated using a CMOS process. We confirm that its coupled modes correspond to a one-dimensional tight-binding model through acquisition of up to 280-GHz bandwidth optical frequency comb-like spectra and by measuring synthetic band structures. Furthermore, we realized two types of gauge potentials along the frequency dimension and probed their effects through the associated band structures. An electric field analog was produced via modulation detuning, whereas effective magnetic fields were induced using synchronized nearest- and second nearest-neighbor couplings. Creation of coupled mode lattices and two effective forces on a monolithic Si CMOS device represents a key step toward wider adoption of topological principles.

Kirchhoff's Thermal Radiation from Lithography-Free Black Metals.

Lithography-free black metals composed of a nano-layered stack of materials are attractive not only due to their optical properties but also by virtue of fabrication simplicity and the cost reduction of devices based on such structures. We demonstrate multi-layer black metal layered structures with engineered electromagnetic absorption in the mid-infrared (MIR) wavelength range. Characterization of thin SiO2 and Si films sandwiched between two Au layers by way of experimental electromagnetic radiation absorption and thermal radiation emission measurements as well as finite difference time domain (FDTD) numerical simulations is presented. Comparison of experimental and simulation data derived optical properties of multi-layer black metals provide guidelines for absorber/emitter structure design and potential applications. In addition, relatively simple lithography-free multi-layer structures are shown to exhibit absorber/emitter performance that is on par with what is reported in the literature for considerably more elaborate nano/micro-scale patterned metasurfaces.

Improvement and stabilization of optical hydrogen sensing ability of Au-Pd alloys.

Formation of metal hydrides is a signature chemical property of hydrogen and it can be leveraged to enact both storage and detection of this technologically important yet extremely volatile gas. Palladium shows particular promise as a hydrogen storage medium as well as a platform for creating rapid and reliable H2 optical sensor devices. Furthermore, alloying Pd with other noble metals provides a technologically simple yet powerful way of enacting control over the structural and catalytic properties of the resultant material. Similarly, in addition to alloying, different top-down and bottom-up Pd nanostructuring methods have been proposed and investigated specifically for creating optical H2 sensors. In this work it was determined that the hydrogen sensing ability of a series of Pd-Au alloy films could be improved by way of a hydrogen over exposure (HOE) treatment. Structural investigation showed that the HOE treatment, in addition to irreversibly altering the film morphology, results in a 1 to 2% expansion in the lattice constant of the metal. By combining a cyclic HOE treatment and alloy aging through annealing, the hydrogen detection sensitivity and response rates of Pd-Au films could be stabilized so that their performance would no longer be appreciably affected by repeated hydrogen uptake and release cycles. This work takes a further step towards routine all-optical detection of part-per-million level hydrogen gas concentrations in Pd-Au alloy films and discussion of ways to enhance response rates is provided.

Metamaterial for Hydrogen Sensing.

A hydrogen sensor based on plasmonic metasurfaces is demonstrated to exhibit the industry-required 10 s reaction time and sensitivity. It consists of a layer of either Y or WO3 sandwiched between a top Pd nanodisk and a Au mirror at the base. The phase change layer (Y, WO3) reacts with hydrogen, and the corresponding change of the refractive index (permittivity) is detected by the spectral shift of the resonance dip in reflectance at the IR spectral window. This direct reflectance readout of the permittivity change due to hydrogen uptake is fast and is facilitated by radiation field enhancement extending into the phase change volume. Numerical modeling was used to elucidate the effects that real and imaginary parts of the refractive index exert on the spectral shifts of resonance. The mechanism of sensor performance is outlined, and a possibility to tune its spectral range of operation by the diameter of the Pd nanodisk and thickness of the phase change material makes this design applicable to other molecular detection applications including surface-enhanced IR absorption.

Nanoscale optical and structural characterisation of silk.

The nanoscale composition of silk defining its unique properties via a hierarchial structural anisotropy needs to be analysed at the highest spatial resolution of tens of nanometers corresponding to the size of fibrils made of ß-sheets, which are the crystalline building blocks of silk. Nanoscale optical and structural properties of silk have been measured from 100 nm thick longitudinal slices of silk fibers with ca. 10 nm resolution, the highest so far. Optical sub-wavelength resolution in hyperspectral mapping of absorbance and molecular orientation were carried out for comparison at IR wavelengths of 2-10 µm using synchrotron radiation. A reliable distinction of transmission changes by only 1-2% as the anisotropy of amide bands was obtained from nanometer-thin slices of silk.

Kirchhoff's metasurfaces towards efficient photo-thermal energy conversion.

