Geometric modulation of induced plasmonic circular dichroism in nanoparticle assemblies based on backaction and field enhancement.

Chiral cysteine-directed assemblies of Au@Ag core-shell nanocrystals (CSNCs) and Au/Ag nanorods with end-to-end (ETE) and side-by-side (SBS) configurations are fabricated and used to explore the definitive factors affecting the chiral response. The interaction between cysteine and metallic nanoparticles leads to intense and widely tunable plasmonic circular dichroism (PCD) ranging from a near-infrared (NIR) to ultraviolet (UV) regime. More importantly, it was observed that, in Ag nanorod and CSNC samples with varied aspect ratios, the ETE assembled patterns exhibit much larger PCD enhancement than SBS assemblies in an l/d-cysteine solvent environment. Very surprisingly, such a giant PCD response in these assemblies is completely different from that of the Au nanorod assembly case as reported earlier. Experimental and theoretical studies reveal that the interplay between the local field enhancement and backaction, triggered by the geometric configuration differentia of covered achiral CTAB molecules on Ag and Au surfaces, plays a crucial role in chiral response variances and leads to geometry-dependent optical activities. This work not only sheds light on understanding the relationship between the configuration of plasmonic nanostructure assemblies and geometry-manipulated circular dichroism, but also paves the way for predictive design of plasmonic biosensors or other nanodevices with controllable optical activities from the UV to the NIR light range.

Ultrafast Light-Controlled Growth of Silver Nanoparticles for Direct Plasmonic Color Printing.

A precision photoreduction technology for the ultrafast high-precision light-controlled growth of silver nanoparticles for printing plasmonic color images is presented. Ultraviolet (UV) patterns with about a million pixels are generated to temporally and spatially regulate the photoreduction of silver salts to precisely create around a million clusters of distinct silver nanoparticles on a titanium dioxide (TiO2)-capped quartz substrate. The silver nanoparticle-TiO2-quartz structure exhibits a Fano-like reflection spectrum, whose spectral dip can be tuned by the dimension of the silver nanoparticles for plasmonic color generation. This technology allows the one-step production of multiscale engineered large-area plasmonic substrates without the use of either nanostructured templates or additional nanofabrication processes and thus offers an approach to plasmonic engineering for a myriad of applications ranging from structural color decoration to plasmonic microdevices and biosensors.

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.

Influence of Plasmonic Effect on the Upconversion Emission Characteristics of NaYF4 Hexagonal Microrods.

The influence of plasmonic effect on the upconversion emission characteristics of Yb3+-Er3+-Tm3+ tridoped ß-NaYF4 hexagonal microrods is studied. Upconversion spontaneous emission can be improved by 10 times if the microrod is deposited on an Ag-coated substrate. The enhancement is also dependent on the emission wavelength and the polarization of the excitation source. Furthermore, upconversion lasing is supported by the geometry of the microrods via the formation of whispering gallery modes. The corresponding excitation threshold can also be reduced by 50% through the influence of plasmonic effect, the coupling between the whispering gallery modes and the surface plasmonic resonance modes.

Quantitative Determination of Contribution by Enhanced Local Electric Field, Antenna-Amplified Light Scattering, and Surface Energy Transfer to the Performance of Plasmonic Organic Solar Cells.

Plasmonic metal nanostructures are widely used as subwavelength light concentrators to enhance light harvesting of organic solar cells through two photophysical effects, including enhanced local electric field (ELEF) and antenna-amplified light scattering (AALS), while their adverse quenching effect from surface energy transfer (SET) should be suppressed. In this work, a comprehensive study to unambiguously distinguish and quantitatively determine the specific influence and contribution of each effect on the overall performance of organic solar cells incorporated with Ag@SiO2 core-shell nanoparticles (NPs) is presented. By investigating the photon conversion efficiency (PCE) as a function of the SiO2 shell thickness, a strong competition between the ELEF and SET effects in the performance of the devices with the NPs embedded in the active layers is found, leading to a maximum PCE enhancement of 12.4% at the shell thickness of 5 nm. The results give new insights into the fundamental understanding of the photophysical mechanisms responsible for the performance enhancement of plasmonic organic solar cells and provide important guidelines for designing more-efficient plasmonic solar cells in general.

