Large Fluorescence Enhancement via Lossless All-Dielectric Spherical Mesocavities.

Nano- and microparticles are popular media to enhance optical signals, including fluorescence from a dye proximal to the particle. Here we show that homogeneous, lossless, all-dielectric spheres with diameters in the mesoscale range, between nano- (≲100 nm) and micro- (≳1 µm) scales, can offer surprisingly large fluorescence enhancements, up to F ∼ 104. With the absence of nonradiative Ohmic losses inherent to plasmonic particles, we show that F can increase, decrease or even stay the same with increasing intrinsic quantum yield q0, for suppressed, enhanced or intact radiative decay rates of a fluorophore, respectively. Further, the fluorophore may be located inside or outside the particle, providing additional flexibility and opportunities to design fit for purpose particles. The presented analysis with simple dielectric spheres should spur further interest in this less-explored scale of particles and experimental investigations to realize their potential for applications in imaging, molecular sensing, light coupling, and quantum information processing.

Extraordinary Fluorescence Enhancement in Metal-Dielectric Core-Shell Nanoparticles.

We show that in metal-dielectric core-shell nanoparticles, unusually thick dielectric coatings can produce extreme fluorescence enhancement with an enhancement factor F̅ ≳ 3000 for emitters located on the surface or in the interior of the shell of Au@dielectric spherical particles under realistic conditions, even for the emitters with 100% intrinsic quantum yield. Thick dielectric coatings facilitate high-quality transverse electric (TE) multipole (l = 7) resonances which are shown as the major cause for the reported extraordinary values of F̅.

Intriguing branching of the maximum position of the absorption cross section in Mie theory explained.

A potential control over the position of maxima of scattering and absorption cross sections can be exploited to better tailor nanoparticles for specific light-matter interaction applications. Here we explain in detail the mechanism of an appreciable blue shift of the absorption cross-section peak relative to a metal spherical particle localized surface plasmon resonance (LSPR) defined as the maximum of the extinction (and scattering) cross section. Such a branching of cross sections' maxima requires a certain threshold value of size parameter (x≈0.7 for dipole channel) and is a prerequisite for obtaining high fluorescence enhancements, because the spectral region of high radiative rate enhancement becomes separated from the spectral region of high non-radiative rate enhancement. A consequence is that the maximum of the absorption cross section cannot be used as the definition of the LSPR position for x≳0.7.

Plasmonic nano-shells: atomistic discrete interaction versus classic electrodynamics models.

Using the extended discrete interaction model and Mie theory, we investigate the tunability of the optical polarizability of small metallic nano-shells. We show that the spectral positions of symmetric and antisymmetric dipolar plasmon resonances vary with the ratio of particle radius to hole radius in a manner similar to one predicted for uniform metallic nano-shells using a semiclassical approach of two coupled harmonic oscillators. We show that, according to the extended discrete interaction model, the dipolar plasmon resonances are also present for nano-shells in the 2-13 nm size region and show the same functional dependence seen for larger nano-shells. Using previously fitted data from experiment, we can predict the size-dependence of the plasma frequency for nano-shells in the 1-15 nm size region. We find that Mie theory, which utilizes the electron mean free path correction for the permittivity, is not able to reproduce the same functional form of the dipolar modes for the nano-shells of the same sizes.

Electromagnetic energy in multilayered spherical particles.

We obtain exact analytic expressions for (i) the electromagnetic energy radial density within and outside a multilayered sphere and (ii) the total electromagnetic energy stored within its core and each of its shells. Explicit expressions for the special cases of lossless core and shell are also provided. The general solution is based on the compact recursive transfer-matrix method, and its validity includes also magnetic media. The theory is illustrated on examples of electric field enhancement within various metallo-dielectric silica-gold multilayered spheres. The user-friendly MATLAB code, which includes the theoretical treatment, is available as a supplement to the paper.

Extended Multiplicative Signal Correction for Infrared Microspectroscopy of Heterogeneous Samples with Cylindrical Domains.

Optical scattering corrections are invoked to computationally distinguish between scattering and absorption contributions to recorded data in infrared (IR) microscopy, with a goal to obtain an absorption spectrum that is relatively free of the effects of sample morphology. Here, we present a modification of the extended multiplicative signal correction (EMSC) approach that allows for spectral recovery from fibers and cylindrical domains in heterogeneous samples. The developed theoretical approach is based on exact Mie theory for infinite cylinders. Although rigorous Mie theory implies utilization of comprehensive and time-consuming calculations, we propose to change the workflow of the original EMSC algorithm to minimize extensive calculations for each recorded spectrum at each iteration step. This makes the modified EMSC approach practical for routine use. First, we tested our approach using synthetic data derived from a rigorous model of scattering from cylinders in an IR microscope. Second, we applied the approach to Fourier transform IR (FT-IR) microspectroscopy data recorded from filamentous fungal and cellulose samples with pronounced fiber-like shapes. While the corrected spectra show greatly reduced baseline offsets and consistency, strongly absorbing regions of the spectrum require further refinement. The modified EMSC algorithm broadly mitigates the effects of scattering, offering a practical approach to more consistent and accurate spectra from cylindrical objects or heterogeneous samples with cylindrical domains.

Dielectric Sphere Clusters as a Model to Understand Infrared Spectroscopic Imaging Data Recorded from Complex Samples.

Understanding the infrared (IR) spectral response of materials as a function of their morphology is not only of fundamental importance but also of contemporary practical need in the analysis of biological and synthetic materials. While significant work has recently been reported in understanding the spectra of particles with well-defined geometries, we report here on samples that consist of collections of particles. First, we theoretically model the importance of multiple scattering effects and computationally predict the impact of local particles' environment on the recorded IR spectra. Both monodisperse and polydisperse particles are considered in clusters with various degrees of packing. We show that recorded spectra are highly dependent on the cluster morphology and size of particles but the origin of this dependence is largely due to the scattering that depends on morphology and not absorbance that largely depends on the volume of material. The effect of polydispersity is to reduce the fine scattering features in the spectrum, resulting in a closer resemblance to bulk spectra. Fourier transform-IR (FT-IR) spectra of clusters of electromagnetically coupled poly(methyl methacrylate) (PMMA) spheres with wavelength-scale diameters were recorded and compared to simulated results. Measured spectra agreed well with those predicted. Of note, when PMMA spheres occupy a volume greater than 18% of the focal volume, the recorded IR spectrum becomes almost independent of the cluster's morphological changes. This threshold, where absorbance starts to dominate the signal, exactly matches the percolation threshold for hard spheres and quantifies the transition between the single particle and bulk behavior. Our finding enables an understanding of the spectral response of structured samples and points to appropriate models for recovering accurate chemical information from in IR microspectroscopy data.

Nondecaying surface plasmon polaritons in linear chains of silver nanospheroids.

We consider propagation of surface plasmon polaritons in linear chains of equidistant metallic nanospheroids. We show that, for suitably chosen parameters, the propagation is free of spatial decay in spite of the full account of absorptive losses in the metal.