Thermo-optical properties of the nanodisc and metal hole array plasmonic perfect absorber (PPA) metasurfaces were designed and characterized at mid-infrared wavelengths. Both, radiation emitter and detector systems operating in various spectral domains are highly sought after for a diverse range of applications, one example being future sensor networks employed in the internet-of-things. Reciprocity of the absorbance and emittance is shown experimentally, i.e., the PPAs are demonstrated to follow Kirchhoff's law where the patterns exhibiting a strong optical absorption were found to be effective thermal emitters. Hence, the Kirchhoff's law is experimentally validated for the metasurfaces in the IR spectral domain where there is a lack of solutions for spectrally narrow-band emitters. The highest efficiency of radiation-to-heat and heat-to-radiation conversion was obtained for Au-Si-Au composite structures.

Infrared Polariscopy Imaging of Linear Polymeric Patterns with a Focal Plane Array.

Polariscopy is demonstrated using hyperspectral imaging with a focal plane array (FPA) detector in the infrared (IR) spectral region under illumination by thermal and synchrotron light sources. FPA Fourier-transform IR (FTIR) imaging microspectroscopy is useful for monitoring real time changes at specific absorption bands when combined with a high brightness synchrotron source. In this study, several types of samples with unique structural motifs were selected and used for assessing the capability of polariscopy under this FPA-FTIR imaging technique. It was shown that the time required for polariscopy at IR wavelengths can be substantially reduced by the FPA-FTIR imaging approach. By using natural and laser fabricated polymers with sub-wavelength features, alignment of absorbing molecular dipoles and higher order patterns (laser fabricated structures) were revealed. Spectral polariscopy at the absorption peaks can reveal the orientation of sub-wavelength patterns (even when they are not spatially resolved) or the orientation of the absorbing dipoles.

First Principles Calculations Toward Understanding SERS of 2,2'-Bipyridyl Adsorbed on Au, Ag, and Au-Ag Nanoalloy.

First principles electrodyanmics and quantum chemical simulations are performed to gain insights into the underlying mechanisms of the surface enhanced Raman spectra of 22BPY adsorbed on pure Au and Ag as well as on Au-Ag alloy nanodiscs. Experimental SERS spectra from Au and Ag nanodiscs show similar peaks, whereas those from Au-Ag alloy reveal new spectral features. The physical enhancement factors due to surface nano-texture were considered by numerical FDTD simulations of light intensity distribution for the nano-textured Au, Ag, and Au-Ag alloy and compared with experimental results. For the chemical insights of the enhancement, the DFT calculations with the dispersion interaction were performed using Au20 , Ag20 , and Au10 Ag10 clusters of a pyramidal structure for SERS modeling. Binding of 22BPY to the clusters was simulated by considering possible arrangements of vertex and planar physical as well as chemical adsorption models. The DFT results indicate that 22BPY prefers a coplanar adsorption on a (111) face with trans-conformation having close energy difference to cis-conformation. Binding to pure Au cluster is stronger than to pure Ag or Au-Ag alloy clusters and adsorption onto the alloy surface can deform the surface. The computed Raman spectra are compared with experimental data and assignments for pure Au and Ag models are well matching, indicating the need of dispersion interaction to reproduce strong Raman signal at around 800 cm-1 . This work provides insight into 3D character of SERS on nanorough surfaces due to different binding energies and bond length of nanoalloys. © 2018 Wiley Periodicals, Inc.

Noble metal-modified faceted anatase titania photocatalysts: Octahedron versus decahedron.

Octahedral anatase particles (OAP, with eight equivalent {101} facets) and decahedral anatase particles (DAP, with two additional {001} facets) were modified with nanoparticles of noble metals (Au, Ag, Cu). The titania morphology, expressed by the presence of different arrangements of exposed crystal facets, played a key role in the photocatalytic properties of metal-modified faceted titania. In the UV/vis systems, two-faceted configuration of DAP was more favorable for the reaction efficiency than single-faceted OAP because of an efficient charge separation described by the transfer of electrons to {101} facets and holes to {001} facets. Time-resolved microwave conductivity (TRMC) and reversed double-beam photoacoustic spectroscopy (RDB-PAS) confirmed that distribution of electron traps (ET) and mobility of electrons were key-factors of photocatalytic activity. In contrast, metal-modified OAP samples had higher photocatalytic activity than metal-modified DAP and metal-modified commercial titania samples under visible light irradiation. This indicates that the presence of single type of facets ({101}) is favorable for efficient electron transfer via shallow ET, whereas intrinsic properties of DAP result in fast charge carriers' recombination when gold is deposited on {101} facets (migration of "hot" electrons: Au→{101}→Au).