Electron Transport Across Plasmonic Molecular Nanogaps Interrogated with Surface-Enhanced Raman Scattering.

Charge transport plays an important role in defining both far-field and near-field optical response of a plasmonic nanostructure with an ultrasmall built-in nanogap. As the gap size of a gold core-shell nanomatryoshka approaches the sub-nanometer length scale, charge transport may occur and strongly alter the near-field enhancement within the molecule-filled nanogap. In this work, we utilize ultrasensitive surface-enhanced Raman spectroscopy (SERS) to investigate the plasmonic near-field variation induced by the molecular junction conductance-assisted electron transport in gold nanomatryoshkas, termed gap-enhanced Raman tags (GERTs). The GERTs, with interior gaps from 0.7 to 2 nm, are prepared with a wet chemistry method. Our experimental and theoretical studies suggest that the electron transport through the molecular junction influences both far-field and near-field optical properties of the GERTs. In the far-field extinction response, the low-energy gap mode predicted by a classical electromagnetic model (CEM) is strongly quenched and hence unobservable in the experiment, which can be well explained by a quantum-corrected model (QCM). In the near-field SERS response, the optimal gap size for maximum Raman enhancement at the excitation wavelength of 785 nm (633 nm) is about 1.35 nm (1.8 nm). Similarly, these near-field results do not tally with the CEM calculations but agree well with the QCM results where the molecular junction conductance in the nanogap is fully considered. Our study may improve understanding of charge-transport phenomena in ultrasmall plasmonic molecular nanogaps and promote the further development of molecular electronics-based plasmonic nanodevices.

Illusion Thermotics.

"Fata Morgana" or "Mirage" phenomena have long been captivated as optical illusions, which actually relies on gradient-density air or vapor. Man-made optical illusions have witnessed significant progress by resorting to artificially structured metamaterials. Nevertheless, two long-standing challenges remain formidable: first, exotic parameters (negative or less than unity) become inevitable; second, the signature of original object is altered to that of a virtual counterpart. It is thus not able to address the holy grail of illusion per se, since a single virtual object still exposes the location. In this study, those problems are successfully addressed in a particular setup-illusion thermotics, which identically mimics the exterior thermal behavior of an equivalent reference and splits the interior original heat source into many virtual signatures. A general paradigm to design thermal illusion metadevices is proposed to manipulate thermal conduction, and empower robust simultaneous functions of moving, shaping, rotating, and splitting heat sources of arbitrary cross sections. The temperature profile inside the thermal metadevice can mislead the awareness of the real location, shape, size, and number of the actual heat sources. The present concept may trigger unprecedented development in other physical fields to realize multiple functionalized illusions in optics, electromagnetics, etc.

Covalent functionalization of MoS2 nanosheets synthesized by liquid phase exfoliation to construct electrochemical sensors for Cd (II) detection.

Surface functionalization is an effective strategy in the precise control of electronic surface states of two-dimensional materials for promoting their applications. In this study, based on the strong coordination interaction between the transition-metal centers and N atoms, the surface functionalization of few-layer MoS2 nanosheets was successfully prepared by liquid phase exfoliation method in N, N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone, and formamide. The cytotoxicity of surface-functionalized MoS2 nanosheets was for the first time evaluated by the methylthiazolyldiphenyl-tetrazoliumbromide assays. An electrochemical sensor was constructed based on glass carbon electrode (GCE) modified by MoS2 nanosheets obtained in DMF, which exhibits relatively higher sensitivity to Cd2+ detection and lower cytotoxicity against MCF-7 cells. The mechanisms of surface functionalization and selectively detecting Cd2+ were investigated by density functional theory calculations together with various spectroscopic measurements. It was found that surface-functionalized MoS2 nanosheets could be generated through Mo-N covalent bonds due to the orbital hybridization between the 5 s orbitals of Mo atoms and the 2p orbitals of N atoms of the solvent molecules. The high selectivity of the sensor is attributed to the coordination reaction between Cd2+ and O donor atoms of DMF adsorbed on MoS2 nanosheets. The robust anti-interference is ascribed to the strong binding energy of Cd2+ and O atoms of DMF. Under the optimum conditions, the electrochemical sensor exhibits highly sensitive and selective assaying of Cd2+ with a measured detection limit of 0.2 nM and a linear range from 2 nM to 20 µM.

