Tunable plasmonic lattices of silver nanocrystals

Silver nanocrystals are ideal building blocks for plasmonic materials that exhibit a wide range of unique and potentially useful optical phenomena. Individual nanocrystals display distinct optical scattering spectra and can be assembled into hierarchical structures that couple strongly to external electromagnetic fields. This coupling, which is mediated by surface plasmons, depends on the shape and arrangement of the nanocrystals. Here we demonstrate the bottom-up assembly of polyhedral silver nanocrystals into macroscopic two-dimensional superlattices using the Langmuir-Blodgett technique. Our ability to control interparticle spacing, density and packing symmetry allows for tunability of the optical response over the entire visible range. This assembly strategy offers a new, practical approach to making novel plasmonic materials for application in spectroscopic sensors, subwavelength optics and integrated devices that utilize field-enhancement effects.     

Tunable plasmonic properties of silver nanorods for nanosensing applications

Localized surface plasmon resonance (LSPR) sensitivity to the surrounding medium refractive index has been studied for silver nanorods using Gans theory including the effect of retardation and surface scattering. The simulation results show the refractive index sensitivity (eV/RIU) maxima positions at width of 9, 6, and 4 nm for aspect ratios of 2, 3, and 4, respectively. Based on the sensing figure of merit (FOM), 9 nm is found to be a significant nanorod width, where the FOM dependence on width with respect to aspect ratio inverts. However, the optimal nanorod width for both the FOM and the modified figure of merit (MFOM) is about 6 nm for aspect ratios of 2, 3, and 4. A comparison with gold shows that silver nanorods exhibit relatively higher FOM and MFOM and thus, making them potential candidates for biochemical nanosensing applications.     

Nonlinear infrared plasmonic waveguide arrays

The large negative permittivity of noble metals in the infrared region prevents the possibility of highly confined plasmons in simple waveguide structures such as thin films or rods. This is a critical obstacle to applications of nonlinear plasmonics in the telecommunication wavelength region. We theoretically propose and numerically demonstrate that such limitation can be overcome by exploiting inter-element coupling effects in a plasmonic waveguide array. The supermodes of a plasmonic array span a large range of effective indices, making these structures ideal for broadband mode-multiplexed interconnects for integrated photonic devices. We show such plasmonic waveguide arrays can significantly enhance nonlinear optical interactions when operating in a high-index, tightly bound supermode. For example, a third-order nonlinear coefficient in such a waveguide can be more than three orders of magnitude larger compared to silicon waveguides of similar dimensions. These findings open new design possibilities towards the application of plasmonics in integrated optical devices in the telecommunications spectral region.

Open image in new window

     

THz generation from plasmonic nanoparticle arrays

We investigate the generation of THz pulses when arrays of silver nanoparticles are irradiated by femtosecond laser pulses, providing the first reproducible experimental evidence in support of recent theoretical predictions of such an effect. We assess our results in the context of a model where photoelectrons are produced by plasmon-mediated multiphoton excitation, and THz radiation is generated via the acceleration of the ejected electrons by ponderomotive forces arising from the inhomogeneous plasmon field. By exploring the dependence of the THz emission on the femtosecond pulse intensity and as a function of metal nanoparticle morphology, and by comparing measurements to numerical modeling, we are able to verify the role of the particle plasmon mode in this process.     

Induced chirality through electromagnetic coupling between chiral molecular layers and plasmonic nanostructures

We report a new approach for creating chiral plasmonic nanomaterials. A previously unconsidered, far-field mechanism is utilized which enables chirality to be conveyed from a surrounding chiral molecular material to a plasmonic resonance of an achiral metallic nanostructure. Our observations break a currently held preconception that optical properties of plasmonic particles can most effectively be manipulated by molecular materials through near-field effects. We show that far-field electromagnetic coupling between a localized plasmon of a nonchiral nanostructure and a surrounding chiral molecular layer can induce plasmonic chirality much more effectively (by a factor of 10(3)) than previously reported near-field phenomena. We gain insight into the mechanism by comparing our experimental results to a simple electromagnetic model which incorporates a plasmonic object coupled with a chiral molecular medium. Our work offers a new direction for the creation of hybrid molecular plasmonic nanomaterials that display significant chiroptical properties in the visible spectral region.     