Subtle Variations in Surface Properties of Black Silicon Surfaces Influence the Degree of Bactericidal Efficiency.

One of the major challenges faced by the biomedical industry is the development of robust synthetic surfaces that can resist bacterial colonization. Much inspiration has been drawn recently from naturally occurring mechano-bactericidal surfaces such as the wings of cicada (Psaltoda claripennis) and dragonfly (Diplacodes bipunctata) species in fabricating their synthetic analogs. However, the bactericidal activity of nanostructured surfaces is observed in a particular range of parameters reflecting the geometry of nanostructures and surface wettability. Here, several of the nanometer-scale characteristics of black silicon (bSi) surfaces including the density and height of the nanopillars that have the potential to influence the bactericidal efficiency of these nanostructured surfaces have been investigated. The results provide important evidence that minor variations in the nanoarchitecture of substrata can substantially alter their performance as bactericidal surfaces.

Enhancement of X-ray emission from nanocolloidal gold suspensions under double-pulse excitation.

Enhancement of X-ray emission was observed from a micro-jet of a nano-colloidal gold suspension in air under double-pulse excitation of ultrashort (40 fs) near-IR laser pulses. Temporal and spatial overlaps between the pre-pulse and the main pulse were optimized for the highest X-ray emission. The maximum X-ray intensity was obtained at a 1-7 ns delay of the main pulse irradiation after the pre-pulse irradiation with the micro-jet position shifted along the laser beam propagation. It was revealed that the volume around gold nanoparticles where the permittivity is near zero, ε ≈ 0, accounts for the strongest absorption, which leads to the effective enhancements of X-ray emission.

Micro-thermocouple on nano-membrane: thermometer for nanoscale measurements.

A thermocouple of Au-Ni with only 2.5-µm-wide electrodes on a 30-nm-thick Si3N4 membrane was fabricated by a simple low-resolution electron beam lithography and lift off procedure. The thermocouple is shown to be sensitive to heat generated by laser as well as an electron beam. Nano-thin membrane was used to reach a high spatial resolution of energy deposition and to realise a heat source of sub-1 µm diameter. This was achieved due to a limited generation of secondary electrons, which increase a lateral energy deposition. A low thermal capacitance of the fabricated devices is useful for the real time monitoring of small and fast temperature changes, e.g., due to convection, and can be detected through an optical and mechanical barrier of the nano-thin membrane. Temperature changes up to ~2 × 105 K/s can be measured at 10 kHz rate. A simultaneous down-sizing of both, the heat detector and heat source strongly required for creation of thermal microscopy is demonstrated. Peculiarities of Seebeck constant (thermopower) dependence on electron injection into thermocouple are discussed. Modeling of thermal flows on a nano-membrane with presence of a micro-thermocouple was carried out to compare with experimentally measured temporal response.

Role of topological scale in the differential fouling of Pseudomonas aeruginosa and Staphylococcus aureus bacterial cells on wrinkled gold-coated polystyrene surfaces.

Wrinkled patterns, which possess an extensive surface area over a limited planar space, can provide surface features ranging across the nano- and microscale that have become an engineering material with the flexibility to be tuneable for a number of technologies. Here, we investigate the surface parameters that influence the attachment response of two model bacteria (P. aeruginosa and S. aureus) to wrinkled gold-coated polystyrene surfaces having topologies at the nano- and microscale. Together with flat gold films as the controls, surface feature heights spanned 2 orders of magnitude (15 nm, 200 nm, and 1 micron). The surface wrinkle topology was shown through confocal laser scanning microscopic, atomic force microscopic and scanning electron microscopic image analyses to consist of air-water interfacial areas unavailable for bacterial attachment, which were also shown to be stable by time-lapsed contact angle measurements. Imposition of the nanoscale wrinkles reduced P. aeruginosa attachment to 57% and S. aureus attachment to 20% of their flat equivalent surfaces whereas wrinkles at the microscale further reduced these attachments to 7.5% and 14.5%, respectively. The density of attachments indicated an inherent species specific selectivity that changed with feature dimension, attributable to the scale of the air-water interfaces in contact with the bacterial cell. Parameters influencing static bacterial attachment were the total projected surface areas minus the air-water interface areas and the scale of these respective air-water interfaces (area distribution) with respect to the cell morphology. The range of these controlling parameters may provide new design principles for the evolving suite of physical anti-biofouling materials not reliant on biocidal agents under development.

Author Correction: Orientational Mapping Augmented Sub-Wavelength Hyper-Spectral Imaging of Silk.

A correction to this article has been published and is linked from the HTML version of this paper. The error has been fixed in the paper.