Metal-Substrate-Mediated Plasmon Hybridization in a Nanoparticle Dimer for Photoluminescence Line-Width Shrinking and Intensity Enhancement.

Metal-film-coupled nanoparticles with subnanometer particle-film gaps possess an ultrasmall mode volume, responsible for a variety of intriguing phenomena in plasmonic nanophotonics. Due to the large radiative loss associated with dipolar coupling, however, the plasmonic-film-coupled nanocavities usually feature a low-quality factor, setting an ultimate limit of the increased light-matter interaction strength. Here, we demonstrate a plasmonic nanocavity composed of a metal-film-coupled nanoparticle dimer, exhibiting a significantly improved quality factor. Compared to a silica-supported dimer, the spectral line width of the nanocavity plasmon resonance is reduced by a factor of ∼4.6 and is even smaller than its monomer counterpart (∼30% reduction). Comprehensive theoretical analyses reveal that this pronounced resonance narrowing effect can be attributed to intense film-mediated plasmon hybridization between the bonding dipolar and quadrupolar gap modes in the dimer. More importantly, the invoking of the dark quadrupole resonance leads to a giant photoluminescence intensity enhancement (∼200 times) and dramatic emission line-width narrowing (∼4.6 times), compared to the silica-supported dimer. The similar spectral characteristics of the measured plasmonic scattering and photoluminescence emission indicate that the radiative decay of the coupled plasmons in the nanocavity is the origin of the observed photoluminescence, consistent with a proposed phenomenological model. Numerical calculations show that the intensity enhancement is mainly contributed by the dimer-film gap rather than the interparticle gap. These findings not only shed more light on the hybridized interaction between plasmon modes but also deepen the understanding of photoluminescence emission in coupled plasmonic nanostructures.

Plasmonic enhancement and polarization dependence of nonlinear upconversion emissions from single gold nanorod@SiO2@CaF2:Yb3+,Er3+ hybrid core-shell-satellite nanostructures.

Lanthanide-doped upconversion nanocrystals (UCNCs) have recently become an attractive nonlinear fluorescence material for use in bioimaging because of their tunable spectral characteristics and exceptional photostability. Plasmonic materials are often introduced into the vicinity of UCNCs to increase their emission intensity by means of enlarging the absorption cross-section and accelerating the radiative decay rate. Moreover, plasmonic nanostructures (e.g., gold nanorods, GNRs) can also influence the polarization state of the UC fluorescence-an effect that is of fundamental importance for fluorescence polarization-based imaging methods yet has not been discussed previously. To study this effect, we synthesized GNR@SiO2@CaF2:Yb3+,Er3+ hybrid core-shell-satellite nanostructures with precise control over the thickness of the SiO2 shell. We evaluated the shell thickness-dependent plasmonic enhancement of the emission intensity in ensemble and studied the plasmonic modulation of the emission polarization at the single-particle level. The hybrid plasmonic UC nanostructures with an optimal shell thickness exhibit an improved bioimaging performance compared with bare UCNCs, and we observed a polarized nature of the light at both UC emission bands, which stems from the relationship between the excitation polarization and GNR orientation. We used electrodynamic simulations combined with Förster resonance energy transfer theory to fully explain the observed effect. Our results provide extensive insights into how the coherent interaction between the emission dipoles of UCNCs and the plasmonic dipoles of the GNR determines the emission polarization state in various situations and thus open the way to the accurate control of the UC emission anisotropy for a wide range of bioimaging and biosensing applications.

Interband Absorption Enhanced Optical Activity in Discrete Au@Ag Core-Shell Nanocuboids: Probing Extended Helical Conformation of Chemisorbed Cysteine Molecules.

Detailed understanding of the interaction between a chiral molecule and a noble metal surface is essential to rationalize and advance interfacial self-assembly of amino acids and metal-mediated anchoring of proteins. Here we demonstrate that individual Au@Ag core-shell nanocuboids can serve as a plasmonic reporter of an extended helical network formed among chemisorbed cysteine molecules, through generating an interband absorption enhanced, Ag-surface-exclusive circular dichroism (CD) band in the UV region. The observed unusual, strong CD response in the hybrid Au@Ag-cysteine system can be used to probe in real time conformational evolution and structural rearrangement of biomolecules in general and also monitor the interfacial interaction between a metal surface and an adsorbed molecule, opening up the possibility of using Ag nanostructures as promising stereochemically attuned nanosensors.