Integration of photonic and silver nanowire plasmonic waveguides

Future optical data transmission modules will require the integration of more than 10,000 x 10,000 input and output channels to increase data transmission rates and capacity. This level of integration, which greatly exceeds that of a conventional diffraction-limited photonic integrated circuit, will require the use of waveguides with a mode confinement below the diffraction limit, and also the integration of these waveguides with diffraction-limited components. We propose to integrate multiple silver nanowire plasmonic waveguides with polymer optical waveguides for the nanoscale confinement and guiding of light on a chip. In our device, the nanowires lay perpendicular to the polymer waveguide with one end inside the polymer. We theoretically predict and experimentally demonstrate coupling of light into multiple nanowires from the same waveguide, and also demonstrate control over the degree of coupling by changing the light polarization.     

Correlation between scattering properties of silver particle arrays and fluorescence enhancement

We report on the nanofabrication of patterned silver particle arrays using electron-beam lithography and the evaluation of their optical properties using backscattering and fluorescence spectroscopy. The silver particles varied in size from 100 to 250 nm and were in the shape of circles, squares, and triangles. Three inter-particle separations, 40, 65, and 90 nm as measured from the side of one particle to the side of the next particle, were used. We observed distinctive patterns of backscattering and fluorescence intensity depending on the particle size, inter-particle spacing, and excitation/emission wavelength used. Our approach allows for a study of the correlation between the backscattering intensities and fluorescence enhancement of silver particle arrays, which can be used to optimize the arrays for multi-fluorophore configuration for advanced sensing designs.     

Self-organized silver nanoparticles for three-dimensional plasmonic crystals

Metal nanostructures that support surface plasmons are compelling as plasmonic circuit elements and as the building blocks for metamaterials. We demonstrate here the spontaneous self-assembly of shaped silver nanoparticles into three-dimensional plasmonic crystals that display a frequency-selective response in the visible wavelengths. Extensive long-range order mediated by exceptional colloid monodispersity gives rise to optical passbands that can be tuned by particle volume fraction. These metallic supercrystals present a new paradigm for the fabrication of plasmonic materials, delivering a functional, tunable, completely bottom-up optical element that can be constructed on a massively parallel scale without lithography.     

Tunable infrared plasmonic devices using graphene/insulator stacks

The collective oscillation of carriers--the plasmon--in graphene has many desirable properties, including tunability and low loss. However, in single-layer graphene, the dependence on carrier concentration of both the plasmonic resonance frequency and magnitude is relatively weak, limiting its applications in photonics. Here, we demonstrate transparent photonic devices based on graphene/insulator stacks, which are formed by depositing alternating wafer-scale graphene sheets and thin insulating layers, then patterning them together into photonic-crystal-like structures. We show experimentally that the plasmon in such stacks is unambiguously non-classical. Compared with doping in single-layer graphene, distributing carriers into multiple graphene layers effectively enhances the plasmonic resonance frequency and magnitude, which is different from the effect in a conventional semiconductor superlattice and is a direct consequence of the unique carrier density scaling law of the plasmonic resonance of Dirac fermions. Using patterned graphene/insulator stacks, we demonstrate widely tunable far-infrared notch filters with 8.2 dB rejection ratios and terahertz linear polarizers with 9.5 dB extinction ratios. An unpatterned stack consisting of five graphene layers shields 97.5% of electromagnetic radiation at frequencies below 1.2 THz. This work could lead to the development of transparent mid- and far-infrared photonic devices such as detectors, modulators and three-dimensional metamaterial systems.     

The rich photonic world of plasmonic nanoparticle arrays

Metal nanoparticle arrays that support surface lattice resonances have emerged as an exciting platform for manipulating light–matter interactions at the nanoscale and enabling a diverse range of applications. Their recent prominence can be attributed to a combination of desirable photonic and plasmonic attributes: high electromagnetic field enhancements extended over large volumes with long-lived lifetimes. This Review will describe the design rules for achieving high-quality optical responses from metal nanoparticle arrays, nanofabrication advances that have enabled their production, and the theory that inspired their experimental realization. Rich fundamental insights will focus on weak and strong coupling with molecular excitons, as well as semiconductor excitons and the lattice resonances. Applications related to nanoscale lasing, solid-state lighting, and optical devices will be discussed. Finally, prospects and future open questions will be described.     