Photoacoustic signal enhancements from gold nano-colloidal suspensions excited by a pair of time-delayed femtosecond pulses.

Photoacoustic signal enhancements were observed with a pair of time-delayed femtosecond pulses upon excitation of gold nanosphere colloidal suspension. A systematic experimental investigation of photoacoustic intensity within the delay time, Δt = 0 to 15 ns, was carried out. The results revealed a significant enhancement factor of ∼2 when the pre-pulse energy is 20-30% of the total energy. Pre-pulse and main pulse energy ratios, Ep(1):Es(2), were varied to determine the optimal ratio that yields to maximum photoacoustic signal enhancement. This enhancement was ascribed to the initial stage of thermalization and bubble generation in the nanosecond time scale. Pre-pulse scattering intensity measurements and numerical finite-difference time-domain calculations were performed to reveal dynamics and light field enchancement, respectively.

Optical readout of hydrogen storage in films of Au and Pd.

For hydrogen sensor and storage applications, films of Au and Pd were (i) co-sputtered at different rates or (ii) deposited in a sequentially alternating fashion to create a layered structure on a cover glass. Peculiarities of hydrogen uptake and release were optically monitored using 1.3 µm wavelength light. Increase of optical transmission was observed for hydrogenated Pd-rich films of 10-30 nm thickness. Up to a three times slower hydrogen release took place as compared with the hydrogen uptake. Compositional ratio of Au:Pd and thermal treatment of films provided control over the optical extinction changes and hydrogen uptake/release time constants. Higher uptake and release rates were observed in the annealed Au:Pd films as compared to those deposited at room temperature and were faster for the Auricher films. Three main parameters relevant for sensors: sensitivity, selectivity, stability (reproducibility) are discussed together with the hydrogenation mechanism in Au:Pd alloys.

Dynamic position shifts of X-ray emission from a water film induced by a pair of time-delayed femtosecond laser pulses.

Femtosecond double-pulsed laser excitation of a water film in air showed enhancements of X-ray intensity as compared with single pulse irradiation. The position of the highest yield of X-rays strongly depends on temporal separation between the pre-pulse and the main-pulse (energy ratios where ∼ 1 : 10). The strongest X-ray emission was observed at 10-15 ns delay of the main-pulse. Nanoscale roughening of water surface can account for the observation.

Optical tweezing and binding at high irradiation powers on black-Si.

Nowadays, optical tweezers have undergone explosive developments in accordance with a great progress of lasers. In the last decade, a breakthrough brought optical tweezers into the nano-world, overcoming the diffraction limit. This is called plasmonic optical tweezers (POT). POT are powerful tools used to manipulate nanomaterials. However, POT has several practical issues that need to be overcome. First, it is rather difficult to fabricate plasmonic nanogap structures regularly and rapidly at low cost. Second, in many cases, POT suffers from thermal effects (Marangoni convection and thermophoresis). Here, we propose an alternative approach using a nano-structured material that can enhance the optical force and be applied to optical tweezers. This material is metal-free black silicon (MFBS), the plasma etched nano-textured Si. We demonstrate that MFBS-based optical tweezers can efficiently manipulate small particles by trapping and binding. The advantages of MFBS-based optical tweezers are: (1) simple fabrication with high uniformity over wafer-sized areas, (2) free from thermal effects detrimental for trapping, (3) switchable trapping between one and two - dimensions, (4) tight trapping because of no detrimental thermal forces. This is the NON-PLASMONIC optical tweezers.

Orientational Mapping Augmented Sub-Wavelength Hyper-Spectral Imaging of Silk.

Molecular alignment underpins optical, mechanical, and thermal properties of materials, however, its direct measurement from volumes with micrometer dimensions is not accessible, especially, for structurally complex bio-materials. How the molecular alignment is linked to extraordinary properties of silk and its amorphous-crystalline composition has to be accessed by a direct measurement from a single silk fiber. Here, we show orientation mapping of the internal silk fiber structure via polarisation-dependent IR absorbance at high spatial resolution of 4.2 µm and 1.9 µm in a hyper-spectral IR imaging by attenuated total reflection using synchrotron radiation in the spectral fingerprint region around 6 µm wavelength. Free-standing longitudinal micro-slices of silk fibers, thinner than the fiber cross section, were prepared by microtome for the four polarization method to directly measure the orientational sensitivity of absorbance in the molecular fingerprint spectral window of the amide bands of ß-sheet polypeptides of silk. Microtomed lateral slices of silk fibers, which may avoid possible artefacts that affect spectroscopic measurements with fibers of an elliptical cross sections were used in the study. Amorphisation of silk by ultra-short laser single-pulse exposure is demonstrated.