Pronounced Fano Resonance in Single Gold Split Nanodisks with 15 nm Split Gaps for Intensive Second Harmonic Generation.

Single metallic nanostructures supporting strong Fano resonances allow more compact nanophotonics integration and easier geometrical control in practical applications such as enhanced spectroscopy and sensing. In this work, we designed a class of plasmonic split nanodisks that show pronounced Fano resonance comparable to that observed in widely studied plasmonic oligomer clusters. Using our recently developed "sketch and peel" electron-beam lithography, split nanodisks with varied diameter and split length were fabricated over a large area with high uniformity. Transmission spectroscopy measurements demonstrated that the fabricated structures with 15 nm split gap exhibit disk diameter and split length controlled Fano resonances in the near-infrared region, showing excellent agreement with simulation results. Together with the plasmon hybridization theory, in-depth full-wave analyses elucidated that the Fano resonances observed in the split nanodisks were induced by mode interference between the bright antibonding dipole mode of split disks and the subradiant mode supported by the narrow split gap. With the giant near-field enhancement enabled by the intensive Fano resonance at the tiny split gap, strong wavelength-dependent second harmonic generation was observed under near-infrared excitation. Our work demonstrated that single split nanodisks could serve as important building blocks for plasmonic and nanophotonic applications including sensing and nonlinear optics.

Grating-coupled Otto configuration for hybridized surface phonon polariton excitation for local refractive index sensitivity enhancement.

We demonstrate numerically through rigorous coupled wave analysis (RCWA) that replacing the prism in the Otto configuration with gratings enables us to excite and control different modes and field patterns of surface phonon polaritons (SPhPs) through the incident wavelength and height of the Otto spacing layer. This modified Otto configuration provides us the following multiple modes, namely, SPhP mode, Fabry-Pérot (FP) cavity resonance, dielectric waveguide grating resonance (DWGR) and hybridized between different combinations of the above mentioned modes. We show that this modified grating-coupled Otto configuration has a highly confined field pattern within the structure, making it more sensitive to local refractive index changes on the SiC surface. The hybridized surface phonon polariton modes also provide a stronger field enhancement compared to conventional pure mode excitation.

Enhanced Photoelectrical Response of Hydrogenated Amorphous Silicon Single-Nanowire Solar Cells by Front-Opening Crescent Design.

We report an approach for substantially enhancing the light-trapping and photoconversion efficiency of hydrogenated amorphous silicon (a-Si:H) single-nanowire solar cells (SNSCs) by engineering the cross section of the nanowire from circular into a front-opening crescent shape. The proposed SNSCs show a broadband and highly tunable optical absorption compared to the conventional circular counterparts under both transverse electric and transverse magnetic incidences, enabling an enhancement ratio of over 40 % in both the photocurrent density and the photoconversion efficiency in a-Si:H SNSCs with a diameter of 200 nm. We further show that the superior performance can be well maintained under a wide range of incident angle and is robust to the blunt crescent edges.

Hybrid plasmonic gap modes in metal film-coupled dimers and their physical origins revealed by polarization resolved dark field spectroscopy.

Plasmonic gap modes sustained by metal film-coupled nanostructures have recently attracted extensive research attention due to flexible control over their spectral response and significantly enhanced field intensities at the particle-film junction. In this work, by adopting an improved dark field spectroscopy methodology - polarization resolved spectral decomposition and colour decoding - we are able to "visualize" and distinguish unambiguously the spectral and far field radiation properties of the complex plasmonic gap modes in metal film-coupled nanosphere monomers and dimers. Together with full-wave numerical simulation results, it is found that while the monomer-film system supports two hybridized dipole-like plasmon modes having different oscillating orientations and resonance strengths, the scattering spectrum of the dimer-film system features two additional peaks, one strong yet narrow resonant mode corresponding to a bonding dipolar moment and one hybridized higher order resonant mode, both polarized along the dimer axis. In particular, we demonstrate that the polarization dependent scattering radiation of the film-coupled nanosphere dimer can be used to optically distinguish from monomers and concurrently determine the spatial orientation of the dimer with significantly improved accuracy at the single-particle level, illustrating a simple yet highly sensitive plasmon resonance based nanometrology method.

