Molecular Chirality Detection with Periodic Arrays of Three-Dimensional Twisted Metamaterials.

Rapid detection of the handiness of chiral molecules is an important topic for pharmaceutical industries because chiral drugs with opposing handiness sometimes exhibit unwanted side effects. In this research, a rapid optical method is proposed to determine the handiness of the chiral drug "Thalidomide". The platform is a large array of three-dimensional (3D) twisted metamaterials fabricated with a novel method by combining nanospherical-lens lithography (NLL) and hole-mask lithography (HML). The fabrication is high-throughput and the twisted metamaterials cover a large area. Strong circular dichroism (CD) response is observed in the near-infrared (NIR) region, which enables the chiral detection to be performed by a low-cost and portable spectroscope system. The proposed nanofabrication method significantly improves the capabilities of NLL and HML, which can be quickly adapted to fabricate various periodic 3D metamaterials. In addition, the results of this research pave the road for the rapid penetration of nanophotonics into the pharmaceutical industries.

Polarization-Selecting III-Nitride Elliptical Nanorod Light-Emitting Diodes Fabricated with Nanospherical-Lens Lithography.

Current-injected elliptical nanorod light-emitting diodes (LEDs) are demonstrated to emit polarized light with a bottom-emitting configuration. The polarization ratio of the electroluminescence reaches 3.17 when the length of the minor axis for the elliptical nanorods is as small as 150 nm. Electromagnetic simulation confirms the occurrence of the polarization selectivity especially when the length of the minor axis is down to 150 nm. Light with different polarization travels at different speeds in these asymmetric elliptical nanorods. Only one polarization experiences destructive interference between the light directly from the source and the reflected light by the top metal interface. A thin light-blocking layer is incorporated to increase the polarization selectivity. It is also not recommended to infill the gap with SiO2 since the polarization selectivity will be reduced. The proposed nanorod LEDs are fabricated using top-down nanofabrication approaches by combining nanospherical-lens lithography and two-step etch processes, which are both fully compatible with current semiconductor manufacturing processes. Results in this study will help to develop a chip-level polarization-selecting LED, which will be very useful for applications that require polarized light. It is especially beneficial for applications that are not suitable for using an external polarizer or require polarized light at the individual chip level.

Large-Scale Nanofabrication of Designed Nanostructures Using Angled Nanospherical-Lens Lithography for Surface Enhanced Infrared Absorption Spectroscopy.

Nanophotonics has been a focused research discipline for the past decade and has resulted in many novel concepts that promise to change human life. However, the actual penetration of this research into real products is severely limited mostly due to the slow development of economic nanofabrication. In this study, we have demonstrated a versatile and low-cost nanofabrication method referred to as "angled nanospherical-lens lithography (A-NLL)", which is able to produce large-scale and periodic nanopatterns. The nanopatterns designed within a two-dimensional polar chart can be carefully fabricated on the substrate. The fabricated patterns easily cover an area larger than 1 cm2, which is beneficial as platforms for surface enhanced infrared absorption (SEIRA) where an expensive and bulky IR microscope is not required. We believe that the proposed A-NLL method is ideal for industrialization of future nanophotonic applications.

Avoided resonance crossing and non-reciprocal nearly perfect absorption in plasmonic nanodisks with near-field and far-field couplings.

Avoided resonance crossings (ARC) in plasmonic nanodisk structures due to near field or far field couplings were numerically demonstrated. Near field coupling in disk dimmer with both vertical or side-by-side arrangement leads to both energy and linewidth anti-crossing by varying one disk size across the other. Far field coupling in double layered disk arrays of extremely small gap size or gap size with Fabry Perot resonant condition close to the frequency selective surface (FSS) stopband center leads to non-reciprocal absorption spectrum as one disk size varying across the other. We observe linewidth anti-crossing but energy crossing of the absorption peak from different side illumination by varying either the size of one disk array or the gap in hetero disk arrays. The disappearing of Fabry-Perot resonant mode from one side illumination and the appearing of nonreciprocal nearly perfect absorption from the other side illumination are well explained by a FSS-Fabry-Perot model.

A nanoscale study of charge extraction in organic solar cells: the impact of interfacial molecular configurations.