Optical impedance matching using coupled plasmonic nanoparticle arrays

Silver nanoparticle arrays placed on top of a high-refractive index substrate enhance the coupling of light into the substrate over a broad spectral range. We perform a systematic numerical and experimental study of the light incoupling by arrays of Ag nanoparticle arrays in order to achieve the best impedance matching between light propagating in air and in the substrate. We identify the parameters that determine the incoupling efficiency, including the effect of Fano resonances in the scattering, interparticle coupling, as well as resonance shifts due to variations in the near-field coupling to the substrate and spacer layer. The optimal configuration studied is a square array of 200 nm wide, 125 nm high spheroidal Ag particles, at a pitch of 450 nm on a 50 nm thick Si(3)N(4) spacer layer on a Si substrate. When integrated over the AM1.5 solar spectral range from 300 to 1100 nm, this particle array shows 50% enhanced incoupling compared to a bare Si wafer, 8% higher than a standard interference antireflection coating. Experimental data show that the enhancement occurs mostly in the spectral range near the Si band gap. This study opens new perspectives for antireflection coating applications in optical devices and for light management in Si solar cells.     

Tunable near-infrared epsilon-near-zero and plasmonic properties of Ag-ITO co-sputtered composite films

Series of co-sputtered silver-indium tin oxide (Ag-ITO) films are systematically fabricated. By tuning the atomic ratio of silver, composite films are manifested to have different microstructures with limited silver amount (<3 at.%). Two stages for film morphology changing are proposed to describe different status and growth mechanisms. The introduction of silver improves the preferred orientations of In₂O₃ component significantly. Remarkably, dielectric permittivity of Ag-ITO films is highly adjustable, allowing the cross-over wavelengths λ_c to be changed by more than 300 nm through rapid post-annealing, and thus resulting in tunable epsilon-near-zero and plasmonic properties in the near-infrared region. Lower imaginary permittivity compared with pure metal films, as well as larger tunability in λ_c than pure ITO films suggest the potentiality of Ag-ITO films as substituted near-infrared plasmonic materials. Extended Maxwell-Garnett model is applied for effective medium approximation and the red-shifting of epsilon-near-zero region with the increase of silver content is well-fitted. Angle-variable prism coupling is carried out to reveal the surface plasmon polariton features of our films at optical communication wavelength. Broad dips in reflectance curves around 52–56° correspond to the SPP in Ag-ITO films.     

Au nanoring arrays with tunable morphological features and plasmonic resonances

Gold nanoring arrays are widely applied in various fields benefitting from their localized surface plasmon resonance (LSPR) properties. A key advantage of gold nanoring arrays is that the dipole resonance peak can be systematically tuned by changing the dimensions of gold nanoring arrays. However, most of the currently reported methods for preparing gold nanoring arrays cannot conveniently control the heights of the nanorings at a low cost. Here we introduce a facile method for preparing gold nanoring arrays with tunable plasmonic resonances using colloidal lithography. The dimensions of the nanorings including diameters, lattice constants, even the heights of the nanorings can be conveniently varied. Fourier transform near-infrared (FT-NIR) absorption spectroscopy was used to obtain the plasmonic resonance spectra of the nanoring arrays. All the prepared gold nanoring arrays exhibited a strong NIR or infrared (IR) plasmonic resonance which can be tuned by varying the nanoring dimensions. This versatile method can also be used to fabricate other types of plasmonic nanostructures, such as gold nanocone arrays. The obtained gold nanoring arrays as well as nanocone arrays may have potential applications in surface-enhanced spectroscopy or plasmonic sensing.

     

Tunable filter and optical buffer based on dual plasmonic ring resonators

We demonstrate the realization of on chip plasmon-induced transparency using dual ring resonators coupling to metal–dielectric–metal bus waveguide. The theoretical results agree well with the finite-difference time-domain simulative ones. Moreover, by adjusting the radius, width, as well as the coupling distance can efficiently operate the wavelengths and bandwidths of our filter. In theory, we propose a feasible method to improve the trade-off between transmission and quality factor. Finally, the ultra-compact structure possesses slow light effect and manifests a low group velocity, which provides a guideline to control the light and has potential application in optical filter and optical buffer.     