Polarization-Independent Multiple Fano Resonances in Plasmonic Nonamers for Multimode-Matching Enhanced Multiband Second-Harmonic Generation.

Plasmonic oligomers composed of metallic nanoparticles are one class of the most promising platforms for generating Fano resonances with unprecedented optical properties for enhancing various linear and nonlinear optical processes. For efficient generation of second-harmonic emissions at multiple wavelength bands, it is critical to design a plasmonic oligomer concurrently having multiple Fano resonances spectrally matching the fundamental excitation wavelengths and multiple plasmon resonance modes coinciding with the harmonic wavelengths. Thus far, the realization of such a plasmonic oligomer remains a challenge. This study demonstrates both theoretically and experimentally that a plasmonic nonamer consisting of a gold nanocross surrounded by eight nanorods simultaneously sustains multiple polarization-independent Fano resonances in the near-infrared region and several higher-order plasmon resonances in the visible spectrum. Due to coherent amplification of the nonlinear excitation sources by the Fano resonances and efficient scattering-enhanced outcoupling by the higher-order modes, the second-harmonic emission of the nonamer is significantly increased at multiple spectral bands, and their spectral positions and radiation patterns can be flexibly manipulated by easily tuning the length of the surrounding nanorods in the nonamer. These results provide us with important implications for realizing ultrafast multichannel nonlinear optoelectronic devices.

Vertically-Aligned Single-Crystal Nanocone Arrays: Controlled Fabrication and Enhanced Field Emission.

Metal nanostructures with conical shape, vertical alignment, large ratio of cone height and curvature radius at the apex, controlled cone angle, and single-crystal structure are ideal candidates for enhancing field electron-emission efficiency with additional merits, such as good mechanical and thermal stability. However, fabrication of such nanostructures possessing all these features is challenging. Here, we report on the controlled fabrication of large scale, vertically aligned, and mechanically self-supported single-crystal Cu nanocones with controlled cone angle and enhanced field emission. The Cu nanocones were fabricated by ion-track templates in combination with electrochemical deposition. Their cone angle is controlled in the range from 0.3° to 6.2° by asymmetrically selective etching of the ion tracks and the minimum tip curvature diameter reaches down to 6 nm. The field emission measurements show that the turn-on electric field of the Cu nanocone field emitters can be as low as 1.9 V/µm at current density of 10 µA/cm(2) (a record low value for Cu nanostructures, to the best of our knowledge). The maximum field enhancement factor we measured was as large as 6068, indicating that the Cu nanocones are promising candidates for field emission applications.

Surface Plasmon Polariton Cross-Coupling Enhanced Forward Emission from Insulator-Metal-Capped ZnO Films.

Increasing light extraction efficiency in the forward direction is being extensively pursued due to its crucial role in realizing top-emitting organic and inorganic light emitting devices. Various surface plasmon polariton (SPP)-based strategies for emission enhancement and light extraction have been developed to improve the top-emitting efficiency of these devices. However, the role of surface roughness of both semiconductor film and metal electrode in improving the emission efficiency of a practical device has not been thoroughly studied yet. In this work, the influence of surface roughness of a top metal electrode on the photoluminescence enhancement of a ZnO thin film is investigated experimentally and numerically based on an insulator-metal-semiconductor system. It is found that the generic surface roughness of the metal electrode plays an encouraging role in increasing the forward-emission intensity by facilitating cross-coupling of SPPs on the two opposite sides of the metal layer. More importantly, the forward emission can be further enhanced by capping a high-index polymer layer on the metal electrode to bridge the momentum mismatch between the two SPPs modes. The experimental observations are well explained by the SPPs cross-coupling mechanism that models the radiation power of a dipolar emitter underneath the metal electrode as a function of the metal surface roughness. Our work opens up the possibility of using cross-coupling of SPPs as an effective means to fabricate high-brightness top-emitting devices without the need of complicated nanoscale patterning.