In the optimization of organic solar cells (OSCs), a key problem lies in the maximization of charge carriers from the active layer to the electrodes. Hence, this study focused on the interfacial molecular configurations in efficient OSC charge extraction by theoretical investigations and experiments, including small molecule-based bilayer-heterojunction (sm-BLHJ) and polymer-based bulk-heterojunction (p-BHJ) OSCs. We first examined a well-defined sm-BLHJ model system of OSC composed of p-type pentacene, an n-type perylene derivative, and a nanogroove-structured poly(3,4-ethylenedioxythiophene) (NS-PEDOT) hole extraction layer. The OSC with NS-PEDOT shows a 230% increment in the short circuit current density compared with that of the conventional planar PEDOT layer. Our theoretical calculations indicated that small variations in the microscopic intermolecular interaction among these interfacial configurations could induce significant differences in charge extraction efficiency. Experimentally, different interfacial configurations were generated between the photo-active layer and the nanostructured charge extraction layer with periodic nanogroove structures. In addition to pentacene, poly(3-hexylthiophene), the most commonly used electron-donor material system in p-BHJ OSCs was also explored in terms of its possible use as a photo-active layer. Local conductive atomic force microscopy was used to measure the nanoscale charge extraction efficiency at different locations within the nanogroove, thus highlighting the importance of interfacial molecular configurations in efficient charge extraction. This study enriches understanding regarding the optimization of the photovoltaic properties of several types of OSCs by conducting appropriate interfacial engineering based on organic/polymer molecular orientations. The ultimate power conversion efficiency beyond at least 15% is highly expected when the best state-of-the-art p-BHJ OSCs are combined with present arguments.

Au nanorod design as light-absorber in the first and second biological near-infrared windows for in vivo photothermal therapy.

Photothermal cancer therapy using near-infrared (NIR) laser radiation is an emerging treatment. In the NIR region, two biological transparency windows are located in 650-950 nm (first NIR window) and 1000-1350 nm (second NIR window) with optimal tissue transmission obtained from low scattering and energy absorption, thus providing maximum radiation penetration through tissue and minimizing autofluorescence. To date, intensive effort has resulted in the generation of various methods that can be used to shift the absorbance of nanomaterials to the 650-950 nm NIR regions for studying photoinduced therapy. However, NIR light absorbers smaller than 100 nm in the second NIR region have been scant. We report that a Au nanorod (NR) can be designed with a rod-in-shell (rattle-like) structure smaller than 100 nm that is tailored to be responsive to the first and second NIR windows, in which we can perform hyperthermia-based therapy. In vitro performance clearly displays high efficacy in the NIR photothermal destruction of cancer cells, showing large cell-damaged area beyond the laser-irradiated area. This marked phenomenon has made the rod-in-shell structure a promising hyperthermia agent for the in vivo photothermal ablation of solid tumors when activated using a continuous-wave 808 m (first NIR window) or a 1064 nm (second NIR window) diode laser. We tailored the UV-vis-NIR spectrum of the rod-in-shell structure by changing the gap distance between the Au NR core and the AuAg nanoshell, to evaluate the therapeutic effect of using a 1064 nm diode laser. Regarding the first NIR window with the use of an 808 nm diode laser, rod-in-shell particles exhibit a more effective anticancer efficacy in the laser ablation of solid tumors compared to Au NRs.

Observation of absorption-dominated bonding dark plasmon mode from metal-insulator-metal nanodisk arrays fabricated by nanospherical-lens lithography.

Plasmon hybridization modes are observed in the extinction spectra of a metal-insulator-metal (MIM) nanodisk array fabricated using nanospherical-lens lithography. Two distinct hybridization modes are observed in this vertically aligned configuration. Theoretical simulation indicates that the bonding mode located at a lower energy level exhibits an antiphase charge distribution and corresponds to the dark plasmon mode. This is vastly different compared to antibonding dark plasmon mode observed in the conventional dimer configuration. The observed mode is tunable over a wide spectral range simply by varying the insulator thickness and the diameters of the MIM nanodisks. Absorption is the dominating extinction process for the dark plasmon, while scattering dominates the bright plasmon mode. The ability to experimentally measure and tune dark plasmon modes using a MIM configuration should catalyze more novel studies that take full advantages of the absorption-dominated dark plasmon mode.

Influence of surface plasmon resonance on the emission intermittency of photoluminescence from gold nano-sea-urchins.

The effect of surface plasmon resonance (SPR) on the blinking emission of photoluminescence from noble metal nanostructures still requires further investigation in quantum mechanics and limits their applications. We investigate one photon luminescent emission intermittency of noble metal nanostructures with differently sized sea-urchin-shaped nanoparticles, known as nano-sea-urchins (NSUs). The probability of the "on" process in one photon luminescent emission intermittency of NSUs increases due to the strong electric field of SPR. This mechanism is explained by the reaction potential threshold model we propose here. Furthermore, the ameliorated photoluminescence of NSUs is strong enough to excite waterweed bioluminescence and can act as an in vivo bio-light emitting device, which has potential applications in cytotoxicity, bio-imaging and bio-labeling.

Surface plasmon-enhanced and quenched two-photon excited fluorescence.