Light propagation in curved silver nanowire plasmonic waveguides

Plasmonic waveguides made of metal nanowires (NWs) possess significant potential for applications in integrated photonic and electronic devices. Energy loss induced by bending of a NW during light propagation is critical in affecting its performance as a plasmonic waveguide. We report the characterization of the pure bending loss in curved crystalline silver NW plasmonic waveguides by decoupling the energy loss caused by bending and propagation. The energy attenuation coefficiency due purely to bending was also determined, which exhibited an exponential relationship with the bending radius. Finite-difference-time-domain (FDTD) methods were utilized for theoretical simulations, which matched the experimental results well.     

Chiroptical effects in planar achiral plasmonic oriented nanohole arrays

Chiroptical effects are routinely observed in three dimensional objects lacking mirror symmetry or quasi-two-dimensional thin films lacking in-plane mirror symmetry. Here we show that symmetric plasmonic planar arrays of circular nanoholes produced strong chiroptical responses at visible wavelengths on tilting them with respect to the incident light beam due to the collective asymmetric nature of their surface plasmon excitations. This extrinsic chiroptical effect can be stronger than the local chiroptical response in arrays of intrinsically chiral nanoholes and may be useful for chiral sensing and negative refraction.     

Holographic control of motive shape in plasmonic nanogap arrays

Here we demonstrate that 4-beam holographic lithography can be utilized to create plasmonic nanogaps that are 70 times smaller than the laser wavelength (488 nm). This was achieved by controlling phase, polarization, and laser beam intensity in order to tune the relative spacing of the two sublattices in the interference pattern of a compound-lattice in combination with the nonlinear resist response. Exemplarily, twin and triplet motive features were designed and patterned into polymer in a single exposure step and then transferred into gold nanogap arrays resulting in an average gap size of 22 nm and smallest features down to 7 nm. These results extend the utility of high-throughput, wafer-scale holographic lithography into the realm of nanoplasmonics.     

Enhanced dual plasmonic photocatalysis through plasmonic coupling in eccentric noble metal-nonstoichiometric copper chakogenide hetero-nanostructures

The extension of plasmonics to materials beyond the conventional noble metals opens up a novel and exciting regime after the inspiring discovery of characteristic localized surface plasmon resonances(LSPRs)in doped semiconductor nanocrystals originating from the collective oscillations of free holes in the valence band.We herein prepare colloidal monodisperse eccentric dual plasmonic noble metal-nonstoichiometric copper chalcogenide(Au@Cu_2-xSe)hybrid hetero-nanostructures with precisely controlled semiconductor shell size and two tunable LSPRs in both visible(VIS)and near-infrared(NIR)regions associated with Au and Cu_2-xSe,respectively.Through systematic evaluations of the photocatalytic performance of Au@Cu_2-xSe upon sole NIR and dual VIS+NIR simultaneous excitations,we are capable of unambiguously elucidating the role of plasmonic coupling between two dissimilar building blocks on the accelerated photocatalytic reactions with greater rate constants from both experimental and computational perspectives.The significantly enhanced strength of the electromagnetic field arising from efficient plasmonic coupling under the excitation of two LSPRs results in the superior activities of dual plasmonic Au@Cu_2-xSe in photocatalysis.The new physical and chemical insights gained from this work provide the keystone for the rational design and construction of high-quality dual-or even multi-plasmonic nano-systems with optimized properties for widespread applications ranging from photocatalysis to molecular spectroscopies.     

Enhanced dual plasmonic photocatalysis through plasmonic coupling in eccentric noble metal-nonstoichiometric copper chalcogenide hetero-nanostructures

The extension of plasmonics to materials beyond the conventional noble metals opens up a novel and exciting regime after the inspiring discovery of characterist...     

Controlled in situ growth of tunable plasmonic self-assembled nanoparticle arrays

Self-assembled silver nanoparticle (NP) arrays were produced by deposition at glancing angles on transparent stepped Al2O3 templates. The evolution of the plasmonic resonances has been monitored using reflection anisotropy spectroscopy (RAS) during growth. It is demonstrated that the morphology of the array can be tailored by changing the template structure, resulting in a large tunability of the optical resonances. In order to extract detailed information on the origin of the measured dichroic response of the system, a model based on dipolar interactions has been developed and the effect of tarnishing and morphological dispersion addressed.