This study investigated theoretically and experimentally that two-photon excited fluorescence is enhanced and quenched via surface plasmons (SPs) excited by total internal reflection with a silver film. The fluorescence intensity is fundamentally affected by the local electromagnetic field enhancement and the quantum yield change according to the surrounding structure and materials. By utilizing the Fresnel equation and classical dipole radiation modeling, local electric field enhancement, fluorescence quantum yield, and fluorescence emission coupling yield via SPs were theoretically analyzed at different dielectric spacer thicknesses between the fluorescence dye and the metal film. The fluorescence lifetime was also decreased substantially via the quenching effect. A two-photon excited total internal reflection fluorescence (TIRF) microscopy with a time-correlated single photon counting device has been developed to measure the fluorescence lifetimes, photostabilities, and enhancements. The experimental results demonstrate that the fluorescence lifetimes and the trend of the enhancements are consistent with the theoretical analysis. The maximum fluorescence enhancement factor in the surface plasmon-total internal reflection fluorescence (SP-TIRF) configuration can be increased up to 30 fold with a suitable thickness SiO(2) spacer. Also, to compromise for the fluorescence enhancement and the fluorophore photostability, we find that the SP-TIRF configuration with a 10 nm SiO(2) spacer can provide an enhanced and less photobleached fluorescent signal via the assistance of enhanced local electromagnetic field and quenched fluorescence lifetime, respectively.

Gap structure effects on surface-enhanced Raman scattering intensities for gold gapped rods.

Gapped rods provide a unique platform for elucidating structure/function relationships, both for single-molecule electrochemical techniques and for surface-enhanced Raman scattering (SERS). This paper attempts to elucidate the dependence of SERS intensities on gap topography and gap distance for gold gapped rods with segment lengths varying over a wide range (40-2000 nm). Significantly, we have determined that rough gaps lead to a smaller SERS enhancement than smooth gaps for these structures even though the rough gaps have a larger total surface area. Both theory and experiment show periodic variation of SERS intensity with segment length as determined by odd-symmetry plasmon multipoles. Excitation of even-symmetry modes is dipole forbidden (for polarization along the rod axis), but this selection rule can be relaxed by roughness or, for smooth gaps, by near-field coupling between the rod segments.

Ellipsometric studies of optical properties of local surface plasmon resonance for Au nanoparticles on the substrate.

Few ellipsometric studies have been conducted on Au self-assembled monolayers (SAM), with large discrepancies obtained for refractive index values. Because the Au NPs layer is a kind of composite layer, Au NPs and void, the effective media approximate (EMA) model was employed to investigate the optical properties of Au NPs. The reflective coefficient (approximately 1.2) was smaller than the extinction coefficient (approximately 2.5), which is different from the previous reports and corresponds to the Drude model. The absorption peak of surface plasmon resonance for Au NPs on the glass substrate was shifted from 580 nm to 480 nm.

Surfactants-aided syntheses of different sizes and triangular shape of gold nanoparticles using trisodium citrate in environmentally friendly and photoinduced methods.

We prepared gold nanoparticles (Au NPs) by only using trisodium citrate as the stabilizer. The detailed reaction mechanisms of S(N)1 and E1 reactions are examined and evidenced in this study by FTIR data. Citric acid is a kind of tertiary substrate. In aqueous solution, the substitution nucleophile path 1 (S(N)1) reaction and Elimination path 1 (E1) reaction usually occur simultaneously. Chloride ions, the substitution nucleophile, play a very important role to launch the mechanisms of S(N)1 and E1 reactions. Controlling the concentration of the chloride ions with the addition of HCl(aq) according to Le Chatelier theory, the average particle size of Au NPs (5.5 nm) was achieved to overcome the minimum limited size (approximately 10 nm). Two stages of the photoinduced method, aggregation into triangular conglomerates and growth into triangular particles, were determined form TEM observations. This preparation of Au NPs has potential in tuning the size, shape, and mechanism of Au NP formation by using only environmentally friendly trisodium citrate and the photoinduced method.

Ellipsometric advances for local surface plasmon resonance to determine chitosan adsorption on layer-by-layer gold nanoparticles.

The ellipsometric measurement of local surface plasmon resonance (LSPR) caused by the adsorption of chitosan on layer-by-layer gold nanoparticles (Au NPs) was investigated. Six nanometer (6 nm) Au NPs were prepared and layer-by-layer Au NPs were fabricated to shift the LSPR to 520, 540, and 560 nm, respectively, due to the Mie theory. The thicknesses and the fractions of the layer-by-layer Au NPs were measured accurately using a combination of the Fresnel equation and the Maxwell-Garnett equations for ellipsometry. Furthermore, the position of the LSPR was shifted by chitosan. Using trajectory to record the trace of polarized light for ellipsometry resulting from LSPR, it was found that LSPR is predominantly induced when the LSPR position is close to the wavelength of the ellipsometric measurement. The trajectory circle of LSPR is very large for an increase of chitosan adsorption on Au NPs when the LSPR position is close to the detected wavelength. The linear approximation aspect quantifying the trajectory corresponds with the change of LSPR for the adsorption of chitosan, except for cases with low incidence and Brewster angles. The aspects and technologies of ellipsometry will benefit from the findings in this study, with potential applications in the fields of determination of molecular adsorption.

Heterodyne apertureless near-field scanning optical microscopy on periodic gold nanowells.

Heterodyne detection for apertureless near-field scanning optical microscopy was used to study periodic gold nanowell arrays. Optical near-field amplitude and phase signals were obtained simultaneously with the topography of the gold nanowells and with different polarizations. Theoretical calculations of the near-fields were consistent with the experiments; in particular, the calculated amplitudes were in especially good agreement. The heterodyne method is shown to be particularly effective for these types of periodic photonic structures and other highly scattering media, which can overwhelm the near-field scattered signal when conventional apertureless near-field scanning optical microscopy is used.

Surface plasmon standing waves in large-area subwavelength hole arrays.

A flexible and parallel procedure to generate large-area, free-standing films of subwavelength hole arrays has been demonstrated. This method is materials-general, and multilayered films of different materials were constructed. The optical quality of these films was tested using a near-field scanning optical microscope, which revealed the formation of surface plasmon standing wave patterns that were consistent with numerical simulations. Because the properties of the holes and the film materials can be easily tailored, new types of plasmonic and photonic devices can be envisioned and tested.

Localized surface plasmon resonance spectroscopy of single silver nanocubes.

In this work, we use dark-field microscopy to observe a new plasmon resonance effect for a single silver nanocube in which the plasmon line shape has two distinct peaks when the particles are located on a glass substrate. The dependence of the resonance on nanocube size and shape is characterized, and it is found that the bluer peak has a higher figure of merit for chemical sensing applications than that for other particle shapes that have been studied previously. Comparison of the measured results with finite difference time domain (FDTD) electrodynamics calculations enables us to confirm the accuracy of our spectral assignments.

Near-field photochemical imaging of noble metal nanostructures.

The sub-diffraction imaging of the optical near-field in nanostructures, based on a photochemical technique, is reported. A photosensitive azobenzene-dye polymer is spin coated onto lithographic structures and is subsequently irradiated with laser light. Photoinduced mass transport creates topographic modifications at the polymer film surface that are then measured with atomic force microscopy (AFM). The AFM images correlate with rigorous theoretical calculations of the near-field intensities for a range of different nanostructures and illumination polarizations. This approach is a first step toward additional methods for resolving confined optical near fields, which can augment scanning probe methodologies for high spatial resolution of optical near fields.

Surface plasmon generation and light transmission by isolated nanoholes and arrays of nanoholes in thin metal films.

Extensive 3-D finite-difference time-domain simulations are carried out to elucidate the nature of surface plasmon polaritons (SPPs) and localized surface plasmon polaritons (LSPs) generated by nanoscale holes in thin metallic films interacting with light. Both isolated nanoholes and square arrays of nanoholes in gold films are considered. For isolated nanoholes, we expand on an earlier discussion of Yin et al. [Appl. Phys. Lett. 85, 467-469 (2004)] on the origins of fringe patterns in the film and the role of nearfield scanning optical microscope probe interactions. The associated light transmission of a single nanohole is enhanced when a LSP excitation of the nanohole itself is excited. Periodic arrays of nanoholes exhibit more complex behavior, with light transmission peaks exhibiting distinct minima and maxima that can be very well described with Fano lineshape models. This behavior is correlated with the coupling of SPP Bloch waves and more directly transmitted waves through the holes.

Numerical study of light correlations in a random medium close to the Anderson localization threshold.

We applied a finite-difference time domain algorithm to the study of field and intensity correlations in random media. Close to the onset of Anderson localization, we observe deviations of the correlation functions, in both shape and magnitude, from those predicted by the diffusion theory. Physical implications of the observed phenomena are discussed.

Finite-difference time-domain model of lasing action in a four-level two-electron atomic system.

We report a new finite-difference time-domain (FDTD) computational model of the lasing dynamics of a four-level two-electron atomic system. Transitions between the energy levels are governed by coupled rate equations and the Pauli Exclusion Principle. This approach is an advance relative to earlier FDTD models that did not include the pumping dynamics, or the Pauli Exclusion Principle. Further, the method proposed in this paper is more versatile than the conventional modal expansion of the electromagnetic field for complex inhomogeneous laser geometries constructed in photonic crystals or light-localizing random media. For such complex geometries, the lasing modes are either difficult or impossible to calculate. The present work aims at the self-consistent treatment of the dynamics of the 4-level atomic system and the instantaneous ambient optical electromagnetic field. This permits in principle a much more robust treatment of the overall lasing dynamics of four-level gain systems integrated into virtually arbitrary electromagnetic field confinement geometries.